Materials Horizons: From Nature to Nanomaterials

Zeba Khanam
Neelam Gogoi
Divesh Narayan Srivastava Editors

2D Nanomaterials
for Energy and
Environmental
Sustainability
Materials Horizons: From Nature
to Nanomaterials

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Zeba Khanam · Neelam Gogoi ·
Divesh Narayan Srivastava
Editors

2D Nanomaterials for Energy

and Environmental
Sustainability
Editors
Zeba Khanam Neelam Gogoi
School of Materials Science School of Life and Environmental Sciences
and Engineering, School of Chemistry
Harbin Institute of Technology University of Sydney
Shenzhen, Guangdong, China Sydney, NSW, Australia

Divesh Narayan Srivastava

Analytical and Environmental Science
Division and CIF
CSIR-Central Salt and Marine Chemicals
Research Institute
Bhavnagar, Gujarat, India

ISSN 2524-5384 ISSN 2524-5392 (electronic)

Materials Horizons: From Nature to Nanomaterials
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Preface

Two-dimensional (2D) nanomaterials are attracting tremendous research interest

ever since the advent of graphene hit the headlines. Inspired by the astonishing
physical, optical, and electronic properties of graphene, other thin-layered 2D nano-
materials have been discovered. These include transition metal dichalcogenides
(TMDs), transition metal oxides (TMOs), transition metal halides (TMHs), transi-
tion metal carbides/carbonitrides/nitrides (MXenes), elemental 2D analogs (silicene,
germanene, phosphorene, tellurene, etc.), layered double hydroxides (LDHs),
2D metal–organic frameworks (MOF), covalent organic frameworks (COF), 2D
polypeptoid, 2D metallenes, and many more. Interestingly, the library of 2D nanoma-
terials expanding enormously has featured more than 150 exotic members so far. The
advancement in 2D nanomaterials has shown very significant contributions toward
a sustainable future. This has driven us to manifest the dynamic applications of 2D
nanomaterials in energy storage/conversion and environmental remediation.
This book 2D Nanomaterials for Energy and Environmental Sustainability aims
to shift the paradigm from fundamental studies on 2D nanomaterials to more
application-oriented studies. With a collection of 12 chapters written by 38 experts
in the field, it covers the wide spectrum of 2D nanomaterials in the field of energy
and environment. It brings together recent breakthroughs and overpowering innova-
tions of 2D nanomaterials engaged in an extended range of fields, such as energy
storage/conversion, photocatalytic degradation and adsorption of pollutants, desali-
nation and membrane filtration, detection and sensing, drug delivery, and nano-
encapsulated fertilizers. This book is aimed to highlight a balanced approach toward
2D nanomaterials by presenting a comprehensive account of potential advantages and
associated risks/shortcomings. The authors have provided an informative outlook for
the future prospects of 2D nanomaterials to offer a way forward.
Chapter 1 introduces the latest trends on top-down and bottom-up synthesis
approaches and properties followed by chapters covering critical status and progress
in energy and environmental applications. Chapters 2 and 3 briefly outline the recent
advancements of 2D nanomaterials in energy conversion and storage devices with
substantial emphasis centered on solar cells, water splitting, piezo-thermoelectric
devices and supercapacitors fabrication, along with properties and their mechanism

v
vi Preface

studies. Moving toward environmental applications, Chap. 4 discusses the state-of-

the art advances in 2D nanomaterials-based photocatalytic systems for degrading
organic dyes and antibiotics. Further, the 2D nanomaterials-based adsorbents are
sequentially presented in Chap. 5, highlighting recent developments in the adsorp-
tion of organic dye pollutants, heavy metal ions, and toxic gases. Then, various types
of functional membrane-based water treatment technologies including desalination
and membrane filtration are presented in Chap. 6. We then expand our discussion
on the 2D nanomaterials-related detection of toxic gases, water pollutants, and other
biological contaminants in environment in Chaps. 7 and 8. Each chapter has covered
the key aspects, viz., preparation methods, analytical techniques followed by mech-
anistic studies relevant to curb environmental issues. Additionally, an overview on
drug delivery applications is presented mainly focusing on the newly emerged 2D
mesoporous silica nanomaterial in Chap. 9. Seeing the current agriculture scenario,
we also included Chap. 10 on 2D nanomaterials-based agro-formulations as nano-
fertilizers and nano-pesticides for nutrient delivery, pest detection, drought resistance,
etc. In spite of largely proven track record, biological/ecological risk assessment of
2D nanomaterials is another important issue that should be taken into considera-
tion. Hence, we provided Chap. 11 to shed some light on the fate and toxicity risks
of 2D nanomaterials on the environment and human health. This book ends with
Chap. 12 addressing the unresolved challenges and promising future research direc-
tions of 2D nanomaterials in the field of energy and environment. This chapter also
covers a special section on the latest patented research/products or potential nanode-
vices/gadgets/appliances that could make way to the market. It concludes that massive
efforts are still needed to gain the commercial success of these exciting materials.
This book is a timely contribution to a research area of eminent significance. It
overviews the current scenarios of targeted applications and provides an impetus
toward the fast development of this highly interdisciplinary research field that
involves material science, chemistry, physics, environmental science, life sciences,
and many others. The editors and contributing authors believe that this book will be
beneficial for researchers from diversified fields to recognize the emerging trends and
to identify persistent knowledge gaps on 2D nanomaterials for sustainable energy
and environment.

Shenzhen, China Zeba Khanam

Sydney, Australia Neelam Gogoi
Bhavnagar, India Divesh Narayan Srivastava
Contents

1 An Introduction to the Wonder 2D Nanomaterials: Synthetic

Approaches and Fundamental Properties . . . . . . . . . . . . . . . . . . . . . . . . 1
Amit K. Rana and Amreen A. Hussain
2 Emerging 2D Nanomaterial Composites for Efficient Energy
Conversion: Insight into the Evolutionary Perspective
of Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Amreen A. Hussain and Amit K. Rana
3 Next-Generation 2D Nanomaterial Composites Electrodes
for Electrochemical Energy Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Harish Mudila, Parteek Prasher, Anil Kumar, M. G. H. Zaidi,
Mousamee Sharma, and Amit Verma
4 Novel 2D Nanomaterial Composites Photocatalysts:
Application in Degradation of Water Contaminants . . . . . . . . . . . . . . 75
Mohd Saquib Tanweer and Masood Alam
5 Advanced 2D Nanomaterial Composites: Applications
in Adsorption of Water Pollutants and Toxic Gases . . . . . . . . . . . . . . . 97
Mohd Saquib Tanweer, Harshvardhan Chauhan, and Masood Alam
6 Progress in 2D Nanomaterial Composites Membranes
for Water Purification and Desalination . . . . . . . . . . . . . . . . . . . . . . . . . 125
Savan K. Raj and Vaibhav Kulshrestha
7 Advancements in 2D Nanomaterial Composites-Based
Electrochemical Sensors for Environmental Contaminants . . . . . . . . 149
Zeba Khanam, Sameer Ahmad, Mohd Saquib Tanweer,
Weqar Ahmad Siddiqi, and Masood Alam

vii
viii Contents

8 Trending 2D Nanomaterial Composites in Detection

and Sensing of Biological Contaminants . . . . . . . . . . . . . . . . . . . . . . . . . 173
Jayanta Sarmah Boruah, Sristi Majumdar, Ankita Deb,
Jahnabi Gogoi, and Devasish Chowdhury
9 Newly Emerged 2D Mesoporous Silica Nanoparticles: Role
in Target-Setting Biomedicines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Prateek Srivastava, Sumit Kumar Hira, and Partha Pratim Manna
10 Futuristic 2D Nanomaterial Composites Agro-Formulations
for Sustainable Agriculture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
Poonam Gogoi Konwar
11 Fate of 2D Nanomaterials and Their Toxic Effects
on the Environment and Human Health . . . . . . . . . . . . . . . . . . . . . . . . . 243
Achyut Konwar, Jayanta Sarmah Boruah, Kabyashree Phukan,
and Sazzadur Rahman
12 Prospective on 2D Nanomaterials for Energy
and Environment: Challenges, Commercial Aspect,
and the Future Research Endeavor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
Zeba Khanam, Neelam Gogoi, and Divesh Narayan Srivastava
About the Editors

Dr. Zeba Khanam is currently working as a postdoctoral researcher at School of

Materials Science and Engineering, Harbin Institute of Technology, Shenzhen, China.
She obtained her Ph.D. in Environmental sciences from G. B. Pant University of
Agriculture and Technology, Pantnagar, India. Her research work encompasses a
broad spectrum of energy and environmental applications including electrochem-
ical energy storage materials, flexible electrodes, polymer electrolytes, anticorro-
sive coatings, electrochemical sensing, and water quality assessment. She authored
11 scientific articles published in leading international journals, 5 popular arti-
cles in national magazines and 5 book chapters. She has presented her work at
numerous national/international conferences including the most prestigious RSC
FD-173 event. She is a recipient of national/international fellowships and recently
received NESA Junior Scientist-2020 award from National Environmental Science
Academy (NESA), India. She is serving as a referee for reputed journals of Springer,
Elsevier, Wiley, and T&F, and holds the membership of scientific societies namely,
RSC-London, NESA-India, and ISCA-India.

Dr. Neelam Gogoi is a postdoctoral research associate at School of Life and Envi-
ronmental Sciences and a research affiliate at School of Chemistry, University of
Sydney. Before that, she worked at Chinese Academy of Sciences. She obtained her
Ph.D. in Chemistry from University of Gauhati, India. Her research areas include
genetic nano-engineering in plants, polymer chemistry, and carbon nanomaterials for
sensors, drug delivery, and gene delivery systems. She published 14 research articles
in American Chemical Society, Royal Society of Chemistry, and Elsevier along with
2 chapters. She received Nature travel grant to present at GRC, Massachusetts. DST,
Government of India, sponsored her work to present at Royal Society of Chemistry,
London. She is a recipient of RSC Nanoscale Best Poster Award, Dr. Shanti Nath
Ghosh Memorial Award for Best Oral Talk, and many more. Dr. Neelam is currently
in the editorial board of JENR, Medwin Publishers.

Dr. Divesh Narayan Srivastava currently holds the position of the senior principal
scientist at CSIR-CSMCRI, India, and a professor, AcSIR. He graduated from BHU,

ix
x About the Editors

India, in 1999, followed by spent few years at Bar-Ilan University, Israel, and IIT
Bombay, India, as a postdoctoral fellow. His current research interest includes electro-
chemical sensors and electrocatalysis. He has 98 research papers, 3 book chapters and
4 patents in his credit and developed technologies such as “Plastic chip electrodes”
and “Tailored Potentiostat”. He is associate fellow of Gujarat Science Academy
and is a recognized member of several other national/international scientific and
administrative organizations.
Chapter 1
An Introduction to the Wonder 2D
Nanomaterials: Synthetic Approaches
and Fundamental Properties

Amit K. Rana and Amreen A. Hussain

1 Introduction

Nanomaterials have been attracting the scientific world because of their unusual phys-
iochemical characteristics due to their high aspect ratio, strange surface morphology,
unique surface chemistry, and quantum-size effect, as compared to their bulk coun-
terparts [1]. Based on their unique properties, they can be applied in a wide range
of multifunctional application. In the last few decades, a large number of research
works are published in the field of nanomaterials with a progressing span of about
30,000 publications per year. Dimensionality is one of the key factors to manipulate
the nanomaterial properties. It is to be noted that the properties of nanomaterials are
mostly attributed to their unique nanostructure and composition. Moreover, in terms
of dimensions or confinement of electrons, nanomaterials have been categorized as
zero (0D-), one (1D-), and two (2D-) nanostructures. For instance, the 0D nanoma-
terials (such as spherical nanoparticles and quantum dots) confine electrons in all
three dimensions in the nanometre range. Similarly, with 1D and 2D structures, the
electrons are confined in either one or two dimensions (2D) in the nanometre range
[1]. In this chapter, we are interested to discuss different types of 2D nanomaterials
along with their synthetic approaches, properties, and material characterizations.
In 2004, Novoselov and co-workers exfoliated a single-atom-thick layer of
graphite using a mechanical cleavage method where the carbon atoms are arranged
in a 2D hexagonal structure, which led to the discovery of Nobel Prize-winning

A. K. Rana (B)
Department of Materials Science and Engineering, Ulsan National Institute of Science and
Technology (UNIST), Ulsan 44919, South Korea
e-mail: [email protected]
A. A. Hussain
Facilitation Centre for Industrial Plasma Technologies (FCIPT), Institute for Plasma Research
(IPR), Gandhinagar 382428, Gujarat, India
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 1
Z. Khanam et al. (eds.), 2D Nanomaterials for Energy and Environmental Sustainability,
Materials Horizons: From Nature to Nanomaterials,
https://doi.org/10.1007/978-981-16-8538-5_1
2 A. K. Rana and A. A. Hussain

graphene [2]. With the discovery of graphene, the scientific community has received
a lot of attention to exploring the other potential 2D nanostructures. Therefore, after
years of hard work, the scientists working in the field of 2D nanomaterials have
found novel ways to synthesize 2D nanomaterials such as mechanical cleavage,
ion-intercalation, liquid exfoliation, chemical vapour deposition (CVD), plasma-
enhanced chemical vapour deposition (PECVD), hydrothermal syntheses [3–6]. For
the synthesis of 2D nanomaterials, a large variety of materials are explored: from
metals to semiconductors to insulators and even to superconductors which show
remarkable properties with better performance than graphene. Based on the electron
confinement in single-layered 2D nanomaterials, they show outstanding electronic
and transport properties. In addition, the nanomaterials have a high surface area,
owing to the exposure of edge sites, and flexibility in atomic level, high thermal
endurance which made them suitable candidates for diverse applications such as
in nano-electronics, optoelectronics, medical, civil fields and in space applications
[5–7].

1.1 Type of 2D Nanomaterials

As already highlighted, graphene is known as a wonder nanomaterial consisting

of crystalline carbon film and exhibits various unprecedented properties, such as
ultrahigh carrier mobility (∼10,000 cm2 V–1 s–1 ), quantum hall effect, high specific
surface area (2630 m2 g–1 ), optical transparency (∼97.7%), and excellent thermal
conductivity (3000–5000 W-m–1 K–1 ) [2]. Inspired by the unexpected properties of
graphene, the quest to explore other ultrathin 2D nanomaterials begins. Efforts are
made by the researchers to exploit new 2D nanomaterials that possess similar features
to that of graphene, yet capable of versatile properties. Among the family of new 2D
materials originates the transition metal dichalcogenides (TMDs; e.g. MoS2 , NbSe2 ,
TaS2 , WS2 , MoSe2 , WSe2 , etc.), hexagonal boron nitride (h-BN), carbon nitride
(CN), transition metal oxides, layered perovskites, metal–organic frameworks, black
phosphorus (BP), and MXenes [7–11], as schematically presented in Fig. 1.
Transition metal dichalcogenides (TMDs): TMD monolayers are semiconductor
materials with atomically thin layers with a general representation of MX2 ; where
M is a transition metal (Mo, W, Te, etc.), and X is a chalcogen atom (X = S, Se,
Te, etc.). In a typical structure of MX2 , one layer of M atoms is sandwich between
two separate layers of X atoms to form X–M–X structure [10]. With this atomic
arrangement, the crystal structure forms a honeycomb, hexagonal lattice. Usually,
the M–X bonds (intralayer) between the transition metal and chalcogen atoms are
known to be covalent bonds, whereas the individual MX2 layers are bonded together
by van der Waals (vdW) (interlayer) forces which are considered as weak bonds.
Moreover, the TMDs can form metal coordination such as trigonal prismatic or
octahedral. This coordination of metals and also the order of staking between the
monolayers describe the phase of TMD materials. Some most common phases are
1 An Introduction to the Wonder 2D Nanomaterials … 3

Fig. 1 Schematic illustration of different kinds of typical ultrathin 2D nanomaterials, such

as graphene, h-BN, TMDs, MXenes, TMOs (2D metal oxides), layered perovskite, and BP
(phosphorene)

1T, 2H, or 3R, where T, H, and R stand for tetragonal, hexagonal, and rhombohedral,
while 1, 2, and 3 denote the number of X–M–X sandwiches per unit cell.
Hexagonal boron nitride (h-BN): h-BN is a layered material that has a similar
structure to graphite, which in turn has similar properties like graphite. The crystal
arrangement of h-BN consists of alternate boron and nitrogen atoms which is bonded
with sp2 hybridization forming an atomic-level thick layer [11, 12]. Usually, the bond
length among two consecutive boron and nitrogen atoms is 0.144 nm. h-BN exhibits
covalent bonding within the plane. Irrespective of this, its interplane bonding is
relatively weak due to vdW forces. In h-BN, the spacing between two successive
layers is 0.334 nm which is analogous to graphene (0.333 nm). Thus, h-BN displays
advantages for efficient electronic and optical applications.
Carbon nitride (CN): Graphitic carbon nitride (general formula g-C3 N4 ) is one of the
hardest and most stable compounds belonging to the library of 2D nanomaterials.
4 A. K. Rana and A. A. Hussain

The fundamental structure of C3 N4 forms a polymeric stacked structure which is

more like graphite containing sp2 hybridized carbon and nitrogen atoms [13]. It
consists of tris-triazine-based patterns where the carbon to nitrogen ratio is typically
¾ with a small amount of hydrogen. Because of the presence of nitrogen (lone
pair) and π-conjugation system with carbon pz -orbital, the C3 N4 shows promising
electronic properties. There are mainly two known structures of C3 N4 , one is based
on heptazine, and the other is poly-triazine imide units based on which the reaction
conditions, reactivities, and the associated properties can vary.
Transition metal oxides: The transition metal oxides from their bulk state can be
transformed into atomically thin nanosheets, thus placing their stand as 2D nanoma-
terials [14]. It is already known that the bulk metal oxides can show unique combi-
nation of both physical and chemical properties with earth abundance. However, the
2D nanosheets of metal oxides provide even more unprecedented features such as
larger surface area, improved active sites, and interplanar charge transport. There
are various metal oxides found in nature, and to name a few are MoO3 , TiO2 , ZnO,
Co3 O4 , V2 O5 , etc. Every 2D metal oxides have different crystal structures which
will be discussed in detail in the succeeding sections of the chapter.
Layered perovskites: The dimensionality of the 3D perovskite structure when reduced
to layered 2D form enables very interesting properties for diverse applications. In
simple terms, the 2D perovskite resembles the slice cut from the 3D perovskite lattice.
Different from the 3D perovskite with ABX3 structure (where a larger cation (A)
simply fills the voids between BX6 octahedra), and in 2D perovskite, some larger
cations are introduced into the structure with acts as spacers [15]. These spacers help
to isolate the inorganic octahedra to form quantum well superlattices. Furthermore,
these extra spacing cations induce asymmetric lattice structure, thereby providing
an additional degree of freedom. Thus, the structural slicing along a definite crystal-
lographic plane forms a layered material that is coupled by weak vdW interactions.
The empirical formula of 2D perovskites is L2 MX4 , where L is the large monova-
lent organic cation/spacer, M the metal cation, and X the anion. Few examples of
2D-layered perovskites are Cs2 PbI2 Br2 , (BA)2 (MA)2 Pb3 I10 , etc.
Metal–Organic frameworks: Metal–organic frameworks also form 2D structures
which are considered as an attractive alternate crystalline porous material [16, 17].
It basically consists of metal bridging nodes and multi-podal organic ligands that
are bonded together. This type of bonding usually forms through basic coordination
chemistry. In general, the metal node is coupled to the organic ligand by a coordina-
tion bond; however, the layers of the metal–organic framework are linked by weak
vdW forces.
Elemental 2D nanomaterials: Elemental 2D nanomaterials are attracting great atten-
tion with the experimental demonstrations of borophene nanosheets belonging to
the group III. Boron forms almost 16 number of allotropes through complex B–B
bonds, out of which only three forms are thermodynamically stable (α-rhombohedral,
β-rhombohedral, γ-orthorhombic, and γ-tetragonal) [18]. These allotropes consist
of the icosahedral B12 units as the building blocks. Notable structure among the
1 An Introduction to the Wonder 2D Nanomaterials … 5

borophene is the B36 , which has a bowl-shaped cluster with a periodic hexagonal
holes arrangement forming a triangular lattice. The hexagonal arrangements of atoms
can be visualized as graphene-like nanosheets [18, 19].
Another interesting 2D nanomaterials are silicene, germanene, and stanene
belonging to the group IV elements [19]. Silicene is derived from silicon which
comprises a buckled sheet and can host non-trivial electronic states, spin-polarized
edges, and a tunable bandgap that allows for application in quantum information.
Similarly, germanene is also a buckled monolayer of germanium that forms a nearly
flat honeycomb nanosheets [18]. Germanene shows strong spin–orbit coupling for
topological insulator properties. Stanene, on the other hand, is derived from tin (α-
Sn). Stanene is epitaxially grown on various substrates; however, its structure is not
well-defined [18, 19].
From the group V elements, phosphorene or black phosphorus (BP) is an allotrope
of phosphorous which is known to be thermodynamically stable at room temperature
(RT). It also emerges as one of the novel 2D semiconducting materials which has
similar properties and colour of graphite. Typically, BP has an orthorhombic crystal
structure, closely analogous to graphene. In the crystal arrangement, the phospho-
rous atoms are organized in a honeycomb lattice with puckered double layers. BP
monolayer has sp3 hybridization where one phosphorous atom is covalently bonded
to three other adjacent phosphorous atoms having a bond length of 2.18 Å [20].
In addition, it has one lone pair of electrons, thus forming a quadrangular pyramid
structure. The adjacent layers of phosphorous atoms interact by weak vdW inter-
actions where the distance between two layers is about 0.5 nm. Similarly, arsenene
also belongs to group V that has a single buckled honeycomb 2D layer of arsenic.
Arsenene has an indirect bandgap of 2.49 eV and a high charge carrier mobility.
Another 2D structures are antimonene and bismuthene which are extracted buckled
honeycomb network of antimony and bismuth [19]. Antimonene has high carrier
mobility and excellent thermal conductivity. Bismuthene is extensively used in topo-
logical insulators through the reduction of bismuth [ref]. Notably, various structures
and properties of BP-like puckered structures (α-phase) of arsenene, antimonene,
and bismuthene have been predicted [18–20]. However, fabrication of monolayer
α-phase is challenging mainly due of the lack of layered allotropes.
MXenes: With the expansion of the family of 2D nanomaterials, the derivatives of
transition metals using carbides, carbonitrides, and nitrides lead to the discovery of
MAX phases where M stands for transition metal (Ti, Zr, Cr, etc.), A is an element
from A-group mainly IIIA, IVA (Ga, Pb, Al, etc.), and X is either carbon or nitrogen.
By introducing selective etching of the A element from the MAX phases, MXenes
are created. MXenes are considered as layered solids linked by strong metallic, ionic,
and covalent bonds. Having a layered hexagonal structure, they belong to space group
P63 /mmc symmetry. MXenes have a general formula Mn+1 AXn , with n = 1–3, and
thereby, the MXene sheets consist of 3, 5, or 7 atomic layers constructing M2 X,
M3 X2 , and M4 X3 , respectively [9]. Some examples of MXenes are Ti2 C, Ti3 C2 ,
Mo2 Ga2 C, Nb4 C3 , etc.
6 A. K. Rana and A. A. Hussain

2 Synthesis of 2D Nanomaterials

The 2D nanomaterials possess both similarities and differences in their funda-

mental crystalline features compared to their 3D counterparts. Therefore, to main-
tain their unique structural/crystalline features and simultaneously retaining their
outstanding properties, atomically thin 2D nanomaterials have become the fore-
front in condensed matter physics, materials science, and nanotechnology. In liter-
ature, there are numerous methods available for the synthesis of 2D nanomate-
rials. However, before addressing the individual experimental techniques, it is worth
mentioning that the nanoscale synthesis methods are broadly categoried into two
types: bottom-up approach and top-down approach (Fig. 2) [21].

2.1 Bottom-Up Approach

The bottom-up approach is also referred as the gathering-up method in which the
2D nanomaterials can be synthesized from atomic or molecular precursors in the
form of nanoparticles or nanocrystals that are allowed to grow in size after under-
going certain chemical reactions. The nanoscale particles thus self-assembled into
larger complex substances or can be supplemented to any substrate of interest [21,
22]. The bottom-up approach is mainly desired for achieving controlled size, shape,
composition, sequential stacking arrangement, and stable chemical structure. There
are various synthetic methods used to prepare 2D nanomaterials using the bottom-up
approach such as hydrothermal or solvo-thermal method, wet chemical synthesis,
CVD, PECVD, organic ligand-assisted synthesis, interface-assisted synthesis, and
template-assisted synthesis [23, 24]. Here, we have discussed the most regularly used
techniques.
Hydrothermal method: This is one of the most common and widely used synthesis
methods of 2D nanomaterials. It is cleared from the name itself that this technique
deals with water (hydro) and heat (thermal). This means that this method is somewhat
analogous to wet thermal synthesis. Although there are few additional requirements
in the hydrothermal method which are the high temperature and pressure. Typically,
the hydrothermal reaction is carried out inside an autoclave (vessel) with a Teflon
liner. At first, the precursor materials are mixed thoroughly in an appropriate concen-
tration and then transferred to the autoclave vessel. The autoclave vessel is designed
in such a manner so that it can easily work under high-pressure conditions. Finally,
the precursor-filled vessel is placed in a heating furnace, setting a specific temperature
and time for the reaction to start till completion. Here, the solvents serve as the catalyst
to initiate the reaction and help the growth of nanostructures [25]. This technique has
several benefits such as high product yield, controlled size/shape, high-quality crys-
tals, and most importantly, the low-cost instrumentation with environment-friendly
synthesis. Yin et al. have presented a novel hydrothermal strategy to synthesize
1 An Introduction to the Wonder 2D Nanomaterials … 7

Fig. 2 Different synthesis techniques for the growth of 2D nanomaterials: top-down and bottom-
up approaches. a Mechanical cleavage method (1) press the adhesive tape against the 2D crystals,
(2) few layers are attached to the tape, (3) the tape with crystals is pressed against a surface, (4)
upon peeling, the bottom layer left on the substrate, b hydrothermal method, c CVD technique, d
sonication derived exfoliation via (1) the addition of exfoliating/stabilizing agents, (2) sonication,
and (3) exfoliated 2D nanosheets. e Ion-intercalation method. Reprinted with copyright permission
from [5–8, 10]

MoSe2 nanosheets [26]. This synthetic approach provides the synergistic regula-
tion of both crystal phase (1T) and disorder engineering. In addition, one modi-
fied approach using the hydrothermal technique is reported by Dai et al., where
graphene-like MoSe2 nanosheets are synthesized under the synergy of graphene and
polyvinylpyrrolidone [27]. Moreover, Alam et al. have synthesized metal oxide-based
2D nanomaterials using Bi-TiO2 nanotube/graphene nanocomposites through simple
hydrothermal synthesis [28]. Similarly, various 2D nanosheets of metal oxides such
8 A. K. Rana and A. A. Hussain

as Ga2 O3 , ZnGa2 O4 , and MnGa2 O4 are prepared by hydrothermal synthesis [29].

These nanosheets exhibit a triangular/hexagonal configuration with ultrathin thick-
ness. In addition, Peng et al. demonstrated the use of a modified hydrothermal route
using some basic etching agent to synthesize 2D MXene (Ti3 C2 ) [30]. They have also
extended their route to other MXene such as Nb2 C. Subsequently, to boost the mate-
rial yield of MXenes, Han et al. have adopted a facile hydrothermal-assisted intercala-
tion approach to form 2D Ti3 C2 Tx and achieved 74% yield which was conventionally
limited to 20% [31]. Hydrothermal synthesis is also used to prepare 2D nanosheets
of boron nitride. Xie et al. reported the hydrothermal exfoliation method where the
bulk h-BN undergoes expansion with the insertion of Li+ and then exfoliated into
ultrathin 2D nanosheets [32]. Catalyst-free g-C3 N4 is also prepared by the low-cost
hydrothermal approach [33].
Chemical vapour deposition (CVD) method: As the name suggests, CVD is a gas
phase deposition method for the preparation of thin films over any desired substrate.
Here, the precursors (volatile or viscous liquids) are injected into the vacuumed
sealed reaction chamber in the form of vapours/gases and are allowed to go through
some specific chemical reactions at a specific ambient temperature. Consequently, the
placed substrates get coated when the reaction products of the precursors are assem-
bled onto it [23, 34]. There are various synthesis parameters to take care of while
performing the deposition such as process temperature, pressure, substrate temper-
ature, and gas mixture composition. Therefore, simply controlling these parame-
ters, it is possible to synthesize good quality thin films with high purity. This tech-
nique has some special advantages: for instance, low film porosity, high purity, and
outstanding stability at air ambient comprehensively adopted in industries. Based on
the CVD method, numerous 2D nanomaterials are synthesized for targeted applica-
tions. McCreary et al. reported the synthesis of large-area monolayers of WS2 using
CVD [35]. Likewise, Dankert et al. have worked on the fabrication of all CVD-
based heterostructures with h-BN/graphene/h-BN configuration for developing high-
performance Hall sensors [36]. As one kind of CVD technique, the researchers have
also explored the PECVD technique to grow CN films using methane (CH4 ) and N2
gases [37]. Again, adopting an in-situ CVD approach, large-area 2D BP is grown
with an average area of > 3 μm2 and about four layers of thickness [38]. A similar
effort has been done by other groups to grow TMDs (WS2 ) atomic layer on h-BN
film by CVD technique [39].
Interface-assisted synthesis: Basically, an interface is referred as any flat or curved
space (more precisely can be known as any phase boundary) between two dissimilar
materials. Likewise, the interface formed between air and matter or between vacuum
and matter is called the surface. Typically, the thickness of any interface ranges
from angstrom (Å) to nanometres to few micrometres. Therefore, once the ratio of
area to thickness in any interface is high enough, it is called a 2D interface. In the
field of materials science, this 2D interface is highly active for multiple reactions as
compared to the bulk phase. Some common interfaces that are involved in chemical
reactions include the air/liquid, liquid/liquid, solid/liquid, and vacuum/solid inter-
faces. These types of 2D interfaces provide space to the precursors to gather and
1 An Introduction to the Wonder 2D Nanomaterials … 9

induce the growth process or nucleation in a confined 2D space. This confined reac-
tion in 2D space plays an important role in controlling the material properties of the
final product [40]. Therefore, as one kind of bottom-up approach, there are various
interface-assisted synthetic approaches reported in the literature for the development
of 2D nanomaterials. Considering the synthesis of graphene (a star material in the
field of materials science), the gas/solid or the vacuum/solid interface is a popular
strategy that can be done using CVD. In CVD, a selective solid substrate is kept in a
vacuumed/air chamber, and the gases of interest (say CH4 for graphene) are inserted
into the chamber which is allowed to react on the substrate. Pollard et al. confirmed
the growth of graphene on a Ni film (Ni is used as a catalyst) deposited on the SiO2 /Si
substrate using CVD [41]. Similarly, using CVD with a vapour/solid interface, h-
BN is also synthesized by Shi et al. [42]. Interfacial synthesis strategies towards the
preparation of TMDs have also been explored. Transition metal selenides such as
TiSe2 , NbSe2 , and TaSe2 are synthesized by surfactant lamellar templating which
acts as efficient 2D catalysts. These 2D structures feature the thickness from single
sheets to tens of nanometres [43]. Other noble 2D metal oxides such as SnO2 , CuO,
and In2 O3 are developed using surfactants. For the growth of 2D metal oxides using
bottom-up approach from molecular precursors, Sun et al. have addressed the surfac-
tant self-assembly, where the surfactants serve as the agents for structure design and
help to confine the growth along the desired 2D direction [44]. In addition, an inter-
esting 2D metal–oxide framework nanosheets are demonstrated by Nishihara and
co-workers. At the air/water interface, they have tried to synthesize a single-layer
nickel bis(dithiolene) nanosheets under atmospheric pressure [45]. Moreover, with
regards to the other 2D nanomaterials such as MXenes, CN, and BP, the current
synthesis methods are primly focused on the physical and chemical exfoliation of
their bulk structures. Thus, the growth of single- to few-layered structures through
the interface-assisted synthesis is still under progressive development.

2.2 Top-Down Method

In contrast to the bottom-up approach, the top-down approach is more complex and
requires sophistication. The top-down approach is also referred as the destructive
method where the nanostructures are formed by removing the building blocks from
the matter or cutting/sizing the solid crystal planes [21]. Particularly considering
the synthesis of 2D nanomaterials, the top-down approach involves the breaking of
interlayer spacing of a 3D matter to prepare atomically thin layers. Again, the top-
down method is grouped into various types such as exfoliation method, chemical
etching, sputtering, nano-lithography, and laser ablation. Here, we have discussed
some of the widely used techniques:
Exfoliation method: The exfoliation method is categorized into two types: chemical
exfoliation and physical exfoliation. Chemical exfoliation is resulted from the thin-
ning of a layered crystal down to atomic-level layers through appropriate chemical
10 A. K. Rana and A. A. Hussain

routes involving intercalants [46] to form 2D-layered structures. A large number of

intercalants are used for chemical exfoliation such as acids/bases (HSO4 − , SO2 2− ,
and KOH), inorganic salts (Li+ , Na+ ), oxidizing agents (hydrogen peroxide and
hydroxyl radicals), and functional molecules (NH+ , pyrene sulfonic acid). Diazo-
nium salts are effectively used to chemically exfoliate the semiconducting bulk MoS2
in the 2H phase [47]. Similarly, some other bulk chalcogenides such as Bi2 S3 and
Sb2 S3 are also exfoliated into 2D nanosheets using this chemistry [48, 49]. On the
other hand, one report addresses that with aryldiazonium modification, it is possible
to exfoliate bulk BP without undergoing any pre-treatment and passivation of the
surface to form 2D nanosheets which can be applied in field-effect transistors (FET)
[50]. Composites of graphene oxide/manganese phosphate are also realized by the
chemical exfoliation process through Hummer’s method as reported by Yuan et al.
[51]. The liquid exfoliation method is also explored by many researchers for the
synthesis of 2D metal oxides. This process is associated with gentle cutting of the
bulk interlayers where different organic cations such as TBA and ammonium ions
are used as the intercalant agents [52]. Chemical exfoliation of MAX phases into 2D
MXenes is also highlighted by the research community. Khazaei et al. have utilized
a series of first-principle calculations based on DFT and studied the exfoliation ener-
gies, forces, bond strengths, and electronic structures of the MAX phase. Based on
their DFT calculations, around 37 MAX phases are proposed for successful exfoli-
ation into 2D MXenes such as Ti3 C2 , Ti4 C3 , Zr2 C, Hf2 C, V3 C2 , V4 C3 , Mo2 C, and
so on [53]. From the above-mentioned examples, now it is clear that with chemical
exfoliation the chemical structure of 2D nanomaterials can be tuned through some
appropriate reactions. During the chemical exfoliation process, sometimes the 2D
nanomaterials suffer from loss of their inherent properties causing rapid degradation.
Physical exfoliation, on the other hand, can preserve the important properties of
exfoliated 2D nanomaterials without experiencing much degradation. Physical exfo-
liation also offers large-scale production suitable for all practical applications. This
type of exfoliation is mainly achieved through some external driving forces such
as sonication, wet/dry ball milling, shear mixing, using some supercritical fluids,
polar/non-polar solvents, and stabilizers. Considering the simplest case of ultrason-
ication, it has been reported by Kim et al. that any layered bulk material such as
graphene, MoS2 , and h-BN can be exfoliated by controlling the temperature in an
ultrasonic bath [54]. The as-exfoliated 2D materials, for instance, h-BN display an
alternating charge distribution with a strong polarity across the boron and nitrogen
termination edges. However, MoS2 and MoSe2 provide moderate polarity, where the
surface has a negative charge with the sulphur atoms and counter-charges inside the
molybdenum atoms. With ultrasonication, the 2D nanomaterials often suffer from the
introduction of undesired defects. Therefore, the use of supercritical fluid is another
approach to physical exfoliation [55]. As one of the most common supercritical
fluids, CO2 presents a solvent-like behaviour which can dissolve non-polar chemical
species. Using CO2 , thick nanosheets of more than ten layers can be formed [56]. A
molecular dynamics study is conducted for stabilizing MXene (Ti2 CO2 ) structures
using supercritical CO2 as reported by Khaledialidusti et al. [57]. In addition, ball
milling is also one type of physical exfoliation technique which is used to prepare
1 An Introduction to the Wonder 2D Nanomaterials … 11

MXenes (Ti2 C2 Tx ). After ball grinding, the Ti3 AlC2 size is found to be uniform and
can be tuned from 4.488 to 1.454 μm, with a well-defined 2D nanosheets structure
[58]. Similarly, g-C3 N4 powders are also synthesized by ball milling from amor-
phous carbon at high temperatures [59]. Graphene, TMDs, and h-BN synthesis with
solvent-stabilizer exfoliation is also addressed using PVA-assisted shear-exfoliation
and using chloroform/acetonitrile and IPA/water [60].
Sputtering: Sputtering is a comprehensively used industrial-based technique that
provides large-scale high purity production of diverse materials maintaining high
quality and controllability. With this technique, it is possible to use any kind of
substrate and even applicable to insulating material deposition. In general, sputtering
is performed under a vacuum with a target material to be sputtered. Generally, an inert
gas (or a reactive gas) is used as a carrier gas to initiate the plasma glow upon applied
bias. The ionized gases are then accelerated to the target material in the presence
of an electric field and thus bombards the target surface with high kinetic energy,
thereby ejection of the target atoms. Those target atoms are then self-assembled or
accumulated on the substrates to form the smooth and uniform coating [61]. Various
2D nanomaterials are synthesized by sputtering. Rigi et al. have demonstrated a
RF magnetron sputtering method to produce MoS2 layers [62]. For the experiment
molybdenum target was used under sulphur environment using an in-situ effusion
cell. A highly pure 2H-MoS2 phase is obtained using RF magnetron sputtering.
Likewise, thin MoSe2 interlayer is prepared by sputtering and selenization process
by pressure variation and applied for efficient Cu(In, Ga)Se2 solar cell (PCE =
10.8%) [63]. Moreover, high-quality boron nitride (BN) films are also deposited by
magnetron sputtering as addressed by Sutter et al. [64]. Here, the boron is sputtered
under N2 and Ar environment, and the thickness of the deposited film is carefully
controlled. Ensuring effective substrate temperature, two atomic layers of BN are
successfully deposited by magnetron sputtering. Li et al. have reported an ionized
magnetron sputtering method to deposit amorphous CN [65]. High purity graphite is
used as the sputtering target with an inductively coupled plasma assembly between
the target and the substrate under Ar/N2 mixture gases. Within the N2 to C ratio
of 0.3–0.4, hardness up to 16–17 GPa is achieved. Moreover, Wang et al. using
magnetron sputtering tried to deposit MXene with molybdenum carbide (Mo2 C)
structure to be applicable in solid-state Q-switched pulsed laser generation [66].
The overall summary of the different synthetic approaches for the preparation of 2D
nanomaterials including their advantages and challenges is tabulated in Table 1.

3 Properties and Characterizations of 2D Nanomaterials

The 2D nanomaterials based on their unique structures and wide range of synthetic
approaches emerge as one of the novel classes of nanoscale materials. With the
unique structural constructions of various 2D nanomaterials, they show interesting
 12

Table 1 Summary of various synthesis techniques to grow 2D nanomaterials with their achievements and challenges
Synthetic methods 2D nanomaterials Achievements Challenges References
Bottom-up Hydrothermal/solvo-thermal TMDs: MoSe2 , MoS2 • Easy processing • Thickness control [20–32]
method Oxides: Ga2 O3 , ZnGa2 O4 , • High product yield • Long synthesis duration
MnGa2 O4 • Controlled size/shape • Repeatability
MXenes: Ti3 C2 , Ti3 C2 Tx • Tunable morphology • Not scalable
CN: g-C3 N4 • Low cost and eco-friendly
CVD, PECVD TMDs: WS2 • High purity • Defect control [33–39]
h-BN • Large-area coverage on any • High temperature
BP substrate • High-cost sophisticated
• Pin-hole free film vacuum technique
• Excellent stability
• High scalability
Interface-assisted synthesis TMDs: TiSe2 , NbSe2, TaSe2 • Composition and design • Small crystallites [40–45]
Oxides: SnO2 , CuO, and function • Thickness control
In2 O3 • Controlled size/shape • Low-yield
• Tunable morphology • Inert atmosphere
Top-down Exfoliation: Physical and TMDs: MoS2 , Nb2 S3, Sb2 S3 • High purity • Small crystallites [46–59]
chemical BP, silicene • High porosity • Thickness control
MXenes: Ti3 C2 , Ti4 C3 , Zr2 C, • Uniform growth • Low-yield
Hf2 C, V3 C2 , V4 C3 , Mo2 C • Wafer scalable • Not scalable
CN: g-C3 N4
Sputtering TMDs: MoSe2 , MoS2 • High purity • Defect control [60–66]
h-BN • Large-area coverage on any • Comparatively high-cost
MXenes: Mo2 C substrate technique
• Pin-hole free film
• Excellent stability
• High scalability
A. K. Rana and A. A. Hussain
1 An Introduction to the Wonder 2D Nanomaterials … 13

Fig. 3 Different properties

of 2D nanomaterials with
their corresponding unique
characteristic features

properties like unprecedented optical or photonic properties and tunable morpholog-

ical features. In addition, the 2D nanomaterials also offer unique electrical transport
properties based on their dimensional restrictions. Moreover, the thermal, mechan-
ical, and magnetic properties are also explored for some targeted applications with
high stability (Fig. 3). Therefore, concerning the new synthesis approaches and
vibrant properties, the 2D nanomaterials are realized in various applications related
to material sciences such as in energy conversion (solar cells, water electrolysis,
photocatalysis, thermoelectric devices, etc.) and energy storage devices (superca-
pacitors, batteries, etc.) [4–11]. In this section, we will elaborate on the individual
properties shown by various 2D nanomaterials.

3.1 Structural Properties

Geim and Novoselov won the Nobel Prize in 2004 for the invention of graphene which
is an important class of 2D nanomaterial [2]. Graphene holds a hexagonal structure
with sp2 hybridized carbon atoms. The structure has alternate single and double bonds
(i.e. a conjugated structure) with p-orbital overlapping and electron delocalization.
Because of this structural arrangement, graphene holds a very stable crystalline form
and offers unique properties such as high surface area, outstanding catalytic features,
high optical transparency, and so on. Graphene has shown its potential as a promising
candidate for diverse applications, for instance, in optoelectronics, supercapacitors,
drug delivery, biosensors, and image sensors. Regardless of consuming numerous
advantages and applications, graphene has some shortcomings too. For example,
14 A. K. Rana and A. A. Hussain

the material is insoluble and infusible in nature. Therefore, for full utilization of
graphene, some structural modifications are always required such as modifications
in the basal plane, edges, and surface functionalization.
Now, expanding the portfolio of 2D nanomaterials from graphene, currently other
new 2D materials such as TMDs, h-BN, g-C3 N4 , MXenes, and black phosphorous
are in the forefront [4–10]. The sandwiched structured TMDs with X–M–X structure
exhibit semiconducting properties with a tuneable bandgap which makes them a suit-
able candidate for optoelectronic devices [9]. Moreover, based on its unique layered
structures, it is also used as an efficient catalyst material for applications in electro-
chemical cells [11]. SnS2 belongs to the class of TMDs which crystallize in hexagonal
CdI2 lattice structure. It shows n-type semiconducting characteristics and is known
to have a wide bandgap (2.03–2.4 eV) [67]. Its strong anisotropy makes it possible
for its use in efficient holographic recording systems. Moreover, other TMDs such
as MoS2 , MoSe2 , WS2 , and TaS2 have out-of-plane mirror symmetry and in-plane
inversion symmetry, owing to which they show complementary characteristics to that
of graphene [9]. Also, in some cases, even these TMDs surpass the performance of
graphene. The main uniqueness of these TMDs is their strong spin–orbit interaction.
The most studied MoS2 is a semiconductor with a 2H phase and tuneable bandgap
from 1.2 to 1.9 eV. In addition, the MoS2 monolayers have in-plane Young’s modulus
of 200–300 GPa. Another special parameter is its high mobility (> 190 cm2 V−1 s−1 ),
high on/off current ratio (108 ), and polarization properties. As such, MoS2 shows
potential applications in several fields such as nano-electronics, solar cells, chemo-
sensing, energy storage, and catalysis [9, 68]. Tran et al. recently announced a new
member of the MXene family: V4 C3 Tx which is prepared by means of chemical
exfoliation of the MAX phase (V4 AlC3 ) using aqueous hydrofluoric acid [69]. The
successfully exfoliated MXene V4 C3 Tx is confirmed from the SEM morphology and
STEM characterizations. In parallel, Rosen’s group has addressed the synthesis of
quaternary MAX solution with (Nb2/3 Sc1/3 )2 AlC structure. They have selectively
etched both Al and Sc atoms to produce Nb1.33 CTx MXene, which is confirmed from
XRD, XPS, and STEM [70]. Likewise, h-BN also belongs to the family of 2D nano-
materials which has a noteworthy structural resemblance to graphene. The 2D h-BN
comprises both armchair and zigzag edge-terminated structures, where the layers are
coupled to one another by the relatively weak vdW forces. The h-BN offers a high
surface area and improved stability [12]. Silva et al. have demonstrated the synthesis
of nanostructured BN through thermal CVD at 1150 °C. For this, iron compound
(FeS/Fe2 O3 ) is used as the catalyst on Al2 O3 nanostructures [71].

3.2 Optical and Photonic Properties

As already highlighted, the 2D nanomaterials provide diverse properties suitable for

a broad spectrum of applications. One important property is the optical/photonic
response of the 2D nanomaterials. The optical characteristics of materials are mostly
1 An Introduction to the Wonder 2D Nanomaterials … 15

determined by the electronic band structure. The precise engineering of the elec-
tronic bands in 2D nanomaterials yields useful optical properties. It is well known
that every 2D nanostructured material shows different optical bandgaps based on
their individual structure–property relationship. The layered 2D halide perovskites
show unprecedented optical properties with a tunable bandgap suitable for opto-
electronic applications such as photodetectors, solar cells, and light-emitting diodes.
[72]. MA3 Bi2 I9 , Cs2 PbI2 Cl2 , and (BA)2 (MA)2 Pb3 I10 have a 2D-layered structure
with bandgaps ranging from 1.5 to 1.9 eV. As one of the typical layered perovskite
derivatives, these are used in solar cells and photodetectors [73]. Moreover, some 2D
nanomaterials have large electronic bandgaps such as TMDs, h-BN, and MXenes.
In particular, significant changes occur in the optical properties of TMDs due to the
existence of indirect-to-direct bandgap transition. This depends on varying the thick-
nesses of MoS2 layers. Monolayered MoS2 with an energy bandgap of 1.8 eV can
detect green light, whereas a triple-layered MoS2 with a bandgap of 1.35 eV responds
towards red light [74]. Moreover, h-BN and BP are also being investigated exten-
sively for their photonic and optoelectronic properties. Brar et al. have demonstrated
the surface phonon–plasmon–polariton modes in a heterostructure based on graphene
and h-BN. They have shown experimentally that the plasmon mode of graphene is
split into two modes which display anti-crossing behaviour near the energy of h-BN
optical phonon at 1370 cm−1 [75]. Preparation of g-C3 N4 nanosheets incorporating
plasmonic silver as an efficient photocatalyst is also explored for enhanced visible-
light photocatalysis experiments. Deng et al. have studied the improved photocat-
alytic activity of plasmonic Ag and N2 doped graphene QDs which are co-decorated
on g-C3 N4 nanosheets [76]. The experimental findings reveal an improved photo-
catalytic activity with 92.8% removal efficacy under white light and NIR irradia-
tion. Plasmonic photodetection of MXenes is also reported based on its atomically
thin layers. Velusamy et al. have reported Mo2 CTx MXene thin films which are
successfully deposited on paper substrates. The as-fabricated photodetectors with
this MXene structure exhibit extended photoresponse within 400–800 nm along
with a high responsivity of 9 AW−1 and detectivity of 5 × 1011 Jones. It also exhibits
reproducible photo-switching featured at a wavelength of 660 nm [77]. Moreover,
a photodetector based on black phosphorous is also reported by Engel et al. for
high-speed imaging [78]. Here, a multi-layered BP is capable of acquiring high
contrast in the visible and infrared region of the electromagnetic spectrum showing
its applicability for broadband optical detection.

3.3 Electrical Properties

Electronic/electrical property is influenced by the presence of localized or delocalized

transport of electrons in a solid material. Based on the electronic properties of various
materials, the economy of numerous industries has improved by adopting state-of-
the-art fabrication technologies. For the case of 2D nanomaterials, the electrons or
holes are restricted to occupy the quantized energy levels in one spatial dimension.
16 A. K. Rana and A. A. Hussain

Based on this, various important electronic properties are arising related to the energy
level, transport, and phonon scattering and excitation in 2D nanomaterials.
Numerous heterostructures have been designed based on graphene for bandgap
engineering such as graphene/h-BN, graphene/ZnO, and graphene/MoS2 [79, 80].
In general, TMDs hold a vast range of electronic properties, from semi-metals to
semiconductors to insulators. Xiong et al. reported the lithium intercalation in MoS2
[81]. Because of Li insertion into the interlayer spacing, the electrical conductivity
enhanced 200 times. Likewise, electrical transport in various TMDs has been inves-
tigated such as in 2H-NbS2 , -NbSe2 , -TaS2 , and TaSe2 , respectively. Here, to inves-
tigate the carrier scattering mechanisms, the charge density wave (CDW) system
is used. Based on this, the measurements of the resistivity and the Hall coefficient
of 2H-TMDs are carried out between 4.2 and 300 K [82]. The resistivity of 2H–
NbS2 displays no CDW transition. On contrary, 2H–TaSe2 shows the highest CDW
transition and along with several anomalous features. The electrical properties of
MXene structure Ti3 C2 Tx monolayers are investigated by Miranda et al. [83]. They
have demonstrated the metallic nature of MXene with a high free carrier density
of 8 ± 3 × 1021 cm−3 and high mobility of 0.7 ± 0.2 cm2 V−1 s−1 . Based on the
electrical performance of MXenes, they have been successfully utilized as promising
candidates for energy storage applications, for example, in Na, Li, K ion batteries,
supercapacitors, and fuel cells. As a 2D equivalent of graphene, the electrical prop-
erties of h-BN are also studied both individually and by forming heterostructure of
graphene and h-BN [84]. In general, h-BN is considered as an insulator with a wide
bandgap; however, forming the heterostructure with graphene (graphene/h-BN) for
transistor application, the electron mobility and the drain current switching ratios
are as high as 573 cm2 V−1 s−1 and −2 × 1011 cm−2 [85]. Moreover, the electrical
properties of sputter-deposited CN thin films are also studied by Broitman et al. [86].
They have reported that by increasing the N2 content during sputtering, the resistivity
decreases from 4 × 10–2 -cm to 4 × 10–3 -cm. The electrical conductivity of BP
has been measured by Keyes et al. [87]. They observed p-type conductivity under
low temperatures. The electron and hole mobilities at room temperature are reported
to be 350 and 220 cm2 V−1 s−1 , respectively.

3.4 Thermal Properties

Thermal property management is an essential subject for designing robust electronic

devices. 2D nanomaterials based on the thermoelectric effects can directly convert
heat into electricity for harnessing waste heat. For this, mainly the Seebeck effect is
used to modulate the conversion of heat into voltage [88]. Numerous studies were
performed to achieve appreciable Seebeck coefficients. For instance, Hippalgaonkar
et al. and Hewitt et al. have reported the Seebeck coefficients of MoS2 and Sb2 Te3
to be 8.5 mW-m−1 K−1 and 371 μW-m−1 K−1 , respectively [89, 90]. In addition,
among all the TMDs, WS2 based on the Boltzmann transport equation provides the
highest thermal conductivity of 142 Wm−1 K−1 followed by MoS2 and MoSe2 with
1 An Introduction to the Wonder 2D Nanomaterials … 17

103 and 54 Wm−1 K−1 [91]. It has been addressed that the heterostructures of 2D
nanomaterials provide an ideal platform to study interfacial heat transport. The inter-
face thermal conductance of MoS2 on Au substrate is as high as 221 MW-m−2 K−1
[92]. Moreover, polymeric carbon nitride (PCN) is investigated for thermoelectric
performance using molecular dynamic simulations. It is found that PCN has a high
figure-of-merit, ZT (ZT = S2 σT/κ, where S is the Seebeck coefficient, σ is the elec-
tronic conductivity, T is the absolute temperature, and κ is the thermal conductivity)
of 0.52 at 300 K which contributes to n-type thermoelectric group materials [93].
Heterojunction devices based on graphene/h-BN also offer a high thermoelectric
power factor of 10.35 W-m−2 K−1 [94]. Introduction of MXene (Ti3 C2 Tx ) into (Bi,
Sb)2 Te3 matrix also provides improved thermoelectric performance with ZT of 1.3
within 300–475 K towards high thermoelectric conversion efficiency [95].

3.5 Mechanical and Magnetic Properties

Mechanical properties of 2D nanomaterials play an important role in various applica-

tions. Some mechanical properties include the fracture strengths, Young’s modulus,
elasticity, etc. [96]. One of the ways to control the mechanical properties of 2D nano-
materials is based on defect engineering, which helps to enhance the toughness of
classical materials from metals to semiconductors to insulators [97].
Magnetic properties of 2D nanomaterials are of utmost importance which can
find interest in applications related to electric motors, computers, and medical diag-
nosis. For example, ferromagnetism is considered as one of the intrinsic properties
of atomically thin layered 2D materials at room temperature [98]. This property has
also shown a broader prospect for nano-device design. In particular, for spintronic
applications, the intrinsic magnetic orders in ultrathin 2D nanomaterials have been
extensively studied [99]. Sanikop et al. have tried to tailor the magnetically active
sites of MoS2 nanosheets for spintronic applications [100]. For this, defect-density
controlled 2H phase of MoS2 nanosheets is prepared at 500–900 °C which shows a
ferromagnetic-like transition at 120 K. Likewise, Du et al. have elaborated the first-
principle prediction of metal-free magnetism in g-C3 N4 [101]. The ferromagnetic
ground state displayed by the g-C4 N3 also possesses an intrinsic half-metallicity.
Kumar et al. have demonstrated the intrinsic ferromagnetism in Mn2 NTx, Ti2 NOx,
and Cr2 NOx, MXene structures [102]. High magnetic moments, high Curie temper-
ature (1877 K), and robust ferromagnetism are found in these MXenes for spintronic
applications. Furthermore, in the heterostructure of Ni(OH)2 and h-BN, a larger
magnetic moment with ferromagnetic coupling is found [40]. Furthermore, ferro-
magnetic 2D nanomaterials with superior electronic and optical properties are used
for the construction of compact magnetic, magneto-electronic, and magneto-optical
devices. Table 2 provides an overview of all the unique properties of various 2D
nanomaterials.
Table 2 Summary of different properties of various 2D nanomaterials
18

2D material Properties References

Structural Optical Electrical Thermal Mechanical Magnetic
Phase; Thickness Eg (eV) Mobility (cm2 Thermal Young’s Fracture
(Å) V−1 s−1 ) conductivity modulus strength
(Wm−1 K−1 ) (GPa) (GPa)
g-C3 N4 Hexagonal, 0.98–3.34 3 × 105 7.6 822 45.4(Z), Ferromagnetic metal [59, 76, 86, 93]
rhombic; 31.4(A)
3.35
MoS2 2H, 1T, 3R, 1T’; 1.2–1.9 (2H) > 190 103 219(Z), 16.9(Z), RT ferromagnetic [8, 89, 92, 99]
6.04 222(A) 7.3(A)
WS2 2H, 1T; 1–2 (2H) 140 142 240(Z), 19.9(Z), Ferromagnetic, [35, 39, 91]
0.608 244(A) 29.9(A) anti-ferromagnetic,
and metallic
MoSe2 2H, 1T; 1.1–1.55 121 54 175(Z), – Anti-ferromagnetic [26, 27, 63]
0.637 178(A)
MoTe2 2H, 1T’; < 1 (2H), 4000 0.35 205 – Diamagnetic and [8, 96]
0.691 60 m (1T’) paramagnetic
WSe2 2H, 1T; 1.4–1.6 66 3.935 194(Z), 15.0(Z), Ferromagnetic upon [8, 96]
0.641 196(A) 24.7(A) doping and creating
defects in WSe2
(continued)
A. K. Rana and A. A. Hussain
Table 2 (continued)
2D material Properties References
Structural Optical Electrical Thermal Mechanical Magnetic
Phase; Thickness Eg (eV) Mobility (cm2 Thermal Young’s Fracture
(Å) V−1 s−1 ) conductivity modulus strength
(Wm−1 K−1 ) (GPa) (GPa)
WTe2 1T’; 55 m 74 3 135(Z), 9.30(Z), RT ferromagnetic [8, 96]
0.691 137(A) 18.7(A) upon doping
h-BN Hexagonal; 5–6 573 10.35 865 70.5 RT ferromagnetic [40, 85, 94, 96]
3.34 upon doping
BP Cubic, 0.3–2.3 350–220 40 166(Z), 18(Z), Non-magnetic, but [87, 96]
rhombohedral; 44(A) 8(A) shows ferromagnetic
5.55 upon doping and
creating defects in BP
√ √
Silicene ( 3 × 3)R30o ; 1.55 m 2.5 × 105 5.4 82.2 12.5 Ferromagnetic upon [18, 19, 96]
4.20 doping and creating
1 An Introduction to the Wonder 2D Nanomaterials …

defects silicene
Bismuthene Hexagonal; 4.94 0.5 5.7 × 106 1.3 26.1 25.5 Ferromagnetic upon [18, 19, 96]
doping
Ti3 C2 Hexagonal; 3 3 2.6 11.57 80–100 – RT Ferromagnetic [9, 30]
Eg bandgap, A armchair, Z zigzag, RT room temperature
19
20 A. K. Rana and A. A. Hussain

4 Future Aspects and Conclusions

This chapter offers an overview of the fundamentals of 2D nanomaterials including

their structure, types, synthesis, and properties. It is now well established that 2D
nanomaterials are the special class of materials which open up a new avenue of
diverse applications including energy conversion, storage, and in the environment
and biomedical fields. We have mainly highlighted the 2D nanomaterials based on
TMDs (MoS2 , WSe2 , MoSe2 , etc.), BP, g-C3 N4 , h-BN, MXenes, 2D metal oxides,
and layered perovskites. The 2D nanomaterials can be synthesized from various
routes, among which we have discussed in detail the bottom-up and top-down
approaches. Finally, numerous interesting properties including structural, optical,
electrical, mechanical, thermal, and magnetic properties are elaborated with exam-
ples of 2D nanomaterials. Based on the special properties of 2D nanomaterials, signif-
icant applications are highlighted related to energy conversion technologies suitable
for energy harvesting and energy storage devices. However, the commercialization
of 2D nanomaterials is still in the progressing stage of technology.
With the intervening time, nanotechnology has been revolutionized by the use of
2D nanomaterials. 2D nanomaterials cover a number of important topics in basic
and applied sciences making a novel class of materials with a promising future. 2D
nanomaterials with high surface area, high electronic and excellent optical properties
will be very useful in the near future for nano-electronic applications to be utilized
in lithium-ion batteries, image sensors, biosensors, solar cells, supercapacitors, and
catalysts. However, it is noteworthy that the cost of 2D nanomaterials is relatively
higher, but as technologies will reach the maturing phase, the use of 2D nanomaterials
will nurture, thus enabling the higher demand for targeted applications with lower
prices that may start to establish themselves in the marketplace. It is anticipated
that the contents summarized in this chapter can afford an important reference and
guideline for further systematic studies on 2D nanomaterials.

Acknowledgements This study is financially supported by the Department of Science

and Technology (DST), Government of India, under the Inspire Faculty Award
(DST/INSPIRE/04/2018/001721).

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Chapter 2
Emerging 2D Nanomaterial Composites
for Efficient Energy Conversion: Insight
into the Evolutionary Perspective
of Devices

Amreen A. Hussain and Amit K. Rana

1 Introduction

Over the span of time, today’s world is confronted with two major predicaments:
one is the rapidly growing climatic change and other is the exhaustion of fossil
fuels. One of the gentlest and yet effective suggestion for generating the world’s
energy prerequisites comes from the renewable energy conversion. The rapid growth
in the renewable energy conversion technologies has spread its horizon during the
past decades thereby providing a clean and sustainable alternative to improve the
associated energy and environmental issues. The concern begins due to the burning
of fossil fuels and nuclear energy relating to carbon waste, radioactive waste, and
high accidental risks [1, 2].
Commonly, the energy conversion system/device is a continuous cycle of reuse
and reform where, mainly three processes such as the energy generation, energy
conversion and energy storage should collaborate to facilitate the targeted applica-
tions. Harnessing energy directly from sunlight is one option to fulfill the need for
clean energy which simultaneously have a negligible effect on the environment. It
is well known that solar energy can be utilized in photovoltaic applications such as
the solar cells, to generate electricity through photoelectric effect or photochemical
effect [3–5]. Additionally, solar energy can also be effective in splitting water to
produce hydrogen fuel [6–8]. Therefore, direct transformation of solar energy into
electricity or chemical fuels is an efficient technology to addressing the intermittency

A. A. Hussain (B)
Facilitation Centre for Industrial Plasma Technologies (FCIPT), Institute for Plasma Research
(IPR), Gandhinagar 382428, Gujarat, India
e-mail: [email protected]
A. K. Rana
Department of Material Sciences and Engineering, Ulsan National Institute of Science and
Technology (UNIST), Ulsan 44919, South Korea
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 25
Z. Khanam et al. (eds.), 2D Nanomaterials for Energy and Environmental Sustainability,
Materials Horizons: From Nature to Nanomaterials,
https://doi.org/10.1007/978-981-16-8538-5_2
26 A. A. Hussain and A. K. Rana

in renewable energy sources. Likewise, the other energy conversion application is

related to the thermoelectric heating/cooling devices that transform electric energy
into thermal energy and vice versa [9, 10].
Concerning to efficient energy conversion, one of the key components required
relies in the design and development of novel advanced materials which are afford-
able. Recently, going from first to third generation of materials, the emergence of
two-dimensional (2D) materials have placed themselves as a strong candidate for
energy conversion and storage [11, 12]. In common terms, the 2D material structures
are referred as nanosheets or layered thin films which are derived by their atomi-
cally thin thicknesses and extremely larger lateral dimensions. There are numerous
materials from where the nanosheets or layered thin films can be exfoliated to form
2D nanomaterials ranging from insulators to semiconductors to superconductors.
In recent times, various configurations of 2D materials or layered structures are
explored with higher surface areas suitable for various environmental applications
such as catalytic, adsorption-related, water splitting, and solar cell applications [12–
15]. The transition metal dichalcogenides (TMDs) such as MoSe2 , SnS2 , MoS2 , and
WSe2 are highlighted as a major compound for hydrogen generation catalysts owing
to their robustness and scalability [16]. Moreover, specific to optoelectronics and
water-splitting applications, the layered perovskite structures are also realized for
instance MA3 Bi2 I9 , Cs2 PbI2 Cl2 , La1–x Srx CoO3–δ , etc. [17, 18]. Apart from these,
2D metal oxides and metal–organic frameworks have also proven their applicability
in effective energy conversion [19, 20].
According to the citation databases (Google Scholar, Web of Science, SciFinder),
the research on energy conversion using 2D nanomaterials has grown tremendously.
Since 2010 till date, over one million journal publications have addressed to efficient
energy conversion through solar cells, water splitting, oxygen reduction/hydrogen
evolution (electrocatalysis), piezoelectricity, and thermoelectricity. This chapter thus
focuses on the emerging importance of 2D nanomaterials for energy conversion. The
sections in this chapter will explore the robustness of the 2D nanomaterials for solar
conversion and catalytic activities and also focus on the possibility for long-term
stability based on their structure–property relationship. Importantly, the strategic
approaches reported till date will be discussed concerning to the various energy
conversion devices such that the 2D nanomaterials might be used as a building block
for production of competent and robust energy conversion technologies. Finally, an
outlook on offering the fundamental scientific opportunities/challenges for inves-
tigating and understanding the intrinsic effects of 2D nanomaterials for proficient
energy conversion devices will be highlighted.
2 Emerging 2D Nanomaterial Composites for Efficient Energy … 27

2 Two-Dimensional Nanomaterials: Fundamental

Properties for Energy Conversion

A comprehensive introduction to 2D nanomaterials becomes necessary in order to

search for their potential applicability for energy conversion. The discoveries related
to both material diversity and new technologies to fulfill the increasing energy
demands have served to categorize the key scientific information and landmarks
to the researchers which might have a significant effect in a global level. Commonly,
the dimensionality spectrum of solid materials, for instances zero-dimension (0D),
one-dimension (1D), two-dimension (2D), and three-dimension (3D) is known to
have different density of states (DOS) (mainly associated with the number of elec-
trons present) which play an important influence on the intrinsic properties of mate-
rials [21]. Among these low-dimensional materials, the 2D nanostructures emerge as
a promising candidate for efficient energy conversion where it can be synthetically
grown by exfoliating the bulk solids into nanosheets bounded by van der waal’s forces
(vdW) [22]. Historically, the 2D nanomaterials are announced with the discovery of
graphene which are derived from atomically thin carbon materials [23]. Graphene
possesses remarkable chemical and electronic properties which brings new innova-
tions in diverse applications materials world. Following the same quest, the library
of 2D nanomaterials grows exponentially every year where the researchers have
stimulated the hunt for new 2D nanomaterials such as TMDs, layered perovskites,
elemental 2D nanomaterials (black phosphorous, silicene, germenene bismuthine,
arsenene etc.), hexagonal boron nitride (h-BN), carbon nitrides, and MXenes for
diverse applications, as presented in Fig. 1 [18, 19, 21, 24–29]. All these 2D nanoma-

Fig. 1 Library of 2D nanomaterials with their corresponding crystal structures and potential
applications. Reproduced with permission [25–29]
28 A. A. Hussain and A. K. Rana

terials show unique characteristics based on their structure–function-property rela-

tionships. Specifically, unlike other bulk materials, 2D materials have a unique crystal
lattice which is analogous to an exposed crystal geometry in the form of nanowires,
nano-pores, nanotubes, nano-sheets, etc., that exposed various active sites for the
targeted reaction/activities to take place. It is important to highlight that graphene,
being a zero bandgap material experiences difficulty in electronic devices.
At par, it is well-established that various features differentiate the 2D nanostruc-
tures with respect to conventional bulk materials. In addition, they are significantly
relevant for the development of novel energy conversion technologies.
Structural and optical properties: Recently, the chalcogenides represent the most
studied 2D nanomaterials [16]. TMDs belongs to the semiconductor group which
has tunable bandgap and interesting electrical properties making them suitable for
nano-electronic devices. For example, monolayers of MoSe2 have moderate direct
bandgaps and very fast electronic responses suitable for energy conversion [24].
However, the direct realization of single 2D nanomaterials for targeted application
is limited due to the ineffective separation of charge carriers (electrons and holes)
in MoSe2 monolayers. This is because atomically thin TMDs display insufficient
surface scattering as compared to other ultrathin metal counterparts. Typically, from
an atomic arrangement perspective, the TMDs structure consist of sandwich layers
of transition metals and chalcogens which are coupled by weak van der waals forces
whereas the intralayer between the atoms has strong covalent character. This struc-
tural arrangement of TMDs makes its bulk crystal highly stable under different envi-
ronmental conditions. Additionally, the crystal structure is also stable under illumina-
tion conditions. The absorption coefficients and bandgap energies of these 2D TMDs
have made them attractive candidates for energy conversion technologies in photo-
voltaics and photo-electrochemical systems. For example, monocrystalline WSe2
demonstrated in achieving solar power conversion efficiency of 17% [30]. Moreover,
wafer-scale monolayers of WSe2 photocatalysts have accorded for direct solar-driven
hydrogen production via effective water splitting [31]. Likewise, hexagonal boron
nitride (h-BN) is another material which shows strong deep ultraviolet absorption
and high emission efficiency that originates from the strong light-matter interaction
of 2D materials [24]. Likewise, as a new family of transition metal carbides, MXene
phases (Ti2 CF2 ) offer maximum absorption coefficient in the infrared region [16].
Furthermore, 2D perovskite structures such as MA3 Bi2 I9 and Cs3 Bi2 I9 , also emerge
as a potential candidate in improving the photovoltaic energy conversion with high
stability [17, 32]. Recently, elemental 2D nanomaterials are attracting great atten-
tion. For instance, the experimental demonstrations of group III element, borophene;
group IV elements, silicene, germanene, stanine; and group V elements, black phos-
phorous (BP), bismuthine, arsenene (group V) show that based on their individual
structure, can host non-trivial electronic states, spin-polarized edges and a tunable
bandgap that allows for application in energy conversion systems [33]. Few layers
of BP with a layer dependent direct bandgap and large tunability are shown to be
promising in IR detectors and emitters, which also provides a new insight into the
light-matter interaction in anisotropic materials [34].
2 Emerging 2D Nanomaterial Composites for Efficient Energy … 29

Electronic properties: The electronic properties of TMDs hinge on the crystal phase
that leads to a range of electronic characteristics, including metallic, semi-metallic,
semiconducting, and superconducting features, for different TMDs [24, 33]. Group
V-B and VI-B metals constructing the 2D TMDs are widely studied being the ability
to form stable compounds with excellent electronic structures. The semiconducting
TMDs, for instance MoS2 , WS2 , and WSe2 , have been highlighted as efficient elec-
tronic device materials because of their comparatively high charge carrier motilities
and appreciable bandgaps, which enable large switching ratios in field effect tran-
sistors (FETs) [33, 35]. At room temperature (RT) the TMDs (MoS2 ) have electron
carrier mobility of about 200 cm2 V−1 s−1 with bandgaps of 1–2 eV in the visible
range. It is worth mentioning that this high carrier mobility is comparative to the
silicon technology [36]. Therefore, based on these unique electronic characteristics
the 2D TMDs represent an attractive platform for energy conversion and for elemen-
tary studies related to light-matter interactions, optoelectronics, and nano-photonics.
In parallel, group V TMDs, specifically TaS2 and NbSe2 , were explored which have
shown their strong potential in electronic phenomena such as in superconductors
and charge density waves [24]. The electronic properties of MXenes based on a
detailed study of their density of states, however, show metallic character thereby
improving their conductivity [26]. Moreover, the electronic properties of h-BN can
be easily modulated by external pressure. It is found that along with the increase in
the hydrostatic pressure, the electrons in the basal planes transfer to the inter-plane
[33]. From the group V elemental group, arsenene has a single buckled honeycomb
2D layer of arsenic. Arsenene has an indirect bandgap of 2.49 eV and a high charge
carrier mobility. Another 2D structures are antimonene and bismuthene which are
extracted buckled honeycomb network of antimony and bismuth [37]. Antimonene
also exhibit high carrier mobility and excellent thermal conductivity.
Catalytic properties: The bulk TMDs are historically studied in the catalysis commu-
nity. Based on this, the recently renewed interest in 2D TMDs has revitalized the
exploration of this class of materials for catalysis in efficient energy conversions
including some biological and chemical sensor devices. One of the important appli-
cations in energy conversion is electrocatalysis. 2D TMDs such as MoS2 , MoSe2 ,
WS2 , and NbS2 have demonstrated their realization as excellent electrocatalyst
where these are extensively investigated for hydrogen evolution reaction (HER)
for hydrogen production [38]. In general, the catalyst reactivity mainly relies on
the physico-chemical properties of the catalyst surface and the interface between
the electrode and electrolyte. Therefore, to achieve effective catalytic activity, the
catalysts should be efficient in lowering the energy barriers and thereby improving
the rate of surface electron charge transfer. To fulfill this prime need for catalytic
activity, the 2D nanomaterials are currently one of the most up-to-date materials in
the research field. MXene-based materials are identified as efficient electrocatalyst
particularly in hydrogen evolution [39]. In addition, 2D metal oxides and hydroxides
such as Pd5 O4 , MnO2 , and TiO2 show very diverse catalytic properties due to their
capability of adopting different binding configurations [19]. Moreover, the elemental
2D nanomaterials like BP also offer unprecedented catalytic properties owing to its
30 A. A. Hussain and A. K. Rana

large specific surface area with more active sites and high theoretical capacity as
Li/Na-ion batteries anode for both electrocatalyst and novel electrode material [33].
Thermal properties: Thermoelectric materials with high figure of merits (ZT) that
have the capability to convert the wasted heat directly into electricity, remains a chal-
lenge. However, with the discovery of 2D nanomaterials, this challenge is addressed
to certain extent [40]. Particularly, 2D TMDs such as MoS2 , MoSe2 , WS2 , and WSe2
are identified as ideal materials which can harvest waste heat with efficiencies about
7–8%. The TMDs show high Seebeck coefficients, for instance, MoS2 gives α 2 σ =
8.5 mW m−1 K−2 with low cross-plane thermal conductivity. The thermal conduc-
tivities of WTe2 and MoS2 are reported to be 3 and 59 Wm−1 K−1 , respectively [41].
For the construction of energy conversion devices, the interfacial contact between the
metal and the 2D nanomaterials also play an important role. Therefore, the manage-
ment of interfacial thermal resistance between the metal side and edge side (TMDs)
is extremely essential. TMDs, such as MoS2 , based on their higher interfacial energy
coupling show better interface contact due to which the internal thermal conductance
increases to 68.6 mW m−2 K−1 [42]. On the contrary, h-BN is electrically insulating
but can offer high thermal conductivity. This feature of h-BN makes it an interesting
candidate for thermal management where it is required to have electrical insula-
tion [43]. Heterostructures based on 2D graphene and transition metal oxides also
show high thermal conductivity with α 2 σ = 2500 μWm−1 K−2 at room temperature
[40, 41].

3 Why Two-Dimensional Nanomaterials for New Energy

Conversion Technologies?

The 2D nanomaterials, specifically the TMDs, 2D perovskites and other metal oxide-
based materials have a restricted role in a fossil fuel-dominated energy scenario.
However, their position is progressively stirring to a new energy scenario largely
based on the use of renewable energy. 2D TMDs heterostructures, MXene, metal
oxide is the current widely used anode materials in commercialized storage devices
such as supercapacitors [44]. Moreover, the TMDs also supports as the efficient elec-
trocatalysis for applications in fuel cells, mainly to produce hydrogen [45]. Normally,
all these processes are associated with energy conversion and energy storage that can
be transferred into a solar energy-based future energy scenario. However, the main
drawback that is faced with these materials is their performance which is below
the requirement with respect to the fossil energy-based society. This is because the
energy requirement demands the use of not only cell phone, laptops, and cars but also
power stations, long-distance transport, lighting, and heating need to be powered.
Therefore, the future energy situation must be the driving force for existing activ-
ities in 2D nanomaterial research for energy conversion applications. There lie many
reasons for choosing 2D nanomaterials: as it is cost effective, stable, earth abundant,
and environmentally friendly. Also, the heterostructures of 2D nanomaterials are
2 Emerging 2D Nanomaterial Composites for Efficient Energy … 31

foreseen to have a special role in the future energy scenario that the classical single
counterpart cannot have.
While comparing with conventional energy conversion materials, the 2D nanoma-
terials possess unique size- and surface-dependent properties such as morphology,
electrical, optical, and mechanical properties that allow a step forward in enhancing
energy conversion and storage performance. Derived from them are the various
nanostructures in the form of quantum dots, nanotubes, nanofibers, nanoribbon,
nanocages, etc. The most common advantages of these new nanomaterials are their
low dimension, specific morphology, and electronic properties. The nano-dimension
with precise morphology enables tunable physical and chemical properties such as
high electro-conductivity, good thermal conductivity, and outstanding mechanical
properties. An interesting characteristic of these 2D materials is the possibility of
tailoring their electronic structure by introducing heteroatoms and heterostructures,
to adapt their physical property by controlling their pore structure, and to change their
chemical property by introducing functional groups onto the surface. In this way, it
is possible to introduce a level of control in the characteristics of these materials that
is not possible in other systems.
Another significant feature of the 2D materials is the possibility of its infusion
in designing the state-of-the-art hybrid or composite heterostructures [46]. An inter-
esting example is found where TMDs and perovskite oxides heterostructures are
developed to improve the energy conversion systems for producing fuels [47]. A
recent study also addresses the first principles calculations to determine the bandgap
energies of porous h-BN. The bandgap engineering is performed using carbon doping
which is able to absorb the visible light. This resulted in the matching of conduc-
tion and valence band with the potentials of both hydrogen and oxygen evolution
reactions [48]. From a similar concept, semi-hydrogenated BN emerge as a novel
2D metal-free photocatalyst for effective water splitting under visible light [49].
Again, the 2D layered perovskites such as (CH3 NH3 )3 Bi2 I9 , Cs2 PbI2 Cl2 , Cs3 Bi2 I9
can serve as photosensitizers or can be used to facilitate charge transport between
different semiconductor materials for achieving remarkable solar power conversion
efficiency of 27% [17, 18, 32, 50]. In parallel, the advantages of 2D nanomaterials in
photo-electrochemical applications are diverse [51]. 2D layered nanomaterials can:
(1) Transfer electrons into the semiconducting material to serve as a photosensi-
tizer that helps in extending the optical absorption range.
(2) Effectively separate the photoexcited electrons and holes in the photoactive
semiconducting materials.
(3) Conduct excess heat away during the catalytic reaction.
(4) Serve as a template and heat sink for stabilizing small catalysts due to which
larger specific surface area can convert more reactant molecules.
(5) Improve the overall lifetime by reducing the amount of active catalyst by
decreasing its weight.
32 A. A. Hussain and A. K. Rana

Therefore, this kind of 2D layered nanomaterials such as TMDs, layered

perovskites, h-BN, C3 N4 , MXenes, metal oxides nanosheets, and black phospho-
rous which are derived from their basic 3D bulk crystalline blocks may have great
potential for efficient energy conversion applications.

4 Energy Conversion Systems Using Two-Dimensional

Materials

4.1 Solar Cells

One of the important sources of sustainable energy conversion is the solar cell devices
which works on the principle of photovoltaic effect thereby directly converting
the incident optical signals (sunlight) into electricity (Fig. 2a). As already known
that the crystalline silicon-based solar cells have been ruling the ever-expanding
global photovoltaic market with about 95% market share. Reaching the theoretical
Shockley-Queisser (S-Q) limit of 33%, silicon solar cells achieved its highest power
conversion efficiency (PCE) of 26.6% [52].

Fig. 2 a Schematic representation showing the working of a solar photovoltaic device. b

MoS2 /graphene/porous Si-based photovoltaic device. Reproduced with permission [65], Copy-
right 2020, Elsevier. c h-BN interface on graphene/Si schottky junction for improving solar cell
efficiency. Reproduced with permission [29], Copyright 2016, Elsevier. d 2D-3D perovskite for
improved solar cell stability and efficiency of 21.6%. Reproduced with permission [25], Copy-
right 2020, Elsevier. e MXene/NiOx for inverted-type solar energy conversion. Reproduced with
permission [68], Copyright 2021, Elsevier
2 Emerging 2D Nanomaterial Composites for Efficient Energy … 33

In the past decade, solar cell with organic–inorganic lead halide perovskites
(CH3 NH3 PbI3 ) have outperformed all other thin film photovoltaics in terms of PCE,
with the highest laboratory record standing at around 25% which is placed in the
NREL chart [52–54]. With the utilization of lead halide perovskites, the record effi-
ciency solar cells have been increasing with an unprecedented speed. For efficient
photovoltaic conversion, the photoactive materials must show high absorption coef-
ficients (≈105 cm−1 ), high charge carrier mobility, low trap density, tunable bandgap
(typically from 1.17 to 2.24 eV) [55]. The merits will be manifold if the photoactive
materials are cost effective and have easy processing/fabrication. A perovskite-based
device holds the most potential as a top cell for a two-terminal tandem solar cell with
silicon as its bottom cell. Sahli et al. have demonstrated an approach of co-evaporating
and spin coating to prepare the perovskite on crystalline-Si pyramids, which yielded
an efficiency of 25.2% [56]. Likewise, an oxford photovoltaic device has been high-
lighted by Snaith’s group that has reported a record PCE for two-terminal tandem
cell up to 28% [57].
Even though the perovskite/Si tandem cells have achieved great success, there
remains a major challenge in the production of the less-toxic, high-quality, and stable
perovskite absorbers. Two-dimensional layered perovskite structures have emerged
as a possible solution to address this issue [18]. Unlike the conventional bulk lead
halide perovskites, the 2D layered perovskites are constructed with additional larger
organic cations which are introduced as spacers. This isolates the inorganic metal
halide octahedral layers to form quantum well super lattices. Emerging novel deriva-
tives of 2D layered perovskites pave new prospects for versatile energy conversion
applications. M. G. Kanatzidis’s group reported the perovskite compound based
on Cs2 PbI2 Cl2 , which displays extremely high ambient and thermal stability [58].
Also, their high density and high atomic number elements also render it as a decent
candidate for ultraviolet radiation detector applications.
Progress on the nanostructured metal oxides are found to have appreciable perfor-
mances in solar cells. Gold (Au) nano-mesh sandwiched between two molybdenum
trioxide (MoO3 ) layers (MoO3 /Au/MoO3 ) is fabricated using mild thermal evap-
oration, which emerge as an excellent electrode material to be utilized in semi-
transparent solar cells. Here, the ultrathin Au nano-mesh affords the high conduc-
tivity and better transparency along with the MoO3 layer acting as an antireflection
layer thereby significantly minimizing the optical loss. Based on this, the PCE of
semi-transparent solar cells is increased to 18.3%. From the similar grounds, the
semi-transparent perovskite layers are utilized in a stacked configuration to form a
heterojunction with silicon solar cell which yielded PCE of 27.0% [50]. Till date,
this is one of the highest reported value for tandem solar cells.
With the discovery of the exfoliated flakes derived from various bulk organic
and inorganic materials, hold the fundamental basis to understand their unique and
tunable optical and electronic properties [59]. Concerning to the ever-growing interest
in the TMDs, the first principle density functional theory calculations exclusively
accords that the band structure of TMDs change dramatically upon exfoliation to
lower dimension owning to strong quantum confinement effects [60]. Particularly, the
bulk TMDs is converted from an indirect bandgap semiconductor to direct bandgap
34 A. A. Hussain and A. K. Rana

semiconductor when thinned to a monolayer. Due to strong light-matter interactions

within the monolayers, resulted in superior light harvesting characteristics compared
with their bulk counterparts suitable for energy conversion. For instance, a single
monolayer of MoS2 with 0.6 nm thickness is projected to generate a maximum
photocurrent of 4.7 mA cm–2 with a PCE of 1.3% under simulated irradiance [61].
The additional benefits of ultrathin 2D TMDs rely on the inertness of chalcogenide
surface, which does not hamper the defect related recombination processes at the
atomic layer heterojunctions. Moreover, the 2D TMD layers do not suffer from
anisotropic electronic properties. A novel method has been freshly executed by using
ultrathin Bi2 Te3 as a supporting material in electron transport layer and based on
which the solar cell conversion efficiency reached up to 19.46% and stable over
1100 h under 1 Sun irradiance [62].
It is worth mentioning that the first demonstration of single or monolayers is
based on lateral p-n junctions [63]. In the intervening time, various p-n junctions
have been addressed using two TMDs layers. To present some examples, a photoac-
tive WSe2 /MoS2 p-n heterojunction has been established which are mechanically
exfoliated from bulk. The photovoltaic performances as characterized by the J-V
curves upon illumination under white light offer a clear photovoltaic effect with a
PCE reaching 10% [64]. Similarly, employing a layer-controlled MoS2 in a hetero-
junction of graphene/Si demonstrated the photovoltaic performance of 13.18% with
a long-term stability for 30 days [65]. Very recently, 2D hexagonal boron nitride is
used for surface passivation to enhance the photovoltaic performance of MoS2 /WSe2
solar cells with 74% improvement in conversion efficiency [66]. Moreover, an inter-
face engineering approach is performed on graphene/Si schottky junction solar cells
with the introduction of h-BN thereby achieving a maximum efficiency of 10.93%
[29]. Another study is conducted with graphitic carbon nitride which acts as a booster
in improving the solar cell efficiency to 70% employing a binary composite of g-
C3 N4 /ZnO NR [67]. Subsequently MXene based on Ti3 C2 Tx is prepared to engineer
the p-i-n perovskite solar cell with an improved power conversion efficiency of 19.2%
[68]. In addition, the elemental 2D nanomaterials like black phosphorous (BP) has
also proven its potential as a hole selective layer in improving the perovskite solar
cell efficiency by 16.4% [69].

4.2 Electrochemical Water Splitting

Water electrolysis is a viable technology to decompose water into chemical fuels,

especially hydrogen, either using electricity (potential) or solar light which can be
efficiently used in a fuel cell for power generation [28]. Based on this technology,
hydrogen is now considered as a green energy carrier. However, to generate hydrogen,
some key factors must be addressed: properly choosing the materials for catalytic
activity, designing the catalysts, and engineering the water-splitting devices [47].
2 Emerging 2D Nanomaterial Composites for Efficient Energy … 35

Fig. 3 a Schematic representation showing the electrochemical reactions for evolution of hydrogen
and oxygen gas. Reproduced with permission [70], Copyright 2019, Elsevier. b Engineering of
2D nanomaterials with respect to defects, strain, increasing edges and doping. Reproduced with
permission [28], Copyright 2017, Royal Society of Chemistry

Extensive investigations on TMDs have been highlighted for electrocatalytic

production of hydrogen. Progressive efforts have been made by the scientific commu-
nity where the hydrogen generation efficiency is promoted using 2D TMDs. This
approach resulted in the minimal use of precious Pt-based catalysts which effec-
tively reduces the cost. Significant amount of both computational and experimental
studies is conducted to understand the underlying reaction mechanisms and the reac-
tion steps involved in such energy conversion systems. Two major reactions that
are associated with water electrolysis are the oxygen evolution reaction (OER) and
the hydrogen evolution reaction (HER). For electrolytic cells, the OER and HER
occur at the cathode and anode surfaces, thus creating H2 and O2 gas, respectively.
Among these, HER (2H+ + 2e− → H2 ) is a complex multiple-step electrochemical
process, which takes place on the electrode surface containing catalysts to generate
pure hydrogen which can be supplied to fuel cells. Mainly, three reaction steps have
been anticipated for HER in an acidic solution (Fig. 3a) [70, 71]:
Discharge reaction (Volmer):

H3 O+ + e− → Hads + H2 O (1)

Electrochemical desorption reaction (Heyrovsky):

Hads + e− + H+ → H2 (2)

Combination reaction (Tafel):

Hads + Hads → H2 (3)

As mentioned in the three reactions, chemical adsorption and desorption of

hydrogen atoms on the electrode surface are the competitive processes. Here the
prime requirement is to have a good HER catalyst that must form an adequately
36 A. A. Hussain and A. K. Rana

strong bond with the adsorbed hydrogen. This will promote the proton-coupled
electron-transfer process. In addition, to ensure the facile release of hydrogen gas,
the bonds should also be weak enough. Thus, these electrochemical reactions serve
an important role in energy conversion and energy storage systems [71].
The typical electrochemical water splitting is performed in an electrolyser
system consisting of three components: a cathode, an electrolyte which act as ionic
conductor, and an anode. The water decomposition by means of electrochemical reac-
tions in an electrolyser is composed of two half-cell reactions: HER on the cathode
and OER on the anode. However, in this system, it is required to have an input energy
to accelerate the two half-cell reaction with the application of an external voltage.
This extra energy comes in the form of a potential difference between the electrodes
and can be calculated using the Gibbs free energy (G0 = 237.2 kJ mol−1 ) is often
referred as the overpotential (η). In order to split water a high activation energy is
required and simultaneously the issues related to the low conductivity of water are
minimized by the utilization of effective electrocatalyst along with the addition of
salts, acids, or bases to improve the water conductivity. Moreover, electrochemical
measurements are carried out in a three-electrode system, where a suitable reference
electrode (RE) is applied according to the nature of the electrolyte solution to check
the proper value of overpotential. The overpotential is reported with reference to the
reversible hydrogen electrode (RHE), normal hydrogen electrode (NHE), and stan-
dard hydrogen electrode (SHE). These three terms are used interchangeably in the
literature, but they are particularly different. For instance, the NHE is constructed
by immersing a platinum electrode into a solution of one normal concentration for
protons and bubbling pure hydrogen gas through the solution at 1 atmospheric pres-
sure. The limitation with NHE is that it is not reversible, and its potential changes
with time due to which its use is restricted. Similarly, the SHE also composed of
Pt dipped in acidic solution and hydrogen gas at 100 kPa. The absolute potential
of SHE is 4.44 ± 0.02 V at 25 °C but its potential is considered as zero in order
to serve as the reference. Unlike NHE, SHE is reversible, however the ideal 1 M
protons never exists because of which SHE is an ideal model and cannot be made.
When expressing the potentials of redox half reactions, without otherwise stated, the
potentials are by default referenced to SHE (vs. SHE). On the other hand, the RHE
conversion from the practically applied RE in most published literature and is widely
accepted based on the simplified theoretical Nernst equation or the extension of SHE.
The only difference between the definition of RHE and that of SHE is that RHE does
not require the proton effective concentration to be unity. This characteristic brings
out the pH dependence of RHE potential [70, 71].
The HER mechanism usually proceeds via the Volmer-Tafel-Heyrovsky steps,
where the different pH value leads to different reactants and products in each step.
As already mentioned, in HER, the electrochemical reduction of proton is mediated
by an appropriate catalyst for which the most commonly used catalyst is based on
platinum (Pt). However, Pt is very expensive which leads to the search for alternative
catalyst materials with highest possible activity. TMDs are considered as a strong
candidate for electrocatalyst material and various efforts have been made to engineer
the TMDs such as creating edges, defects, and strain as illustrated in Fig. 3b. Liu et al.
2 Emerging 2D Nanomaterial Composites for Efficient Energy … 37

have systematically optimized various TMDs (with MX2 structure) catalysts such
as MoS2 , NbS2 , and TaS2 for efficient hydrogen evolution [72]. They proposed that
highly basal plane active MX2 sites are favorable for HER activity. Likewise, Swesi
et al. have reported another catalyst with textured NiSe2 film for water splitting with
an energy efficiency of 83% at high current density [73]. Very recently, Kwon et al.
have addressed the synthesis of Se-rich MoSe2 nanosheets for improved electrocat-
alytic performance [74]. They have reported the best HER activity with low overpo-
tential of 0.13 V and a Tafel slope of 46 mV dec−1 at 10 mA cm−2 . Furthermore, the
heterostructures of MoSe2 and perovskite oxide with La0.5 Sr0.5 CoO3-δ highlight as
a superior bifunctional electrocatalyst for stable water electrolysis over 1000 h [75].
Efficient catalysts for anodic OER have been realized where prime importance is
given to perovskite oxides with ABO3 structure. Liu et al. have prepared hierarchical
mesoporous La1−x Srx CoO3−δ and presented its improved OER activity in a lithium
oxygen battery [76]. Again, with the same perovskite oxide structure, Mefford et al.
have reported a strategy where the OER can be enhanced by exploiting the oxygen
vacancy defect [77].
In addition to TMDs, elemental 2D materials, layered metal oxides, oxyhalides,
and layered double hydroxides are being actively investigated for their potential
application to photo-electrochemical water splitting. It is known that numerous metal
oxides such as TiO2 , Fe2 O3 , ZnO, SnO2 , and WO3 have been extensively used as
photocatalyst for solar water splitting [78]. Yao et al. have shown the feasibility of
constructing a porous hybrid structure containing Fe2 O3 nanothorn/TiO2 nanosheet
photoanodes that exhibited high PEC activity under visible light [79]. He et al.
synthesized the heterostructure of carbon nitride and h-BN nanosheets (CN/BN)
using an annealing mixture of h-BN and urea. The CN/BN heterostructure exhibited
enhanced photocatalytic productions of H2 and H2 O2 of 2.4 and 59.8 μmol h−1 ,
respectively [80]. Additionally, few layers of phosphorene (or BP) also emerge as a
promising candidate for HER activity. Lu et al. have investigated the edges, defects,
strain, and metal doping on BP, and a linear relationship is highlighted between the
lowest occupied state and hydrogen adsorption energy [81].

4.3 Piezo- and Thermoelectric Devices

It has been discovered that many of the 2D nanomaterials such as TMDs and transi-
tion metal oxides, and h-BN show piezoelectric properties unlike their bulk counter-
parts [82]. As one of the energy conversion system, the piezoelectric devices basi-
cally convert mechanical energy (in the form of pressure, sound wave, or force)
into electricity (Fig. 4a). Piezoelectricity may also be used to generate charge
carriers or construct relays in an electronic circuit. Moreover, various research work
exploits piezoelectric nanomaterials as piezo-phototronic facilitators for light emis-
sion including some prototype devices such as transistors, photodiodes, and sensors
[83].
38 A. A. Hussain and A. K. Rana

Fig. 4 a Schematic representation of a piezoelectric device. b Piezoelectric behavior of MoS2 using

lateral piezo-response force microscopy and output the nanogenerator response. Reproduced with
permission [87], Copyright 2016, Elsevier. c Thermoelectric effects: Seebeck and Peltier effects. d
Thermoelectric performance of layered carbon nitride with high ZT. Reproduced with permission
[97], Copyright 2018, Royal Society of Chemistry

Piezoelectricity is a property of electric polarization triggered by macroscopic

strains, that couples the mechanical and electrical behaviors to promote competent
mechanical-to-electrical energy conversion. Currently, the most prominent piezo-
electric crystals should have non-centrosymmetric structure which are identified in
hexagonal boron nitride (h-BN) and the broad family of TMDs. Li et al. demon-
strated the non-centrosymmetric structure of h-BN using optical second-harmonic
generation, thus validating the existence of h-BN piezoelectricity [84]. Likewise,
the experimental evidence for the generation of piezoelectric fields in monolayer
h-BN is reported with a piezoelectric coefficient of 2.91 × 10–10 cm−1 which is
comparable to bulk ZnO [85]. Blonsky et al. adopted the first principle calculation
to uncover the presence of in-plane piezoelectricity in TMDs such as MoSe2 , MoS2 ,
WS2 , NbSe2 [86]. The 2D piezoelectric materials play an important role in energy
harvesting devices which have the capability in future wireless nano-systems without
any external power source including environmental monitors, implantable medical
sensors, and personal electronics. A flexible piezoelectric nanogenerator based on
CVD grown MoS2 was highlighted by Kim et al. for scavenging the mechanical
energy for low power consuming devices and realizing self-powered electronics
(Fig. 4b) [87]. Motivated by the work, Lee et al. established a monolayer WSe2 piezo-
electric nanogenerator, which gives a peak voltage of 45 mV under a strain of 0.39%
[88]. Piezo-phototronic devices are also developed where the principle is based on
the piezo-polarized charges to tune the charge carrier generation, separation, diffu-
sion, and recombination processes. The strategy of this novel device has been also
proved in the monolayer MoS2 photodetectors [89].
The existing status of thermoelectric has been marked from its debut by Mahan in
1998 [90]. Ever since, by means of thermoelectricity the energy conversion technolo-
gies have been progressively growing. Thermoelectric is considered as a direct energy
2 Emerging 2D Nanomaterial Composites for Efficient Energy … 39

conversion technology by the transport of electrons in solids [91]. Based on this ther-
moelectric phenomenon in solids, various advancements in realizing devices with
high thermal endurance are explored which finds applications in harsh environments
including space applications.
The predominant thermoelectric effects are the Seebeck effect and Peltier effect
(Fig. 4c) [92]. In solids (specially, semiconductors), the elementary charge carriers
(electrons) are known to reside under thermal equilibrium. Along with this, the
electrons also carry heat and entropy from the fundamentals of thermodynamics.
These electrons can therefore flow from hot side to a cooler side wherever there is
a temperature gradient. Because of this, arises the correlation between thermal and
electronic phenomena, which is now called as the thermoelectric effects. The Seebeck
effect is based on the existence of a voltage proportional to a temperature gradient
(V = ST ), where, S is the Seebeck coefficient (also referred as thermoelectric
power or thermos-power). Whereas, the Peltier effect is a phenomenon that where
the heat absorption or emission is induced at the junctions which leads to the applied
current (Q =  I), where  is the Peltier coefficient. With the help of these two
effects, it is possible to convert heat into electrical energy and vice versa. Such type
of energy conversion technology leads to the discovery of various thermoelectric
generators/coolers.
The commonly adopted approach to harvest the waste heat into electricity is
based on Seebeck effect. In general, the thermoelectric devices are characterized by
the figure-of-merit (denoted as ZT ) given by [93]:

T α2
ZT = (4)
Kl
μne
+ LT

where α, K l , n, μ, e, and T are the Seebeck coefficient, lattice thermal conductivity,

carrier density, carrier mobility, elementary electronic charge, and absolute tempera-
ture. L is the Lorentz number given as 2.44 × 10–8 W  K−2 . Equation (4) is mainly
used to predict the discrepancies between the theoretical and experimental measure-
ments. During 1990s, the best ZT is achieved for Bi2 Te3 alloy with value 1.0 at
300 K. After that, progressive research efforts based on novel 2D nanomaterials and
their interfacial engineering to reduce lattice thermal conductivity and to improve
the carrier mobility leads to the improvement in ZT value to 3.0 [94, 95]. With these
progresses, recently the heterostructures of 2D nanomaterials based on graphene
and TMDs are addressed that show improved thermoelectric performances. Liang
et al. have reported that the thermionic energy conversion using graphene/MoSe2
or graphene/WSe2 are two ideal configurations having the ability to harvest the
waste heat at 400 K with 7–8% efficiency [40]. Kim et al. have developed a stretch-
able thermoelectric generator using a nanocomposite of TMDs and single-walled
carbon nanotubes (SWCNT). The thermoelectric power factor with WS2 /SWCNT
was reported to be 46 μW/K2 m [96]. Also, they have shown that the thermoelectric
properties were preserved within the range of 290–330 K. It has been addressed that
40 A. A. Hussain and A. K. Rana

Table 1 Summary of different 2D nanomaterials in energy conversion systems

Application 2D nanomaterial and its role Performance description
Solar cell 2D perovskites as light Light harvester: PCE = 12.51%,
harvesting and passivation layer Stable for 2250 h [58]
Passivation layer: PCE = 21.6%
[25]
TMDs as hole transport layer PCE = 17% [24]
(MoS2 , WS2 ) and p-n PCE = 10% [64]
heterojunction (WSe2 /MoS2 )
MXene (Ti3 C2 Tx ) as electron PCE = 19.2% [68]
transport layer
h-BN fusion in Si/graphene PCE = 10.93% [29]
Schottky junction
BP as hole transport layer with PCE = 16.4% [69]
perovskite
Electrochemical water Textured NiSe2 Film OER:
splitting (bifunctional electrocatalyst) η = 0.14 V, Tafel slope =
48.7 mV dec−1
HER:
η = 170 mV, Tafel slope =
107 mV dec−1
[73]
Se rich MoSe2 nanosheet HER:
(Transition from the 2H to the η = 130 mV, Tafel slope = 46 mV
1T phase) dec−1
[74]
MoSe2 /La0.5 Sr0.5 CoO3 (TMD, OER:
Perovskite heterostructure) η = 0.29 V, Tafel slope = 77 mV
dec−1
HER:
η = 0.20 V, Tafel slope = 34 mV
dec−1
(1000 h stability at 100 mA cm−2 )
[75]
L- BP(Co) HER:
L-BP η = 194 mV, Tafel slope = 47 mV
S-BP dec−1
η = 355 mV, Tafel slope = 91 mV
dec−1
η = 299 mV, Tafel slope = 85 mV
dec−1
[81]
Piezo-electronic device h-BN Piezoelectric coefficient:
291 pC m−1 [85]
2H-MoSe2 383 pC m−1 [86]
2H WS2 243 pC m−1 [86]
2H NbSe2 222 pC m−1 [86]
(continued)
2 Emerging 2D Nanomaterial Composites for Efficient Energy … 41

Table 1 (continued)
Application 2D nanomaterial and its role Performance description
2H TaS2 267 pC m−1 [86]
BP 240 pC m−1 [86]
ZnO (Planar) 266 pC m−1 [86]
Thermoelectric device MoS2 Thermal conductance:
221 mW m−2 K−1 [41]
WS2 /SWCNT 46 μW m−2 K−1 [96]
Graphene/h-BN 10.35 W m−2 K−1 [98]
CN ZT: 0.52 at 300 K [97]
MXene ZT: 1.3 at 300–475 K [99]
PCE power conversion efficiency (solar), η overpotential, ZT thermal figure of merit

the heterostructures of 2D nanomaterials provide an ideal platform to study the inter-

facial heat transport. The interface thermal conductance of MoS2 on Au substrate is as
high as 221 mW m−2 K−1 [41]. Moreover, polymeric carbon nitride (PCN) is inves-
tigated for thermoelectric performance using molecular dynamic simulations. It is
found that PCN has high ZT of 0.52 at 300 K which contributes to n-type thermoelec-
tric group materials (Fig. 4d) [97]. Heterojunction devices based on graphene/h-BN
also offer high thermoelectric power factor of 10.35 Wm−2 K−1 [98]. Introduction
of MXene (Ti3 C2 Tx ) into (Bi, Sb)2 Te3 matrix also provides improved thermoelectric
performance with ZT of 1.3 within 300–475 K toward high thermoelectric conversion
efficiency [99] (Table 1).

5 Conclusions and Outlook

This chapter offers an overview of the energy conversion technologies/systems

specifically relating to 2D nanomaterials. The 2D nanomaterials have had a signifi-
cant role in energy conversion technologies suitable for energy harvesting and energy
storage devices. However, the commercialization of 2D nanomaterials is still in the
progressing stage technology. Starting from the small-scale production of 2D nano-
materials by the small start-up companies, the industrialization will soon push an
advancement towards a wide range of possibilities for on-field application of such
2D nanomaterials in energy conversion systems/devices. Our motive is to deliver
an up-to-date view research progress with a balanced experimental perspective on
2D devices for energy conversion. It is anticipated that the contents summarized in
this chapter can afford an important reference and guideline for further systematic
studies on 2D nanomaterials.
42 A. A. Hussain and A. K. Rana

We have focused on the specific material properties of 2D nanomaterials based

on TMDs, layered perovskite structures and inorganic semiconductor oxides rele-
vant for energy conversion systems or devices. Particularly, how the 2D nanomate-
rials can have a significant impact on the energy generation system is highlighted.
Moreover, an elaborated discussion on the energy conversion devices is presented.
First the progress of 2D nanomaterials in the field of solar cell devices is addressed.
Second, the influence of 2D nanomaterials on improving the electrochemical activity
for water splitting is discussed in detail. Finally, the direct influence of the piezo
and thermal property management and dissipation related to the applications of 2D
semiconductors have been discussed including the thermoelectric effects.

Acknowledgements This study is financially supported by the Department of Science

and Technology (DST), Government of India under the Inspire Faculty Award
(DST/INSPIRE/04/2018/001721).

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Chapter 3
Next-Generation 2D Nanomaterial
Composites Electrodes
for Electrochemical Energy Storage

Harish Mudila, Parteek Prasher, Anil Kumar, M. G. H. Zaidi,

Mousamee Sharma, and Amit Verma

1 Introduction

The sustainable energy sources like solar energy, wind/tidal energy, etc., have an
immense potential to meetup with the energy requirement of current and future gener-
ations. However, owing to their intermittent energy supply these non-conventional
resources are required with energy storage/backup to meet the challenging and
endless energy demand. The intermittent energy supply can cost loss of billions
of dollars annually, thereby making the requirement of efficient electrical energy
storage devices (EESD) very critical. Also, the stored energy should be able to use
whenever and wherever needed [1, 2]. EESDs that find their immense application in

H. Mudila (B) · A. Kumar

Department of Chemistry, Lovely Professional University, Phagwara 144411, Punjab, India
e-mail: [email protected]
A. Kumar
e-mail: [email protected]
H. Mudila · M. G. H. Zaidi
Department of Chemistry, G. B. Pant University of Agriculture and Technology, Pantnagar
263145, Uttarakhand, India
e-mail: [email protected]
P. Prasher
Department of Chemistry, UPES, Dehradun 248007, Uttarakhand, India
e-mail: [email protected]
M. Sharma
Department of Chemistry, Uttaranchal University, Dehradun 248007, Uttarakhand, India
e-mail: [email protected]
A. Verma
Department of Biochemistry, Sardarkrushinagar Dantiwada Agricultural University, Palanpur
385506, Gujarat, India
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 47
Z. Khanam et al. (eds.), 2D Nanomaterials for Energy and Environmental Sustainability,
Materials Horizons: From Nature to Nanomaterials,
https://doi.org/10.1007/978-981-16-8538-5_3
48 H. Mudila et al.

energy storage include various sorts of electrochemical capacitors, primary batteries

(Alkaline Leclanché cell, Li-MnO2 etc.), secondary batteries (Li-ion, Na-ion, etc.)
etc., where an electrochemical conversion of redox chemical reaction to electrical
energy takes place. A variety of electrode materials of different dimensions has
been proposed for high-performing EESDs. These electrode materials are required
to have properties such as high power density which can be achieved with rapid
ion/electron transport. Maximum charge storage capacity is required for achieving
this high energy density which can’t be supplied by conventional electrode materials
due to their limited sites available for ion intercalation and small surface to volume
ratio, a major hindrance in high charge storage capacity [2]. These conventional
materials also suffer from drop in capacity because of the generation of redox inac-
tive levels and disintegration of materials caused by continuous electrode contraction
and expansion due to reversible intercalation of ions [3]. In this quest for a material
with higher energy and power densities and extended cyclability, 2D nanomaterials
have become a promising contender for EESDs owing to their explicit mechan-
ical, electrical, chemical, and optical properties. In this regard, graphene has find
its unambiguous position, but other 2D nanomaterials for instance, transition metal
compounds (TMOs, TMDs, TMNs, etc.), conducting polymers, boron nitride, black
phosphorous, etc., have also been explored. Studies show that atomic-thin layer
arrangements and extended surface area of most of the 2D nanomaterial generate a
slit shaped ion diffusion channels thereby allowing them for ultra-fast charge carrier
mobility and greater energy transfer efficiency. This ultra-fast charge carrier mobility
of 2D nanomaterials depends on numerous factors such as polarity of charge carrier,
number of layers, localized states, defects present, and various other physical factors.
Most of the 2D nanomaterials are bestowed with high redox properties and excellent
performance but carries certain limitations, such as (i) consumption of excess of elec-
trolytes causing irreversible capacity during first cycle by forming a solid-electrolyte
interface, (ii) electrolytic decomposition due to parasitic reactions resulted due to
numerous active sites. These suicidal factors limit the performance of 2D nano-
materials which can be regulated by various modifications, for instance, collective
layer formation of different 2D nanomaterials, etc. However, in-depth knowledge and
detailed studies are required to understand the associated problems and to generate
the possible solutions. Therefore, it is important to figure out the specific properties
of 2D nanomaterials, factors affecting them and how these factors can be modified
to alleviate the associated challenges.
This chapter brings a detailed insight on the superiority of 2D nanomaterials
over other dimensional materials, their properties, and the factors affecting their
performance. A highlight on the application of 2D nanomaterials for their use in
EESDs by considering the various aspect of energy, power, and cyclability is also
included. This chapter reviews the mechanism involved in the charging of EESDs
along with the detailed advantages and disadvantages associated with the variety
of 2D nanomaterials-based electrodes. A focus on the current and probable future
challenges to introduce such hetero-structured 2D nanomaterials as the material of
future EESDs is also addressed.
3 Next-Generation 2D Nanomaterial Composites Electrodes … 49

2 Mechanism of Charge-Storage in EESDs

Electrochemical capacitors, also designated as ultracapacitor or supercapacitors, are

typically classified into electric double layer capacitors (EDLCs) and pseudoca-
pacitors based on their potential to store electrochemical energy [3]. Each class of
the supercapacitors is characterized by its specific charge storage mechanism (non-
faradaic and faradaic mechanisms for EDLCs and pseudocapacitors, respectively)
(Fig. 2).

2.1 EDLCs (Electric Double-Layer Capacitors)

EDLCs is an electrochemical capacitor which generally involves carbonaceous mate-

rial (activated carbon, carbon nanotubes (CNTs), graphene, etc.) as electrodes. In
EDLCs, a reversible and infinite cyclable process is carried on, where electric double
layers are formed next to the electrode and electrolyte junction, which store charge
physiochemically by charge–discharge mechanism with porous electrode materials
(Fig. 1a, b) [1, 2]. The EDLCs have extraordinary power density but low energy
density (but higher as compared to early capacitors), hence, an augmentation in elec-
tric double layer capacitance is required in order to develop the applications related
to energy storage. EDLCs don’t undergo any specific chemical mechanism/change
and the charges are distributed on the surface of electrode via physical processes
only. The mechanism of generation of electrical energy in EDLCs is similar to the
conventional capacitor. In EDLCs, the process of adsorption and desorption of the
electrolyte ions (chemisorption) through the electric double layer on the porous elec-
trode material generates the charge–discharge process, while dielectric way of storing
charge is followed in conventional capacitors. The pore size of the electrode material
significantly effects the movement of ions and hence the charge–discharge mecha-
nism. Greater is the specific accessible surface area (m2 /g), higher is the capacitance
of the electrode material employed. However, micropores (< 2 nm) of narrower size
prevent the process of adsorption by sieving the electrolytic ions, while mesopores
(2 nm ≤ pore size < 50 nm) alter this effect and enhance the capacitance [4, 5].
During applied voltage, ions diffuse into the oppositely charge electrodes (through
ion permeable separator), the instant charge accumulation at the junction of each elec-
trode and electrolyte generates two electric double layers. A large surface area at a
small distance/thickness (0.1 nm) is generated in the interface between electrolyte and
electrodes due to highly porous structure thereby generating high capacitance. The
capacitance of a conventional capacitor can be determined by the distance between
the electrodes, while in a supercapacitor it is determined by the electrical double
layer generated in the interface between electrolyte and electrodes [6] (Fig. 2).
50 H. Mudila et al.

Fig. 1 Electric double layer capacitor: a charge state, b discharge state, c schematic representation
of fuel cell, d evolution of LIBs-based stationary energy storage (reproduce with permission [2, 6,
10])

Fig. 2 Comparison of energy and power densities of various EESDs

3 Next-Generation 2D Nanomaterial Composites Electrodes … 51

2.2 Pseudocapacitors

It is also termed as faradic supercapacitor which stores electrochemical energy

not only on the concept of EDLCs but also on the redox mechanism. A pseudo-
capacitance is developed on the surface and bulk of the electrode material by the
process of insertion (intercalation) or surface redox reaction (electrosorption) [7].
This reversible and rapid redox reaction passes the charge carriers through the
double layer resulting in the passage of faradic current through the pseudocapac-
itor [8]. When compared to EDLCs, pseudocapacitors have comparatively low power
density and cyclability owing to the slower faradic processes, but their energy density,
specific/volumetric energies, and capacitance value are much higher [8, 9]. Also, the
condition of having two oxidation states in a particular studied potential window can
be considered as one of the most distinguishing property of pseudocapacitor mate-
rials. In general, pseudocapacitors involve three types of faradic (redox) processes;
reversible adsorption, redox reaction (in transition metal oxide), and reversal elec-
trochemical doping-de-doping (in CPs) [8, 10, 11]. Mostly, metal oxides (TMO),
conducting polymers, etc., are used as electrode material for pseudocapacitors.

2.3 Fuel Cells

These are unique energy sources with potential applications which can run a simple
computer or even large power station. As compared to the conventional energy system
these fuel cells convert chemical energy to electrical energy with greater efficiency
and zero hazardous emission. The phenomenon behind fuel cell is similar to batteries
(conversion of chemical energy to electrical) but without need of recharging. In fuel
cells (for instance, H2 –O2 ) oxidation of fuel (of H2 , HOR) takes place at anode and
reduction (of O2 , ORR) occurs at cathode, while in reverse process H2 O undergoes
H2 and O2 evolution, i.e., HER and OER at cathode and anode, respectively (Fig. 1c).

At Anode (HOR): 2H2 → 4H+ 4e− (1)

At Cathode (ORR): O2 + 4e− + 4H+ → 2H2 O (2)

In recent times, Polymer Electrolyte Membrane Fuel Cells (PEMFC) have

emerged as an efficient and ecofriendly clean source of energy, which are coated
with catalyst layers over the electrodes. Numerous 2D catalysts such as RuO2 , IrO2 ,
FeCoNi, and graphene have shown their ability to enhance the performance of fuel
cells [12–14]. For an electro-catalyst to be used in HER or HOR, etc., processes high
specific surface area, high catalytic activity, low energy barrier, appreciable elec-
trical conduction and stability is essential. Pt is successfully replaced via N-doped
CNT and graphene, for the ORR in fuel cells [15, 16]. GO and graphene membrane
are established as a capable membrane material for microbial, alkaline, fuel cells
52 H. Mudila et al.

[17, 18]. Transition metal macrocyclic complexes also show their explicit position
in PEMFC for ORR [19].

2.4 Batteries

These are the electrochemical cells where energy is generated via redox reaction
occurring at the junction of electrode and electrolyte. Batteries offer superior energy
density compared to any type of capacitors, while the energy is stored chemically
resulting in more storage of energy. However, the power density and life cycle of these
batteries as compared to supercapacitor is very low. With time electrochemical cell
develops irregularities across the surface of the electrode which decreases its storage
capacity and also the heat produced by the system limits its performance. A variety
of battery systems are introduced to meet the energy demand which includes lead
acid batteries (specific energy of 60–75 Wh/L), alkaline batteries (specific energy of
160 Wh/L), Ni–Fe battery (specific energy of 30 Wh/L), metal-air batteries, Nickel-
metal hydride battery, Li-based batteries (energy density of 150–200 Wh/kg), etc.
(Fig. 1d) [6, 7, 10]. A variety of 2D nanomaterials are considered over the decade for
understanding their application in battery technology. In this field, graphene and its
analogue, MXenes, monoelemental form (P, Si, Ge, etc.), metal oxide, chalcogenides
and hydroxide, etc., have gained significant results with a major focus on in Li-
based batteries [20]. Although these battery systems are vastly modified from their
initial stages, still some major hindrances (high polarization, huge capacity loss, poor
reversibility and low electrochemical performance) have limited their applications in
high energy density and high-performance systems [20, 21]. Therefore, an extensive
and judicious research is required in this direction.

3 Various EESDs Electrodes Based on 2D Nanomaterials

and Their Composites

2D nanomaterials are the material of current and future generation for applications
related to various sectors, mainly in energy production and storage. A variety of 2D
nanomaterials such as graphene, transition metal dichalcogenides (TMDs), transition
metal oxides (TMOs), transition metal oxides (TMHs), transitional metal carbides
(TMCs), various CPs and material such as boron nitride, black phosphorous, etc.,
[22] are being employed due to their specific characteristic, which strongly effect
the performance of the active material to be used for EESD applications [23–25].
The section below details the characteristics of different 2D nanomaterials used in
EESDs.
3 Next-Generation 2D Nanomaterial Composites Electrodes … 53

3.1 Graphene

Graphene has been the most investigated 2D nanomaterial since its discovery.
Graphene is established as the strongest material present in the nature, where high
Young’s modulus, high surface to volume ratio, rapid reaction kinetics and low mass
are the key factors for establishing this material effective for all its applications.
Graphene monolayer (sp2 hybridized, honeycomb) with extraordinary mechanical
strength, flexibility, toughness, chemical stability, enhanced conductivity, etc., has
paved its role in the arena of transparent and flexible electronic devices and sensors
[26, 27]. Researchers have reported very high specific capacitance for graphene-
based supercapacitors while the resistance of graphene is lower than silver [28].
Graphene-based supercapacitors are in great demand due to factors like great cycla-
bility (minimum performance loss), high galvanic charge–discharge (GCD) rate,
great power density, no issue of short circuit, etc. Although graphene is being
employed from some last decades only, a lot of advancement is achieved with super-
capacitor based on graphene as an active material. Hydrogen annealed nanoporous
graphene, carbon nanodots converted to graphene, porous graphene-based carbons,
etc., are found to have high energy and power density [29, 30]. Similarly, graphene-
based hybrid material with judicious combinations of carbon dots, transition metals
composites (NiCo2 S4 , V2 O5 , etc.), and other doping are observed to have similar
results [31, 32]. Graphene along with CP is also one of the major research areas for
generating potential supercapacitor materials. CPs like PAni, PPy, etc., are witnessed
to enhance the electrochemical performance of graphene-based composites [33, 34].
Figure 3 represents the CV curves of the graphene/CP nanocomposite electrode-
based supercapacitor. The superior properties of as-prepared electrode, viz., ideal and
uniform pore size, along with excellent ion accessibility supports superior perfor-
mance of device. Therefore, graphene alone or in hybrid form is being extensively
employed in the field of energy such as EESD, photovoltaic cells, optoelectronics,
and Li-ion batteries.

Fig. 3 a CV curves of G (Graphene), CDG, G-NiCo2 S4 and CDG-NiCo2 S4 electrodes at a scan

rate of 5 mV/s; b CV curve of PPY, GO/PPY and rGO/PPY (reproduce with permission [31, 33])
54 H. Mudila et al.

3.2 Transitional Metal Dichalcogenides (TMDs)

Though graphene is most prevalent material to be used in EESD, but lack of a

considerable bandgap in graphene generates a quest for finding other 2D nanomate-
rials with semiconducting properties to be employed for energy storage. A variety
of 2D transition metal compounds possess the potential to substitute graphene as a
perfect candidate for EESDs (Fig. 4). In this regard, 2D TMDs (bandgap of 0 to ~
2 eV) are emerging as a contender to effectively replace the graphene from various
applications. The general formula for TMDs is MX2 , where M suggests the presence
of a transition metal (most common are W, Mo, Re, Ta, etc.) while X is a chalcogen
(gr. 16 family including, S, Se, and Te). A variety of TMDs (viz. MoS2 , WS2 etc.) is
being used for various applications including EESDs [35].
The structure of TMDs plays a significant role in generating their specific proper-
ties. TMDs exist in two common structural phases which are characterized by trigonal
prismatic (1T, metallic phase), octahedral/hexagonal coordination (2H, semiconduc-
tive phase), or rhombohedral (3R, semiconductive phase) structure. These are resulted
due to different coordination spheres of the transition metal atoms, while the ideal
phase of the TMD monolayer depends on the number of d-electron present in the
metal. TMDs of gr. VI (chalcogens of Mo, W, etc.) exhibit a direct bandgap range
of 1–2 eV showing their semiconductive nature. The thin layered TMDs readily
provide catalytic sites for redox reaction to generate their electrochemical activity
which is independent on the analyte used. The interface between electrolyte and
electrode (along with catalyst) marks the position of electrolytic reaction where the
performance of catalyst is found to be critical [36]. Similarly, the catalytic edges also
play crucial role in electrochemical activities of TMDs. Wang et al. explained that
the active sites of MoS2 are positioned at the edge planes which provide a signif-
icant enhancement in the electrochemical performances [37]. A high anisotropic
behavior with an exceptional crystal structure is demonstrated by 2D TMDs. These

Fig. 4 Types of transition

metal compounds employed
for EESDs
3 Next-Generation 2D Nanomaterial Composites Electrodes … 55

Fig. 5 CV of MoS2 /Graphene nanocomposite (a); Charge–discharge cycling of MoO2 electrode

(b); CV profile of the Ni(OH)2 (c); Charge–discharge curve of TiN electrode (d) (reproduce with
permission [38, 59, 74, 82])

TMDs can be easily tuned up via variety of methodologies (alloying, intercalation,

reduction in dimensions, heterostructured formation) as to be used in EESDs. A
variety of combinations of TMDs with other 2D nanomaterials are studied for their
electrochemical behavior so as to generate hybrid composites having superior elec-
trochemical output, performance, and stability (Fig. 5a). Hybrid composite of MoS2
(with graphene, MnO2 , ZnO, poly(ethyleneimine)-modified graphene oxide, PEI-
GO/activated-carbon, etc.) [38–41], and WS2 (with AC, W2 C, etc.) are the most
studied TMDs as electrode material for EESDs [42, 43].

3.3 Layered Post-transition Metal Chalcogenides (PTMCs)

PTMCs also entail layered 2D structure like TMDs, which generate explicit prop-
erties (higher photo-responsivities, great mobility, in-plane anisotropy, etc.) in the
electrodes generated through them. The compounds have semiconductive charac-
teristics with appreciable band gap (1–3 eV) which ranges from UV region to the
near-infrared region [44, 45]. These PTMCs follow the general formula of MX,
56 H. Mudila et al.

where M is Ga and In, while X represents chalcogens (like S, Se, and Te). Unlike
TMDs which have X–M–X type of motif, PTMCs theme layer composed of X–M–
M–X type of arrangement, exception being GaTe. These PTMCs found their explicit
application in the field of Li-ion and Na-ion batteries (LIB and SIB), electrocatalysis,
transistors, photodetectors, optoelectronics, EESDs, sensors, etc. [44, 46]. Owing to
the presence of weak Van der Waals interactions between the deposits/layers, a few
layered 2D PTMCs can be isolated which helped the material to endure against a
heavy strain and undergo a change in its structure [47]. PTMCs of Ga and In are the
most studied composite materials. These materials are employed as anode in LIBs
and SIBs to produce high energy density batteries [48–50].

3.4 Transition Metal Oxides (TMOs)

TMOs owing to their extraordinary properties such as stability, great gravimetric

capacities tunable redox potential are of great interest to be employed for EESDs
[51]. A variety of TMOs are studied for EESDs including MnO2 (polymorphs),
MoO3 , V2 O5 , sodium metal oxides (Nax MO2 ), TiO2 , NiMn2 O4 , iron oxides, RuO2 ,
ZrO2 , cobalt oxide, copper oxide, etc. [52, 53]. Most of the metal oxides undergo basi-
cally three different alkali cation storage mechanisms, viz., insertion/intercalation,
alloying, and conversion. However, process Insertion generates a little volume vari-
ation, where there is no deterioration of the original crystal organization. It allows
reasonable cyclability and hence excellent capacity retention but this mechanism is
restricted to generate high-power devices in spite of high power density [52, 53].
Alloying: a mechanism that presents a rapid method for Li and Na storage capac-
ities, but extensive volume variation decreases the cyclability of these electrodes
(of Si, Sn, Ge, Zn, etc.), also drying up of cell can take place due to decompo-
sition of electrolyte owing to introduction of fresh layers of electrode to the used
electrolyte. These issues can be partially overcome by using metal oxides, which
however generates the problem of agglomeration of elemental particle thus enhance
capacitive degradation on discharging. Conversion: TMO’s negative electrode are
generally used in LIBs and SIBs, the conversion of TMO to TM0 or to Li/Na oxides
permits electron conduction thus generating great cyclability, less volume variation
[51, 54, 55]. MnO2 , MoO3 , V2 O5 , RuO2 , Fe2 O3 , etc., have been majorly studied for
their electrochemical behavior (CV, CD, etc. Fig. 5b), most of these TMOs prove
their supremacy with outstanding specific capacitance, high capacitive retention,
and high energy densities [56–63]. TMOs with other 2D nanomaterials generate
high end hybrid electrode material to be used as a component for EESDs. TMOs
such as MoO3 and TiO2 with graphene have been majorly studied and are found to
exhibit high energy and power density [64, 65]. Few other reported composites of
ZrO2 and RuO2 with carbonaceous material are observed to have appreciable specific
capacitance and retention [9, 66].
3 Next-Generation 2D Nanomaterial Composites Electrodes … 57

3.5 Transition Metal Hydroxides (TMHs)

Likewise, other 2D nanomaterial THMs are also employed for EESDs, with certain
properties, viz. abundance, cost effective, greater surface area, fast electron and
charge transfer, high and easy tunable composition, etc. [67]. Similar to TMOs, these
TMHs are compatible with range of electrolytes and are chemically stable and envi-
ronmentally benign. Also, they have higher theoretical capacitance as compared to
graphene. Generally, TMHs are featured with wide energy bandgaps, thus endowing
low electronic conductivities, which results in reduced redox reversibility conse-
quently restricting their application in high-rate measurements. This is where
tunablity of TMHs generates a solution for the mentioned drawback through complete
utilization of all the accessible sites. Additionally, the multiple oxidation states and
redox reactions make these TMHs a promising contender for EES [67–70]. Generally,
TMHs can be studied as layered single metal hydroxides (LSHs) and layered double
metal hydroxides (LDHs). Nanoparticles of β-Ni(OH)2 , Fe(OH)3 , Co(OH)2 , etc.,
are synthesized via a variety of procedure (hydrothermal, ultra-sonication method,
etc.), which when subjected to electrochemical studies (Fig. 5c shows CV profile of
Ni(OH)2 ) generate high energy and power density with great cyclability [72–74].

3.6 Transition Metal Nitrides (TMNs)

Similar to other 2D materials, TMNs are also employed as a potential candidate

to be used in EESDs which have a great charge–discharge character (Fig. 5d). In
TMNs, the metal entails interstitial sites which are covered by nitrogen atoms to
generate cubic, hexagonal closed packing (hcp) and simple hexagonal structures.
These TMNs have metallic, covalent, and ionic characteristics which endow specific
properties, viz., high volume to surface area, appreciable electrical conductivity,
comprehensive catalytic properties, great volumetric energy density, etc., which has
drawn significant research attention toward TMNs [75, 76]. But, a few drawbacks
like restricted number of active sites (leading to low ionic kinetics), low durability
and brittleness restrict their electrochemical performance. These shortcomings can
be easily tuned via various synthetic approaches and modification in morphology,
which eventually leads to even dispersity (prevent agglomeration), generates higher
specific surface with numerous active sites, and facilitates high ionic kinetics, thus
improves the electronic conductivity [77, 78].

3.7 Transition Metal Carbides (TMCs)

TMCs (Mn+1 Xn , same for TMNs) are generally fabricated by incorporating atoms of
carbon into the interstitial sites/locants (radius ratio 0.491–0.576) of transition metals
58 H. Mudila et al.

[76]. TMCs owing to their specific and unique properties is fascinating research
community to employ them in variety of applications [79, 80]. The characteristics
such as significant chemical and thermal stability (high melting point), high electrical
conductivity (due to low electrical resistivity), corrosion resistance are the major
reason behind their explicit use [76, 81]. Likewise, other combination of transition
metal with non-metals, TMCs also exhibit covalent bond, ionic bond, and metallic
bond, which impart characteristics such as toleration to stress (during lithiation and
delithiation), chemical stability excellent electronic properties (Table 1).

3.8 Conducting Polymers (CPs) Composites

CPs based on their nanostructure can be classified into 1D, 2D and 3D nanostructures.
All of these nanostructures find their exceptional application in the field of EESDs. 2D
CPs are of boundless length but are ultrathin materials possessing spatially confined
structure generated via in-plane interactions [87]. The CPs demonstrate similar elec-
trochemical and electrical properties as of metals and semiconductors; however,
CPs comprise of decent specific capacitance but does associate with a few limi-
tations like low cyclability and swelling in electrolytes [88]. Some of the unique
features of 2D CPs such as tunable surface morphology, high porosity, more active
sites, manageable thickness, synthesis ease and variety of processibility, and low
cost give CPs a superiority over other 2D nanomaterials [89]. Techniques such as
layer by layer, spin coating, sonication, electrochemical polymerization are the most
common and fruitful method for generation of ultrathin, porous, large surfaced, 2D
CPs [90]. PANI, PPY, and various other CPs that are being employed for EESDs
applications. These CPs are subjected to various electrochemical studies like CV,
GCD, etc., to establish them as potential 2D electrode materials. Generally, these
CPs offered a low electrical conductivity which limits their excessive use in energy
storage and conversion. However, many a times with specific polymerization tech-
nique, modified physical factors, use of specific electrolytes, and doping-dedoping
conditions can help in improving the conductivity. Owing to the merits mentioned
earlier numerous efforts have been carried to fabricate novel 2D CP nanocompos-
ites with high specific capacitance, energy and power densities with fast charging
characteristics [58]. Band gap theory established on quantum theory and molecular
orbital theory provides the explanation why materials conduct charge, however band
gap doesn’t generate the clear picture in case of CPs, though the theory of conju-
gation, present the accurate condition of conduction of charge in these CPs by the
delocalization of electronic states, and mobility of charge carriers. Yet a drawback
is present with most of the CPs is that they are devoid of intrinsic charge carrier
and thus need the condition of doping (p/n-type) which generates the polarons,
bipolarons, and solitons in the CP chain that act as charge carriers [91]. The in-
built limitations of these CPs can be astounded by judiciously modifying them with
other heterogeneous material thus enhancing their conductivity, stability, cyclability,
etc. To improve the electrochemical properties, hybrid electrode materials are being
3 Next-Generation 2D Nanomaterial Composites Electrodes … 59

Table 1 Transition metal compounds, their types and EESDs related data
Species Specific Power density Energy Cyclic References
capacitance density retention
Transitional metal dichalcogenides (TMDs)
MoS2 128 F/g 50 W/Kg 6.15 Wh/kg 80% after 4 [37]
× 103 cycles
WS2 170 mAh/g 1134.4 W/kg 132.7 Wh/kg 100% after [42]
100 cycles
WS2 /AC 47.2 F/g 224.9 W/kg 132.7 Wh/kg [42]
MoS2 /ZnO 42 F/g – – – [40]
MoS2 /PEI/GO 153.9 F/g 4500 W/kg 19.3 Wh/kg 96% after [41]
6.8 × 103
cycles
MoS2 /PEI-GO/AC 42.9 F/g 93.1% after [41]
8 × 103
cycles
W2 C/WS2 1040 mAh/g 50% after [43]
100 cycles
MoSe2 1287 mAh/g 50 W/kg 6.15 Wh/kg 100% after [44]
100 cycles
Transition metal oxides (TMOs)
ZrO2 /GO 300 F/g 59.40 W/kg – – [9]
MnO2 459.0 F/g – – 94.8% after [56]
3 × 103
cycles
α-MnO2 535 F/g – – 80% after 3 [57]
× 103 cycles
α-MoO3 1249.2 F/g – – 85% after 5 [58]
× 103 cycles
MoO3 600 mAh/g – 86% after 30 [59]
cycles
V2 O5 350 F/g – 48.6 Wh/kg 75% [60]
RuO2 192 F/g 1·5 kW/kg 41·6 Wh/kg 95% [61]
α-Fe2 O3 138 F/g – – 89% after [62]
500 cycles
α-MoO3 /graphene 483 F/g 2.67 kW/kg 12.35 Wh/kg 100% after 5 [63]
× 103 cycles
Li4 Ti5 O12 173 mAh/g – – [64]
Ru/RuO2 /AC 1460 F/g – – 94% after 1 [66]
× 104 cycles
Transition metal hydroxides (TMHs)
β-Ni(OH)2 404 F/g – – 85.37% [71]
(continued)
60 H. Mudila et al.

Table 1 (continued)
Species Specific Power density Energy Cyclic References
capacitance density retention
β-Ni(OH)/CNT 724 F/g – 92.10% [71]
Fe(OH)2 1066 F/g 1.27 kW/kg 104 Wh/kg 91% after 1 [72]
× 104 cycles
Co(OH)2 3.4 C/cm2 – – 91% after [73]
1.4 × 103
cycles
Ni-Co/MWCNT 502 F/g – 69 Wh/kg 80% after 5 [74]
× 103 cycles
Transition metal nitrides (TMNs)
Ni/Co–Co2 N 361.93 C/g 9.85 kW/kg 20.4 Wh/kg 82.4% after [77]
5 × 103
cycles
P/MoN 400 mF/cm2 – – – [78]
NbN/NC 143 mAh/g – – 100% after 2 [79]
× 103 cycles
Ni3 N 593 mAh/g – – 81% [80]
VN 64.2 F/g 512.3 W/kg 109.3 Wh/kg – [81]
TiN 407 F/g – – 90.2% after [82]
2 × 104
cycles
TiN 53.66 – – 97% after 1 [83]
mF/cm2 × 104 cycles
Transition metal carbides (TMCs)
Ti3 C2 447 F/g – – – [84]
Ti2 C 248 F/g – – – [85]
Nb2 C 354 mAh/g – – 63.6% after [85]
800 cycles
Mo2 C 218 F/g – – 94.7% after [86]
1 × 104
cycles
Mo2 C/AC – 9028.8 W/kg 23.5 Wh/kg 99% after 5 [86]
× 103 cycles

explored thus combining energy storage through electrostatic attraction and faradic
reaction. Numerous carbonaceous composites such as metal oxide/carbon [92] and
conducting polymer/carbon composites [93] had been developed in this regard (Table
2).
3 Next-Generation 2D Nanomaterial Composites Electrodes … 61

Table 2 EESDs data for CPs and hybrid material polymer

CPss Additive Specific Energy density Power density References
capacitance
PIND – 24.48 F/g 1 Wh/kg 36.00 W/kg [94]
PIND Graphene 389.17 F/g 13.51 Wh/kg 511.95 W/kg [94]
PPY GO 526.33 F/g – 731.19 W/Kg [95]
PANI – 772 F/g – – [58]
PANI Graphene 909 F/g – – [58]
PANI SWCNTs 128 ± 5 320 mWh/g 8,000 mW/g [96]
mAh/g
PPY – 245 F/g – – [97]
PPY Cu–TCPP 500 F/g 0.29 mWh/cm3 270 mW/cm3 [97]
PPY Graphene 137 F/cm3 4.8 mWh/cm3 645.1 mW/cm3 [98]
PPY Carbon black 366 F/g – – [99]
PTH – 3.5 F/g 0.7 Wh/kg – [100]
PTH GO 16.39 F/g 2.28 Wh/kg – [100]
PTH Graphite 28.68 F/g 3.98 Wh/kg – [100]

3.9 Carbonitrides (CN)

Generally, the composite of CN is employed as protective covering and finds its appli-
cation in the field of diffusion barrier layers; CNs have excellent electrical conduc-
tivity, thermal and mechanical stability with great corrosion resistance [101]. Due to
the condition such as disintegration of crystalline structure, lithiation/delithiation,
poor specific capacity, and cyclability, CN finds somewhat lower application in
LIBs. However, certain modifications in the structure can overcome these specific
issues; Angamuthu et al., synthesized CN (C3 N4 ) in varying temperature (500 and
600 °C by direct heating melamine (10 g, C3 N6 H6 ), the CN synthesized at 600 °C
displays an excellent initial charge–discharge capacity (2221/1986 mAh/g), while
after 300 cycles a reversible charge capacity of 1701 mAh/g was produced [102].
A graphite/C3 N4 material over ZnCo2 O4 was fabricated via hydrothermal method,
the as prepared composite material was found to have the extended surface area,
enhanced electroactive sites and was chemically stable. The hybrid composite at 4
A/g current density was observed to have a specific capacity of 157 mAh/g, while a
capacity retention of 90% was obtained even after 2500 cycles. The device was able
to display an energy density of 39 Wh/kg with a power density of 1478 W/kg [103].
62 H. Mudila et al.

3.10 Hexagonal-Boron Nitride (h-BN)

Isostructural to graphene also known as “white graphene”, h-BN consists of sp2

hybridized alternate presence of boron and nitrogen atoms, where the different layers
are held together via Van der Waals force of attraction. Owing to their specific charac-
teristics of having distinctive structure and semiconductive nature, h-BN (nanotubes)
found their specific use in the field of EESDs [104]. Study claims that h-BN has chem-
ical inertness and poor electronic conductivity (band gap 5.9 eV) [105], though tuning
of h-BN via certain physical and chemical modification can help them to be used
in energy conversion and storage. Studies suggest that doping (with heteroatoms)
and grafting (functional groups) can minimize the band gap of h-BN in a range of
0.3–3.1 eV, thus, modifying its surface, electrical, and optical characteristics.
Attribute to nested assembly, h-BN/rGO composite material enhances the specific
capacity (179.5 mAh/g) and stability of Lithium Titanium oxide (LTO, Li4 Ti5 O12 ),
the specific capacity of rGO/LTO (161.6 mAh/g) and h-BnN/LTO was way below
than the h-BN/rGO/LTO composite material. The nested assembly permits facile
Li-ion diffusion, better electron transport and thus enhanced lithium ion storage
[106]. Functionalized h-BN (OH, O and LiO) in LIBs was used by Zhang et al.,
through a reaction between h-BN and LiOH (molten) which leads to exfoliation and
functionalization of h-BN. The agglomerated Fh-BN was able to charge/discharge
reversibly and exhibit a specific capacity of 400 mAh/g at 0.01 V with appreciable
cyclability [107]. BN (along with MOS2 and WS2 ), a 2D layered material, was used
as fixers for the compounds of S and sulfide and the effect of immobilization through
the repeated charge/discharge processes was studied, BN/S/C composite at a current
density of 100 mA/g was observed to display a very high capacity of 532 mAh/g
while a 94.3% columbic efficiency was generated after 300 continuous cycles at ~
1.15 V [108].

3.11 Phosphorene (Black Phosphorous)

Phosphorene (allotrope of phosphorus) is 2D in nature where the different layers

are held along with weak Van der Waals bonds. Phosphorene resembles graphene
in many of its properties; therefore, it is employed in various arenas of electronics
(nano and opto), energy conversion/storage, sensors, and infrastructure [109, 110].
The electrocatalytic effect of 2D phosphorene over iodide ions in 1 M H2 SO4 and
0.5 M KI undergoes redox reactions. This generates a high specific discharge capacity
of 3181.5 F/g with a specific energy density is 203.7 Wh/kg, while specific energy
remains 36.6 Wh/Kg even after 1000 charge–discharge processes [111]. Few layered
phosphorene hybridized along with layers of graphene generates a 2D hybrid elec-
trode material. The conductive graphene layers act as the pathway for charge transport
which further generate a buffer space where the anisotropically expanded phospho-
rene layer can be accommodated. This hybrid 2D material displays a very high
3 Next-Generation 2D Nanomaterial Composites Electrodes … 63

Fig. 6 CV curve of Phosphorene (a); CV curves of VS/Sb (reproduce with permission (b) [112,
117]

specific capacity of 2440 mA/g at a current density of 0.05 A/g with a substantial
capacity retention of 83% after 100 cycles in the potential window of 0 to 1.5 V
[112] (Fig. 6a).

3.12 Antimonene

Isostructural to Phosphorene, Antimonene isolated (epitaxial growth, solution-phase

synthesis, mechanical and liquid-phase exfoliation) from its layered allotrope is
an emerging 2D nanomaterial to be employed for electrochemical applications,
solar cells, electrocatalysis. Properties like thermodynamic, air and environmental
stability, lamellar structure (gap of 3.73 Å), tunable band gap (0–2.28 eV), appre-
ciable electrical conductivity (1.6 × 104 S/m) and rapid ion diffusion are associated
with Antimonene [113]. However, its strong binding energy, fast interlayer ionic
transport, small layer distance, etc., restrict its application in EESDs [114]. A number
of research carried out in recent times have suggested that Antimonene is a material of
high specific capacitance (597–1578 F/g), good cyclability, and appreciable energy
and power densities [115, 116]. Antimonene electrodes are modified to enhance their
performance by reducing its limitations (Fig. 6b). The 2D fillers such as MXenes,
TMCs, graphene are also employed for this purpose [116–118].

3.13 Xenes

Likewise, other 2D Xene materials (X = Si, Ge, Sn, etc.) owing to their mechan-
ical flexibility, distorted atomic layer, high surface/volume ratio, and higher electron
mobility are anticipated to have potential to be used in EDLCs and LIBs [119–121].
Silicene, Stanene, and Germanene are graphene equivalent, having similar electronic
64 H. Mudila et al.

properties as of graphene and can be successfully synthesized over metallic and

ceramic substrates by molecular beam-epitaxy deposition method, solid-state reac-
tion method, etc. (as can’t be exfoliated from bulk material). However, production
of high-quality freestanding silicene is still a great task to researchers. Also, violent
volume alterations and unstable solid electrolyte interface limit the application of use
of Group IVA elements. Studies suggest that the defect present in Xenes is respon-
sible for its enhanced quantum capacitance [122, 123]. Various reports significantly
establish high theoretical capacitance (4200, 1625, and 994 mAh/g), electrical perfor-
mance and long cyclabilty of Xenes (Si, Ge, Sn), and establish them as significant
materials to be used for EESDs [124, 125].

4 Factors Affecting 2D Materials Performance

Various parameters such as temperature, defects, and doping have deep effect on the
performance of any electrode. The judicious variation in these parameters can result
in an improved extraordinary electrode material which can be used efficiently in the
field of EESDs [125].

4.1 Effect of Temperature

Temperature is a critical aspect for energy storage material as it can significantly

augment or limit the application of various EESDs. Mudila et al. studied the effect
of reduced temperature (10 ± 1 °C) on the electrochemical performance of PPY/GO
nanocomposite, CV studies in 1 M KOH (at 0.2–0.001 V/s) rendered a specific
conductivity of 526.33 F/g with 731.19 W/Kg of power density, while a high capac-
itive retention (96%) after 500 cycles rate was observed [95]. Co3 O4 /rGO nanocom-
posites (anode) prepared through microwave irradiation method (at 100 °C) for LIBs
demonstrate good electrochemical performance, an initial charge/discharge capacity
of 47 and 42.7 mAh/g at 500 mA/g, while a 100% coulombic efficiency after 50 cycles
was gained [126]. Gel electrolytes of fumed silica and fumed silica/TiO2 character-
ized by CV and EIS show the increased anodic peak currents (at 30 °C for fumed silica
and 40 °C for fumed silica/TiO2 ) and redox capacities with increasing temperature
[127]. PAN co-MMA (Polyacrylonitrile/methyl methacrylate) copolymer nanofibers
synthesized by electrospinning technique were further converted to carbon nanofibers
on heating at varying temperature (1000, 1800, and 2200 °C). These prepared carbon
nanofibers were studied for their application in LIBs. It was observed that with an
increasing temperature the specific capacitance was decreased (254, 238 and 105
mAh/g for 1000, 1800, and 2200 °C). However, an improved microstructure and
surface area (~60 m2 /g) were determined at 2000 °C which could be attributed to the
distribution of pore in fibers along with a low electrolyte wetting, also at 1000 °C, a
high capacitance (238 mAh/g) was retrieved after 500 cycles [128].
3 Next-Generation 2D Nanomaterial Composites Electrodes … 65

4.2 Effect of Dopant

Doping of electrochemical active material with variety of dopants tune their perfor-
mance multifold and a variety of dopants are used in energy conversion/storage sector
for the above-mentioned purpose. Graphene doped with hetero atom (N-doped) give
a few layer nanocomposite with density of ~ 2.1 mg/cm3 which delivers a specific
capacitance of 484 F/g in 1 M KOH [129]. Co-doped Ni(OH)2 enhances the specific
capacitance of TMH to 1500 F/g at current density of 10 A/g, which falls to 1560
F/g after 100 discharge/charge cycles [130]. Co-doped cobalt oxide was tuned to
have appreciable pore size and surface area which helped in generating synergistic
effect of ordered nanopores (which enables osmotic solution flux and diffusive solute
transport) and small nanoparticles (paving channel for electron transportation and
ion diffusion), that generate a specific capacitance of 902.3 F/g at 2 A/g with better
cyclability [131]. Li2 MoO3 doped by cation (Zn, Mg, Cr, and La) generate materials
with good structural stability and electrical conductivities. Undoped Li2 MoO3 gives
the lowest specific capacity of 246.87 mAh/g while the highest specific capacity was
generated by Cr doped Li2 MoO3 (Li2 Mo0.96 Cr0.04 O3 ). La-doped Li2 MoO3 displays
a specific capacity of 149.89 mAh/g after 50th cycle at current density of 34 mA/g
[132].

4.3 Effect of Defect

Though 2D nanomaterial is presented significantly by many researchers to be

employed in the direction of energy conversion/storage, but the performance of
EESDs can be optimized considerably through the introduction of certain defects
in electroactive materials. These introduced imperfections expose the unsaturated
sites which play a crucial role in electrochemical reactions. Defects/imperfections
generate novel functionality in electrode which enhances ion diffusion by gener-
ating new active sites. Also, the surface energy is evolved which enhances the
electrochemical phase revolution. [133–135].
Structurally defective and non-defective graphene were allowed to adsorb Mg over
their surface. Mg energy storage capacity was enhanced with increasing the defect
concentration or altering the organization of available carbon rings of graphene. High
availability of Mg enhances the electrochemical energy storage specific capacity to
1042 mAh/g (25% di-vacancy defects) [136]. Mgx Fe2 –xB2 O5 and MgVBO4 (metal
borate) with high specific capacities of 186 and 360 mAh/g, respectively, were synthe-
sized. At higher temperature (200–500 °C) by thermal oxidation Mg can be removed
from the lattice, the diffusion of Mg through interstitial channels thus with Mg
mobility in the sites enhances the capacity [137]. Introduction of certain cationic
defects (of Li, Si and P) into the surface of TiS2 through using a thermal annealing
66 H. Mudila et al.

method was carried by Liu et al. showed that the presence of cationic defects effi-
ciently increases cyclability and reaction rate of the electrodes. The presence of phos-
phorus impurities generates highest 63.56% of retention after 450 cycles which was
much higher (35.13%) than TiS2 electrode alone. Thus, Ti vacancy defect were found
to be advantageous in generating interlayer spacing, weakening of strain, generating
perfect interstitial sites for cationic doping [138]. n-type Ag particle were doped to
CdSe via electronic tuning to cover certain imperfections where these defects cover
were found to behave as charge trappers. The densities of the charge trapping defects
in the material were found to be in the range of 1018−1020 cm3 [139].

5 Conclusion

Various EESDs in different forms offer a potential alternative to meet the present and
future energy/power demands. Though different types of materials are present which
render high power density, comes with great charge-recharge cyclability and also have
specific capability to work in extreme physical condition of temperatures, etc. These
capabilities increase the efficiency of the end-product and eventually condensing
the expenses and being environmental friendliness. In this direction, 2D nanoma-
terials (graphene, TMDs, MXenes, etc.) have presented themselves significantly to
be employed in the direction of energy conversion/storage. 2D nanomaterials are
present with certain unique properties which help them to show their marked perfor-
mance in the area of energy storage and conversion. Tuning the nanostructures via
doping with certain heteroatoms and functional group generates micro/nano pores
which modify the electronic and surface properties of these 2D nanomaterials. But,
many of the inherent deficits limit the ultimate use of these 2D nanomaterials in phys-
ical devices due to the issues such as low conductivity (compared to other nanos-
tructures), limited electroactive sites (limited electrochemical performance), poor
reversibility high cost, reduced oxidation resistance. Though continuous and efficient
research approaches have produced many significant nanomaterials of 2D nature
which however fulfill the energy demand of current time, a continuous and scal-
able effort along with noble modifications in the morphology is required to achieve
high-quality, powerful and economical 2D nanomaterial for enormous future energy
demands.

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Chapter 4
Novel 2D Nanomaterial Composites
Photocatalysts: Application
in Degradation of Water Contaminants

Mohd Saquib Tanweer and Masood Alam

1 Introduction

The ubiquitous presence of residuals of organic contaminants such as toxic dyes and
pharmaceuticals in wastewaters significantly poses an extreme damage to both flora
and fauna including human health. Manufacturing industries related to textile, paper,
bleaching, and leather tanning generate and discharge untreated dye effluents into
water sources resulting in water pollution due to their recalcitrance nature. It gives the
water an unpalatable color, reduces sunlight penetration and makes aquatic lives more
resilient due to photochemical and biological threats. Besides, the pharmaceutical
industries and hospitals are primarily accountable for the production and discharge
of untreated antibiotic residues into natural water bodies. Tetracycline is the most
widely used antibiotics in humans, veterinary and aquaculture medicine [1]. When
environmental bacteria encounters with tetracycline residues, they develop changes
in genes that make them resistant to stronger antibiotics, resulting in pathogenic
strains. Several researchers have recently shown that these harmful contaminants
can have detrimental effects on the aquatic environment, even at very minute levels
[2]. Table 1 shows the classification of dyes based on their chemical structure and
Table 2 shows possible impact of dyes and antibiotics on living systems in aquatic
environment. Hence, the development of environmental remediation technologies to
eliminate these toxic contaminants is on priority. Several technologies have recently
been developed by the researchers to remediate the environmental pollution [3–6].
Among these technologies, photocatalysis has emerged as a very promising and
eco-friendly technique for water purification [7]. Photocatalysis is a phenomenon

M. S. Tanweer · M. Alam (B)

Environmental Science Research Lab, Department of Applied Sciences and Humanities, Faculty
of Engineering and Technology, Jamia Millia Islamia, New Delhi 110025, India
e-mail: [email protected]
M. S. Tanweer
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 75
Z. Khanam et al. (eds.), 2D Nanomaterials for Energy and Environmental Sustainability,
Materials Horizons: From Nature to Nanomaterials,
https://doi.org/10.1007/978-981-16-8538-5_4
76 M. S. Tanweer and M. Alam

Table 1 Classification of dyes on the basis of chemical structure adapted from [16]
Class Chromospheres Example
Azo dyes

Anthraquinone
dyes

Indigoid dyes

Nitroso dyes

Nitro dyes

Triarylmethane
dyes
4 Novel 2D Nanomaterial Composites Photocatalysts … 77

Table 2 Impact on living system by residues of dyes and antibiotics in the aquatic environment
Model contaminants Impact on living system References
Reactive dyes Skin allergy [22, 23]
Disperse blue 106 and 124 Skin allergy [24]
Orange II Carcinogenic [25]
Rose Bengal Cytotoxic, cytostatic, genotoxic and mutagenic [26, 27]
Eriochrome black T Carcinogenic [28]
Indigo carmine Damaging the aquatic life [29]
Malachite green Carcinogenic effects in immune and reproductive [30]
system
Methyl violet • Reduces photosynthesis reactions of aquatic [31–33]
plants
• Respiratory tracks injury, diarrhea, pain,
vomiting, headache and dizziness
• Mutagenic and carcinogenic
Rhodamine B Carcinogenic, neurotoxicity and chronic toxicity [34]
Brilliant blue-R Irritation to the skin, eyes, respiratory system [35]
Crystal violet Mitotic poisoning [36]
Basic fuchsin Severe eye, skin, gastrointestinal and respiratory [37]
tract irritation
Penicillin Nephritis, eosinophilia, and haemolytic anaemia, [38]
impaired platelet aggregation
Chloramphenicol Pancytopenia [38]
Erythromycin Headache, ototoxicity (deafness), ventricular [38]
arrhythmias
Ampicillin Diarrhoea [38]
β-Lactams Drug fever, drug rash [38]
Ciprofloxacin Neuroexcitatory symptoms, tendon rupture [39]
Levofloxacin Genotoxicity [40]
Gentamicin Nephrotoxic [41]

which occurs when any light source interacts with the surface of any semiconductor
materials, called photocatalysts. Generally, it is a two-step process. First, the process
of oxidation takes place after the formation of photogenerated holes, and then finally,
the process of reduction occurs after the generation of photogenerated electrons.
Photocatalysts are responsible for capturing solar energy to degrade contaminants
thus, making photocatalysis an economically viable treatment approach. The desire
for innovative and robust photocatalysts led to the exploitation of nanomaterials
that are now being used in every field of science and technology due to their excellent
physicochemical properties. Till date, numerous types of nanomaterial photocatalysts
such as CdS [7], ZnO [8], TiO2 [8], and 2D nanomaterials [9, 10] have been developed
and utilized to remediate the polluted water under UV irradiation, visible light and
78 M. S. Tanweer and M. Alam

sunlight. Among the nanomaterial photocatalysts, 2D nanomaterial photocatalysts

based on MXene, TMDs and phosphorene are regarded as highly effective for the
degradation of dyes and antibiotics, due to their exceptional physical and chemical
properties.
With increasing interests in applications of 2D nanomaterial-based photocatalysts,
we have focused to write an overview of the recent progress of 2D nanomaterial
photocatalysts in eliminating the environmental pollution. This chapter discusses
various types of water contaminants such as dyes and antibiotics and their impact on
living systems including humans. The synthesis and properties of 2D nanomaterial-
based catalysts are briefly discussed. The role of nanomaterial photocatalysts in the
photocatalytic degradation of organic contaminants is also elaborated followed by a
conclusion and future perspectives of the 2D nanomaterial-based photocatalysts.

2 Impact of Organic Contaminants on Living Systems

The term “contamination” in environmental chemistry is a synonym to pollution,

where the primary focus is the damage done to living organisms and environment on
a wide scale. Water contaminants may be suspended and dissolved chemicals (dye
and antibiotic residues) or biologicals (pathogenic bacteria, virus, invasive species) in
nature. In this chapter, we have briefly discussed organic contaminants in particular,
organic dyes and antibiotics and their impact on living systems.

2.1 Organic Dyes

Dyes are chemical compounds that are commonly used to color a variety of goods,
including textile, leather, paper, rubber, plastics, etc. Unfortunately, the dye wastes
enter the aqueous environment through the effluent and become a major source of
water pollution due to its recalcitrant and non-biodegradable nature [11]. Presence of
dye residues blocks the penetration of sunlight needed beneath water by aquatic lives
for normal functioning of life-saving processes like respiration and photosynthesis
[12]. Globally, 7 × 105 tonnes of organic dyes are produced annually, out of which
more than 15–20% is discharged into aqueous environment [13]. Dyes can be clas-
sified according to structure, color and their application purposes (Table 1). On the
other hand, dyes could also be categorized based on their dissolution of their particle
charge in solution, namely, cationic (all basic dyes), anionic (direct, acid and reactive
dyes) and non-ionic (dispersed dyes). Cationic dyes have high color strength and are
visible even in minute concentrations [14, 15]. Dyes are very toxic and carcinogenic
in nature. The presence of dyes in aquatic ecosystems can significantly affect photo-
synthesis reactions causing oxygen deficiency due to reduced penetration of sunlight;
thereby affecting the viability of aquatic flora and fauna. Sardar et al. [13] reported
4 Novel 2D Nanomaterial Composites Photocatalysts … 79

that dyes could also be teratogenic and mutagenic to various types of microbiological
species and fishes.
Azo dyes can be anaerobically reduced to produce very toxic aromatic amines by
the intestinal microflora and are proven to be a potential carcinogenic, and mutagenic
in humans [17, 18]. In addition, it may also cause significant harms to humans, in
the form of renal malfunction and sexual, liver, brain and central nervous system
dysfunction [19]. Anthraquinone-containing dyes are the most resistant to degrada-
tion and its color persists in effluents for a longer time [20]. As reactive dyes are
highly soluble in water, it is difficult to remove them from the effluent, thus causing
serious harms to the environment [21]. Some reactive dyes form complexes with
metals such as Cu, Cr, Co and Ni. When these metal-complexed dyes degrade, toxic
heavy metals get free from the dyes and finally end up in the food chain leading
to biomagnification. The use of different dyes has created a great concern because
of their toxicity and adverse effects on the living systems (Table 2). Therefore, 2D
nanomaterial-based photocatalysts are required for photocatalytic degradation of
dyes from different types of wastewaters.

2.2 Antibiotics

Selman Waksman coined the term Antibiotic in 1942. He described antibiotic as a

substance produced by a microorganism that is antagonistic to the growth of other
microorganisms. After the discovery of first antibiotic, viz., Penicillin by Alexander
Fleming in 1928, a decent progress resulted in controlling a large variety of bacterial
diseases [42]. A study reveals that approximately 90% of the antibiotics excreted
by animals enter into the water sources directly or indirectly. A data published in
year 2013 by World Health Organization states that out of the total antibiotic’s
consumption of two lakh tons per year, 80% of it is consumed for veterinary use
alone. It thus recognizes animal husbandry as the primary cause for developing
antibacterial resistance. It is further estimated that by the year 2050, the diseases
caused by multi-resistant bacteria can engulf about 10 million people per year world-
wide [43]. Besides toxicity, the antibiotics have an advantage to control infectious
diseases. It is, therefore, an important factor for the abuse of antibiotics. Rise in
the consumption of antibiotics causes more resistance by bacteria and therefore,
more harm. The inoculation of antibiotics in aqueous media is largely because
of intensive farming throughout the world as food sector is considered the fastest
growing industry. As a result of it, sewage and water treatment plants contain an
abundant quantity of antibiotics of pharmaceutical origin [44]. Different types of
antibiotics, namely, Fluoroquinolones, sulphamethoxazole, lincomycin, trimetho-
prim, sulphonamides and beta-lactams have been found in hospital effluents in large
quantities with 35,500 ng/L detection rate [45]. Other sources of antibiotics include
veterinary, pharmaceutical plants, animal excreta, dairies, municipal wastes, animal
husbandry and poultry industries [46]. The antibiotic pollution not only disturbs
microbial populations but also badly effects human lives (Table 2). Since, there is an
80 M. S. Tanweer and M. Alam

antagonistic effect of antibiotics, a long-term exposure even of very low concentration

could alter drinking water, food and other consumer goods. Triclosan is an antimicro-
bial agent that is largely present in soaps and clothes causing reproductive problems
and muscle weakness. About 75% of US population is exposed to triclosan or other
antibiotics through consumer goods [47]. Tetracycline causes gastrointestinal effects
like vomiting, nausea and diarrhea. It changes the normal intestinal flora that stops
coliform organisms. Vaginal candidiasis is also reported due to unintended uptake of
tetracycline. The patients with pre-developed hepatic insufficiency are likely to face
liver toxicity [48]. In sewage treatment plants, antibiotics are only partly removed.
During the water treatment process, antibiotics pass through the sewage plant and end
up in the aqueous environment. Therefore, there is an urgent need for the complete
removal of antibiotics residues from sewage water effluents. Previous studies show
that 2D nanomaterial-based photocatalysts could be a better option to remediate the
environment [49, 50].

3 Preparation and Properties of 2D Nanomaterial-Based

Photocatalysts

Photocatalysis has received great attention as an exciting and promising replacement

for conventional water purification technologies to remove waterborne contaminants.
2D nanomaterial-based photocatalysts have shown great potential in photocatal-
ysis field because of their unique optical, electronic and physicochemical proper-
ties. In the past decade, graphene-based photocatalysts were the most extensively
studied 2D nanomaterial-based photocatalysts. The rapid development of graphene-
based photocatalysts motivated many researchers in exploring their potential in 2D
nanomaterial-based photocatalysts for photocatalysis applications. Generally, two
types of synthetic strategies are reported, namely (a) in situ growth and (b) ex
situ assembly method. In case of in situ growth, low dimensional nanomaterial
is either directly grown on the surface of the 2D materials (template) or the 2D
materials are developed in the presence of low dimensional nanomaterials. While in
ex situ assembly method, nanomaterials are pre-synthesized with defined composi-
tions, shape and size then mixed with 2D nanomaterials through covalent or non-
covalent interactions. In situ methods, which include one-step in-situ calcination
[51], hydrothermal [52, 53] or solvothermal methods [54] are employed to synthe-
size 2D nanomaterial-based photocatalysts. Shen et al. [54] synthesized CeO2 /Ti3 C2 -
MXene hybrids by in-situ growth of cube-like CeO2 onto 2D ultrathin Ti3 C2 -MXene
nanosheets via simple hydrothermal route. The close contact between in situ grown
CeO2 and 2D Ti3 C2 -MXene nanosheets generated a built-in electric field which
induces Schottky junction favoring the charge transfer from CeO2 to 2D Ti3 C2 -
MXene nanosheets. It enhanced the separation efficiency and subsequently increased
the photocatalytic activity. Novel flower-like WS2 /Bi2 O2 CO3 photocatalysts were
developed via one-pot hydrothermal approach [53]. Flower-like heterojunctions
4 Novel 2D Nanomaterial Composites Photocatalysts … 81

showed synergistic effects between the enhanced separation efficiency of photo-

induced charge carriers and a high specific surface area (SSA) thereby, improving the
photocatalytic degradation activity. 2D TMDs-based photocatalysts possess various
properties such as quantum confinement effect with rearranged energy levels, large
SSA and the variation of the electronic band structure which are considered appro-
priate for the activation of the photocatalytic process. The introduction of ZnO during
synthesis of ZnO/MoS2 photocatalyst results in an increase of photocatalytic proper-
ties because of the enhanced interfacial charge transfer and absorption strength in UV
region, large SSA and favorable in-plane carrier transport [55]. The photocatalytic
properties of 2D TMDs-based photocatalysts can be enhanced by loading of TMDs
as co-catalysts on semiconductors/metal-semiconductors which produce junctions
and a greater number of interfaces. Bahadur et al. [56] successfully improved the
photocatalytic properties of Ag3 PO4 /MoS2 after loading of MoS2 as co-catalyst in
comparison to pristine Ag3 PO4 nanoparticles. It has been reported that about 97.6%
MB dyes were degraded by Ag3 PO4 /MoS2 within 15 min in the presence of visible
light illumination. Authors have reported that the rate of photocatalytic degradation
of MB using Ag3 PO4 /MoS2 could further be enhanced. The photocatalytic enhance-
ment resulted due to interfacial energy band (conduction band (CB) and valence band
(VB)) alignment between MoS2 sheets, and Ag3 PO4 nanoparticles, increased elec-
tron–hole pair separation, uniform distribution of Ag3 PO4 nanoparticles (5.4 nm)
and large SSA of MoS2 . 2D MXene-based photocatalysts have recently drawn the
attention of several researchers due to their exceptional electrical conductivity, large
SSA, tunable band gap and hydrophilic behavior. In 2D MXene-based photocatalysts,
MXenes are used as a substrate to support one or more catalyst materials to gain higher
photocatalytic property. Improvement in Schottky barriers with different composi-
tion of MXenes heterostructures are efficient and unambiguous ways to accelerate
the photocatalytic activity. Shahzad et al. [57] demonstrated a facile hydrothermal
treatment strategy to produce a hybrid photocatalyst based on Ti3 C2 Tx (MXene)
nanoflakes TiO2 /MXene. The photocatalytic property of TiO2 /MXene was signif-
icantly enhanced due to construction of a Schottky barrier between interfaces of
TiO2 -MXene.

4 Application of 2D Nanomaterial Photocatalysts in Water

and Wastewater Treatment

4.1 Mechanism of Photocatalytic Degradation

In the photodegradation of organic contaminants such as organic dyes and antibi-

otics, both electrons and holes play a pivotal part. The first step in the photocat-
alytic degradation is the segregation of electrons and holes. Photogenerated elec-
trons captured by oxygen molecules to produce superoxide radicals (·O2 ¯ ) make
82 M. S. Tanweer and M. Alam

them capable of taking part in photocatalytic degradation process. In the mean-

time, photogenerated holes are bonded with surficial hydroxyl groups or adsorbed
water molecules to readily produce hydroxyl radicals (·OH), which are oxidative
in nature and participate in degradation of environmental contaminants. Therefore,
it can be said that the engagement of photogenerated electrons holes and radicals
like superoxides and hydroxides are solely responsible for photocatalytic degrada-
tion of environmental contaminants. Meenakshi et al. [58] developed a novel 2D/2D
heterojunction of Z-scheme Chitosan@g-C3 N4 /MXene (CS@g-C3 N4 /MX) hybrid
composite via one-pot hydrothermal reaction. The construction of the heterojunc-
tion increases the separation of photogenerated charge carriers which facilitates
charge transmission-bridge along Z-scheme heterojunction resulting in increased
photodegradation of organic contaminants (MB and RhB). The process of charge
separation and its transmission is shown in Fig. 1a. The inclusion of chitosan (CS) in
between g-C3 N4 (PS-II) and MXene (PS-I) leads to the formation of photogenerated
electrons and holes, which hinder the recombination of electron and hole pairs. This
substantially increases the photocatalytic degradation rate of MB (99.1%) and RhB
(98.5%). A possible Z-scheme photocatalytic mechanism has been proposed for the
Chitosan@g-C3 N4 /MXene heterojunction. The main reaction steps are depicted as
follows:

Fig. 1 a Schematic illustration of the possible separation of charge carriers during the photocat-
alytic degradation of MB and RhB in the Vis/Chitosan@g-C3 N4 /MXene hybrid composite system.
Reprinted with permission from [58]. Copyright 2018, Elsevier; b schematic mechanism of magnetic
α-Fe2 O3 /ZnFe2 O4 @Ti3 C2 MXene photocatalyst. Reprinted with permission from [63]. Copyright
2019, Elsevier; c photocatalytic mechanisms of the Ti3 C2 –OH/In2 S3 /CdS composites, Reprinted
with permission from [66]. Copyright 2019, Elsevier; and d proposed mechanism for pollutant
degradation in the InTi-16 system under visible light illumination, Reprinted with permission from
[65]. Copyright 2018, Elsevier
4 Novel 2D Nanomaterial Composites Photocatalysts … 83
 
CS@g-C3 N4 /MXh ν → h+ + e− CS@g-C3 N4 /MX

H2 O + e− + h+ → 2 ·OH

H2 O2 → ·OH + ·OH

H2 O2 + ·OH → ·OOH + H2 O

CS@g - C3 N4 /MX + dyes → OH + ·O−

2

MB + RhB + (·OH + ·O2 and H2 O2 ) → H2 O + CO2 + Intermediates

In another investigation, Wu et al. [51] developed a highly photoactive Z-type

heterojunction catalyst with a graphene layer embedded TiO2 /g-C3 N4 (GTOCN)
photocatalyst via one-step in-situ calcination of Ti3 C2 . In between graphene, TiO2
and g-C3 N4, solid phase interaction occurs to segregate photogenerated electrons and
holes. The aggregation of g-C3 N4 electrons with high reduction capability and TiO2
holes with high oxidation activity occur. Organic contaminants such as tetracycline
(TC) and ciprofloxacin (CIP), bisphenol A (BPA) and rhodamine B (RhB) have
shown tremendously high degradation rate under visible light irradiation. The as-
prepared GTOCN photocatalyst presented substantial enhancement due to visible
light absorption and photogenerated charge carrier segregation. The single-electron
O-vacancy of GTOCN photocatalyst generated at a modest calcination temperature is
the foremost accountability for enhancing its photocatalytic activity and contaminant
degradation stability.

4.2 MXenes-Based Photocatalysts

MXenes are among the latest addition to the family of 2D transition metal carbides,
nitrides and/ or carbonitrides with the general formula Mn+1 Xn Tx , where M is an early
transition metal (e.g., Ti, Zr, V, Nb, Ta, or Mo), X is carbon and/or nitrogen, and Tx
denotes the surficial functional groups of MXene. Over the past decade, more than 20
varieties of MXene materials have been synthesized in laboratory, including Ti3 C2 ,
TiNbC, Ti2 C, V2 C, Nb4 C3 and Mo2 C [59–75]. 2D MXenes photocatalysts proved
to be a model material for the photocatalytic degradation process because of their
excellent electronic and optical properties along with excellent surface functionality
[59–77].
Degradation of organic dyes: Gogotsi et al. [61] investigated the photocatalytic
properties of Ti3 C2 Tx for the degradation of cationic methylene blue (MB) and
anionic acid blue 80 (AB80). The presence of surficial functional groups like –OH
84 M. S. Tanweer and M. Alam

and –F makes MXene negatively charged in water, thus enabling cationic methy-
lene blue to be adsorbed more favorably than anionic acid blue 80. Therefore, MB
can be firmly bound with Ti3 C2 Tx , while AB80 suffered to adsorb. Within 5 h, MB
was degraded by 81% under UV irradiation, while only 18% of MB degraded in
the dark. In the same manner, within 5 h, 62% of AB80 was degraded under UV
irradiation, whereas no degradation took place in the dark, even after 24 h. The
formation of titanium tetrahydroxide and titanium dioxide triggers the photocat-
alytic effect on the surface of MXene under UV irradiation. The intimate contact
of MXene to dissolved O2 in water for a long period facilitates MXene’s surface
to oxidize to form TiO2 . As a result, MB degradation is enhanced in the dark and
speeding up photodegradation under UV illumination. In another study, TiO2 /Ti3 C2
photocatalysts were successfully synthesized and efficiently used to degrade MB
under UV irradiation. This can be mainly attributed to hole-electron segregation
of the TiO2 /Ti3 C2 composite under UV light [62]. Zhang et al. [63] ultrasonically
fabricated α-Fe2 O3 /ZnFe2 O4 @Ti3 C2 MXene photocatalyst through a simple self-
assembly method. The well distributed and incorporated Fe2 O3 nanoparticles on the
surface of MXene can effectively use visible light, resulting in successfully photo-
catalytic degradation of rhodamine B (RhB) and Cr(VI) adsorption. It is mainly
due to properties like high charge-transfer rate, numerous heterostructure interfaces,
high conductivity and charge separation efficiency. Figure 1b displays the possible
photocatalytic mechanism of α-Fe2 O3 /ZnFe2 O4 @Ti3 C2 MXene.
Undoubtedly, metal sulfides such as CdS, ZnS and In2 S3 (Indium sulfide) perform
a critical role in the application of photocatalytic degradation [64–66]. To gain
super-efficient photocatalysis of metal sulfides, visible-light-driven ternary Ti3 C2 –
OH/ln2 S3 /CdS composites were constructed by Pan and coworkers [66] using
hydrothermal method. Ti3 C2 –OH/ln2 S3 /CdS composites with 4-weight percentage
of Ti3 C2 –OH are in spherical shape; have larger surface area thus providing more
active sites for better degradation of selected contaminants. In addition, excel-
lent electrical property of Ti3 C2 –OH and close contact between Ti3 C2 –OH, ln2 S3
and CdS boost the degradation performance of Ti3 C2 –OH/ln2 S3 /CdS compos-
ites. Figure 1c illustrates the photocatalytic mechanisms of Ti3 C2 –OH/In2 S3 /CdS
composites. To check the photocatalytic performance of another ternary meso-
porous catalyst, In2 S3 /anataseTiO2 @Ti3 C2 Tx [65] composites were investigated by
degrading methyl orange and tetracycline hydrochloride. The degradation reaction
constant of hybrid photocatalyst (InTi-16: Ti3 C2 Tx content 16 mg) possessed higher
activity than bare In2 S3 and Ti3 C2 Tx . For this quasi-core–shell photocatalyst frame-
work, MXene and derived TiO2 served as unique and novel methods for the embed-
ment of In2 S3 . MXene’s surface and its edge paved with plentiful asymmetrical In2 S3 .
The Schottky barrier formed between In2 S3 , TiO2 and Ti3 C2 Tx facilitates multiple
channels for the migration of photoinduced electrons (Fig. 1d). Upon exposure to
visible light, the electrons of In2 S3 are excited and transferred to TiO2 along the
heterojunction. In addition, the Schottky barrier between TiO2 and Ti3 C2 Tx enhanced
the charge segregation and migration and inhibited the back diffusion of electrons.
4 Novel 2D Nanomaterial Composites Photocatalysts … 85

Degradation of antibiotics: Ti3 C2 -MXene is recognized as a promising noble-metal-

free co-catalyst to produce effective photocatalysts for the degradation of pharma-
ceutical contaminants. For instance, on ultrathin Ti3 C2 -MXene nanosheets cube-
like CeO2 has been grown to form CeO2 /Ti3 C2 -MXene hybrids [52] by a facile
hydrothermal method. The CeO2 /Ti3 C2 -MXene hybrid with the optimum weight
percentage of Ti3 C2 -MXene showed efficient photocatalytic degradation of tetra-
cycline and CO2 reduction under sunlight illumination. The photocatalytic degra-
dation by hybrid material is greater than bare CeO2 . The photocatalytic degrada-
tion of hybrid material increased due to Schottky junction in between CeO2 and
Ti3 C2 -MXene that was triggered by built-in electric field. It leads to transfer of
photoinduced electrons from CeO2 to Ti3 C2 -MXene, thus causing the separation
between electrons and holes. Shen et al. [67] developed ternary MXene-based Z-
scheme composite, namely, CdS@Ti3 C2 @TiO2 nanohybrids through a simple calci-
nation method followed by hydrothermal method. The as-prepared nanostructure
was employed for efficient degradation of sulfachloropyridazine, methylene blue,
rhodamine B and phenol under visible light illumination. The CdS@Ti3 C2 @TiO2
nanohybrids with 2:1 ratio showed 100% degradation for selected model contam-
inants under visible light irradiation. The increased photocatalytic degradation of
organic contaminants is due to “sink” effect of MXene together with well-defined
band gap of CdS@Ti3 C2 @TiO2 nanohybrids. The photogenerated charge electron
and hole pairs in the Z-scheme type photocatalyst are segregated in efficient manner
which successively produce free radicals such as ·O2 − and ·OH that play pivotal roles
in oxidizing the organic contaminants. Various 2D MXene-based photocatalysts used
in degradation are listed in Table 3.

4.3 TMDs-Based Photocatalysts

Transition metal dichalcogenides (TMDs) are comprised of hexagonal metal atom

(M) layers sandwiched between the layers of chalcogen (S, Se and Te) with a general
formula MX2 . TMDs possess various properties associated with their compositional
formulation. Among TMDs, MoS2 and WS2 are the most widely used for photocat-
alytic degradation due to their robust nature and easy availability of raw materials
[53–55, 78–80].
Degradation of organic dyes: Generally, TMDs are used as co-catalysts embedded on
semiconductors to form junctions between them, thereby, facilitating charge transport
of the photogenerated charge carriers such as electrons and holes. Yu et al. [79] have
successfully developed flower-like MoS2 /BiVO4 composite by two-step approach.
The coupling of MoS2 with BiVO4 significantly enhanced the photocatalytic perfor-
mance of MB (94.2%) degradation compared with bare MoS2 and BiVO4 in the
presence of visible light irradiation. This can be attributed to a special charge-transfer
mechanism. Since, the conduction band (CB) and valence band (VB) of BiVO4 lie
below the energy bands of MoS2 , the migration of excited photogenerated electrons
86 M. S. Tanweer and M. Alam

Table 3 2D nanomaterial-based photocatalysts for degradation of contaminants

2D nanomaterial Target Removal Morphology References
photocatalyst contaminants capacity
MXenes
a-Fe2 O3 /Ti3 C2 Rhodamine B 98% Nanosheets/nanosheets [68]
CeO2 /Ti3 C2 -MXene Tetracycline 80.2% Cubic/nanosheets [52]
g-C3 N4 /Ti3 C2 Ciprofloxacin – Nanosheets/nanosheets [69]
MXene-Co3 O4 Methylene blue 128.91 mg/g Nanosheets/cubic particle [70]
and Rhodamine (MB),
B 47.076 mg/g
(RhB)
Sm-doped Ciprofloxacin More than Hollow porous [71]
g-C3 N4 /Ti3 C2 MXene 99% seaweed/nanosheets
CuFe2 O4 /MXene Sulfamethazine 59.4% Nanoparticles/nanosheets [72]
(001)TiO2 /Ti3 C2 Methyl orange 97.4% Nanosheets/nanosheets [73]
Bi3 TaO7 /Ti3 C2 Methylene blue 99% Nanoparticles/nanosheets [74]
Ti3 C2 -Bi/BiOCl Ciprofloxacin 89% Nanosheets/microspheres [75]
Ti3 C2 /g-C3 N4 Diclofenac 100% Nanosheets/nanosheets [76]
TiO2 /Ti3 C2 Rhodamine B 95% Nanorods/nanoparticles [77]
TMDs
MoS2 /TiO2 Rhodamine B 98.2% Nanosheets/nanofibers [78]
MoS2 /BiVO4 Methylene blue 94.2% Nanoflower [79]
MoS2 /Bi2 WO6 Methylene blue 82% Core–shell [80]
heterostructure
WS2 /Bi2 O2 CO3 Lanasol Red 5B 91% Nanoflower [53]
WS2 /Bi2 O2 CO3 Ciprofloxacin 95% Nanoflower [53]
WSe2 /RGO Rhodamine B – Nanosheets/nanosheets [54]
ZnO/MoS2 Tetracycline – Nanosheets [55]
ZnO/MoS2 Methylene More than Nanosheets [55]
blue, 90% for
Rhodamine B both

take place to CB of BiVO4 and holes to VB of MoS2 . Thus, photocatalysis reactions

occur. In addition, the segregation of photogenerated charge carriers enhances the
photocatalytic degradation reactions. Xiao et al. [81] have fabricated a novel 2D/2D
heterostructure composite, namely, 1T/2H MoSe2 /pg-C3 N4 with Z-scheme hetero-
junction in two steps. First, 1T/2H MoSe2 is developed in an orderly manner using
NaBH4 -assisted hydrothermal method. Second, 1T/2H MoSe2 with different weight
percentage gets embedded as co-catalyst on proton g-C3 N4 to produce final product
through solvothermal strategy. The coupling of 1T/2H MoSe2 (1 wt%) with proton
g-C3 N4 significantly improved the photocatalytic degradation of tetracycline and
rhodamine B degradation under solar light irradiation, which is more than pristine
4 Novel 2D Nanomaterial Composites Photocatalysts … 87

1T/2H MoSe2 and proton g-C3 N4 . This is because of a narrow band gap, surplus active
sites, excellent photocurrent response and conductivity of 1T/2H MoSe2 /pg-C3 N4 .
Figure 2a illustrates the synthesis and Z-scheme photocatalytic mechanism of 1T/2H
MoSe2 /pg-C3 N4. A 2D photocatalyst phosphorene/MoS2 hybrid was developed by
liquid exfoliation procedure. The as-prepared nanocomposites were employed for
the photocatalytic decomposition of Congo red (CR), Methylene blue (MB) and
Methyl orange (MO) dyes in the presence of UV illumination. The results indicated
that the synthesized photocatalysts have a very high photocatalytic efficiency at a
very low concentration (0.58 ppm). This can be attributed mainly to an increase in
energy band gap, large specific surface area, interfacial charge transfer and spatial
separation [82].
Degradation of antibiotics: TMDs are another type of 2D nanomaterials that are often
employed to degrade antibiotics (Table 3). For example, NiS and MoS2 nanosheet
co-modified graphitic C3 N4 (NiS/MoS2 /g-C3 N4 hybrids) ternary heterostructures
were synthesized through hydrothermal method followed by ultrasound method
(Fig. 2b). The NiS/MoS2 /g-C3 N4 hybrids were applied to photodegrade antibiotics
like ciprofloxacin and tetracycline hydrochloride under the visible light. After 2 h
visible light irradiation, the optimum photodegradation rate of the NiS/MoS2 /g-C3 N4
hybrids exceeds approximately 96%, which is 2.1 times greater than that of bare g-
C3 N4 for tetracycline hydrochloride degradation. The higher rate of photocatalytic

Fig. 2 a Illustrates the synthesis and Z-scheme photocatalytic mechanism of 1T/2H MoSe2 /pg-
C3 N4 . Reprinted with permission from [81]. Copyright 2020, Elsevier; b displays the photocatalytic
degradation mechanism of NiS/MoS2 /g-C3 N4 hybrids. Reprinted with permission from [83]. Copy-
right 2018, Elsevier; c the possible steps of the photocatalytic process and the charge-transfer mech-
anism in the CN/MS/BOC composite. Reprinted with permission from [84]. Copyright 2020, Else-
vier; and d schematic illustration of alignment of the energy level of 3:1 MoS2 /ZnSe nanocomposite.
Reprinted with permission from [85]. Copyright Catalysts 2020, MDPI
88 M. S. Tanweer and M. Alam

degradation is mainly attributed to enhanced visible light harness and charge sepa-
ration efficiency. Figure 2b displays the photocatalytic degradation mechanism of
NiS/MoS2 /g-C3 N4 hybrids [83]. Very recently, dual Z-scheme ternary heterojunction
photocatalysts, namely, g-C3 N4 /MoS2 /Bi24 O31 Cl10 (CN/MS/BOC) composite were
developed by Wang et al. [84] via impregnation-calcination method. The as-prepared
CN/MS/BOC composite exhibited a superb and durable photocatalytic performance
in the decontamination of tetracycline under the visible light. The photocatalytic
degradation rate of CN/MS/BOC was 97.5% for tetracycline after 50 min under
visible light irradiation, which was 5.38, 1.96 and 2.51 times more than that that of
BOC, CN/BOC and MS/BOC catalysts, respectively. The high rate of photocatalytic
degradation is due to enhanced optical absorption, increase in separation, trans-
portation of the electron–hole pairs and robust redox competence resulting from the
dual Z-scheme heterostructure of CN/MS/BOC. The possible steps of the photocat-
alytic process and the charge-transfer mechanism in the CN/MS/BOC composite are
shown in Fig. 2c. In another study, photocatalytic activity of MoS2 /ZnSe heterostruc-
tures [85] was investigated to degrade levofloxacin under visible light irradiation.
MoS2 /ZnSe nanocomposites were synthesized by a facile ultrasonication method.
The results showed that the degradation activity of MoS2 /ZnSe nanocomposites was
73.2% for levofloxacin, whereas bare MoS2 and ZnSe degraded levofloxacin only
about 29 and 17.1%, respectively, in 2 h under visible light. The synergistic interaction
between MoS2 and ZnSe produces superoxide and hydroxide radicals subsequently
accounting for levofloxacin degradation in the MoS2 /ZnSe process (Fig. 2d). Various
TMDs-based photocatalysts used in degradation are listed in Table 3.

4.4 Phosphorene-Based Photocatalysts

Phosphorene is a new family member of 2D nanomaterials. It has characteristic

properties like extraordinary carrier mobility, excellent optical and better absorp-
tion in the range of ultraviolet along with a tunable bandgap that depends on the
number of layers. Additionally, phosphorene materials are remarkably anisotropic
due to the presence of two different P-P bond lengths [86]. Because of these charac-
teristics phosphorene has fascinated significant attention in a variety of fields such
as electronic, optical, and sensing [87, 88]. Like graphene, phosphorene exhibits
much higher surface-to-volume ratio due to its “puckered” lattice structure [89]. The
above-mentioned properties can make a material to be a potential photocatalyst.
Degradation of organic dyes: The photocatalytic activity of phosphorene can be
enhanced by improving interfacial charge relocation and segregation of the photoin-
duced charges. Farbod and coworkers developed few-layered black phosphorus (FL-
BP) nanosheets by exfoliation of bulk black phosphorus in an organic solvent such as
N-Methyl-2-Pyrrolidone (NMP) using ultrasonication. FL-BP exhibited direct band
gap and high stability in NMP which was chosen as a suitable solvent to prevent
oxidation of black phosphorus. Author investigated the photocatalytic performance
4 Novel 2D Nanomaterial Composites Photocatalysts … 89

of FL-BP to reduce dyes such as Congo red, methylene blue and methyl orange under
UV light irradiation. It has been reported that small amount of FL-BP (4.5 mg/L) is
enough to degrade the model dyes [90]. The same author has designed a 2D semicon-
ductor hybrid, namely, phosphorene/MoS2 to enhance their photocatalytic activity
[82]. In this investigation, phosphorene/MoS2 was prepared by liquid-phase exfoli-
ation method and its photocatalytic activity in degradation of Congo red, methylene
blue and methyl orange dyes under UV radiation was checked. Upon UV light irradia-
tion, model dyes and phosphorene/MoS2 photocatalyst start to generate electrons and
holes in CB and VB of hybrid semiconductors. The photoinduced electrons and holes
react with NMP to produce free radicals such as ·CH3 + , ·O2 − and H+ ions (Fig. 3a).
Further, these free radicals start to decompose model dyes and convert them into
harmless species. Additionally, photoinduced electrons and holes segregate in lower
energy levels, inhibit recombination rate and increase their lifetime, consequently
further enhancing degradation efficiency of phosphorene/MoS2 photocatalyst. Semi-
conductor like ZnO was coupled with black phosphorus for pollutant degradation. For
example, Liu et al. [91] developed the black phosphorus nanosheets-ZnO nanohybrid
(BPNs-ZnO nanohybrid) through a facile one-step co-precipitation method. BPNs-
ZnO nanohybrid showed excellent photocatalytic degradation for methylene blue
(dye) and ciprofloxacin (antibiotic) under visible light illumination. The BPNs-ZnO
nanohybrid exhibited better photocatalytic degradation in comparison to bare BPNs,

Fig. 3 a Schematic illustration for the band structure of phosphorene/MoS2 2D system and the
proposed mechanism of electron-holes generation and producing free radicals by NMP. Reprinted
with permission from [82]. Copyright 2021, Elsevier; b, c illustrates the proposed mechanisms
for degradation of MB and CIP by BPNs-ZnO nanohybrid. Reprinted with permission from [91].
Copyright 2019, Elsevier; and d schematic representation of photocatalytic performance of BPNs-
BiOBr photocatalysts. Reprinted with permission from [96]. Copyright 2021, Elsevier
90 M. S. Tanweer and M. Alam

ZnO and the bulk black phosphorus. Data showed that recombination rate of photoin-
duced charge carriers is effectively suppressed, and segregation of charge carriers
occurs by BPNs-ZnO nanohybrid. This causes photocatalytic degradation of selected
pollutants. Further, photodegradation efficiency of BPNs-ZnO can be attributed to
large specific surface area of composites, enhanced optical adsorption of visible light
for BPNs-ZnO nanohybrid and suitable band gap between BPNs and ZnO. Figure 3b,
c illustrate the proposed mechanisms for the degradation of MB and CIP by BPNs-
ZnO nanohybrid. Shen et al. [92] prepared a double phosphorus-based semicon-
ductor composite BP/RP (black phosphorus/red phosphorus) and chose rhodamine
B (RhB) as the target contaminant to evaluate its photocatalytic efficiency. The results
revealed that BP/RP heterojunction exhibited the efficient degradation for RhB (89%)
in 30 min under visible light illumination. Whereas after increasing reaction time
to 120 min, the RhB removal enhanced and the maximum amount of RhB (97%)
degraded. The results also revealed that in the first 30 min illumination, the BP/RP
(89%) heterostructure photocatalyst showed higher catalytic degradation rate than
CdS (32%) for RhB removal. Another advantage of using phosphorus as a photocat-
alyst over CdS is that phosphorus does not release toxic metals during photocatalysis
reaction. The BP/RP heterostructure showed more absorption of visible light leading
to segregation of photoinduced charge carriers. Consequently, photocatalytic activity
of BP/RP nanocomposites was increased.
Degradation of antibiotics: For the first time, silver nanoparticle was loaded on
black phosphorus to prepare AgNPs@BP with more active sites using ultrasonication
followed by centrifugation [93]. The photocatalytic efficiency of AgNPs@BP was
investigated to degrade norfloxacin in wastewater under near infrared (NIR) light
illumination. The resulting data revealed that 85% of model pollutants quickly got
photo-catalytically degraded. The increased photocatalytic efficiency of AgNPs@BP
nanocomposite can be attributed to the sensitization of black phosphorus nanosheets
by completely harvesting of NIR light and high electron–hole segregation capability.
Interestingly, AgNPs@BP exhibited no reduction in photocatalytic activity even
after five cycles of pollutant degradation. Bismuth oxyhalide (BiOX) is a common
catalytic material and finds a special position in the field of photocatalysis due to
its eco-friendly nature, compatible energy band and non-toxic properties [75, 94,
95]. To solve the problem of capturing the full spectrum of solar light, Li et al.
[96] developed black phosphorus nanosheets/BiOBr (BPNs-BiOBr) nanocomposites
through one-step co-precipitation technique. BPNs-BiOBr photocatalysts presented
a remarkable photocatalytic performance toward methyl orange and ciprofloxacin
degradation under visible light illumination (Fig. 3d). The nanocomposites displayed
better degradation capability as compared to pure BPNs and BiOBr. The type I
BPNs-BiOBr nanocomposites (with 15 ml of BPNs dispersion) exhibited higher
BET surface area than BiOBr indicating that there were more active sites on BPNs-
BiOBr. The photostability of black phosphorus nanosheets (BPN) was enhanced by
passivation effect of poly dimethyldiallyl ammonium chloride (PPDA). The enhanced
photocatalytic efficiency of BPNs-BiOBr photocatalysts was mainly derived due to
4 Novel 2D Nanomaterial Composites Photocatalysts … 91

the Type-I bandgap configuration, the increased light absorption and the huge surface
area.

5 Conclusions and Future Outlooks

The chapter summarizes the progress of 2D MXene-based photocatalysts, TMDs-

based photocatalysts and phosphorene-based photocatalysts for their application in
degradation of dyes and antibiotics. Types of common water pollutants such as
organic dyes and pharmaceutical residues and their effect on living systems are
briefly studied. Moreover, the application of MXene, TMDs and phosphorene as
photocatalysts in the photocatalytic field and degradation of water-borne organic
contaminants is systematically studied. Though more than 20 forms of MXene nano-
materials have been discovered, yet only a few of them, such as Ti3 C2 , TiNbC,
Nb2 C, Nb4 C3 , Mo2 C, Ti2 C and V2 C are commonly used as photocatalyst nanoma-
terials. Therefore, theoretical study must be implemented for the efficient designing
of MXene-based photocatalysts. This approach will help to identify possible struc-
tural behavior and deep insights of photocatalytic reaction at micro level. Doping
and surface functionalization of 2D nanomaterial-based photocatalysts affect its elec-
tronic and optoelectronics properties, thus enhancing photocatalytic performance. As
so far, fundamental theoretical investigations can be done. 2D nanomaterial-based
photocatalysts must be low cost. Additionally, it is also important to understand the
effect of 2D nanomaterial photocatalysts on energy and the environment. The 2D
nanomaterial-based photocatalysts which are discussed in this chapter are efficient
photocatalytic semiconductors. However, there are several challenges that still exit
to produce nanocatalyst with long-term stability. A robust and detailed assessment of
ecotoxicity and life cycle study of these nanomaterials is needed to be conducted. The
2D/2D heterostructures show higher stability and intimate interfaces that facilitate
photogenerated charge migration and segregation. As the synergistic effects of 2D/2D
heterostructures are presently less studied, new designs of 2D/2D heterostructures
with exceptional photocatalytic activity must be studied. All in all, many opportu-
nities remain awaited for researchers to explore possibilities of new insight into 2D
nanomaterials in various fields in the near future.

Acknowledgements One of the authors, Tanweer S. M. thankful to the University Grants

Commission (UGC) for the Non-NET Fellowship.

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Chapter 5
Advanced 2D Nanomaterial Composites:
Applications in Adsorption of Water
Pollutants and Toxic Gases

Mohd Saquib Tanweer, Harshvardhan Chauhan, and Masood Alam

Abbreviations

Au NPs Gold nanoparticles

BPNs/ZnO Black phosphorus nanosheets/ZnO
CeO2 –MoS2 Cerium-doped molybdenum disulphide
CH4 N2 S Thiourea
CNFs Carbon nano fibers
CR Congo red
EY Eosin Y
FA Fuchsin acid
HCl Hydrochloric acid
MB Methylene blue
MG Malachite green
MNP-PN-TNT Magnetic nanoparticle-Phosphorene-Titanium
nano tubes
MO Methyl orange
MoS2 /CuS NCs Molybdenum disulfide/copper(II)sulphide
nanosheet composites
MoS2 /GQD Molybdenum disulfide/graphene quantum dot
nanocomposite
MoS2 @2DMMT Molybdenum disulfide-montmorillonite

M. S. Tanweer (B) · H. Chauhan · M. Alam

Environmental Science Research Lab, Department of Applied Sciences and Humanities, Faculty
of Engineering and Technology, Jamia Millia Islamia, New Delhi 110025, India
e-mail: [email protected]
H. Chauhan
e-mail: [email protected]
M. Alam
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 97
Z. Khanam et al. (eds.), 2D Nanomaterials for Energy and Environmental Sustainability,
Materials Horizons: From Nature to Nanomaterials,
https://doi.org/10.1007/978-981-16-8538-5_5
98 M. S. Tanweer et al.

MoS2 -g-PDMA Molybdenum disulfide-grafted-poly(diethyl (4-

vinylbenzyl) phosphonate-co-maleic anhydride)
MoS2 -rGO hybrid Molybdenum disulphide-reduced graphene oxide
MX@ Fe3 O4 MXene decorated with Fe3 O4
MXene-COOH@(PEI/PAA)n Carboxyl modified MXene@(polyethylene poly-
imide/poly (acrylic acid)
MXene/LDH MXene/Layered double metal hydroxide
NaF Sodium fluoride
NMP N-methyl-2-pyrrolidone
NR Neutral red
RhB Rhodamine B
RhB 6G Rhodamine 6G
RSM Response surface methodology
ST Safranine T
Ti3 C2 –SO3 H Sulfonic groups functionalized titanium carbide
Ti3 C2 Tx -PDOPA MXene-Levodopa composite
TNT Titanium nano tubes
TPAOH Tetrapropylammonium hydroxide
WO3 –BPNs Tungsten trioxide-black phosphorus composites
WS2 Tungsten disulfide
WSe2 Tungsten diselenide
ZnIn2 S4 /protonated g-C3 N4 Zinc indium sulfide/protonated graphitic carbon
nitride

1 Introduction

Over increasing pace of industrialization, uncontrolled growth of human popula-

tion and vast expansion of urban areas have become principal factors to produce
hazardous wastes. It poses serious toxicological impact on health of living systems
including humans and different ecosystems resulting in huge negative effect on the
global economic development [1, 2]. The environmental pollutants that are chiefly
encountered are water pollutants and air pollutants. The water pollutants include
pharmaceutical residues (namely antibiotics, analgesic, anti-inflammatory drugs and
steroid hormones), heavy metal ions (namely chromium (Cr), mercury (Hg), lead
(Pb), cadmium (Cd), arsenic (As) and their salts), organics (namely textile dyes,
agricultural herbicides and pesticides, detergents surfactants, and oil) and bio-toxins
(namely bacteria, fungi, and virus). And the air pollutants include different types of
toxic gases specifically oxides of sulfur (SOx ), oxides of nitrogen (NOx ) and oxides
of carbon (namely CO, CO2 ). These pollutants may cause several diseases in humans,
for instance, kidney damage and skeletal damage caused due to Cd exposure, lung
and kidney damage, neurological and psychological disorder caused due to Hg expo-
sure, headache, irritability, abdominal pain and neurological disorder caused due to
5 Advanced 2D Nanomaterial Composites: Applications … 99

Pb poisoning gastrointestinal problems, disturbances to cardiovascular systems and

even death can occur due to As poisoning; while Cr exposure may cause mutagenic
and carcinogenic effects [3, 4].
Several physiochemical and biological treatment methods such as precipitation
[5], advanced oxidation [6], ion exchange [7], membrane filtration [8], adsorption [9]
and aerobic/anaerobic digestion [10] are developed to eliminate and reduce environ-
mental pollutants. Among these, adsorption is regarded as one of the most effective
conventional methods due to its simplicity of design, ease of operation, efficient and
low cost [11]. So far, various nanomaterials are developed as adsorbents for envi-
ronmental remediation, such as activated carbon [12], clay [13], silica [14], zeolites
[15], polymers [16] and metal–organic frameworks (MOFs) [17].
After the discovery of single-layered graphene in 2004, numerous two-
dimensional (2D) nanomaterials such as MXenes, phosphorene, transition metal
dichalcogenides (TMDs), hexagonal boron nitride (h-BN), silicene and germanene
have garnered a lot of attention from scientific community because of their aston-
ishing physicochemical properties [18]. MXenes are a new and rapidly rising family
of 2D transition-metal carbides, nitrides and carbonitrides that are analogous to
graphene. More than 30 types of MXenes compositions are reported so far with and
dozens more are being developed by computational methods. Ti-based MXenes such
as Ti3 C2 Tx , and Ti2 CTx are the most commonly used adsorbents in environmental
remediation [19, 20]. The existence of functional groups like oxygen, hydroxyl, fluo-
rine, chlorine on the surface of MXenes allows sites for direct ion exchange, although
it also eliminates certain cations and organic molecules [21–23]. The most widely
studied among TMDs is MoS2 because of their robustness and abundant availability
of raw materials [24]. Numerous types of 2D TMDs nanocomposites are developed
and used as nanoadsorbents for water treatment and toxic gas adsorption because of
their remarkable properties such as large specific surface area (SSA), tunable band
gaps, excellent chemical resistance and thermal stability [25, 26]. Besides them, 2D
Phosphorene, a mono- or few-layered material is arising as a star material at 2D plat-
form in nanotechnology field. In the context of environmental remediation, a tremen-
dous amount of resources is spent to explore the adsorption properties of bulk black
phosphorus and 2D phosphorene either by theoretical calculation or experimental
measurements [27, 28]. 2D nanomaterial composites are found to be the most privi-
leged adsorbents to remove water and toxic air pollutants because of their hydrophilic
behavior. They have several reactive surficial functional sites which make them good
candidates for removing pollutants from the environment. Recent studies proved
that these composites exhibited excellent adsorption capacities when compared with
traditional adsorbents.
This chapter provides an overview on the preparation and properties of 2D nano-
materials composites. The use of 2D nanomaterial composites as an adsorbent for
toxic gases, heavy metals ions (HMI) and dye removal is also discussed, alongwith
the mechanism of the adsorption process. The chapter finally concludes with the
future prospects and challenges of 2D nanomaterial composites.
100 M. S. Tanweer et al.

2 Preparation and Properties of 2D Nanocomposites-Based

Adsorbents

2D nanomaterial composites have been primarily synthesized through two methods,

(a) top-down method such as mechanical exfoliation and liquid exfoliation,
(b) bottom-up method such as hydrothermal method, self-assembly method and
solvothermal method (Fig. 1a). Under top-down method, mechanical exfoliation is a
basic and useful method to fabricate dense 2D-layered inorganic sheets or compos-
ites by splitting the weak van der Waals forces (VWFs) between two adjacent layers
in layered bulk materials. This method is facile, fast and low cost to produce large
sized and high quality 2D nanosheets or composites but with extremely low yield.
As an example, polyaniline@MoS2 -based organic–inorganic nanohybrid composite
was prepared using mechanical exfoliation followed by a facile in-situ oxidative
polymerization. Firstly, bulk MoS2 was exfoliated using simple mechanical ball
milling method and then it was dispersed in 1M HCl by ultra-sonication. Subse-
quently, aniline monomer was added followed by potassium persulphate as an oxidant
to initiate the polymerization under stirring, forming polyaniline@MoS2 compos-
ites. The result showed that the polyaniline deposited as a flat sheet with irregular
structure (Fig. 1b). The final product was used as an adsorbent to sequestrate CR
dye from aqueous solutions [29]. Zhang and co-workers [30] also used exfoliation
method to synthesize MXene@Fe3 O4 composites to remove MB dye. Liquid exfo-
liation method can be exploited to produce 2D composites on a larger scale for wide

Fig. 1 a Schematic representation of synthesis of 2D nanomaterial composites; b schematic

diagram of the MoS2 exfoliation and its Pani@MoS2 composite synthesis process. Reprinted with
permission from [29]. Copyright 2018 Royal Society of Chemistry; c schematic procedure for the
synthesis of Fe3 O4 /MoS2 nanocomposites. Reprinted with permission from [33]. Copyright 2015
Elsevier B.V.; d schematic illustration of the synthesis process of the TiO2 /Ti3 C2 Tx composites.
Reprinted with permission from [45]. Copyright 2020 Elsevier B. V.
5 Advanced 2D Nanomaterial Composites: Applications … 101

applications. This method can be categorized into four different forms: (i) oxida-
tion, (ii) intercalation, (iii) ion exchange and (iv) ultrasonic cleavage. Liu et al. [31]
prepared 2D MoS2 /carbon composites using liquid-phase shear exfoliation method
followed by annealing. 2D MoS2 /carbon composites were effective in the removal
of MB dye with a maximum adsorption capacity of 272 mg g−1 . In another study,
MoS2 /g-C3 N4 composites were fabricated using liquid exfoliation method assisted by
sonication, suitable for hydrogen generation [32]. The main advantage of top-down
approach is that almost none or very less requirement of any chemicals. The disad-
vantages include low yield, broad size distribution (10–100 nm) and more defects in
composites.
In bottom-up methods, hydrothermal technique is generally used to fabricate
2D composites for environmental applications. This technique is especially suit-
able to produce good quality 2D nanocomposites with a better-controlled composi-
tion. For example, Jia and co-workers [33] synthesized Fe3 O4 /MoS2 nanocompos-
ites via a facile hydrothermal technique in a water–ethanol system. The prepared
nanocomposite displayed excellent performance in water treatment processes. MoS2
is dispersed in ethanol–water (1:1) and ultrasonicated followed by the addition of
ferric and ferrous salts aqueous solution. The solution was then doped with ammonia
followed by heating in Teflon-lined stainless-steel autoclave at 100 °C (Fig. 1c). This
method was extensively used to synthesize various types of 2D nanocomposites such
as CeO2 –MoS2 [34], MoS2 @2DMMT [35], MoS2 @Kaolin [36], MoS2 /graphene
quantum dot [37], magnetic titanium nanotubes coated phosphorene [4], MoS2 /CuS
[25], Bi2 S3 /MoS2 [38] and phytic acid (PA)-MXene composites [39].
Self-assembly method is a type of interfacial modification technique, employed to
synthesize different composite materials. It is a simple process, requiring mild prepa-
ration condition and different types of forces such as electrostatic interaction, coordi-
nation bond, hydrogen bond, hydrophobic interaction, π-π stacking [40]. Jiao et al.
[41] synthesized MXene-COOH@(PEI/PAA)n core–shell nanocomposites via layer-
by-layer self-assembled method to achieve increased adsorption capacities. The elec-
tronic force from –NH3 + of polyethylene polyimide and hydrogen bond from COO−
groups of polyacrylic acid helped to form MXene-COOH@(PEI/PAA)n nanocom-
posites. In another study, 2D/2D ultrathin ZnIn2 S4 /protonated g-C3 N4 compos-
ites were synthesized via electrostatic self-assembly technique [42]. Very recently,
MXene-based nanocomposites are developed by Jiao et al. using self-assembly
method for water purification [43]. Solvothermal method is somewhat similar to
hydrothermal method. The solvent used in hydrothermal method is water while in
solvothermal method solvent is other than water [44]. A group of researchers have
successfully developed TiO2 /MXene composites via in-situ solvothermal method.
Firstly, Ti3 AlC2 was etched by HF to obtain Ti3 C2 Tx which was then mixed with
different organic solvents. The solution was transferred to a Teflon-lined stainless-
steel hydrothermal reaction kettle and placed in an oven at 200 °C to obtain the final
product (Fig. 1d) [45]. The solvothermal method is employed to produce various
2D nanocomposites such as MXene-Co3 O4 [46], MoS2 /C3 N4 [47], MoS2 /ZnIn2 S4
[48], 2D MoS2 -2D PbS [49]. These have been efficiently used to remediate the
environment.
102 M. S. Tanweer et al.

2D nanomaterial composites with limited thickness and larger SSA show unique
structural, physical and chemical properties compared with the conventional adsor-
bents. These properties make 2D nanomaterial composites more competitive in fabri-
cating novel adsorbent. The last decade has observed more successful efforts for
the application of 2D-based adsorbents in environmental remediation. This field is
explored using a variety of 2D nanomaterial composites, including MXene-based
composites, TMDs-based composites and phosphorene-based composites. Due to
specific structural properties of these materials, different modification strategies are
carried out to take advantages of their adsorptive behavior. The surface function-
alization of MXenes leads to changes in its physical properties and consequently
enhances its adsorption behavior toward certain species. Yang et al. [50] synthesized
Ti3 C2 Tx -PDOPA composites for efficient Cu(II) removal through surface functional-
ization of Ti3 C2 Tx using an amino acid i.e., levodopa (DOPA) as a modification agent
under alkaline conditions. The main purpose to use DOPA was to introduce carboxyl
groups (- COOH) on the outer surface of Ti3 C2 Tx which enhances the adsorption
capacity and selectivity toward adsorption of Cu(II). A lack of separation and poor
dispersibility of composites dramatically reduces its adsorption property and restricts
the application of 2D nanomaterial composites. In order to enhance the adsorp-
tion property, Zhang et al. [30] introduced an in-situ growth approach to success-
fully synthesize 2D MXene/Fe3 O4 composites. The Fe3 O4 NPs cover and disperse
uniformly on the surface of MXene. It can effectively increase the SSA and active
functional groups enhancing the adsorption capacity of nanocomposites for MB
removal. It has been found that 2D MXene/Fe3 O4 nanocomposites show an excellent
superparamagnetic property which can be quickly obtained from the heterogeneous
environment using an external magnetic field. Similarly, MoS2 /Fe3 O4 nanocompos-
ites showed a strong dispersion and magnetic separation property in water remedi-
ation [33]. Among TMDs, MoS2 -based nanocomposites exhibited some fascinating
properties including peculiar 2D structure, richness in sulfur, excellent mechanical
flexibility, huge SSA and exceptional chemical and thermal stability. Tong et al. [51]
first time reported MoS2 /CeO2 nanocomposites capable of specific adsorption of
Pb(II) ions with an adsorption capacity of 333 mg g−1 at pH 2.0. The properties of
MoS2 /CeO2 nanocomposites like richness in sulfur content, broad spacing between
layers, strong soft–soft interactions between sulfur and lead species and low ion-
exchange interaction play a critical role in effective removal of Pb(II) ions. Lin and
co-workers showed that the presence of titanium nanotubes and magnetite nanopar-
ticles should contribute to improved adsorption property due to the presence of large
amount of hydroxides on the resultant nanocomposites [4].
5 Advanced 2D Nanomaterial Composites: Applications … 103

3 Applications of 2D Nanomaterials in Adsorption

Processes

Various types of 2D nanomaterials are recently being extensively used for the purifi-
cation of water. The primary reason lies in their extraordinary behavior due to unique
properties, which are very distinct from their counterparts. Different 2D nanomate-
rial composites used as adsorbents for the sequestration of heavy metal ions and dyes
from aqueous environments are listed in Table 1.

3.1 Adsorption Mechanism

The adsorption of heavy metal ions on the surfaces of 2D nanomaterial compos-

ites can be explained by various mechanisms. For instance, the mechanism for the
removal of Pb(II) and Cu(II) ions using Mxene/alginate nanocomposites involve
ion exchange and chemical coordination processes [52]. After adsorption of Pb(II)
and Cu(II), Na 1 s peak disappears, and Pb 4d and Pb 4f (or Cu 2p) peaks emerge
implying that an ion-exchange mechanism is involved in the adsorption process. The
chemical coordination process between metal ions and composites occurs after the
adsorption of Pb(II) (or Cu (II)) ions onto the surface and is identified by the shifting
of carboxylated peaks from 1410 to 1386 and 1398 cm−1 (Fig. 2a).
The adsorption mechanism of Pb(II) ions on MoS2 @Kaolin nanocomposites
is explained in Fig. 2b [36]. The adsorption of lead ions onto MoS2 @Kaolin
composites occurs due to the attachment of Pb(II) ions with S atoms on the
surface of composites under oxidation conditions forming an insoluble compound
β-Pb3 O2 SO4 , which is effectively eliminated from the solution. The adsorption of
Cu(II) onto MoS2 @2DMMT hydrogel nanocomposites occurs mainly due to the
reaction between Cu(II) and functional groups such as carboxyl, hydroxyl and
amidogen on the surface of composites [35]. As confirmed by XPS and EDS,
ion exchange occurs between MoS2 @2DMMT and Cu(II) resulting in enhanced
adsorption of Pb(II).
Dye sorption on composites is mainly caused by the interaction between dye
molecules and different functional groups present on the surface of the nanocom-
posites. Figure 2c presents the proposed mechanism of MB adsorption onto
MXene@Fe3 O4 [30]. As presented in Eqs. (1) and (2), MB+ molecules probably
bond with hydroxyl groups on the surface of MXene to ionize H+ (Eq. 1), forming
monodentate complex through the M–O–H· · · N bond.

TiOH  Ti-O− + H+ (1)

Ti-O− + MB+  TiO− MB (2)

Table 1 Different 2D nanocomposites-based adsorbents for adsorption of heavy metal ions and dyes
104

2D nanomaterial composites Surface area Target pollutant Sorption capacity (Qmax Isotherms/kinetics References
(m2 /g) mg g−1 )/efficiency (%)
MNP-PN-TNT NA Cr(VI) 35 mg g−1 Pseudo-second-order [4]
alk-MXene/LDH NA Ni(II) 222.717 mg g−1 Redlich-peterson/pseudo-second-order [11]
MoS2 /CuS 106.27 RhB, MB, MO, 273.23, 432.68, 98.78, Langmuir/pseudo-second-order [25]
and RhB 6G and 211.18 mg g−1
Pani@MoS2 nanocomposite 50 CR 70.921 mg g−1 Langmuir/pseudo-second-order [29]
MXene@Fe3 O4 NA MB 11.68 mg g−1or 94% for Langmuir [30]
MB, 17% for MO and
5% for RhB
Fe3 O4 /MoS2 nanocomposites 72.0727 RhB 71 mg g−1 NA [33]
CeO2 -MoS2 NA Cr(VI) 99.6% NA [34]
MoS2 @2DMMT NA Pb(II) 65.75 mg g−1 Langmuir/pseudo-second-order [35]
MoS2 @Kaolin 14.56 Pb(II) 280.39 mg g−1 Langmuir/pseudo-second-order [36]
MoS2 /GQD 151.4 RhB, MB and MO 285, 210, and NA [37]
140 mg g−1
MXene-COOH@(PEI/PAA)n NA MB 81.9672 mg g−1 Langmuir/pseudo-second-order [41]
MXene-COOH@(PEI/PAA)n NA ST 35.5999 mg g−1 Pseudo-second-order [41]
MXene-COOH@(PEI/PAA)n NA NR 46.1255 mg g−1 Pseudo-second-order [41]
MXene-Co3 O4 NA MB and RhB 136.24 and Pseudo-first-order/pseudo-second order [46]
47.687 mg g−1 Pseudo-second-order
Ti3 C2 TX -PDOPA NA Cu(II) 65.126 mg g−1 Freundlich/pseudo-first-order [50]
Mxene/alginate composites NA Pb(II) and Cu(II) 382.7 and 87.6 mg g−1 Langmuir/pseudo-second-order [52]
(continued)
M. S. Tanweer et al.
Table 1 (continued)
2D nanomaterial composites Surface area Target pollutant Sorption capacity (Qmax Isotherms/kinetics References
(m2 /g) mg g−1 )/efficiency (%)
2D-MX@Fe3 O4 NA MB 9.85 mg g−1 at 55 °C, Freundlich (40 and 55 °C) [66]
3.95 mg g−1 at 40 °C and Langmuir (25 °C)
1.71 mg g−1 at 25 °C
Ti3 C2 –SO3 H NA MB 111.11 mg g−1 Langmuir/pseudo-first-order [68]
Iron doped phosphorene 1594 Å2 As(III) NA NA [77]
MoS2 /Fe3 O4 NA Pb(II) and Hg(II) 263.6 and 428.9 mg g−1 Langmuir/pseudo-second-order [81]
Ti3 C2 Tx /PmPD 55.93 Cr(VI) 540.47 mg g−1 Redlich-Peterson/pseudo-second-order [82]
MoS2 -rGO hybrid 102.8 Pb(II) and Ni(II) 322 and 294 mg g−1 Langmuir [83]
BiOCl/WS2 NA Cr(VI) 94.9% Pseudo-second-order [84]
BiOCl/WS2 NA MG 98.4% Pseudo-first order/pseudo-second-order [84]
WO3 –BPNs 10.50 RhB 19.8% First order reaction [85]
Phosphorene/MoS2 NA CR, MB and MO NA NA [86]
BPNs/ZnO 27.36 MB 96% Langmuir–Hinshelwood pseudo-first [87]
5 Advanced 2D Nanomaterial Composites: Applications …

order
NA Not available
105
106 M. S. Tanweer et al.

Fig. 2 FT-IR spectra of a MXene/alginate composite, b Mxene/alginate composite loaded Pb(II)

and c Mxene/alginate composite loaded Cu(II). Reprinted with permission from [52]. Copyright
2019 RSC Advances; b schematic view of the adsorption mechanism of Pb(II) on MoS2 @Kaolin.
Reprinted with permission from [36]. Copyright 2020 Elsevier B.V.; c proposed mechanism for
the adsorption of MB on the surface of MXene@Fe3 O4 . Reprinted with permission from [30].
Copyright 2019 ACS Applied Materials and Interfaces; d schematic illustration of two-stage rapid-
adsorption and photocatalysis-based dye pollutant removal. Reprinted with permission from [53].
Copyright 2021 Elsevier B.V.

The electrostatic adsorption of MB facilitates MXene-MB complexation, whereas

the complex formation is hampered by the electrostatic repulsion between MB +
and positive charges on the surface of MXene@Fe3 O4 composites. As a result, MB
adsorption is primarily dependent on the interactions between Ti site and OH group
present on MXene@Fe3 O4 . There are also dipole–dipole interactions between N
of MB and Ti–OH groups, forming OH···N bonds. Cai et al. [39] explained that the
adsorption of MB and RhB onto phytic acid (PA)-MXene composites with an increase
in the adsorption capacity as the temperature increased. In acidic conditions, MB was
adsorbed onto composites via electrostatic attraction. While adsorption potential of
RhB is unaffected by the changes in pH since it is a neutral dye. Similar results are
reported by Ansari et al. [29] in their studies to remove CR from aqueous solutions
using polyaniline@MoS2 -based composites. The removal of cationic dye MB using
2D MoS2 /TiO2 (TM) nanocomposite occurs via two-stage integrated adsorption and
photocatalytic decomposition processes [53]. In stage-I, namely adsorption stage,
anionic (RhB, MO) and cationic (MB, CV), dye molecules are adsorbed onto TM
surface due to electrostatic interactions between dye molecules and TM composites.
In stage-II, namely photocatalytic stage, the photocatalytic degradation of dyes takes
place under sunlight illumination, possibly due to photo charge career transfer from
TiO2 . Figure 2d presents the proposed adsorption/photocatalytic mechanism for the
dye on 2D MoS2 /TiO2 (TM) nanocomposites.
5 Advanced 2D Nanomaterial Composites: Applications … 107

3.2 MXenes-Based Composites

2D MXenes have the general formula Mn+1 Xn Tx (n = 1–3), where “M” denotes
an early transition metal (mostly Sc, Ti, V, Cr, Mo, W, Nb, Ta, Ti, Zr, Hf), “X”
represents carbon (C) and/or nitrogen (N) and “T” stands for surficial functional
groups, such as oxygen (–O), hydroxyl (–OH), fluorine (–F) and chlorine (–Cl),
which are bonded with the outer layers of early transition metal where “x” stands for
number of surficial functional groups [54–57]. Typically, MXenes can be developed
from their precursor MAX phases by a chemical etching process [11, 21, 58]. The
term “MAX” has the general formula Mn+1 AXn (n = 1, 2, or 3), where “M” is a
transition metal element (primarily Ti, V, Cr, Y, Zr, Nb, Mo, Hf, Ta and W), “A”
element is from groups IIIA (Al, Ga, In and Tl), IVA (Si, Ge, Sn, Pb), VA (P,
As, S and Bi), VIA(S), “X” is carbon and/or nitrogen element [55, 59]. Due to
the extraordinary properties such as significant high SSA, availability of abundant
–OH sites, biocompatible nature, ease of surface functionalization, hydrophilicity
and high conductivity, 2D MXenes have drawn the considerable attention of several
researchers to utilize them in environmental remediation [54, 60]. Recently, MXenes-
based nanocomposites have risen to a prominence as compared to other adsorbent
materials in the field of water purification, for instance, adsorption, membranes and
capacitive deionization [61–63]. The unique combination of properties of MXenes
including in situ reduction plus adsorption makes MXenes a distinct material and
opens a new door for the remediation of water pollutants.
Adsorption of HMIs: MXenes-based nanocomposites are shown to be superior
adsorbents for the removal of heavy metals. For instance, Ti3 C2 Tx -based films
prepared via Coulombic assembly process followed by vacuum-assisted filtration
were exploited for the removal of Cr(VI), Ag(I), Au(III) and Pd(II) from water. The
reduced graphene oxides (rGO) were inserted in between the layers of Ti3 C2 Tx -
MXene to mitigate the restacking of Ti3 C2 Tx nanosheets thus enabling an inter-
action between Ti3 C2 Tx and HMIs in aqueous systems. The surface hydroxy-
lation of Ti3 C2 Tx was done by using HCl to increase the number of hydroxyl
groups on Ti3 C2 Tx resulting in higher wettability and adsorption capacity. The
maximum adsorption capacities of Cr(VI), Ag(I), Au(III) and Pd(II) on Ti3 C2 Tx -
based films were 84, 890, 1241 and 1172 mg g−1 , respectively [64]. A novel 2D
Ti3 C2 Tx MXene nanosheet having 57 m2 g−1 SSA was developed via interca-
lation followed by exfoliation process in 10% HF solution. It showed an excel-
lent Cr(VI) adsorption capacity of 250 mg g−1 (pH 5 and at room temperature)
because of its larger SSA, well dispersibility in water, and reductivity. Especially,
after purification of the effluent, Cr(VI) content reached as low as 5 ppb, which
is lower than the drinking water standard set by the World Health Organization
(0.05 ppm). At the same time, this kind of 2D Ti3 C2 Tx MXene nanosheets can
reduce Cr(VI) to Cr(III) and simultaneously adsorb the less toxic Cr(III). Addi-
tionally, the experimental data suggests that this reductive 2D Ti3 C2 Tx MXene
nanosheet can also be used to remove strong oxidant agents, including K3 [Fe(CN)6 ],
KMnO4 and NaAuCl4 . This substantially widens the practical applications of 2D
108 M. S. Tanweer et al.

Ti3 C2 Tx MXene nanosheets in water and wastewater treatment [21]. Another 2D-
layered alk-MXene material (Ti3 C2 (OH/ONa)x F2-x ) was prepared through chem-
ical exfoliation followed by alkalization intercalation method using 5% sodium
hydroxide solution. It strongly captured Pb(II) from water with a maximum sorption
capacity of 140 mg g−1 at pH 6.5, even under the presence of competing cations
(Ca(II)/Mg(II)) at high concentrations. Figure 3a shows a schematic illustration of
the synthesis and applications of Ti3 C2 (OH/ONa)x F2-x nanocomposite. The results
revealed that Pb(II) loaded Ti3 C2 (OH/ONa)x F2 -x could be regenerated with an effi-
ciency of 95.2% using 0.1% HNO3 and 5% Ca(NO3 )2 solution. The preferential
adsorption of Pb(II) was due to low hydration energy (−1425 kJ mol−1 ) as compared
to Ca(II) (1505 kJ mol−1 ) and Mg (II) (−1830 kJ mol−1 ) [65]. In another method,
a 2D/2D (alk-MXene/LDH) nanocomposite was successfully synthesized using a
cautious and facile hydrothermal method and mechanical self-assembly method to
remove carcinogenic Ni(II) from wastewater treatment systems (Fig. 3b) [11]. It
showed an ultra-high adsorption capacity (222.717 mg g−1 ) under a broad range of
pH conditions (pH = 5–13) and best fitted with Redlich Peterson isotherm followed
by multi-molecular layer adsorption i.e., Freundlich isotherm model (R2 = 0.99202)
and effectively suited with pseudo-second-order kinetic models (R2 = 0.99992). The
far more remarkable thing is that the alk-MXene/LDH nanocomposite possessed a
good adsorbent capacity of more than 85.32% in eight successive sorption–desorption
cycles.

Fig. 3 a Schematic illustration of synthesis and application of Ti3 C2 (OH/ONa)x F2x composite.
Reprinted with permission from [65]. Copyright 2014 JACS; b schematic illustration of adsorption
and desorption of alk-MXene/LDH nanocomposite. Reprinted with permission from [11]. Copy-
right 2020 Elsevier B.V.; c Adsorption capacity of MXene@Fe3 O4 for MB at different tempera-
tures. Reprinted with permission from [30]. Copyright 2019 ACS Applied Materials and Interfaces;
d schematic diagram of membrane dye removal process. Reprinted with permission from [67].
Copyright 2020 Elsevier B.V.
5 Advanced 2D Nanomaterial Composites: Applications … 109

Adsorption of Dyes: The adsorptive performance of MXenes toward MB dye

removal can be substantially enhanced by increasing the number of functional
groups via in situ growth approach. The interlayer spacing of 2D-Ti3 C2 Tx MXene
was increased by functionalization with magnetic Fe3 O4 nanoparticles that led
to the formation of final product, MXene@Fe3 O4 [30]. MB adsorption onto the
MXene@Fe3 O4 was found to be 11.68 mg g−1 at 55 °C as calculated from the Lang-
muir isotherm model. Adsorption mechanism between MB and MXene@Fe3 O4 is
primarily because of the presence of Ti site and hydroxyl group of MXene@Fe3 O4
nanocomposites. The reusability tests demonstrated that MXene@Fe3 O4 nanocom-
posites could be reused for five times and the retained adsorption capacity exceeded
upto 77%. In another report, a 2D-MX@Fe3 O4 was synthesized by a two-step exfo-
liation of Ti3 AlC2 MAX-phase ceramic (as bulk), including HF etching followed
by intercalation by TPAOH [66]. It exhibited good adsorption capacity toward MB
(cationic dyes) at various temperatures i.e., 9.85 mg g−1 at 55 °C which decreased
to 3.95 mg g−1 at 40 °C and 1.71 mg g−1 at 25 °C (Fig. 3c). The high removal rate
of MB (about 91.93%) at higher temperature is primarily because of the intimate
interaction of surficial Ti–OH group of 2D-MX@Fe3 O4 , as well as the availability
of the unsaturated nitrogen heteroatoms in the MB, which additionally facilitates MB
adsorption process. Langmuir (at high temperature) and Freundlich (at low tempera-
ture) models were chosen to suit the isotherm experimental data. The mechanism of
MB on 2D-MX@Fe3 O4 involved hydrogen bonding accompanying with electrostatic
interaction at 55 °C, while electrostatic interactions at 25 °C. The RGO/PDA/MXene
composite membrane exhibited excellent dye molecule separation performance (over
96%) against MB, MO, MR, CR and EB and oil–water separation [67]. Figure 3d
represents a schematic diagram of the membrane dye removal process. It may be
attributed to hydrophilicity behavior by MXenes surface and regular straight-rigid
channels of RGO/PDA/MXene composite material. The structure and separation
efficiency of RGO/PDA/MXene composite was significantly influenced by varying
the MXene ratio. More specifically, RPM/PDA/MXene composite membrane was
found to be extremely stable which could be operated for a longer time. The introduc-
tion of sulfonic group improved the adsorption capacity of MXenes (Ti3 C2 –SO3 H)
toward MB (111.11 mg g−1 within 70 min). The main binding mechanism between
Ti3 C2 –SO3 H and MB was predicted to be electrostatic interaction in an alkaline
environment, showing monolayer coverage [68].

3.3 TMDs-Based Composites

Transition metal dichalcogenides (TMDs) have the general formula MX2 , where
“M” is a transition metal (such as Mo, W, V, Nb, Ta, Ti, Zr, Hf, Tc, and Re), “X” is a
chalcogen element of group 16 (such as S, Se and Te). The unit layer of TMDs is in
the form of X–M–X, in which one center atom layer of transition metal (M) is placed
between two chalcogen’s atom layers (X). Various types of TMDs nanocomposites
110 M. S. Tanweer et al.

were synthesized and exploited for the removal of water pollutants due to chalcogen’s
strong affinity toward heavy metal ions and organic dyes.
Adsorption of HMIs: TMDs nanocomposites are frequently used as a potential
competent adsorbent for the elimination of several divalent cations including Pb(II),
Co(II), Hg(II) and Cd(II). For example, flower-like WSe2 and WS2 microspheres
were prepared by a simple and scalable approach i.e., solvothermal method, and used
to sequestrate As(V), As(III), Cd(II), Pb(II) and Hg(II) from water. They showed
an extremely high adsorption capacities for Pb(II): 288 and 386 mg g−1 for the
WSe2 and WS2 , respectively, and for Hg(II): 1512 and 1954 mg g−1 for the WSe2
and WS2 , respectively. The excellent adsorption abilities of WSe2 and WS2 micro-
spheres toward Pb(II) and Hg(II) are due to their structural rigidity and the abundance
of chalcogen’s ligands with an instinctive reactivity to soft heavy metal ions [69].
Among TMDs, MoS2 exhibited some fascinating properties such as a peculiar 2D
structure, rich in sulfur, excellent mechanical flexibility, huge SSA and exceptional
chemical and thermal stability. A novel super adsorbent, 2D MoS2 , containing less
than five S−Mo−S layers and huge sulfur-rich surface area was synthesized via exfo-
liation method for the removal of Hg(II) metal ions in water. The authors reported that
Hg(II) adsorption onto 2D MoS2 was mainly relied on the temperature (maximum
adsorption capacity: 518.135 mg g−1 at 20 °C, and 584.795 mg g−1 at 35 °C). This
might be due to more availability of sulfur atoms on the surface of 2D MoS2 [70].
MoS2 @Kaolin nanocomposites were synthesized by a simple one-step hydrothermal
method to adsorb Pb(II) from the aqueous solution. It showed maximum adsorption
capacity of 280.39 mg g−1 at pH 4 that followed the Langmuir isotherm model
for pseudo-second-order kinetic model. In addition, MoS2 @Kaolin nanocompos-
ites showed an excellent regeneration properties with more than 77% adsorption
capacity even after five cycles [36]. Figure 4a illustrates the adsorption of Pb(II)
using MoS2 /CeO2 nanocomposites [51]. The superior selectivity of the MoS2 /CeO2
nanocomposites toward Pb(II) could be attributed to the strong soft–soft interactions
between Pb and S of MoS2 surface. Figure 4b presents schematic illustration of
preparation and application of a novel ternary nanocomposite (MoS2 @PDA@PAM)
to sequestrate Cu(II) ions [71]. The result suggested that the addition of PAM to MoS2
increased the adsorption capability by 2.5 folds against Cu(II). Freundlich models
and pseudo-second order were chosen to suit the isotherm and kinetic experimental
data. The adsorption mechanism of Cu(II) on MoS2 @PDA@PAM involved an elec-
trostatic interaction and/or a chemical chelation between Cu (II) ions and -NH2
of MoS2 @PDA@PAM nanocomposites. Another novel material, MoS2 -g-PDMA
exhibits an excellent adsorption capacities of 448.4 and 171.2 mg g−1 toward U(VI)
and Eu(III), respectively, as obtained from the Langmuir model. The high adsorption
capacity is mainly because of the existence of a large number of phosphates, carboxyl
and sulfur groups on the MoS2 -g-PDMA. The equilibrium adsorption data closely
followed the pseudo-second-order kinetic model which means that the adsorption
process was controlled by chemical sorption [72]. Further studies suggested that the
cation selectivity of MoS2 followed the order Pb(II) > Cu(II)  Cd(II) > Zn(II),
Ni(II) > Mg(II), K(I), Ca(II) [73]. The regeneration experiments showed that the 2D
5 Advanced 2D Nanomaterial Composites: Applications … 111

Fig. 4 a Schematic illustration of the application of MoS2 /CeO2 nanocomposites. Reprinted with
permission from [67]. Copyright 2020 Elsevier B.V.; b schematic illustration of preparation and
application of MoS2 @PDA@PAM nanocomposites. Reprinted with permission from [71]. Copy-
right 2018 Elsevier B.V.; c the adsorption spectra of Congo red aqueous solution of Fe3 O4 /MoS2
nanocomposites. Reprinted with permission from [33]. Copyright 2015 Elsevier B.V.

MoS2 nanosheets could be reused from two to five adsorption cycles with 85–95%
lead removal.
Adsorption of Dyes: Like as heavy metal ion adsorption, the organic dye adsorption
on MoS2 also solely depends on SSA. Therefore, it is utmost important to increase
the SSA of MoS2 by tuning its surface to achieve more exposed sites for a better
adsorption of pollutants. For example, MoS2 microspheres based on different sulfur
sources such as Na2 S, C2 H5 NS, CH4 N2 S and (NH4 )2 S were investigated for the
sequestration of anionic dye RhB [74]. The mesoporous MoS2 –CH4 N2 S microsphere
showed the highest adsorption capacity (136.99 mg g−1 at 293.15 K, 1 atm) with
a BET SSA of 72.0 m2 g−1 . This could be attributed to a significant degree of
puckering and pore structure. Furthermore, the synthesized mesoporous MoS2 /GQD
with a pore size of 8.6 nm and SSA of 151.4 m2 g−1 demonstrated an excellent
selective adsorption capacity and ultrafast adsorption for RhB dye within 2 s under
ultrasound assistant [37]. The MoS2 /GQD showed a high adsorption performance
for RhB dye (285 mg g−1 ). It also exhibited a high cycling adsorption stability
for RhB removal with more than 98% reclaim ratio. A highly active sites containing
ultrathin-layered MoS2 nanoflowers were synthesized through hydrothermal method
and used as an efficient adsorbent to sequestrate RhB from wastewater [75]. The
MoS2 nanoflowers were polycrystalline in nature, comprised of irregular and non-
uniform nanoflowers that looked like “sponges” with a smooth surface (BET SSA
(SBET ): 71.7 m2 g−1 , average pore diameter: 280.7 Å). The adsorption kinetic data of
MoS2 nanoflowers for RhB fitted with Langmuir isotherm model with a maximum
112 M. S. Tanweer et al.

adsorption capacity of 365 mg g−1 . The possible adsorption mechanism of MoS2

nanoflowers to remove RhB includes electrostatic attraction, π-π conjugated effect
and van der Waals force. The regeneration capability of MoS2 nanoflowers seems to
be excellent, as their results indicated the elimination of RhB even after six cycles
and it was approximately 85%. A study reported the maximum adsorption capacity of
71 mg g−1 for CR and adsorption equilibrium in only 2 min using superparamagnetic
Fe3 O4 nanoparticles (average size: 10–15 nm) anchored to MoS2 nanosheets (Fig. 4c)
[33].

3.4 Phosphorene-Based Composites

Phosphorene is one of the most rapidly emerging 2D nanomaterials which finds

wide applications due to its desirable properties such as puckered hexagonal layered
structure, adjustable band gap, high SSA, abundance, high carrier mobility and high
dispersion capability [28, 76]. Several theoretical studies are done on phospho-
rene nanocomposites in order to remediate heavy metal ions and dyes, however,
experimental approaches are still very less due to their associated stability problems.
Adsorption of HMIs: Novel phosphorene composite, MNP-PN-TNT adsorbents are
prepared via hydrothermal process to remove Cr(VI) from synthetic water in acidic
environments. Adsorption capacity of MNP-PN-TNT was found to be 35 mg g−1 at
50 ppm initial Cr(VI) concentration and 318 K temperature. The possible adsorp-
tion mechanism of Cr(VI) on MNP-PN-TNT might be due to the displacement of
surface hydroxyl groups (Fig. 5a). The regeneration test showed that the adsorption
capacity of MNP-PN-TNT for Cr(VI) was 6 mg g−1 even after three cycles [4].
The iron-incorporated phosphorene nanoadsorbents were studied for the removal
of arsenic from water using density functional theory (DFT) calculations [77]. The
obtained results suggested that As(III) uptake incurred as a consequence of strong
inner-sphere surface complex formation in between the As(III) and Fe-doped phos-
phorene nanoadsorbents from the aqueous system at 25 °C. Adatom doping scheme
showed a better adsorption behavior than substitutional doping in water. The effect
of H2 O studies showed that arsenic adsorption onto the nanocomposite remains
stable under acidic to neutral condition (Fig. 5b). As(III) adsorption onto Fe-doped
phosphorene nanocomposite attributed to permanent electrostatics, polarization and
charge-transfer stabilizing effects. Further, it was reported that this nanocomposite
can also be used to remove As(III) and As(V) directly and concurrently, without a pre-
oxidation step to transform As(III) to As(V). The mutual interaction and permanency
between trivalent arsenic and pristine with metal (Ni and Cu)-doped phosphorene
using DFT were further explored [78]. The purpose of using dopants (Ni and Cu) was
to create adsorption sites on the phosphorene nanoadsorbents, which consequently
allowed the inner-sphere surface complexation of As(III) onto the chosen nanoad-
sorbents. The DFT study showed that metallic dopants significantly enhanced the
interaction and adsorption stability between phosphorene and As(III) as compared to
5 Advanced 2D Nanomaterial Composites: Applications … 113

Fig. 5 a Schematic illustration of the Cr(VI) removal mechanism with MNP-PN-TNT. Reprinted
with permission from [4]. Copyright 2019 Elsevier B.V.; b comparative of adsorption energies
(Eads ) of As(III) versus H2 O versus OH− anions. Reprinted with permission from [77]. Copyright
2020 Elsevier B.V.; c pore size distributions of BP, BPR, and BPRS. Reprinted with permission
from [80]. Copyright 2020 sustainability, MDPI; d MB dye removal as function of time. Reprinted
with permission from [80]. Copyright 2020 sustainability, MDPI

the intrinsic phosphorene. The adsorption process of As(III) on single-layer phospho-

rene and graphene was elucidated as a function of temperature, pH and concentration
[79]. The results revealed that As(III) adsorption was more favorable for phosphorene
under acidic conditions having the maximum adsorption capacity of 4.83 mg g−1 ,
which was found to be higher than graphene (1.33 mg g−1 ) under similar conditions.
The thermal dynamic analysis suggested that As(III) adsorption on phosphorene was
a non-spontaneous, irreversible reaction with chemisorption.
Adsorption of Dyes: 2D black phosphorus (BP), black phosphorene (BPR) and
sulfonated BPR (BPRS) comparatively studied as adsorbents for the adsorptive
removal of MB dyes from water [80]. The SSA of BP, BPR and BPRS was calculated
to be 6.78, 6.92 and 7.72 m2 g−1 , respectively (Fig. 5c). BPRS provided more number
of free active sites for MB adsorption, thus exhibited a higher adsorption capacity
which was 140.85 mg g−1 (it was 84.03 mg g−1 for BP and 91.74 mg g−1 for BPR).
Figure 5d presents the removal of MB dye as a function of time. The study suggested
that adsorption mechanisms included electrostatic interaction, hydrophobic inter-
action, intraparticle diffusion, chemical adsorption, sulfonic acid functional group-
guided adsorption and wrinkle-induced adsorption. As revealed by the desorption
study, the as-prepared BP-based adsorbents could not be reused. MB has a tendency
to attach with adsorbents due to the presence of hydrogen bonds between them which
resulted in a lesser chance for MB to diffuse through the adsorbents.
114 M. S. Tanweer et al.

3.5 Adsorption of Toxic Gases and Volatile Organic

Compounds

The burning of fossil fuels indisputably emits and increases the concentration of
CO2 in the atmosphere causing global warming and greenhouse effects. 2D nano-
materials with high surface-to-volume ratio such as zeolites, MOFs, functionalized
GO, MXenes, and TMDs features as a potential solid adsorbents. To date, various
2D nanomaterial composites are theoretically and experimentally studied to remove
toxic gaseous contaminants [88].
MXenes-based nanocomposites are theoretically investigated for CO2 abate-
ment, storage and activation [89]. The studies revealed that M2 C (MXene carbides)
compounds enable to capture CO2 within a range of 2.34–8.25 mol CO2 per kilogram
even at high temperatures and low partial pressures. Furthermore, different findings
indicated that the high value of adsorption energies (about 3.69 eV), bent structures
and activation verified by high charge transfer from MXene to CO2 confirmed the
conversion of CO2 molecules to strongly anionic CO2 δ− species with δ-Bader values
ranging between −0.90 and −2.86e [90]. The theoretical investigations using DFT
demonstrated that bare 2D-M2 N MXenes even without surficial functional groups
could efficiently uptake CO2 (2.32–7.96 mol CO2 Kg−1 ) even at low partial pressures
of CO2 and elevated temperatures [91]. M2 C, M2 N MXenes show higher adsorption
energies values accompanied by CO2 activation, supported by the bent structures,
appearance of a strongly anionic CO2 δ− adsorbed species, and high charge transfer
from MXenes to CO2 . Therefore, these studies suggest that MXenes can act as a
potential material for the capture, storage and activation of CO2 . It was found that a
change in the composition does not significantly affect MXenes’ properties, while the
functionalization of pristine MXenes can lead to change in the electronic properties
[92]. In a theoretical study, the improvement of the selectivity of MXenes through
O-functionalization; O-MXenes or M2 CO2 was proposed for the adsorption of small
gas molecules such as H2 , H2 O, CO, CO2 , N2 , NO, NO2 , NH3 , H2 S and SO2 . The
results depicted that the adsorption of small gas molecules on MXenes occurred
predominantly by the chemisorption process. Pristine MXenes seem to be very reac-
tive and thus suitable for catalytic process with a low selectivity toward these gas
molecules. Among these gases, only NH3 gets adsorbed on MXenes. In this case,
functionalization of MXenes reduces its reactivity, whereas selectivity is enhanced
for gas sensing and separation. Mo2 CO2 and V2 CO2 strongly adsorb NO molecules
as compared to others, while Nb2 CO2 and Ti2 CO2 prefer NH3 [93]. Recently, the
gas adsorption behavior of S-functionalized M2 N (M = Ti, V) MXenes i.e., Ti2 NS2
and V2 NS2 were considered as model nanomaterials to theoretically examine the
inorganic gases including CH4 , CO, CO2 , NH3 , NO, NO2 , H2 S, and SO2 by DFT.
Among all these gases only nitric oxide (NO), and nitrogen dioxide (NO2 ) showed
exceptional sensitivity toward S-terminated nitride MXenes because of appreciable
amount of charge transfer from NO, and NO2 gas molecules to Ti2 NS2 (adsorption
energy, E B , of −0.406 eV) and V2 NS2 (adsorption energy of −0.208 eV), respec-
tively [94]. A non-functionalized MXene having a general formula 2D M2 C (M
5 Advanced 2D Nanomaterial Composites: Applications … 115

= Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W) was developed, isolated and investigated
using first-principle simulations for CO2 abatement. The high adsorption energies
(−3.69 eV) of M2 C and effective adsorption of CO2 at a very low CO2 partial pres-
sure and high temperatures suggested that the 2D M2 C MXenes can be a potential
material for CO2 capture, and its storage was followed by activation [90].
TMDs may be considered for tackling the air pollution through the sensing and
adsorption of toxic gases. To date, several studies are done to adsorb toxic gases
like CO, SOx , H2 S, NOx on TMDs. For instance, first-principles calculations by
DFT are systematically implemented to investigate the adsorption of gas molecules,
including CO and NO on metal-(Au, Pt, Pd, or Ni) doped MoS2 monolayer [95]. The
adsorptive removal of CO and NO on a metal-doped MoS2 monolayer is exothermic
i.e., chemisorption. It may be due to a higher adsorption energy value (larger than
0.9 eV for CO and NO) and the short distance between the adsorbed CO or NO and
the metal-doped MoS2 . In case of CO adsorption, the transport properties of Pt-,
Pd-, or Ni-doped MoS2 monolayer change due to the charge transfer. However, in
case of NO, the transport properties of metal-doped MoS2 monolayer changed due
to the alteration in band gap and charge transfer [95]. Apart from this, several other
TMDs including Pt/Au-decorated WSe2 monolayer [96], Al2 O3 -doped MoS2 [97],
Au nanoparticles on monolayer MoS2 [98], Rh-doped MoSe2 [99] are also inves-
tigated against CO adsorption. The incorporation of Cu nanoparticles into MoS2
nanosheets greatly enhanced its adsorption capability for CO2 uptake [100]. SnO2 -
doped MoS2 [26] and Bi2 S3 /MoS2 [38] are theoretically investigated for CO2 reduc-
tion process, while N-doped TiO2 /WSe2 nanocomposite for SOx [101], and MoS2 -g-
C3 N4 nanocomposite for NO [102] using DFT. CO2 adsorption on MoS2 monolayers
was found to drastically increase in the presence of an external applied electric field,
which is mainly attributed to a decrease in C–S bond length, an increase in adsorp-
tion energy accompanied by high charge transfer [103]. However, in the absence
of an applied electric field, the interaction between CO2 and MoS2 monolayers is
very week due to van der Waals forces between them. Monolayer MoS2 sheets are
also studied for the adsorption of polyatomic species such as O3 and SOx (SO2
and SO3 ) with respect to charge transfer, adsorption energy, band structures and
charge density differences by using first-principles calculations [104]. The weak van
der Waals (vdWs) interactions between polyatomic gas molecules and MoS2 sheets
confirmed the physisorption. It thus formed the most stable configurations which
were energetically favored. It subsequently elongated oxygen–oxygen (O –O) and
sulfur-oxygen (S–O) bonds of the gas molecules. Electronic band structure calcu-
lations confirmed the alteration in MoS2 sheets after the adsorption of selected gas
molecules. Charge density difference studies showed that O3 , SO2 and SO3 molecules
served as charge acceptor from MoS2 . Another novel gas adsorbent, Ni-doped MoS2
monolayer (Ni-MoS2 ) was projected for the adsorption of SO2 and H2 S molecules
[105]. The molecules of SO2 and H2 S may be strongly chemisorbed on Ni-MoS2
with apparent charge transfer and strong adsorption energy which made Ni-MoS2 a
potential candidate as a SO2 and H2 S capturer. Besides these 2D TMDs, some other
types of TMDs; Rh-doped MoSe2 (Rh-MoSe2 ) monolayer for CO, NO, NO2 and SO2
[99], Pd-doped MoSe2 (Pd-MoSe2 ) monolayer for NO, NO2 , SO2 and H2 S [106],
116 M. S. Tanweer et al.

N-doped TiO2 /WSe2 nanocomposite for SOx [101], Pd, Ag, and Au, Pt-doped mono-
layer WSe2 for CO2 , NO2 and SO2 [107], MoS2 -g-C3 N4 nanocomposites for NO
[102] were widely studied. Elemental 2D nanomaterials such as silicene, germanene
and phosphorene reported to have a better adsorption capacity for gas contaminants.
Theoritical study revealed that NO2 molecules can be strongly physisorbed on 2D
monolayer phosphorene (E B = −0.50 eV), while gas molecules with low adsorption
energies (CO (E B = −0.31), H2 (E B = −0.13), H2 O (E B = −0.14), NH3 (E B = −
0.18), NO (E B = −0.32), and O2 (E B = −0.27)) are weakly physiosorbed [108].
Based on the charge transfer study, NO, NO2 and O2 gas molecules act as acceptor,
and the electronic and magnetic properties of 2D phosphorene change significantly
after the adsorption of NO, NO2 and O2 molecules, together with strong binding
energy which indicated that 2D phosphorene can be a potential molecular sensor.
Another DFT study indicated that Li-decorated phosphorene was favorable for CO2
molecules adsorption because of a high value of adsorption energy (Eads ) of 0.376 eV
[27]. And Al-decorated phosphorene proved to be more competent to adsorb NO2
and SO2 due to the large adsorption energies of 3.951 and 3.608 eV, respectively.
In addition, Pt-decorated phosphorene turned out to be efficient for NO2 and SO2
dissociations because of the low energy barriers of acidic gases and exothermic
reaction process. The adsorption energy values as calculated form DFT seem to
indicate that Pt-, Al- and Ni-decorated phosphorene exhibited the maximal adsorp-
tion behavior toward H2 S, HCN and NH3 , respectively [109]. Very recently, red
phosphorene nanosheets (P-NS) are used to adsorb the toxic cigarette vapors such
as acrolein (causing lung cancer), acrylamide (causing neurological disorders) and
nicotine (affecting central nervous system). The adsorption behavior of P-NS at two
different sites (top and middle site) computed by first-principles calculations. The
value of Bader charge transfer (Q) and energy gap variation enunciated that the
middle site of P-NS has astonishing adsorption tendency due to a high transmission
of electron and larger energy gap variation [110].
In addition to inorganic toxic gases adsorption, the volatile organic compounds
(VOCs) can also be sensed and removed using 2D nanomaterial composites. Ti3 C2 Tx
MXene with properties like low electrical noise and strong signal are synthesized to
detect VOCs gases such as acetone, ethanol, propanal and ammonia in a concentration
range of 50–100 ppb at 25 °C [111]. On the surface of Ti3 C2 Tx MXene, the terminal
hydroxyl groups were solely responsible for capturing the targeted contaminants.
Furthermore, the study suggested that Ti3 C2 Tx MXene showed intrinsically ultra-
high signal-to-noise ratio (SNR) due to its high metallic conductivity, and the func-
tionalized surfaces made it a suitable material for high sensitive gas-sensing appli-
cations. S-doped MXene(S–Ti3 C2 Tx ) showed an astonishing response for different
VOCs such as ethanol, hexane, hexyl acetate and toluene. The binding mechanism
and the unique selectivity of toluene by both undoped and S-doped MXene are
theoretically studied by DFT [112]. 2D MoS2 nanoflakes were utilized in detecting
oxygen-based VOCs such as acetone, ethanol and 2-propanol at room temperature.
DFT calculations demonstrated that Au nanoparticles functionalization enhanced
the adsorption performance of MoS2 nanoflakes toward acetone by more than two
5 Advanced 2D Nanomaterial Composites: Applications … 117

folds (i.e., 31.6%) [113]. In another study, the adsorption enthalpies (Had ) of non-
polar VOCs including 1,4-dioxane, benzene, cyclohexane and polar VOCs including
acetone, acetonitrile, nitromethane, and tetrachloromethane on black phosphorus
were experimentally determined using inverse gas chromatography technique [114].
The properties like anisotropic and deformed layers of black phosphorus exhibited
an affinity enhancement to polar VOCs (e.g., HCN) due to dipole–dipole interactions
and molecule-surface attachment.

4 Conclusions, Challenges and Future Prospects

2D nanomaterial composites have emerged as excellent adsorbent materials for the

environmental remediation. However, there are many challenges and stubborn prob-
lems that must be thoroughly studied and experimentally verified in the laboratory
in order to completely leverage their physicochemical properties. The low yield and
massive cost of MXenes synthesis are two of the biggest problems faced by the
research community. In near future, it is expected that the ease of design, low cost
and efficient production of MXenes on a larger scale will be advantageous for further
advancement of research to a new doorway to widen their applications. Furthermore,
it is found that many MXenes compositions are only theoretically studied using DFT
for water treatment and toxic gases’ adsorption. To validate the outcomes of these
theoretical calculations, systematic experiments and strategies of efficient systems
must be designed and proved. In case of TMDs, MoS2 is widely exploited for water
purification because of its high adsorption capacity, but pollution blocks its active
sites thereby reducing its adsorption capacity. It needs to be resolved by creating
more free active surficial sites. The research work on 2D phosphorene is still in its
infancy for environment remediation as compared to other 2D nanomaterials. More
studies are needed to focus on the development of different types of phosphorene
nanocomposites with hydrophilic nature, super adsorption behavior for applications
in water purification in real environmental conditions.

Acknowledgements One of the authors, Tanweer S. M. is thankful to the University Grants

Commission (UGC) for the Non-NET Fellowship.

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Chapter 6
Progress in 2D Nanomaterial Composites
Membranes for Water Purification
and Desalination

Savan K. Raj and Vaibhav Kulshrestha

1 Introduction

Water is the most crucial part of living life, and its supply has become progressively
intense. It is abundant in nature, but only some of its portion is available and suitable
for human life [1]. Many regions in the world do not have the facility to make the
water clean and safe. As of today, rapid expansion in population and industrializa-
tion causes increases in demand for high-quality water [2]. According to the World
Water Council report, approximately 4 billion people will live in water shortage
areas by 2030 [3]. The water resource prices will simultaneously increase as the
water resources are restricted, which automatically gives rise to the operating cost
in many of the water-consuming industries [4]. After this, the other parameter is the
quality of water used for drinking, which should be pollutant-free. Water pollution is
a severe risk of water consumption. It happens when any unwanted material is entered
or diffused in water and makes the water unsafe for drinking, agriculture, or indus-
trial consumption [5, 6]. Such polluted water is not suitable for plants and aquatic
and land animals. So, removing pollutants from the water is a must for all the uses,
as mentioned earlier. The potable groundwater contains several hazardous contam-
inants like a viruses, heavy metals, bacteria, and other toxic materials, affecting the
environment and human health [7–10]. The poor quality of water and scarcity of
functioning water resources is another major problem to resolve. High attentive-
ness should be given to the conservation of water resources to meet the increasing
demand for freshwater. In the prospect of this, better technology for water purifica-
tion and desalination is required. Recently, renewable and cost-efficient membrane

S. K. Raj · V. Kulshrestha (B)

CSIR-Central Salt and Marine Chemicals Research Institute, Gijubhai Badheka Marg, Bhavnagar
364002, Gujarat, India
e-mail: [email protected]
S. K. Raj
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 125
Z. Khanam et al. (eds.), 2D Nanomaterials for Energy and Environmental Sustainability,
Materials Horizons: From Nature to Nanomaterials,
https://doi.org/10.1007/978-981-16-8538-5_6
126 S. K. Raj and V. Kulshrestha

science for water purification applications is a highly attractive area for research [11,
12]. Such membrane technologies have advantages over other technologies like low
power consumption, operated at low cost, need no chemical additives or thermal
energy, or any regeneration of used media. These membranes, with various phys-
ical and porous aspects, can successfully desalinate the water [13]. The alteration
in physicochemical properties (like pore size, surface charge, hydrophilicity, etc.)
will enhance its working efficiency. At present, commercial membrane technolo-
gies like microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), and reverse
osmosis (RO) are assessable. Generally, the MF membranes are used to remove the
suspended solids and bacteria. The UF membranes typically remove colloids and
viruses. The organic matter and bulky cations can be removed using NF membranes
[14, 15]. The preparation of ultrapure water, desalination, and water reuse can be
done using RO membranes. Water desalination technologies (like adsorption, reduc-
tion, oxidation, membranes, and filtration) can be enhanced dramatically using two-
dimensional nanomaterials (2D materials) [16]. Immobilization of 2D nanomaterials
on or within the membrane matrix is a promising approach. There will be an improve-
ment in the overall performance by improving separation performance, mechanical
and thermal stability. Even though a simple fabrication technique for the preparation
of 2D material membranes has gained a lot of attention in the scientific community,
understanding suitable methods for fabrication and mechanism is still a challenge.
At present, these 2D based membranes can be prepared in two forms, that is, pristine
and modified membranes. Generally, the pristine nanosheets contain monolayers or
a few layers of a 2D material with uniformly distributed nanopores, like graphene-
based, metal–organic framework (MOFs), MXenes, transition metal dichalcogenides
(TMDCs), and hexagonal boron nitride nanosheets (hBN). Even though outstanding
separation efficiency can be achieved using pristine membranes, but fabrication on
a large scale and pore-controlled nanosheets of such 2D material membranes is still
challenging. Our objective is to review the basic concepts of 2D material-based
membranes, methods of fabrication, and application in water desalination.

2 Different Synthesis Techniques for 2D Material-Based

Membranes

Membrane filtration process can be classified into different categories including

microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), gas separation, reverse
osmosis (RO), dialysis, and electrodialysis (ED) based on their pore size (Table 1)
[17]. As per International Organization for Standardization (ISO), 2D nanomaterials
can be divided into two categories: nanostructured materials and nano-objects, for
the synthesis of 2D material-based membranes [18].
There are different techniques available for the synthesis of 2D material-based
membranes; the brief description is given below.
6 Progress in 2D Nanomaterial Composites Membranes … 127

Table 1 Classification of various types of membrane filtration process [17]

Technique Pore size Driving force Average permeability
L/m2 h bar
Microfiltration 0.05–10 μm 1–3 bar 500
Ultrafiltration 0.001–0.05 μm 2–5 bar 150
Nanofiltration < 2.0 nm 5–15 bar 0–20
Reserve osmosis < 1 nm 15–75 bar 5–10
Gas separation < 0.5–1 nm – –
Membrane distillation 0.5–2 nm – –
Electrodialysis MW < 200 Da Electrical potential, 1–2 V/cell –

2.1 Drop-Casting

One of the most straightforward process to fabricate the 2D material membranes

is drop-casting. The colloidal solution of that 2D material is drop cast onto the
substrate on the surface of silica or paper, followed by drying at room temperature.
The freestanding membrane is then peeled off from the underlying substrate. Due to
enormous surface tension and low vapor pressure, water is not an ideal choice for
drop-casting. Some other polar solvents like alcohol or organic solvents like toluene,
hexane, and halogenated solvents can be superior choices for nanoparticles with
hydrophobic capping ligands [19]. Due to its ease of performing and preparation
of thin film on a small substrate, this technique was favored by many researchers.
However, the main disadvantage of this strategy is that the evaporation rates within
the substrate or the concentration gradient in the fluid phase can lead to the variation
in the internal structure and the thickness of the membrane [20].

2.2 Vacuum Filtration

For the large scale synthesis of the self-standing membrane, the most common and
uncomplicated way is vacuum filtration (Fig. 1a). In this process, there is no change in
the physicochemical properties of 2D nanomaterial because the interaction is mostly
van der Waal, hydrogen, or electrostatic repulsion but cannot be the covalent bonding
[21]. The vacuum filtration method can be used to prepare composite membranes with
the homogeneous distribution of nanomaterials. Some 2D materials like GO, when
used in the membrane, bear good hydrophobic properties. The papery membrane can
be prepared using a vacuum filtration method, but the thickness of the membrane
mostly depends on the material suspension volume introduced into the system (Fig. 2)
[22]. 2D material membrane can be prepared by depositing specific material on the
polymeric membrane, followed by the determination of the surface wettability and
roughness [21, 22].
128 S. K. Raj and V. Kulshrestha

Fig. 1 a Systematic procedure to fabricate MoS2 nanosheets from layered bulk using vacuum
filtration method [42], b Systematic presentation of synthesis of a 2D Ti3 C2 Tx lamellar membrane
nanosheets on AAO [50], c Freestanding BN-laminated membrane, the photograph shows the
colloidal solution of few layered BN sheets. A freestanding BN membrane with size of 15 mm × 4
mm. Cross-sectional SEM image of a BN membrane, with the inset showing the lamellar structure.
AFM image showing the few layered BN nanosheets [44]. d Systematic method to fabricate MOF
membranes @ PVDF-HFV. The cross section SEM image of the membrane [57]

Fig. 2 A schematic diagram demonstrating membrane-based desalination assembly [32]

2.3 Spin Coating

Another method for film deposition is spin coating, used in numerous industries
like thin-film coating technologies and microelectronics industries. This technique
provides many advantages such as thickness control of the film, high uniformity film
deposition, easy and fast process, and low-cost equipment [23]. Although some of
drawbacks like the shape and size of the substrate are a significant concern when
6 Progress in 2D Nanomaterial Composites Membranes … 129

talking about the industrial-scale implementation of this technique. Currently, this

technique has been used widely for the preparation of high-quality 2D material
membrane. These 2D materials can be deposited on the substrate directly or dispersed
in the membrane solution and then deposited on the opaque substrate (like glass
or any other polymeric support) to fabricate uniform and thin films [24]. In this
process, the nanomaterial suspension is dropped using dropper, and then, the substrate
is spinned at various speeds as per requirement until the uniformity is achieved.
The fabricated membrane is then obtained by applying etchants corresponding to
multiple substrates. The obtained membrane is lastly cleaned and dried at a moderate
temperature. The fabricated thin film with dense layers of 2D sheets is expected in
this method.

2.4 Langmuir–Blodgett (LB)

At present, Langmuir–Blodgett (LB) is broadly used method for 2D material-based

membranes preparation. For example, GO sheets have been considered to have
amphiphilic nature because of sp3 hybridized carbon atom, further bonded with
oxygen-containing functional groups [25]. The thickness and staking layers of the
sheets can be controlled using this method. For the formation of GO membranes
using this method, trough must be washed and carefully rinsed with chloroform
and then filled with deionized water. The GO solution was very slowly delivered
onto the water surface at constant speed using a glass syringe to a total volume
by using tensiometer (surface pressure measurement). The monolayer of the mate-
rial is deposited by submerging the substrate vertically into the trough and slowly
(2 mm min−1 ) bring it up [26]. Among the above techniques, the most frequently
used is vacuum filtration [27]. Moreover, issues like requirement of large volume of
liquid, alignment, and scalability are also significant concerns. Some potential prob-
lems can also be observed in dip-coating, drop-casting, or layer-by-layer assembly
methods. Thus, it is a major challenge to produce the 2D material-based membranes
using stable and robust processing techniques. Mostly, the ideal membrane used in
filtration process has a defect-free, thin, and dense structure; besides, the porous
structure will enhance the mechanical strength and permeability in the membrane.
Therefore, attention is required to fabricate these kind of membranes by cost-effective
and straightforward synthesis techniques [28, 29]. Many approaches are going on to
develop 2D material-based membrane on extensive scale application, which includes
the methods using a conventional rotogravure printer. A small amount of material
was deposited on the printer plate and outspread using a doctor blade. Afterward, the
rubber-coated roller pressed the substrate onto the printing sheet, and the liquid film
was transported to the substrate from the printing plate. The fabricated membranes
contain good stacking layers of nanosheets and exhibit high rejection rate of small
organic particles and water permeability compared to conventional membranes used
for nanofiltration [30].
130 S. K. Raj and V. Kulshrestha

3 Various 2D Nanomaterials Based Membranes

3.1 Graphene Membranes

Graphene, a trendy carbon-based 2D material, is currently being examined for

different water purification applications. This 2D sheet material has hexagonally
arranged sp2 carbon atoms [31, 32]. The layer is several atomic thick with excel-
lent mechanical strength, microscopic pores, and is impermeable to helium [33].
The desired pore size can be created by utilizing different techniques like electron
beam irradiation, oxidation, ions bombarding, doping, and chemical etching [34–
36]. Theoretical studies suggest that regular size distribution of pore size can lead
to forming a novel 2D material for RO membrane. Recent study concludes that
salt rejection is feasible though graphene membranes having pore diameters up to
5.5 Å [37]. Graphene sheets need to be produced on a large scale to get popularity
in the membrane market. The antifouling properties and scaling factors are some
other severe matters which need serious attention. Only then, it will be viable to
operate these membranes at a higher flux, which ultimately reduces the operational
and capital cost. Graphene is more economical and has far better characteristic prop-
erties than CNTs and having an enormous theoretical specific surface area of around
2600 m2 g−1 [38]. Additionally, graphene at ambient temperature shows high elec-
trical conductivity of about 7200 S m−1 [39]. All these outstanding qualities make
graphene a promising nanomaterial for water desalination.

3.2 Transition Metal Dichalcogenides (TMDCs) Membranes

TMDCs can be synthesize in both nanosheets and laminar membrane structures.

These 2D TMDCs nanosheets can be manufactured via mechanical cleavage and
chemical vapor deposition (CVD) methods. This is not reasonable for the functional
application as the eventual outcome has low yield and other drawbacks as well, as
uncontrolled development of sheets and layers [40]. At present, a couple of studies
have been reported on separation using TMDC-based membranes, the reason being
the low aspect ratio of the nanosheets (exfoliated) that make this challenging to form
defect-free membranes [41–43]. Some new highlights of these TMDCs membranes
provide diverse surface chemistries, but excluding various advantages over these
materials, some disadvantages like low yield and uncontrollable growth of sheet size
and number are still a hindrance to overcome.
6 Progress in 2D Nanomaterial Composites Membranes … 131

3.3 Hexagonal Boron Nitride (hBN) Membranes

Recently, hBN membranes were fabricated from the colloidal solution of BN

nanosheets through one-step functionalization and exfoliation [44]. These BN
membranes were prepared through the vacuum filtration method (Fig. 1c). Similar
to other 2D nanomaterial-based membranes, the solution of BN is dispersed through
an anodisc filter membrane having a diameter and pore size, 25 mm and 0.02 μm,
respectively. The fabricated membranes, after drying, peeled off from the filter. White
translucent membrane is obtained and further detached using a razor blade into any
shape and size. The thickness of the fabricated membrane was 10–25 μm. These BN
nanosheets are well aligned and forming a laminar structure. Apart from this, hBN
membranes can be combined with nafion for the fabrication of composite membranes
via eco-friendly and water-phase exfoliation methods (nafion-assisted). Nafion and
BN nanocomposite membranes can be fabricated; as nafion has amphiphilic nature,
it can provide support via hydrophilic or hydrophobic interaction and hydrogen
bonding [45]. Even though sufficient studies are reported on these 2D material-based
laminar membranes, but other 2D materials like MOFs, layer double hydroxides
(LDHs), and graphene are still needed for the fabrication of membranes efficiently
to attain the current demand for the separation application [46, 47]. These materials
are successfully examined theoretically for the separation membranes but are yet to
be explored experimentally because of few fabrication and engineering issues.

3.4 MXene Membranes

MXene, class of another 2D materials, fascinates the research community due to

its unique and exciting properties. Above all MXenes, Ti3 C2 Tx is the most used
MXene until now for different applications. Ti3 C2 Tx is synthesized using Ti3 C2 T2
by HF etching technique (Fig. 1b). Tx is the termination group in Ti3 C2 Tx, where
T denotes O, OH, or F groups, while x represents the number of terminating groups
[48, 49]. Ti3 C2 Tx has been broadly utilized in lithium-ion batteries, supercapacitor
fabrication, oxygen evolution reaction (OER), adsorption of heavy metal ions, and
recently in nanofiltration membranes for water desalination [50]. Only a few studies
are reported on MXenes membrane for separation of gas and water distillation. The
chemistry behind the MXenes and TMDC-based membranes is the same and can be
fabricated the same as the GO-based membranes. MXene membranes showed flex-
ibility and good mechanical strength. Ti3 C2 Tx membrane with controlled thickness
was fabricated, using PVDF as support [51]. These membrane was fabricated via the
filtration method and used further for molecules and ions separation application. The
hydrophilic surface of Ti3 C2 Tx membranes makes these 2D materials suitable for the
separation application and used for investigating antibacterial and bio-fouling prop-
erties by altering the membrane layers in a colloidal solution of MXene [50]. Ti3 C2 Tx
membrane shows excellent water permeability (1000 Lm−2 h−1 bar−1 ) and rejection
132 S. K. Raj and V. Kulshrestha

capability (up to 90%) for various molecules that have size < 2.5 nm. The stability
of these membranes can be improved by the incorporation of other 2D materials
via a suitable cross-linking agent [51]. These membranes show good performance,
although some of their properties still need to be enhanced to achieve excellent water
diffusion, separation capability, and mechanical strength under severe conditions for
the nanofiltration application [52]. The need for the self-supported membrane is still
there with incredible mechanical strength via improvement in ongoing fabrication
techniques or little modification in these methods to improve the properties of the
membranes.

3.5 Metal Organic Frameworks (MOFs) Membranes

MOF, another class of advanced 2D material, is used to fabricate laminar membranes.

MOFs can be exfoliated into thin sheets, just like other 2D material (Fig. 1d). In addi-
tion to this, MOFs possess high oxygen content and high pore density in comparison
with other 2D materials, hence promising materials for the membranes fabrication
[53]. Highly porous MOF is incorporated to the polymer matrix to increase the sepa-
ration capability. Only a few reports have been published on MOF based membranes
because of strenuous synthesis. These parameters restrict MOF exploration in the
membrane field. In terms of mechanical properties, MOFs have relatively low elastic
modulus (~ 7 GPa) in comparison with monolayer graphene (~ 1000 GPa) and GO
(~ 207 GPa) [54]. In another report, MOF membranes have been fabricated via
hot drop-casting technique; the substrate used was porous ceramic to enhance the
mechanical strength of the laminated MOF membranes [55]. Many approaches were
made to fabricate the MOF membranes via top-down methods [56, 57]. This method
involves wet ball-milling of 2D MOF sheets under ultrasonication using appropriate
solvent followed by the addition of required chemical substance for the successive
applications. In this process, due to external forces like solvent intercalation and
ultrasonication, the internal forces like van der Waals are demolished [58, 59]. In
spite of all these studies for the development of MOF membranes, only a few have
been utilized for industrial and analytical applications. The prime reason being is
difficulty in quality control when these are produced on a large scale. To utilize such
membranes on an industrial level, these hurdles must be overcome.

3.6 Zeolite Membranes

Zeolite, another class of 2D material, is having a porous structure and is broadly

studied for various applications related to separation and water purification. The
overall performance of the porous membrane fabricated using zeolite is depends
upon the pore structure, crystal shape, and size [60, 61]. In recent years, the precisely
crystal growth of the 2D zeolite layer and fabrication of freestanding laminar
6 Progress in 2D Nanomaterial Composites Membranes … 133

membranes with superior mechanical strength and flexibility is still a tough job for
the researchers. The fabrication method for the zeolite membranes is quite similar
to the MOF and GO membranes. The preparation of 2D zeolite membrane depends
upon many factors like thickness uniformity in zeolite nanosheets, high aspect ratio,
the stability of the colloidal solution, and contaminant-free colloidal solution. Apart
from this, the growth in deposition techniques for the transfer of 2D nanomaterial
to the porous substrate is also necessary [62]. Different approaches have been made
to make the dispersed zeolite nanosheets suspension by utilizing exfoliation tech-
niques, but during the process, the structure and the morphology of the nanosheets
are destructed. Due to such issues, so far, only a few studies have been reported
regarding the fabrication of the pristine zeolite membranes for the separation-based
application. In recent research, 2D zeolite nanosheets were fabricated on the silicon
wafer via Langmuir–Blodgett method by Tsapatsis et al. [63]. These nanosheets were
then calcined at 500 °C, and the size of these nanosheets was ~ 3 mm. Additionally,
in another work, zeolite nanosheets were prepared to have a thickness of ~ 3.5 nm
using the same method as above [64]. Apart from these attempts, the fabrication of
these such membranes at a large scale is still a hurdle. Although, the fundamental
focus should be on nanostructured membranes, having required orientation, grain
boundaries, well-designed interfaces, and stability under multi-component compo-
sition. Apart from this, modification in fabrication processes is still necessary to meet
the requirement for high yield large-scale production. Parameters such as high cost
and low yields of 2D zeolites are matter of concern in terms of large-scale produc-
tion. Such high-quality materials are significantly needed for the separation and
purification-based applications with excellent permeability and selectivity. There-
fore, to fulfil the requirement, 2D zeolite nanosheets are incorporated with a suitable
polymer matrix (Fig. 3).

Fig. 3 Graphene nanosheet

for the removal of large
hydrated ions [32]
134 S. K. Raj and V. Kulshrestha

4 Proposed Mechanism for Water Desalination Using 2D

Material-Based Membranes

It is very important to recognize the diffusion process of water molecules or any

solvent for designing the membranes for desalination. The transportation of water is
generally based on the solution diffused model.

Jw = A(P − π m ) (1)

where J W and A represent water flux and permeability coefficient, respectively. P

and π m represent the applied hydraulic pressure and osmotic pressure difference
(both side, feed, and permeate). In reverse osmosis (RO), the water movement is
driven by hydraulic pressure, which drives the flow of water in RO, while in forward
osmosis (FO), water flow is caused by osmotic pressure. Thus, increment in external
pressure in RO mode on the feed solution, or raising the drawn solution concentration
in FO mode both can accelerate the diffusion process across the membrane. The flux
of solute can be modeled by Fick’s law, given as

Js = Bcm (2)

where J s is the solute flux, B is solute permeability coefficient, and cm is the solute
concentration difference across the membrane. According to Fick’s law, regardless
of FO or RO operation, increasing the concentration of feed solution accelerates
solvent diffusion across membranes.
The solute/solvent permeability is affected by the coefficients A and B. The
commercial membranes can be modified by tailoring these coefficients by changing
the polyamide layer’s thickness. Generally, the polyamide layer reduction can
increase the water diffusion, but the salt refusal rate will be affected (lower down).
Therefore, controlling the thickness compactness and the chemistry of the layers
affects the desalination performance [65]. The mechanism is identical for the 2D
materials, and instead of dense layers, the nanosheets promote mass transporta-
tion. The filtration of ions can be attained by drilling nanopores on the surface of
the sheets or by creating nanochannels in stacked membranes. Mainly two prin-
cipal mechanisms are proposed for the desalination via 2D material membranes,
i.e., size exclusion and Donnan electrostatic exclusion. Size exclusion concludes the
permeation of smaller ions while blocking the hydrated ions. The second mecha-
nism principle concludes the blockage of hydrated ions using an electrically charged
surface [66, 67]. Nevertheless, in stacked and nanoporous membranes, this effect
promotes selective transportation. For this instance, ions are blocked either on the
pore edges or on the nanosheets’ line edges through electrostatic surface charges. In
stacked membranes, as the interlayer distance increases, the values of J w and J s also
increase. Despite this, J w and J s are directly proportional to the pore size in the case
of nanoporous membranes. One can achieve the ideal selectivity (J s ), permeability
6 Progress in 2D Nanomaterial Composites Membranes … 135

(J w ), and mass transfer by altering the pore size and the interlayer spacing of the
stacked nanosheets. Additionally, the surface chemistry and polarity are crucial in
altering the salt rejection performance of nanopores and nanosheets.

5 2D Nanomaterial-Based Membranes in Water

Purification and Desalination

Problems related to the water across the globe is the most crucial issue [1]. The
research community is trying to resolve this issue by developing suitable technolo-
gies to use saline water for different purposes at affordable values. Utilizing the
nanotechnology in desalination membranes will elevate this approach to resolve the
water catastrophe. Fouling decreases membrane life and increases operational cost;
thus, most of the research operates to fabricate membranes with antifouling properties
[68, 69]. To date, researchers made considerable efforts to resolve these limitations
by incorporation of new materials like carbon nanomaterials, zeolites, silica, and
other inorganic material in membranes [70–72]. Although synthesis technique and
properties of these materials play an essential role in membrane processing. Recently,
research based on 2D materials in membrane for ionic and molecular separation has
increased immensely [73, 74]. Therefore, this chapter mainly focus on nanoporous
and laminated membranes for desalination applications.
In the list of 2D materials, GO is one of the most utilized nanomaterials for
different separation and purification applications. Some studies have also shown
graphene as a filler material in composite membranes to enhance its barrier proper-
ties. The addition of graphene as a filler in the composite membrane can change the
membranes’ structure by altering the polymer filler interfaces. Till now, many mech-
anisms using molecular dynamics have been proposed to define the layer-by-layer
and porous structure of graphene-based materials [37]. Graphene oxide (GO) flakes
generally have two regions, i.e., oxidized (functionalized) and nonoxidized (pris-
tine). The similar functional groups were repelled by formers, and this increases the
interlayer spacing between the flakes. The oxides surface promotes strong bonding
between the polymers and the graphene flakes. Although, the cluster formation of
flakes within the membranes during the synthesis is still a hurdle to resolve. In some
reports, the graphene and its derivatives are modified to the unique porous structure
that enhances membrane properties (Fig. 4). Thus, nanosheets with highly dense
nanochannels and interedge spaces are preferred to fabricate graphene membranes
to upgrade water diffusion. The size of the interlayer can be variate by using different
sized intercalating agents. In a computational study, Grossman et al. examined a
high-performance single-layered graphene to separate out NaCl from the water and
conclude the relationship between flux and pore area [37]. The hydrophobic pores
with a small area cause low pressure and effectively reject more salts due to direct
size exclusion, whereas large volumes of ions and deficiency of hydrogen bonds
cause high energy hurdle to the ionic passage. Outstanding properties like the mono-
layer thickness of sheets with high mechanical stability and chemical inertness have
136 S. K. Raj and V. Kulshrestha

Fig. 4 Graphene membrane (porous) preparation. a Graphene membrane loaded on a silicon

substrate. SiN membrane caped on a vial filled with distilled water after that rotate the vial upside
down and put in an oven at 40 °C. b Water loss and ionic conductivity after 24 h. c Water/salt
selectivity versus I D /I G showing exceptionally large selectivity for a less etching time [79]

inspired the researchers to drill holes in the graphene nanosheets to grow more
nanopores to fabricate nanoporous graphene membranes. In theoretical studies, the
nanoporous graphene has shown ultrafast high water permeance and chokes the
movement of species larger than surface pores [75]. Obtaining the required porous
membrane having controlled pore size distribution within the graphene layers is still a
crucial parameter to resolve for the scientific community. Consider this; many perfo-
ration techniques are proposed to create pores in the graphene nanosheets like electron
beam ablation, ion beam ablation, ultraviolet-induced oxidative etching, and various
other etching techniques [76–79]. Well-distributed pores can be drilled in graphene
monolayer by using the electron beam irradiation technique. Still, this technique is
limited to a certain area of membranes, and the size of the pore is in the range of
3.5–100 nm, which is unfit for successive sieving separation. Scalability and pore
size can be effectively improved by the oxidative etching route. However, from the
practical point of view, the pore size distribution density still requires improvement.
Thus, enhancement in these techniques to produce high density and uniformly
6 Progress in 2D Nanomaterial Composites Membranes … 137

distributed pores improves the existing performance, which enables the energy-
efficient filtration and separation processes. In another investigation (Fig. 4a–c),
Mahurin et al. demonstrated that nanoporous single-layer graphene as nanofiltra-
tion membrane could be utilized in desalination [79]. In another reported study,
the author has produced porous monolayer graphene using atmospheric pressure
chemical vapor deposition (APCVD) on catalyst made up of copper for the desali-
nation applications [80]. The graphene was transferred onto the microchip (silicon
nitride) with 70% yield by utilizing polymer transfer technique, followed by oxygen
plasma method to fabricate nanoporous graphene. Oxygen plasma is the most suit-
able method to produce the nanoporous monolayer graphene carrying the desire pore
size and chemical properties with exceptional precision. The fabricated membranes
show excellent salt rejection (100%) for many metal ions (K+ , Na+ , Li+ , and Cl) with
rapid transportation of water [79].
Computational studies propose that nanoporous graphene can exhibit high permi-
tivity and selectivity exceeding to those of existing state-of-the-art membranes by
orders of magnitude. Moreover, experimentally, such membranes are strenuous to
manufacture on an industrial scale. This is due to numerous engineering barriers
to develop controlled-subnanometer pores using ion bombardment and selective
etching. In computational studies, nanoporous graphene has shown high permeance
and selectivity although these membranes are experimentally challenging to fabricate
on a large scale. As the nature of the technique used is very random, such pores with
high density and uniformity are very difficult to achieve to fulfill the industrial appli-
cations. In comparison with nanoporous monolayer graphene, GO is a more suitable
material for water desalination applications [81–83]. It can be easily used as lami-
nated sheets and can be incorporated with other materials to form composites. Due to
the availability of oxygen-containing groups on the basal plane and the edges of GO,
it shows fascinating properties in filtration and separation application [84, 85]. These
GO sheets having nanochannels work as a strainer, which removes all the molecules
of large size by blocking them, and the resultant membrane showed excellent separa-
tion properties. Moreover, carbon atoms in GO are generally bonded to oxygen atoms
in the form of carboxyl, hydroxyl, and epoxy groups. Due to these groups, an amor-
phous region is created, which tends to form nanocrinkles and compositional defects
in the GO nanosheets’ basal plane. These defects and winkles are the prime reason
for water transportation when GO sheets are mustered in membranes. The func-
tional groups (oxygen containing) present on the GO surface act as reactive handles
to different surface enhance reactions that can fabricate GO-based membranes with
escalated the separation capabilities. Till now, GO-based membranes have been inves-
tigated widely from both experimental and theoretical approaches for the separation
of ions and molecules [82–85]. Although, some factors such as controlling the d-
spacing, permeability, fouling properties, and stability are still needed to be explored
for the total utilization of these laminar sheets in the desalination technology. In
the reported study, the GO membranes have been demonstrated to have a thick-
ness in few microns. This membrane has shown good permeance of water vapor. It
blocks other liquids and gases under the dry state as the nanocapillaries formed due
to the empty interlayer space between the nonoxidized regions in GO sheets [23].
138 S. K. Raj and V. Kulshrestha

The transportation of water vapor was quite rapid. Although, hydration of the GO
sheets will increase the d-space in the membrane after water immersion and allow the
permeation of the small-sized molecules and ions (< 0.45 nm) while choking other
molecules having bigger sizes than 0.45 nm. Another study demonstrated the perme-
ation of the selective ions through GO membranes [86]. The investigators conclude
that the sodium salts penetrate from the membranes very freely, but the membrane
partially blocked other heavy metal salts (Fig. 5a–d). The fabricated membrane was
able to block copper salts and other organic pollutants. Generally, the metal salts
penetrate through nanocapillaries present in the GO membrane, but in heavy metal
salts, the collaboration between them and the membrane blocks the diffusion. The
mechanism was suggested by Nair et al. (Fig. 6a–d), and as per the study, the distance
between the layers is responsible for the flow of water in the membrane, and friction-
less flow of water was due to the high capillary pressure [23]. Thus, ions can easily
pass through the membranes’ channels in their hydrated form when the distance is
large. Hence, the species having a larger size cannot penetrate, while little ones can
proceed through the capillaries easily. Although, fascinating permeable properties

Fig. 5 a Conductivity variation with time for different salts. b The plot shows salt transport process
through GO membrane. c Diffusion process with respect to the mixture (NaCl + CuSO4 ) through
GO membrane. Insert photograph reveals the feed solution and penetrate. d Same procedure for of
NaCl and RB mixture [86]
6 Progress in 2D Nanomaterial Composites Membranes … 139

Fig. 6 a Schematic illustrating the direction of ion/water permeation along graphene planes. b
Photograph of a PCGO membrane glued into a rectangular slot within a plastic disk of 5 cm in
diameter. Scanning electron microscopy image at 1 μm [29]. c Images showing the alignment of
water layer between graphene sheets, the image of bulk water, and water layers between the GO
sheets [89]. d Permeation rates through PCGO membranes with different interlayer distances and
hydrated diameter (color coded). The salts used were KCl, NaCl, LiCl, CaCl2 , and MgCl2 [29]

were reported, which was independent of the size of the species tested. In the reported
study, ions follow the fashion, i.e., Na > Mn > Cd, but actual size trend follows Mn >
Cd > Cu > Na. Additionally, the investigation also includes the resistance separation
properties and the filtration of sodium salts from the copper salts and other organic
particles by utilizing GO membranes. This study demonstrated the ion permeation
from the GO membrane just by managing the d-spacing using physical confinement.
The study revealed that the membrane had d-spacing in the range of 9.8–6.4 Å, which
provides accuracy and tunability in ion sieving, smaller than hydrated ions in diam-
eter [86]. The GO laminates have been cut into rectangular strips of 4mmX10mm
under humid conditions for 1–2 weeks. The interlayer d-spacing was switch to 6.4–
9.8 Å as the humidity increases from 0–100%. The membrane was soaked in water
and the d-spacing noted was 13.7 ± 0.3 Å. The membranes were stacked up together
using epoxy to meet the required cross section area (1 mm). The above-staked lami-
nates of GO were mentioned as physically confined GO membranes (PCGO) as it
restricts the laminates’ swelling on humid exposure. Eventually, the membrane was
successfully fabricated, having a limited swelling ratio, and utilized for the effective
NaCl separation. In a recent investigation done by Chen et al., they demonstrated the
selective ion rejection by GO membranes just by improving the interlayer spacing
of the membranes by utilizing cations like K+ , Na+ , Ca2+ , Li+ and Mg2+ themselves
[87]. The required interlayer spacing can be managed as precisely as 1.0 Å. This
membrane can be directed by one type of cation that can eliminate the other cations
140 S. K. Raj and V. Kulshrestha

having a larger radius and that can be sheltered with larger spacing between the
interlayers.
Implementing first-principle calculations, authors have revealed that the nonco-
valent cation interactions between the aromatic rings of GO and the hydrated cations
present in solution are the reason behind unpredicted behavior. However, consider-
able progress for GO-based membranes has been achieved for water filtration and
desalination applications. Even so, some good topics like the interlayer spacing,
the pore dimensions, modification chemistry, and the number of layers in graphene
still need more attention. As the pore size increases larger than 0.8 nm, graphene
derived membranes show more water flux than CNT membranes as the center cause
higher velocity [88]. Several efforts were made to alter the interlayer spacing. Reports
suggest that the interlayer spacing can be widened by inserting large nanomaterials
or cross-linking large and firm molecules to increase the permeability [87–89]. RGO
membranes are highly impenetrable for most liquids, gases, and many inorganic
chemicals. The interlayers are very small, so the task to reduce the interlayer spacing
while maintaining the separation process constant and excluding the small ions when
immersed in the aqueous solution is quite challenging. These issues become a barrier
when the process is done on a large scale to separate selective ions of a particular
size from the bulk ion solution. Additionally, swelling of GO in the presence of
an aqueous solution is still a hurdle to overcome [89]. About TMDCs, only a few
investigations have been reported of filtration using these materials [90–92]. TMDC
membranes have shown high rejection (> 80%) of large organic impurities; still,
ionic rejection properties and nanocapillary behavior in TMDCs layers need serious
attention for full utilization of these membranes in filtration and desalination applica-
tions. In recent work, Bissett et al. prepared the MoS2 membrane with excellent ionic
sieving up to 99% for all the cationic components (Na+ , K+ , Ca2+ , and Mg2+ ) present
in seawater [16]. The water flux maintained was significantly five times greater in
comparison with those reported GO-based membranes. The fabricated functionalized
MoS2 membranes exhibited high mechanical stability with no swelling in 6 months
immersed in water. The ion rejection capability of this membrane remained the
same for 6 months. This membrane’s stability was exposed using different organic
solvents, but the performance remained the same for the membrane and was desir-
able for the filtration applications. Besides this, only a few studies are reported
regarding MXenes, TMDCs, and other LDH membranes for the desalination appli-
cation [90–92]. Recently, a freestanding membrane was fabricated using 2D MXene
(Ti3 C2 Tx ) by Gogotsi et al. on PVDF support using the vacuum filtration method
[51]. This membrane was used to separate the selective ions (Li+ , Na+ , K+ , Mg2+ ,
and Ca2+ ) and heavy metal ions (Ni2+ and Al3+ ) from the water; also in the same
investigation, the membrane shows excellent separation for the methylene blue dye
(Fig. 7a–d). This fabricated MXenes membrane showed an acceptable water flux of
37.4 L m−2 h−1 bar−1 . The metal ions carrying a high charge and smaller hydra-
tion radius than the interlayer spacing of Ti3 C2 Tx show slower penetration than the
cations having a single charge. Lamellar membranes using a stack of 2D MXenes
nanosheets have been fabricated by Ding et al. and demonstrated the separation of
different molecules (> 2.5 nm) with a 90% rejection rate with outstanding water
6 Progress in 2D Nanomaterial Composites Membranes … 141

Fig. 7 Water flux through Ti3 C2 Tx membranes. a Water flux when thicknesses is varying. b
Number of cations diffused through the MXene membranes versus time plot. c The diffusion
rates of different cations versus their hydration radii plot [51]. d Flux of water salt solutions versus
cation’s charge plot; and e, f performance of the various MXene membranes for the separation of
ethylene blue (EB) molecules and other various molecules with different sizes [50]

permeability of 1000 L m−2 h−1 bar−1 and was better than the previous reports
(Fig. 7e, f) [50]. Moreover, the performance of separation can be enhanced by incor-
porating MXenes with other 2D materials using appropriate cross-linking agents
for the fabrication of composite nanostructures. Just as GO laminar membranes,
the Ti3 C2 Tx membranes also have hydrophilic nature and have intergalleries that
promote water flow. Zongli Xie et al., fabricated a 2D lamellar composite MXene
membrane (MXMA) fabricated on microporous nylon substrate by vacuum filtration.
Fabricated membranes have structurally well-defined nanochannels (~ 0.49 nm) and
have swelling resistance and mechanical strength. The MXMA membrane showed
magnificent desalination with large flux and salt rejection [93]. Yan Yang et al. fabri-
cate a composite MXene membrane embedded with polyamide layer using in-situ
polymerization with outstanding water permeability of 2.53 Lm−2 h−1 bar−1 and
high NaCl rejection (98.5%) [94].
Furthermore, 2D zeolite sheets can be used as a surface enhancer to prepare
composite membranes for water desalination [95]. The different loading of zeolite
enhances the hydrophilicity of the membranes and structural and thermomechanical
properties. Zeolites reduced the undesirable voids of the membranes. Huanting et al.
have fabricated ultrathin graphene membrane (subatomic pores) on a porous ceramic
substrate using carbonization [96]. The fabricated membrane shows water flux of
49.8 ± 1.5–472.3 ± 14.2 Lm−2 h−1 with 99.99% NaCl rejection at various tempera-
tures (20–70 °C). The flux reported was remarkably higher than the previous reports.
Kaisong et al., prepare nanocomposite membrane using functionalized molybdenum
142 S. K. Raj and V. Kulshrestha

disulfide (O-MoS2 ). High oxidation of MoS2 increases the hydrophilicity and elec-
tronegativity of the membrane. Accordingly, the rejection of Na2 SO4 was 97.9%,
including excellent antifouling properties [97]. Jinyu Lia et al. have investigated the
ion separation efficiency by hBN membrane by implementing molecular dynamics
molecular. The simulation promotes the fact of using hBN as a promising candi-
date in membranes for desalination [98]. On the other hand, the synthesis of MOF
membranes has some severe limitations like grain boundary defects and intercrys-
talline cracks. A study was reported in which MOF membrane was fabricated by
using plant polyphenol tannic acid as an interlayer to overcome this hurdle. The
membrane showed a good water permeation of 3.6 L m−2 h−1 bar−1 along with the
rejection of NaCl and Na2 SO4 up to 64.7 and 92.2%, respectively, and demonstrating
great potential toward efficient water desalination [99].
The comparison study of different 2D material membrane is given in Table 2. Satis-
fying efforts have been made to enhance the aseptic properties, increase diffusion, and
also enhance the mechanical properties for desalination applications. Mostly their
work is dedicated to graphene-based materials, while other 2D materials are limit-
edly touched. Due to hydrophilic groups present at the basal plane of the GO sheets,

Table 2 2D material-based membranes for different water purification applications

Membranes type Fabrication Types of Permeability (L Rejection References
technique feed/conc m−2 h−1 bar−1 ) (%)
Porous grapheme Oxygen KCl (1 M) 250 100 [79]
monolayer plasma
etching
Base-refluxing Vacuum MB (0.02 mM) 21.8 99.2 [100]
reduced filtration Na2 SO4 (20 mM) 3.3 20
GO/PVDF NaCl (20 mM) – 40
PAH cross-linked Layer by Sucrose (1 M) 2.1–5.8 99 [101]
GO/PAN layer
MoS2 membranes Vacuum EB (15 μM) 245 89 [53]
filtration
NSC-WS2 membranes Vacuum EB (15 μM) 704 82 [54]
filtration
MXene membranes Vacuum NaCl 45.7 – [64]
filtration MgCl2 24.2 – –
AlCl3 18.3 – –
Ti3 C2 Tx MXene Vacuum EB (15 μM) 1084 90 [63]
nanosheet membrane filtration
GO15WS2 /Nylon Vacuum [Fe(CN)6 ]3− 178.1 64.3 [102]
filtration
GO-SWCNT/AAO Vacuum Rhodamine blue 710 97.4 [103]
filtration
GO/FLG/deoxycholate Spray NaCl – 85 [104]
membrane coating
rNPGO Vacuum Na2 SO4 39.93 99 [105]
filtration
6 Progress in 2D Nanomaterial Composites Membranes … 143

these GO-based fabricated membranes show excellent permeability and antifouling

properties. Pore size adjustment and altering the nanochannels by modification and
installation of oxygen-rich groups, narrow pore size distributed membranes can be
created. Incorporation of such 2D materials in membrane fabrication increases the
selectivity and decreases hydrophobicity on the membranes’ surface, enhances the
pore density, and reduces the cost of production. Oxygen functional groups in abun-
dance result in the hydrophilic nature of GO and make the membrane swell in the
aqueous or humid environments due to the water absorption, which can decrease
the overall required performance of the membrane. GO membranes have natural
tendency to swell in the aqueous phase due to water absorption by GO nanochannels,
which ultimately increases the size of interlayer spacing.
Apart from the chemical stability, mechanical stability is vital when the
membranes are fabricated on a large scale at various high-pressure conditions.
Recently, many other 2D material membranes beyond graphene, such as MXene and
TMDCs, have shown better performance in different water purification applications.

6 Challenges Associated with 2D Nanomaterial-Based

Membranes

Several technical challenges listed below are still need overcome to utilize such
membranes at large scale.
• Membrane fouling reduction.
• Flux increment is needed.
• Pressure drop and accordingly energy consumption reduction.
• Membrane performance should be accurately simulated and modeled.
• Achieve uniform pore-size distribution.
• Enhance chemical and mechanical stability of the membranes.
• Selectively of the membrane should be improved.
Fouling in membranes is a very technical problem. It is generally the deposition
of material accumulated on the membrane. Fouling causes a decrease in flux due to
the pore-clogging. Thus, membranes must be cleaned at regular intervals of times.
Another hurdle is performance modeling, which interrupts membranes’ formation
on a large scale and not enough to predict the performance at the industrial level.
The membranes depend on the quality of the particular source of water used for
the experiments. Up to now, only laboratory-scale experiments are performed with
these 2D material-based membranes. Recent reports are dedicated to the growth
of solvent-resistant nanostructured membranes, but the extensive installation of the
nanostructured membrane units is not economically viable. Generally, the water
industry utilizes conservative methods to process and resist new techniques with
rules and regulation. However, in most cases, 2D nanomaterial-based membranes
need an entirely different maintenance structure.
144 S. K. Raj and V. Kulshrestha

7 Conclusion

This chapter is mainly focused on various characteristics of the 2D material-based

membranes and classifications of water desalination application with possible chal-
lenges. The discussed 2D nanomaterials are promising candidates for membranes
fabrication. Selectivity and scalability are the core limitations of these type of
membranes. Improving the selectivity can enhance the quality of separation of water.
The other prime characteristic of the membrane is its durability and mechanical
strength. Furthermore, to explore the broad application, some serious efforts should
be made to enhance membrane design. Therefore, MOF and GO-based composite
materials utilize a high surface area and can be modified using various functionalities.

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Chapter 7
Advancements in 2D Nanomaterial
Composites-Based Electrochemical
Sensors for Environmental Contaminants

Zeba Khanam, Sameer Ahmad, Mohd Saquib Tanweer,

Weqar Ahmad Siddiqi, and Masood Alam

1 Introduction

The booming technologies are providing great comfort in livings but with a conse-
quence of a distressful environment. Rapid urbanization and population explosion
have stretched the use of natural resources to the maximum, rendering severe environ-
mental hazards. Owing to industrial, agricultural, and other anthropogenic activities,
every year over million tons of contaminants including toxic gases, heavy metals,
organic compounds, and other harmful wastes, etc., are being released into the envi-
ronment. The undesirable interaction of these pollutants with the air/water brought
unhealthy changes in the innate physiochemical properties of the ecosystem [1–8].
New chemicals are constantly being produced; hence, the research efforts should be

Zeba Khanam, Sameer Ahmad and Mohd Saquib Tanweer are first co-authors.

Z. Khanam (B)
School of Materials Science and Engineering, Harbin Institute of Technology, Shenzhen 518055,
China
e-mail: [email protected]
S. Ahmad (B) · W. A. Siddiqi
Department of Applied Sciences and Humanities, Faculty of Engineering and Technology, Jamia
Millia Islamia, New Delhi 110025, India
e-mail: [email protected]
W. A. Siddiqi
e-mail: [email protected]
M. S. Tanweer (B) · M. Alam
Environmental Science Research Lab, Department of Applied Sciences and Humanities, Faculty
of Engineering and Technology, Jamia Millia Islamia, New Delhi 110025, India
e-mail: [email protected]
M. Alam
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 149
Z. Khanam et al. (eds.), 2D Nanomaterials for Energy and Environmental Sustainability,
Materials Horizons: From Nature to Nanomaterials,
https://doi.org/10.1007/978-981-16-8538-5_7
150 Z. Khanam et al.

directed to curtail the release of such chemicals to avoid any risk to the environ-
ment and the life forms. It is highly demandable to regulate, monitor, and evaluate
the dynamics of the emerging contaminants for the safety of human health and the
environment and aiding sustainable growth on the earth.
The conventional techniques (such as mass spectrometry, optical methods, and
high-performance liquid chromatography) are unable to quantify trace levels of
contaminants and are complex, time-consuming, and relatively expensive. Besides,
the lack of monitoring standards and efficient regulatory programs has further crip-
pled the environmental protection management system. On this account, advanced
electrochemical sensing techniques are acknowledged for the efficient monitoring
and detection of pollutants at trace levels. Electrochemical sensing methods hold
the attributes of fast response, high accuracy and precision, superior sensitivity,
good selectivity, short analysis time, reproducibility, stability, cost-effectiveness,
simplicity, and easy data readout [1–15]. Nevertheless, the sensor’s performance
directly relies upon the active sensing electrode material. The sensing materials may
act as, or be responsible for, the recognition/sensing element and signal amplifi-
cation [9–15]. In trends, 2D nanomaterials are receiving great attention as sensing
material because of their unique quantum size effect, tunable surface properties,
enhanced mass transport, sufficient conductivity, and redox activity. The electronic
properties arising from the electrons/holes confinement make 2D nanostructures
very sensitive to external perturbations and matter [9–15]. On exposure to the target
analyte, 2D nanomaterials-based sensing electrode induce a fast change in current,
potential, impedance, or any other parameter that can be recorded and analyzed.
The detection mechanism mainly involves the binding of the target analyte to the
surface of 2D nanomaterial electrode through physical/chemical interactions, viz.
absorption, charge transfer, intercalation, and shifts in permittivity and lattice vibra-
tions [15]. To date, various 2D nanomaterials including transition metal compounds
(TMDs, TMOs, TMHs), MXenes (transition metal carbides/nitrides/carbonitrides),
2D organic frameworks (MOF, COF), phosphorene, etc., have been extensively
explored to develop high-performance electrochemical sensors for detecting toxic
gases [5, 16], heavy metals [15, 17], and other organic contaminants [9, 17], etc.,
and a lot of research is still in progress.
This chapter summarizes the recent advances of 2D nanomaterials in electro-
chemical sensing applications particularly emphasizing on detection of toxic gases
and water pollutants along with a brief presentation of the underlying principle and
performance of different electrochemical sensors.

2 Advanced Electrochemical Sensing Techniques

Typically, a sensor is composed of (a) the receptor that recognizes the target analyte
(e.g., pollutant), and (b) the transducer which converts and produces a quantifiable
sensing signal. The receptor, being the crucial component, accounts for the speci-
ficity, affinity, response time, and lifespan of the sensor. In general, the receptor binds
7 Advancements in 2D Nanomaterial Composites-Based … 151

to a specific analyte in a given environment and the transducer amplifies the sensing
signal proportional to analyte concentration which can be measured and analyzed [3,
18–20]. Based on different signal transduction mechanisms, the sensing event could
be a change in current, potential, amplitude, conductivity, fluorescence, or lumines-
cence activity. Sensors could be designated according to the detection principles—
for instance, electrochemical, optical, thermal, piezoelectric, field-effect transistor
sensors, etc. [3, 9, 13–15, 18–20]. Herein, our focus is on the electrochemical sensors
as they dominate much of the current literature.
Electrochemical sensing of pollutants typically relies on active electrodes that
are able to produce a quantifiable electrical signal in response to the electrochemical
adsorption or reaction with target analytes. The presence of pollutants is detected and
recorded in the form of a measurable sensing signal induced by a change of current,
resistance, capacitance, or potential [1, 3, 10, 13]. Different modes of electrochemical
techniques can be employed for the pollutant’s detection
• Potentiometry: Potentiometric sensors analyze the chemical activity of the
targeted ions under thermal equilibrium conditions by measuring the difference in
electrical potential. The possible analytes are redox-inert species [9, 10, 18–20].
• Voltammetry: Voltammetric sensors monitor the relative concentrations of the
target analyte by measuring the change in current arising due to the electron
transfer under applied potential. Cyclic voltammetry is a fingerprint technique
to identify the presence of targeted analytes through a redox reaction. Numerous
other voltammetric methods could enhance the selectivity and sensitivity, like
square-wave voltammetry (SWV), normal pulse voltammetry (NPV), anodic strip-
ping voltammetry (ASV), cathodic stripping voltammetry (CSV), and differential
pulse voltammetry (DPV). Among these, ASV or CSV are widely known for trace
metals analysis, involving the electrochemical accumulation of analyte at the elec-
trode surface, followed by its oxidation in a linear sweep or pulsed reverse scan.
Voltammetry methods can detect specific redox analytes giving information about
the reversible reactions and the nature of the analyte present [9, 10, 18–20].
• Amperometry: Like voltammetric sensors, amperometric sensors measure the
magnitude of current as a function of analyte concentration at a fixed potential.
The response times, dynamic ranges, and sensitivities are similar to potentiometric
sensors and can only detect redox-active species like voltammetric sensors. It is
worth noting that any perturbation or disturbance causes no effect on the sensor
performance [9, 10, 18–21].
• Impedance: Impedimetric sensors determine the current response by applying
a small sinusoidal AC voltage. Impedance methods are quite powerful as they
are capable of characterizing physicochemical processes of widely differing time
constants, sampling electron transfer at high frequency and mass transfer at low
frequency. It does not require voltage scanning which is time-consuming and may
degrade the electrochemical interface during wide potential sweeps. In addition,
impedance sensing is largely insensitive to environmental disturbance, which is
often problematic for other sensors [5, 9, 10, 18–22].
152 Z. Khanam et al.

3 Fabrication of 2D Nanocomposites-Electrochemical
Sensing Platforms/Electrodes

Tremendous research interest has been stimulated among the scientific commu-
nity to develop novel, facile, cost-effective, portable, miniaturized 2D nanomate-
rial composite electrodes for precise and rapid electrochemical detection of envi-
ronmental contaminants. The fine structural and compositional tuning of 2D nano-
materials can improve their electrochemical and electrical characteristics, enabling
efficient signal transduction after an analyte binding event. Recent studies demon-
strated that creating heteroatoms, metal or chemical doping, hybridizing/compositing
with other nanomaterials or polymers, and integrating with biological entities such
as enzyme/nucleic acid/protein immobilization can effectively tune the bandgap
of resulting 2D nanomaterials composite and thereby enhancing the strength and
selectivity of the sensing element–analyte interactions [3, 7, 9, 15, 17, 23, 24].
Up to now, several methods such as wet chemical, hydrothermal, solvothermal, co-
precipitation, sol–gel, chemical oxidative polymerization, micro-emulsion, layer-by-
layer assembly, pyrolysis, and ultrasonic/high-shear/supercritical-assisted dispersion
have been reported to prepare such 2D nanomaterial-based composites [3, 7, 9, 12–
17, 23, 24]. The prepared 2D nanocomposites are then usually drop-casted over
the glassy carbon electrodes (GCE) or screen-printed electrodes (SPE) or interdig-
itated electrodes (IDE). Alternatively, 2D nanomaterials composites dispersion can
be coated over flexible substrates (such as carbon paper, cellulose paper, fiber, cloth)
by means of inkjet printing, pencil drawing, painting, spin coating, dip-coating,
spray coating, drop-casting, electrophoretic deposition, electrospinning, and rolled-
up technologies. Most recently, the template-free self-standing flexible electrodes
are in high demand which can be directly fabricated as thin films or hydrogel/aerogel
membranes by simple solution casting [3, 7, 9, 12–17, 23–26]. The related studies
are summarized in Table 1.
The major key factors of a 2D nanocomposite electrode impacting the electro-
chemical sensor performance are:
• Specific surface area: 2D nanomaterials electrodes with large surface area ensure
sufficient material–analyte interactions, beneficial to realize high sensitivity even
at extremely low concentrations of the analyte [9, 15].
• Electrical conductivity: 2D nanomaterials exhibit a range of electrically conduc-
tive behaviors including metallic, semimetallic, semi-conductive, and insulating
behavior. In addition, they have direct and indirect bandgaps ranging from ultra-
violet to infrared, and throughout the visible spectrum. In 2D nanomaterials,
the confinement of charge transport is in the 2D plane which may instigate
considerable change in the electrical conductivity upon analyte binding [9, 15].
• Electrochemical activity: The intrinsic electrochemical properties of 2D nanoma-
terials are advantageous for electrochemical sensing applications. The intriguing
confined nanospaces between adjacent 2D layers interfaces can accelerate many
electrochemical reactions such as faradic, capacitive, electron mobility, current
density, and mass transport [9, 15].
Table 1 Summary of various 2D nanocomposite-based electrochemical sensors for detection of toxic gases/VOCs, heavy metals, and other water pollutants
2D nanomaterials-based sensing platform Fabrication method Air/water Sensing techniques References
contaminants
TMDs
MoS2 /C3 N4 aerogel @IDE Thermal decomposition and freeze NO2 gas Electrochemical, I–V [27]
drying
MoS2 /MoO3 @GCE Hydrothermal NH3 gas Electrochemical, I–V [37]
MoS2 /WO3 @GCE Probe-sonication NH3 gas Electrochemical, I–V [38]
1T WS2 @IDE Exfoliation Methanol vapor Impedance [39]
MoS2 -Au hybrid @IDE Simple solution mixing Acetone vapor Electrochemical sensing [40]
MoS2 /rGO @GCE Hydrothermal Pb(II) ions SWASV [41]
DNA1–QD–PDDA–MoS2 @GCE Multi-step immobilization Hg(II) ions Electrochemiluminescence [42]
MoS2 -DMF @GCE Sonication Cd(II) ions SWASV [43]
MoSe2 /MoO3 @GCE Hydrothermal Nitrite ions Amperometry [44]
MXenes
MXene(V2 C)/PANI @IDE In-situ polymerization NH3 gas Integrated self-powered [49]
7 Advancements in 2D Nanomaterial Composites-Based …

electrochemical sensing
MXene/PU core–sheath fibers Wet spinning of PU, spray coating of Acetone vapor Amperometry [50]
(template-free) MXene over PU fibers
MXene (Ti3 C2 Tx ) @IDE MXene etching and drop-casting Ethanol vapor Impedance [51]
over IDE
MXene-bismuth @PET microgrid Solution mixing, micromilling Pb(II), Cd(II) and SWASV [52]
assembly Zn(II) ions
MXene-bismuth @GCE Sonication Pb(II) and Cd(II) ions SWASV [53]
(continued)
153
Table 1 (continued)
154

2D nanomaterials-based sensing platform Fabrication method Air/water Sensing techniques References

contaminants
Ti3 C2 Tx /BiVO4 @ITO BiVO4 electrodeposition over ITO Hg(II) ions Photoelectrochemical sensing [54]
followed by spin coating of Ti3 C2 Tx
Ti3 C2 Tx /Nafion @GCE Sonication Bromate ions DPV [55]
Au@CQDs-MXene @GCE One-pot green synthesis Nitrite ions DPV [56]
Pt@Ti3 C2 Tx @GCE Sonication Bisphenol A DPV [57]
MOFs
Cu-BTC (MOF-199) @Cu Electrochemical synthesis of a thin Ethanol and methanol Capacitive sensing [63]
film of MOF over Cu plate vapors
PANI-cobalt zeolitic benzimidazolate Chemical oxidative polymerization H2 gas Chronoamperometry [64]
MOF
Silica-coated-CuBTC Polymerization NH3 gas Electrochemical, I–V [65]
MOF-PAN-graphene @Cr
CDMOF-2 pellet Solution mixing CO2 Impedance [66]
Ni-MOF-74 @IDE Sonication and thermal reflux NO2 gas Impedance [67]
MOF-derived Co3 V2 O8 Solvothermal, screen-printing over NO2 gas Electrochemical, I–V [68]
solid electrolyte
UiO-66-NH2 MOF-PANI @GCE Hydrothermal, sonication Cd(II) ions DPSV [70]
Polypyrrole-MOF film free-standing Interfacial polymerization Cd(II) ions SWASV [71]
DNA Hydrothermal, solution mixing Pb(II) ions DPV [69]
immobilized-AgPtNPs/MIL-101(Fe)
MOF @GCE
Zn-MOF/GO @GCE Solvothermal As(III) ions DPASV [72]
(continued)
Z. Khanam et al.
Table 1 (continued)
2D nanomaterials-based sensing platform Fabrication method Air/water Sensing techniques References
contaminants
Zirconium-porphyrin-MOF-525 Solvothermal Nitrite ions Amperometry [73]
Phosphorene (BP)
BP @IDE CVD Methanol vapor Impedance [83]
Platinoid-BP @IDE Electrochemical synthesis Methanol vapor Impedance [84]
BP @IDE Exfoliation NO2 NH3 and H2 gas Amperometry [85]
Polyethyleneimine-BP @GCE One step electrostatic adsorption Cu(II) ions Amperometry [87]
method
Porous Gr-BP @GCE Sonication, pyrolysis Bisphenol-A DPV [88]
BP quantum dots-ZnO @GCE Sonication, hydrothermal H2 O2 Amperometry [89]
Hexamethylenediamine (HA)-coated Sonication, seed-induced growth Polychlorinated DPV [90]
AuNPs-BP biphenyl (PCB77)
7 Advancements in 2D Nanomaterial Composites-Based …
155
156 Z. Khanam et al.

• Surface defects or functionalization: The rich surface chemistry could effectively

enhance the selectivity and sensitivity of the targeted species. Integration with
other recognition components (e.g., metallic nanoparticles, metal oxides, and
enzymes) could provide more active sites to further improve the sensing perfor-
mance of a device. It can influence the electron or photon movement and interfacial
charge transfer between sensing material and analyte [9, 15].
There lies a co-relationship between the electrical conductivity, active sites,
electrochemical activity, and surface defects/functionalization. The high electrical
conductivity and abundant active sites can considerably improve electrochemical
activity. An increase in the degree of structural disorders usually improves the number
of active sites which can enhance the electron scattering, beneficial for sensing
applications [9, 15].

4 2D Nanocomposites-Based Electrochemical Sensors

for Toxic Gases and Water Pollutants

As a result of anthropogenic and natural activities, many toxic gases, such as

carbonous (CO and CO2 ), sulfurous (H2 S and SOx), and nitrogenous (NH3 , NO,
N2 O, N2 O4 , etc.) or their by-products and volatile organic compounds (VOCs) such
as ethanol, methanol, acetone, benzene, are deteriorating the air quality. Even a
low concentration exposure to these hazardous gases and VOCs can cause fatal
respiratory nuisance and turn lethal to life forms. The detection of such harmful
gases and VOCs is crucial for efficient air quality monitoring, industrial process
management as well as effective emissions control [5, 6, 9, 16, 21–27]. On the other
hand, there is a high need to regulate the discharge of inorganic/organic chemi-
cals and heavy metals into aqueous systems. They mainly include nitrites, pesti-
cides, dyes, lead, arsenic, mercury, etc., which not only pollutes surface water but
groundwater as well. Many chronic diseases and billion deaths are reported due
to the intake of contaminated water [1–4, 7, 9–15, 28–31]. Over the decade, elec-
trochemical sensors have made significant advances in the field of environmental
monitoring. As mentioned above, the sensor performance depends on the sensing
material. Therefore, various 2D nanocomposites have been explored as an active
sensing material for the electrochemical detection of a range of analytes. The broad
chemical diversity of 2D nanomaterials provides a great deal of surface structure
tunability for specific host–analyte interactions [9]. So far, numerous 2D nanocom-
posite electrochemical sensing devices have been developed for the detection of toxic
gases and water pollutants, a few of which are reviewed here. Substantial progress is
toward integrated electrochemical sensors like electrochemiluminescence (ECL) and
photoelectrochemical (PEC) sensors. In ECL sensing, electrochemical reactions by
electron transfer trigger chemiluminescence, which is then recorded and analyzed.
While PEC sensors involve photon-electricity conversion through charge separa-
tion and subsequent charge transfer after absorption of photons during illumination
7 Advancements in 2D Nanomaterial Composites-Based … 157

where light energy is an excitation source and electrical signals were recorded [32].
Some recently developed 2D nanocomposites-based ECL and PEC sensors are also
included herein. This section has mainly addressed the 2D TMDs, MXenes, MOFs,
and phosphorene-based electrochemical sensing devices for detecting toxic gases
and water contaminants.

4.1 TMDs/TMOs-Based Sensors

2D transition metal compounds (TMDs, TMOs, TMHs) have diverse structural and
electronic behaviors (semi-conductors, conductors, or insulators), allowing them to
be incorporated into different analytical devices. Benefitted with the atomically thin
layer structure, high surface-to-volume ratio, tunable bandgaps, and fast electron
transfer kinetics, render these materials as promising candidates for detecting gases,
VOCs, heavy metal ions, etc. The charge transport can be easily modulated through
surface engineering of TMDs, providing abundant host–analyte active sites along
with thermal and chemical stability [7, 9–11, 33–36].

4.1.1 Detection of Toxic Gases

Various 2D transition metal compounds and their composites or heterostructures are

successfully applied for sensing toxic gases, such as MoS2 /C3 N4 [27], MoS2 /MoO3
[37], MoS2 /WO3 [38], and 1T WS2 [39]. A recent study reported the preparation
of heterostructure of MoS2 /MoO3 via hydrothermal process that was efficiently
employed for selective electrochemical sensing of NH3 under highly humid condi-
tions. Figure 1a, b displays the change in corresponding resistance of as-prepared
MoS2 /MoO3 based sensor on exposure to different reducing gases (hydrogen sulfide,
formaldehyde, methanol, ethanol, and acetone) and oxidizing gases (NO and NO2 )
at relative humidity (RH) of 40% and 60%, respectively. It was found that the
sensor exhibited superior sensitivity and selectivity toward NH3 (down to 1 ppm) as
compared to others. It is believed that the selectivity behavior is mainly governed by
operating temperature, concentration, and the lowest unoccupied molecular orbital
(LUMO) energy of adsorbed gas. And it is probably due to the matched LUMO
energy of NH3 with that of electronic energy of adsorbed oxygen on the sensor
surface at ambient temperature which enhances their interaction, thereby enhancing
the selectivity of the sensor toward NH3 [37]. The authors conducted another study
with MoS2 /WO3 composite, prepared by a facile probe-sonication method, for the
detection of NH3 . The composite sensor exhibited p-type semiconducting behavior
with better selectivity and sensitivity toward NH3 (down to 1 ppm) and excellent
response-recovery features in contrast to individual MoS2 (p-type) and WO3 (n-
type) counterparts at an operating temperature of 200 °C. As shown in Fig. 1c,
the composite sensor displayed an increased resistance response toward NH3 as
compared to different reducing gases. This is mainly due to the creation of n-p
158 Z. Khanam et al.

Fig. 1 Selectivity behavior of the MoS2 /MoO3 sensor toward NH3 and other analytes at room
temperature and a RH = 40% and b RH = 60%. Reprinted with permission from [37] Copyright
2021 American Chemical Society. c Selective response of the MoS2 /WO3 composite-based sensor
toward NH3 (50 ppm) at 200 °C compared to other reducing gases (100 ppm). Reprinted with
permission from [38] Copyright 2021 American Chemical Society. d Corresponding response bar
chart showing the selectivity of MoS2 sensors is significantly enhanced by the adequate decoration
of AuNPs. Reprinted with permission from [40] Copyright 2019 American Chemical Society

heterojunction which formed a depletion layer at the interface through the interdiffu-
sion of the majority carriers. The width of the depletion layer reduces on exposure to
NH3 where the oxygen ions interacted with the adsorbed gas molecules releasing the
trapped electron back to the conduction band, thus reflected an increased resistance
[38]. Another study reports the incorporation of gold nanoparticles (AuNPs) on 2D
MoS2 nanoflakes through simple solution mixing to form MoS2 -Au hybrid electro-
chemical sensor for detection of VOCs including acetone, ethanol, and 2-propanol at
room temperature. Results indicated that the developed sensor was highly sensitive
to oxygen-containing VOCs delivering an improved response (131%), particularly
for acetone as compared to bare MoS2 (Fig. 1d). The proposed mechanism suggested
that its due to the electro-donating effect of AuNPs that caused an increase in electron
density on the MoS2 -Au channel. On exposure to a high concentration of oxygen
species, the channel traps more electrons and increased the adsorption energy of
oxygen ions which in turn makes Au-decorated MoS2 more responsive and selective
toward oxygen-containing VOCs [40]. These studies indicate that among transition
metal compounds MoS2 -based sensors are promising in electrochemical sensing of
toxic gases.
7 Advancements in 2D Nanomaterial Composites-Based … 159

4.1.2 Detection of Water Pollutants

TMDs exhibit a strong binding affinity toward heavy metals due to their numerous
intrinsic chalcogen atoms. Many studies have been carried out to detect the heavy
metal ions (HMIs) using 2D TMDs nanocomposites-based electrochemical sensors.
The detection relies heavily on electrode modification materials that can enhance
sensor sensitivity. For instance, a sensitive and anti-interference electrochem-
ical sensing interface based on flower-like MoS2 /rGO composite modified GCE
(MoS2 /rGO-GCE) was developed to detect Pb(II) using square wave anodic strip-
ping voltammetry (SWASV). A low detection limit (LOD) of 0.005 μM and high
sensitivity of 50.80 μA μM−1 evince the excellent Pb(II) detecting performance
of the MoS2 /rGO-GCE sensor. This is due to the superb adsorption capacity and
electrical conductivity of the MoS2 /rGO nanocomposite where the redox reaction
of Pb(II) occurs directly on the surface (Fig. 2a) [41]. In another study, quantum
dots (QD)-functionalized MoS2 -composite and DNA/gold nanoparticles/glucose
oxidase (DNA2 –AuNP–GOD) conjugates were prepared and immobilized onto the
GCE surface, constructing a novel electrochemiluminescence (ECL) biosensor for
detecting Hg(II) ions in water samples. Under optimized experimental conditions, the
ECL biosensor demonstrated a linearity range between 1.0 × 10−12 and 1.0 × 10−6 M

Fig. 2 a Redox reaction of Pb(II) on the surface of MoS2 /rGO nanocomposite sensor. Reprinted
with permission from [41] Copyright 2019 Elsevier B.V. b The effects of different species on the
ECL intensity of Hg(II) at the biosensor. Reprinted with permission from [42] Copyright 2019 RSC.
c Selectivity investigation of the proposed sensor for Cd(II) detection. Reprinted with permission
from [43] Copyright 2018 Elsevier B.V. d CV of MoSe2 -MoO3 modified GCE (curve a) and GCE
(curve b) in 50 μM NO2 − containing 0.1 M pH 4.75 acetate buffer at a scan rate of 50 mVs−1 .
Reprinted with permission from [44] Copyright 2019 Wiley Analytical Science
160 Z. Khanam et al.

with LOD of 1.0 × 10−13 M of Hg(II) ions. The detection mechanism involved the
glucose oxidation that was marked by the production of H2 O2 which in turn enhanced
the ECL property of QDs and facilitated signal amplification selectively for Hg(II).
The experimental results (Fig. 2b) suggested that the ECL biosensor possessed good
stability and selectivity for Hg(II) compared to other heavy metals [42]. Yet another
study reported the surface functionalization of MoS2 in N, N-dimethyl formamide
(DMF) using sonication to construct an electrochemical sensor for Cd(II) detection.
The sensor showed a LOD of 0.2 nM and a linear range from 2 nM to 20 μM under
optimized conditions. The strong binding energy between Cd(II) and oxygen donor
atom of DMF-functionalized MoS2 contributes to higher sensitivity and selectivity
toward Cd(II) as compared to other analytes, as shown in Fig. 2c [43]. A recent study
reported the single-step hydrothermal preparation of MoSe2 /MoO3 heterostructure
to design a highly sensitive electrochemical sensor for amperometric detection of
nitrite in real water samples collected from industrial areas. The sensor displayed
high electrocatalytic activity as revealed with CV curves (Fig. 2d). It showed a well-
defined oxidation peak for MoSe2 -MoO3 modified GCE (curve a), due to conversion
of NO2 − to NO3 − , in contrast to bare GCE (curve b). Under optimal amperometric
i-t conditions, the sensor demonstrated good stability, reproducibility (<3 s), high
sensitivity (10.84 A M−1 cm−2 ), and LOD (0.1 μM) in a linear range of 2.5–80 μM
for nitrite with negligible effect toward the interfering ions that coexist in water
bodies. The high surface area from 1T phase MoSe2 and α phase MoO3 accredited
the superior performance of the sensor [44].

4.2 MXenes-Based Sensors

Bestowed with rich surface functional groups, high conductivity, tunable bandgap,
large aspect ratio, good hydrophilicity, and mechanical flexibility, MXenes are widely
under consideration to design electrochemical sensors for the detection of environ-
mental contaminants including toxic gases, VOCs, HMIs, and other inorganic or
organic contaminants [32, 45–48].

4.2.1 Detection of Toxic Gases

Few studies related to MXenes and their composites have been reported for electro-
chemical detection of toxic gases and VOCs. Recently, an integrated self-powered
electrochemical sensory system based on MXene(V2 C)/PANI composite was devel-
oped for NH3 detection (Fig. 3a). The sensor displayed an astonishing sensing
response (14.9%), good stability, and fast response time (9 s) toward NH3 at 1 ppm
concentration. The suggested mechanism is related to the creation of a depletion
region due to p-n heterojunctions interactions that widen when the NH3 molecules
adsorbed on the N–H group of PANI and thus amplified the resistance signals [49].
Yet another study reported a wearable sensor based on MXene/polyurethane (PU)
7 Advancements in 2D Nanomaterial Composites-Based … 161

Fig. 3 a Schematic of the PANI/MXene gas sensor driven by self-powered device for NH3 sensing
in an ultra-low concentration. Reprinted with permission from [49] Copyright 2021 Elsevier B.V.
b Sensing response of MXene/PU core–sheath fiber under different concentrations of acetone
in contrast to MXene/IE sensor. Reprinted with permission from [50] Copyright 2021 Elsevier
B.V. c SWASV analysis for simultaneous detection of Pb(II), Cd(II), and Zn(II) in wide detection
range. Reprinted with permission from [52] Copyright 2019 Springer. d A photoelectrochemical
sensing platform based on the Schottky heterojunction between 2D Ti3 C2 Tx MXene and BiVO4 was
constructed for sensitive determination of Hg(II). Reprinted with permission from [54] Copyright
2020 Elsevier B.V

core–sheath fibers that were prepared by spray coating of MXenes over PU fibers
for the detection of VOCs using the amperometry method. As seen in Fig. 3b, the
MXenes/PU core–sheath fibers-based sensor showed high sensitivity toward acetone
(down to 50 ppm) across a wide sensing range (up to saturated vapor) and high
signal-to-noise ratio, contrary to the MXene/IDE-based sensor. It is believed that
the swelling-induced stretching of MXenes due to acetone interaction with PU and
the simultaneous charge transfer due to acetone adsorption onto MXene through
H-bonding synergistically contributed to change in resistance and lead to high sensi-
tivity response toward acetone [50]. Another study proposed a virtual sensor array
(VSA) fabricated by depositing a thin film of MXene (Ti3 C2 Tx ) over IDE for precise
and selective detection of VOCs using the electrochemical impedance method. VSA
exhibited a unique fingerprint for each VOC and showed a selective response toward
ethanol. The possible detection mechanism involved the interaction of VOCs with
surface functional groups/defects of MXenes that increased the interlayer spacing,
162 Z. Khanam et al.

thereby resulted in a change in impedance with a highly sensitive response toward

ethanol [51].

4.2.2 Detection of Water Pollutants

MXenes nanocomposites have also been employed for the detection of varied water
pollutants. For instance, a study reported a microgrid electrochemical sensor based
on MXene-bismuth nanocomposite for the simultaneous detection of HMIs using
SWASV. The Bi(III) were accumulated on delaminated Ti3 C2 surface through elec-
trostatic attraction, and subsequently, ultrasmall bismuth nanorods were in-situ grown
at hybridization matrix which was then integrated to microgrid assembly via mechan-
ical milling. The microgrid sensor exhibited high sensitivities for Pb(II), Cd(II), and
Zn(II) with LOD of 0.2, 0.4, and 0.5 μg L−1 , respectively, in a linear range from 1 to
20 μg L−1 under optimum conditions (Fig. 3c). The uniformly dispersed Bi nanorods
and the microgrid structure facilitated the hemispherical diffusion and improved the
cathodic accumulation of HMIs, thereby enhanced the sensing performance [52].
Similar studies were reported for the quantification of Pb(II) and Cd(II) ions in
water using MXene-Bi nanocomposite sensor. At optimized conditions, as-prepared
nano-sensor simultaneously detected Pb(II) and Cd(II) with LOD of 10.8 nM and
12.4 nM, respectively, using SWASV. The excellent sensing properties toward model
pollutants are due to high surface area and quick transfer of electrons [53]. Another
study reported the designing of an integrated photoelectrochemical (PEC) sensor
using BiVO4 /Ti3 C2 Tx composite for the selective detection of Hg(II) ions from the
water (Fig. 3d). Coating of BiVO4 over Ti3 C2 Tx facilitated the charge transfer of
the photo-generated carriers and abated the charge recombination. The photocurrent
was boosted along with the addition of a hole scavenger (reduced glutathione-GSH).
However, the chelation of GSH with Hg(II) considerably decreased the photocur-
rent by retaining the photo-generated holes. Consequently, the sensor displayed a
high sensing and selective response toward Hg(II) with LOD of 1 pM in a linear
range from 1 pM to 2 nM. Moreover, the PEC sensor also showed acceptable
accuracy and repeatability in real sample water [54]. Besides HMIs, MXenes were
also investigated for several other inorganic/organic contaminants. For instance, a
Nafion/Ti3 C2 Tx modified GCE displayed excellent selective electrocatalytic reduc-
tion capacity toward bromate (BrO3 − ) ions in drinking water among other interfering
ions with LOD of 41 nM using DPV [55]. Next, an Au-carbon quantum dots immo-
bilized MXene nanocomposite (Au@CQDs-MXene)-based electrochemical sensor
was developed to detect nitrite ions in water. At optimized conditions, the sensor
displayed with LOD of 0.078 μM in linear detection range from 1 to 3200 μM
[56]. In another study, Pt@Ti3 C2 Tx was employed for electrocatalytic reduction and
detection of Bisphenol A using DPV which showed a fast response with LOD of
32 nM and good stability [57].
7 Advancements in 2D Nanomaterial Composites-Based … 163

4.3 Metal–Organic Frameworks-Based Sensors

Metal–organic frameworks (MOFs) are porous coordination polymers (CPs) that

are constructed by the metal-based inorganic linkage and organic ligands bonded
through a chemical bond. In recent years, 2D MOFs have been extensively studied
as a promising material to fabricate electrochemical sensors for the removal
of environmental contaminants, due to their notable properties such as high
surface area, porosity, excellent electrochemical activity, and controllable structure
[16, 23, 25, 58–62].

4.3.1 Detection of Toxic Gases

The potential of MOFs and their composites have been explored for electrochemical
detection of gases and VOCs. For instance, a capacitive sensor was fabricated by
growing a thin film of Cu-BTC (MOF-199) on a Cu substrate to quantify VOCs. It
displayed the high selectivity and sensitivity toward ethanol and methanol vapors with
LOD of 130.0 ppm and 39.1 ppm, respectively [63]. Recently, polyaniline (PANI)-
cobalt zeolitic benzimidazolate MOF composite has been synthesized by chemical
oxidative polymerization for electrochemical sensing of H2 gas. The electrocatalytic
capability of the PANI-MOF sensing composite was tested with hydrogen evolution
reaction using chronoamperometry. It exhibited higher sensing efficiency, and a high
catalytic rate constant with fast response time accredited to increased electron density
at the interface [64]. In a recent study, a new electrochemical sensory material based
on a ternary composite of silica-coated-CuBTC MOF-PAN-graphene was proposed
for the detection of NH3 gas. It showed high selectivity and sensitivity with LOD
for of 0.6 ppm due to synergetic effects of the materials [65]. In another study,
a cyclodextrin-based MOF (CDMOF-2) was reported to detect CO2 gas using the
impedance method. The reduction in ionic conductivity by 500-folds was observed
due to the loss of –OH base ions that help in catalytic deprotonation of the methanolic
medium. The sensitivity was affected by the reaction rate related to carboxylation,
and it is relatively high at a low concentration of CO2 [66]. Another study reported
a Ni-MOF-74 modified IDE sensor for impedimetric detection of NO2 gas. The
sensor showed a sharp decline in impedance magnitude within 4 h of exposure to
NO2 gas, indicating its superior sensing response [67]. In another report, a novel
solid-state electrochemical sensor was developed based on MOF-derived Co3 V2 O8
for the detection of NO2 gas (Fig. 4a). The sensor showed a high sensing response
(78.2 mV/decade) toward NO2 in a detection range of 50–500 ppm at 575 °C. It also
exhibited long-term stability, reproducibility, and anti-interference ability toward
other gases such as CH4 , CO2 , O2 , NO, and CO. The mixed potential mechanism
justified the enhanced sensitivity and selectivity of the sensor [68].
164 Z. Khanam et al.

Fig. 4 a Schematic diagram of NO2 detection by Co3 V2 O8 MOF sensor [68]; b schematic illus-
tration of the electrochemical aptamer sensor for detection of Pb(II) ion. Reprinted with permission
from [69] Copyright 2017 Elsevier B.V

4.3.2 Detection of Water Pollutants

Various MOF-nanocomposite-based electrochemical sensors have been developed

for the detection of HMIs in water. For instance, a conductive polyaniline (PANI)
polymer-UiO-66-NH2 MOF composite (UiO-66-NH2 -PANI)-based sensor was
fabricated for electrochemical detection of Cd(II) using DPSV. It demonstrated excel-
lent repeatability with a LOD of 0.3 μg L−1 . The sensing mechanism was attributed
to the fast diffusion of electrons/ions in the matrix due to the chelation between
7 Advancements in 2D Nanomaterial Composites-Based … 165

Cd(II) and the amine groups of composite [70]. In a recent report, interfacial poly-
merization was adopted to prepare a free-standing polypyrrole-MOF hybrid film for
electrochemical detection of Cd(II) using SWASV. It exhibited excellent selectivity
and sensitivity with a LOD of 0.29 μg L−1 , which is significantly below the standard
value for Cd(II) in drinking water [71]. Yet another study reported the fabrication
of a lead (Pb)-specific-aptamer (LSA) enzyme-free electrochemical sensor based on
AgPtNPs/MIL-101(Fe)-MOF which acted as sensing probes and signal enhancer.
The DNA immobilized AgPtNPs/MIL-101(Fe)-MOF exhibited redox activity along
with the superior electrocatalytic activity. In the presence of Pb(II) ions, the LSA
grabbed the signal through a DNA hybridization reaction and the signal amplified
with electrocatalysis of AgPtNPs/MIL-101(Fe) which promoted the electron transfer
at the interface (Fig. 4b). In consequence, the sensor anticipated excellent Pb(II)
specificity and stability with LOD of 0.032 pM in a wide detection range from 0.1 pM
to 100 nM [69]. In another study, a simple solvothermal method was used to prepare
Zn-MOF/GO composite modified GCE for electrochemical sensing of As(III) using
DPASV. The sensor showed a high response with LOD of 0.06 ppb in the detection
range of 0.2–25 ppb (μg L−1 ) and good reproducibility [72]. Another study reported
the preparation of thin-film zirconium-porphyrin MOF (MOF-525) by solvothermal
method for amperometric detection of nitrite. The high sensing response with LOD
of 2.1 μM was due to the electrocatalytic oxidation of nitrite which contributed to
fast charge transfer at the sensing surface [73].

4.4 Phosphorene and Other 2D Elemental

Nanomaterial-Based Sensors

2D mono-elements (such as phosphorene, arsenene, silicene, etc.) are emerging as

outstanding materials for widespread applications [74–76]. Among them, phospho-
rene (black phosphorus) is gaining significant interest in sensing applications owing
to its remarkable characteristics including ultrahigh surface–aspect ratio, anisotropic
electric conductance, high electrochemical activity, tunable direct bandgap, and
excellent carrier mobility [10, 77–82].

4.4.1 Detection of Toxic Gases

An impedimetric sensor based on layered black phosphorus (BP) modified IDE

(BP@IDE) was developed for selective quantification of methanol vapor, showing
LOD of 28 ppm (Fig. 5a). On exposure to methanol vapor, it exhibited a high
impedance response, while the capacitance decreased at the BP@IDE interface,
suggesting its superior selectivity and sensitivity [83]. In another study, an electro-
chemically synthesized platinoid-decorated few-layer phosphorene was employed
166 Z. Khanam et al.

Fig. 5 a Impedance module for layered BP@IDE in the absence (air) and the presence of 1140 ppm
methanol vapor (experimental (••••) and simulated (—) data) and equivalent electrical circuit model
(inset). Reprinted with permission from [83] Copyright 2015 Wiley. b Schematic illustration for
sensing mechanism of PEI-BP composite, compared to BP for reduction of Cu(II). Reprinted with
permission from [87] Copyright 2019 Elsevier. c Schematic illustration of graphene-BP nanocom-
posite modified GCE fabrication for electrochemical sensing of BPA at different concentrations.
Reprinted with permission from [88] Copyright 2019 Elsevier B.V

for the detection of methanol vapor using impedance measurements. The high selec-
tivity and sensitivity were attributed to change in local carrier concentration at elec-
trode due to the adsorption of gas molecules on phosphorene which induced variation
in impedance sensing signals [84]. Another study reported the gas sensing proper-
ties of exfoliated BP. The BP modified IDE was tested for sensing of oxidizing
gases (NO2 , CO2 ) and reducing (NH3 , H2 , CO) gases using a volt–amperometric
method at room temperature. The sensor showed high selectivity and p-type sensi-
tivity toward NO2 and NH3 with LOD of 20 ppb and 10 ppm, respectively. Also, a
steady sensing response was recorded for H2 ; however, no signals were observed for
CO and CO2 . The mechanism was justified based on the structural morphology of BP
and the binding energies of the adsorbed gas molecules [85]. Apart from this, other
2D elemental materials are at the evolutionary stage and very few reports are avail-
able on gas sensing applications. One of the recent studies is based on a few-layered
arsenene modified IDE sensing interface employed for impedimetric detection of
VOCs (methanol, ethanol, chloroform diethyl ether, acetonitrile, tetrahydrofuran,
acetone, hexane, dichloromethane). Compared to others, a notable phase shift in
resonance frequency was analyzed for methanol, suggesting ultrahigh sensitivity
and selectivity [86].
7 Advancements in 2D Nanomaterial Composites-Based … 167

4.4.2 Detection of Water Pollutants

Recently, a polyethyleneimine PEI-BP composite was synthesized via the single-

step electrostatic adsorption method and deposited over GCE for its application in
electrochemical sensing of Cu(II) using amperometry. The sensor achieved a fast
response (1.5 s) and high sensitivity with a LOD of 0.02 μM in a wide detection
range of 0.25–177 μM, which is much below permissible limits for Cu(II) according
to EPA drinking water standards. The superior performance was explained due to
the synergistic effect of BP and PEI which enhanced the intercalation and adsorption
of Cu(II) (Fig. 5b). PEI acted as an agent to specifically capture Cu(II) for BP
and improved its electrochemical reduction while providing stability to BP. The
presence of abundant N atoms favored PEI Cu(II)-PEI chelation which increased
the reaction sites and eventually resulted in a high reduction current. The sensing
efficiency of nanocomposite was also tested in real water samples by fabricating a
flexible PEI-BP modified SPE and successfully employing it for selective detection
of (II) in river water [87]. In another study, porous graphene functionalized BP
nanocomposite (Gr-BP) was prepared for electrochemical detection of bisphenol-
A (BPA) in plastic water bottle samples using DPV (Fig. 5c). The sensing involved
the diffusion-controlled electrochemical oxidation of BPA, where the trace levels are
quantified in a wide detection range of 4 × 10−8 ~ 5 × 10−5 mol L−1 with LOD of 7.8
× 10−9 mol L−1 along with good response time and stability [88]. Further, a recent
study reported the fabrication of BP quantum dots doped ZnO modified GCE sensing
platform for detection of H2 O2 in tap water samples using amperometry. The high
sensitivity of 195.4 μA mM−1 cm was delivered by the sensor in linear range from
5 μmol L−1 to 0.05 mmol L−1 along with excellent response and repeatability [89].
Next, a novel aptamer sensor based on hexamethylenediamine (HA)-coated AuNPs-
BP nanocomposite was developed for electrochemical detection of polychlorinated
biphenyl (PCB77) in tap water samples using DPV. It exhibited excellent sensitivity
of 391.1 μA cm−2 and LOD of 33 pg L−1 with high reproducible efficiency [90].

5 Conclusions

Conclusively, the advancements in electrochemical sensors based on 2D nanoma-

terials composites (mainly TMDs, MXene, MOF, and phosphorene) have been
discussed in the context of their significance toward combating environmental pollu-
tion. The fascinating physicochemical properties of 2D nanomaterials, such as unique
morphological structure, large specific surface area, tunable bandgap, and good
mechanical stability, encouraged lots of research toward designing active sensing
platforms for the detection of toxic gases and water pollutants. Several fabrica-
tion strategies to achieve superior sensing performance using 2D nanomaterials have
been highlighted in this chapter, such as the creation of heterostructure, hybridization
with other materials, compositing with polymers, or immobilization with enzymes.
168 Z. Khanam et al.

In addition, the fundamental principles in electrochemical detection such as poten-

tiometry, voltammetry, amperometry, and impedance have been briefly described.
The chapter has overviewed the research studies from the past decade on developing
novel, reliable, efficient 2D nanocomposites-recognition element/sensory systems
which act as or are responsible for signal amplification or transduction. The experi-
mental results of detection limit, selectivity, stability, and reproducibility for different
2D nanocomposite-based electrochemical sensing devices toward a diverse range of
contaminants, particularly, toxic gases, VOCs, heavy metals, nitrites, etc., have been
summarized. It is seen that the progress in the fabrication strategies and integrated
device designing has largely advanced the development of 2D nanocomposites-based
electrochemical sensors with desired strong interfacial interactions. From the survey,
it is ascertained that the inherent 2D basal plane ensures rich-active sites for host–
analyte interactions as well as shortens the ion diffusion paths which effectively facil-
itates the charge transfer processes and consequently enhances the sensing response.
Nevertheless, 2D nanocomposites-based electrochemical sensors are still far behind
real applications and need tremendous research effort to develop sensing devices for
real-time onsite monitoring of air/water contaminants as a future perspective.

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Chapter 8
Trending 2D Nanomaterial Composites
in Detection and Sensing of Biological
Contaminants

Jayanta Sarmah Boruah, Sristi Majumdar, Ankita Deb, Jahnabi Gogoi,

and Devasish Chowdhury

1 Introduction

Nanomaterials are small-sized materials that typically have at least one dimension
ranging from sub-nanometers to hundred nanometers. The materials in nanometer-
scale differ in their physical and chemical properties significantly from those of bulk
counterparts of the same composition due to an increase in surface area, tunable
mechanical, electrical, and optical phenomena. With the evolution of facile, low-
cost, efficient, and innovative synthetic protocols for the synthesis of nanomaterial
and advanced characterization techniques, nanomaterials in diverse applications have
attracted immense attention among the scientific community. As such, the range of
applications of nanomaterials has broadened to biomedical, electronics, chemical
processes, building materials, catalysis, etc. Particle size is an important aspect of
nanomaterials, and with the difference in sizes, the properties and the function of the
nanomaterials also vary. In 2D nanomaterials, the electron confinement is restricted to
only one dimension resulting in a quantum well or plane. Ever since the first isolation

All the Authors contributed equally.

J. S. Boruah · S. Majumdar · A. Deb · J. Gogoi · D. Chowdhury (B)

Material Nanochemistry Laboratory, Physical Sciences Division, Institute of Advanced Study in
Science and Technology, Paschim Boragaon, Garchuk, Guwahati 781035, India
e-mail: [email protected]
J. S. Boruah
e-mail: [email protected]
S. Majumdar
e-mail: [email protected]
A. Deb
e-mail: [email protected]
J. Gogoi
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 173
Z. Khanam et al. (eds.), 2D Nanomaterials for Energy and Environmental Sustainability,
Materials Horizons: From Nature to Nanomaterials,
https://doi.org/10.1007/978-981-16-8538-5_8
174 J. S. Boruah et al.

of graphene in 2004 [1], an increasing addition into the library of 2D nanomaterials

has been observed, which includes materials such as transition metal dichalcogenides
(TMDs) [2], hexagonal boron nitride [3], 2D metal oxides/sulfides [4, 5], transition
metal carbides, nitrides, carbonitrides (MXenes) [6–8], graphitic carbon nitride [9],
black phosphorus [10], layered double hydroxides (LDHs) [11], silicene [12], and
so on. The overall types, significant properties, and their use in different areas can
be represented in Fig. 1.
2D nanomaterials have a high surface-to-volume ratio compared to other nano-
materials with dense active surface sites in a large area, making them a very suitable
material for various biosensing applications. Moreover, through surface function-
alization and the introduction of defects, 2D materials can be made as desired for
selective and sensitive detection of different analytes [13]. The active surface binding
sites in a sensor material increase with the increase in surface area that results in
enhanced interaction between the sensor and analyte. This, in turn, contributes to
a greater modulation in the electrical properties of the material system, creating a
sensitive method with a lowered limit of detection (LOD) [14]. The surface area
per gram (SAPG) of a material is the deciding factor for the LOD of a nanomate-
rial system. Monolayer graphene was reported to have the highest SAPG value of
2630 m2 /g among the nanomaterials [15]. Also, for 2D nanomaterials, as the number

Fig. 1 A representative view depicting the types, properties, and various applications of 2D
nanomaterials. Source “Author”
8 Trending 2D Nanomaterial Composites in Detection and Sensing … 175

of layers decreases, the SAPG value increases while going from bulk to a few layers
[16]. Therefore, 2D nanomaterials are proven to be an excellent candidate for sensing
and identification of wide-ranged chemical as well as biological analytes.
Biological contaminants are a category of toxins including bacteria, viruses,
fungus, protozoa, and insects that can cause serious health hazards and environ-
mental issues by affecting food, air, water, and soil. These contaminants cause
various diseases like molds and pollens that can cause allergies to significant human
populations. It is noted that foodborne illness is primarily driven by contaminants
like pathogenic microorganisms. Aflatoxins, one of the cancer-causing mycotoxins
(fungal toxins), are related to agricultural grain contamination leading to serious
fatalities. These molecules can be devastating when they get into the body of other
organisms [17]. The degradation of air quality due to such biological toxins is also
alarming. The growth and spreading of such contaminants are primarily affected
by temperature, relative humidity, sources of nutrients, and air motion. Identifying
such biological contaminants and their source, which is causing a particular human
disease, is very difficult and hence their prevention [18]. Therefore, attempts are
being made to detect or sense them by utilizing various external systems made up of
organic or inorganic substances. The involvement of nanostructures has demonstrated
paramount importance for the detection and sensing of such microscopic toxins.
Among them, 2D nanomaterials are considered as superior platforms to perform
such critical detections due to their unique physicochemical properties attributed to
their ultrathin layers. Some of the 2D nanomaterials mentioned above are directly or
indirectly linked with the detection and sensing of biological contaminants. Most of
them have also been involved in environmental pollutants sensing (like toxic gases
and heavy metals) [19]. Here, in this chapter, we have discussed the use of different
2D nanomaterial and their composites that have been studied and reported for the
sensing and detection of different biological contaminants.

2 Different Types of Sensors

Typically, as illustrated above, sensors are platforms that can collect a physical,
chemical, or biological change, and a measurable signal is used for identification.
Basically, it is a material with some affinity for a particular analyte of interest owing
to the presence of some binding sites on it. In the case of a biosensor, a biolog-
ical component is combined with a physicochemical detector to find the presence
of different biomolecules like proteins, DNA, aptamer, amino acid, and microbial
toxin by the base material showing significant changes like color, conductivity, fluo-
rescence behavior depending on the properties of the target. Biosensors are always
associated with an enzyme or an antibody, or even microbial components. On the
other hand, chemosensors can detect chemical compounds which are also very much
selective to the functionality of those analytes. Nanomaterials and their compos-
ites are well known for their capability to work as both biosensors and chemosen-
sors. Sensors can be categorized based on the transducer or the detector element
176 J. S. Boruah et al.

Fig. 2 A typical biosensor with its components and basic principle. Source “Author”

like (a) electrochemical, (b) optical, (c) calorimetric, (d) piezoelectric, (e) microbial
biosensor, (f) enzyme biosensor [20, 21].
In principle, the biological/chemical part of the sensor interacts with the specific
analyte generating a signal that can be studied using the transducer element. For a
biosensor, the essential components are a bio-recognition site, transducer component,
and electronic system, which consists of a signal amplifier, processor, and display.
Membrane, enzyme, antibody/antigen, receptor, protein, intact cells, tissue, or whole
organ can be used as bio-recognition sites. A schematic of a typical biosensor with
its sensing principle is shown in Fig. 2.
The mechanism for some important types of sensors is discussed below.

2.1 Fluorescence-Based Sensors

The fluorescent sensing techniques are developed and appreciated over the last
few decades as a highly sensitive and selective technique for the use as an ideal
biosensor. However, various working strategies can be observed for the detection
of various analytes. Different molecules exhibit fluorescence in their natural state,
and certain modifications can cause minor to major changes in their fluorescence
intensity. This property is utilized to develop simple fluorescence-based biosensors.
However, various fluorescent labels are used for the detection of non-fluorescent
analytes. Fluorescent labels are strategically attached to the analyte via any reactive
group such as carboxyl, sulfhydryl, hydroxyl, or amino groups that assists in forming
a chemical linkage. Aptabeacon is one of the most commonly used formats among
fluorescence aptasensors [22]. The hairpin-like structure at the end of aptabeacons is
labeled with a quencher and a fluorophore. Attachment of the target molecule with
8 Trending 2D Nanomaterial Composites in Detection and Sensing … 177

the aptamer disrupts the initial confirmation of the Forster resonance energy transfer
(FRET) pair, causing a turn-on fluorescence signal. The fluorescent label must be
selectively excitable without exciting the other components in the system and must be
able to generate a clear, demonstrable signal. Certain examples of different types of
fluorescence labels are organic dyes, nanomaterials as fluorophores, and quenchers.

2.2 Field-Effect Transistor (FET)-Based Sensors

Field-effect transistors (FET) are mainly used as chemosensors [23]. The system
consists of parts like source and drain electrodes, a channel, an insulating gate oxide,
and a gate electrode [24]. The channel is composed of a semiconducting material
sensitive to the target analytes. It is operated by monitoring the change in current in
the channel before and after the adsorption of target molecules [23]. When the current
flows through the channel, it is called the drain current, I DS . I DS can be modulated by
an electric field perpendicular to the semiconductor resulting from the voltage (V GS )
applied. The I DS is given by
 
Ci µW 1
I = (VGS − Vth ) − VDS VDS
L 2

where C i is the capacitance of the gate insulator per unit area,

µ is the charge carrier mobility in the channel,
W /L is the width-to-length ratio of the channel,
V GS and V DS are the applied gate-source and drain-source voltage, and
V th is the threshold voltage required on the gate to create charge carriers.
When V DS << (V GS − V th ), it signifies a linear region and, when V DS > (V GS −
V th ), it denotes a saturation region. At low drain-source voltages, the I DS current
is proportional to V DS (at constant V GS ) following Ohm’s law. FET sensors are
known to operate in the linear range of I DS . Besides this, the bandgap is another
important parameter to consider for the performance of a sensor [23]. In the FET-
based sensors, the type of semiconductor (p-type/n-type), the morphology of the
sensing materials, and reactivity of the analyte (reducing/oxidizing) will control the
electrical conductivity [25, 26]. FET-based sensors have attracted attention because
of the varied features like miniaturization, parallel sensing, high sensitivity, and
selectivity. One notable advantage is that FET sensor platforms can work in both
gas and liquid environments, making the detection for a wide range of analytes,
including gases, ions, and biomolecules easier [23, 25]. For example, 2D MoS2 was
integrated into a FET device to detect NO by exhibiting n-type dopant behavior [23].
Because of the flexibility of modulating the charge carrier mobility by controlling the
gate voltage, FET devices are used to increase the sensitivity compared with other
device architectures. However, the integration of materials into FET devices requires
178 J. S. Boruah et al.

advanced techniques such as lithography and a high degree of control over material
morphology.

2.3 Colorimetric Sensors

Colorimetric sensors are a class of optical sensors that change color under the influ-
ence of external stimuli (temperature, pH, radiation, etc.). Colorimetric sensors are
extensively used for the sensing of protein, DNA, pathogens, heavy metal ions,
toxic gases, and organic compounds. It is used to sense biological contaminants,
particularly on-site detection compared to plate colony counting method, polymerase
chain reaction (PCR), and ELISA [27–29]. Mainly, colorimetric detection of bacteria
involves enzymatic assay and glucose metabolism but has some limitations asso-
ciated with enzymatic instability. Hence, the incorporation of diverse nanomate-
rials comes into the picture. Metal nanoparticles have unique optical properties like
surface plasmon leading to a noticeable change in the color by aggregation or surface
chemical reaction [30, 31]. With various surface modification using DNA, RNA,
and antibodies, they perform a rapid and sensitive colorimetric response to target
bacteria. Typically, conjugation of pathogen-specific receptors like antibodies or
DNA aptamers on the surface of nanomaterials can detect bacteria via sandwich-type
colorimetric assay procedures [32].

2.4 Electrochemical Sensors

Electrochemical sensors are designed for rapid, sensitive, and reliable recognition of
the presence of pathogens [33]. There are basically three common electrochemical
methods for pathogen detection: voltammetric, potentiometric, and impedance spec-
troscopy. Voltammetry method of detection captures the change in the potential that
is applied as a function of time to the electrode–solution interface and measures the
current in the process [34]. In potentiometric methods, the pathogens are detected
by the change that occurs in current/potential when the electrode is kept at a fixed
potential/current with respect to the reference electrode. In impedimetric methods,
the sensor detects the change in impedance as a function of frequency with applied
potential. Here, the biological recognition factors such as nucleic acids, aptamers,
antibodies, bacteriophages are immobilized onto the sensing surface through adsorp-
tion, entrapment, or covalent linkage methods [35]. Two kinds of strategies come into
play while sensing pathogens. In one case, the bare electrodes or modified electrodes
with the bio-receptors are subjected to changes in current or potential when they
encounter some targeted or untargeted analyte. In the other case, the metabolites
secreted by the pathogens are detected [36].
8 Trending 2D Nanomaterial Composites in Detection and Sensing … 179

3 Preparation of 2D Nanocomposite-Based Sensors

2D nanomaterials are well known for their sensing ability toward different toxic gases,
hazardous chemicals, pathogenic microbes, and many bioactive molecules. The high
surface area-to-volume ratios and multiple reaction sites on 2D nanomaterials are
the leading factors to fabricate chemical and biosensors with high performance. 2D
nanomaterials that are being used for the sensing of biological contaminants are
graphene family, transition metal dichalcogenides, Mxenes, and their composites
and phosphorene family [37, 38].
Graphene is advantageous as a sensing platform because different bioreceptor
ligands can be integrated densely onto the surface through non-covalent, covalent, π–
π, and electrostatic interaction [39]. But graphene facilitates interactions with blood
serum components when these sensors are used for real-time application creating
limitations [40]. As reduced graphene oxide (rGO) is more conducting than graphene
itself, rGO is extensively used to fabricate electrochemical labels. In general, an elec-
trochemical sensing layer is fabricated using a thermal reducing agent to deposit rGO
on nanocellulose paper or using electrophoretic deposition of rGO/polyethylenimine
(PEI) on gold electrode or rGO coated on gold nanoparticles (AuNPs) is used.
Another 2D nanomaterial that is being used is transition metal dichalcogenides.
The most widely used transition metal dichalcogenides (TMD) are MoSe2 and MoS2 .
2D nanomaterial MoSe2 and MoS2 are synthesized by a hydrothermal process at
200–220 °C. MoS2 can also be obtained by electrodeposition on a gold electrode or
in-situ prepared with AuNPs to form MoS2 -AuNPs nanocomposite, which can be
subsequently deposited on the electrode. MoS2 can also be fabricated via a simple
ultrasound exfoliation method.
MXenes are another unique 2D nanomaterial having layered morphology that
includes early transition metal carbides, nitrides, and carbonitrides. MXenes, in
general, are prepared by exfoliation of Ti3 AlC2 in 40–50% hydrogen fluoride (HF)
at room temperature for 2 h.
Two-dimensional-layered semiconductor material known for its unique single-
layer feature is phosphorene. Black phosphorene (BP) nanosheets can be prepared
by mechanical exfoliation. BP can also be prepared by sonochemical exfoliation with
in-situ reduction of BP on HAuCl4 to form BP-Au nanocomposite.
In the following section, the use of 2D nanomaterials in the detection and sensing
of biological contaminants is described in detail. What strikes out in these examples
is that the mostly utilized technique in the fabrication of detection and sensing system
for biological contaminants is electrochemical sensing platform. This could be due
to the large surface area of 2D nanomaterials which can be modified to tune the
conductivity to felicitate electron transfer between electrochemical species and the
underlying electrode surface.
180 J. S. Boruah et al.

4 2D Nanomaterials for Detection and Sensing of Biological

Contaminants

4.1 Nanomaterials from Graphene Family and Their

Composites

Nanomaterials derived from carbon and other sources serve a better purpose owing to
their high surface area as compared to their traditional adsorbent counterparts, such as
activated charcoal [41]. Out of the various nanomaterials, graphene and its compos-
ites have been widely used for the same. Graphene has sparked great interest for an
exceptionally large surface area, high thermal, and electron mobility. In graphene,
carbon atoms are hexagonally arranged in sp2 bonded aromatic structures [42, 43].
It is obtained by exfoliation of graphite which contains a stack of sheets with an
interlayer spacing of 3.34 Å between them [44]. Micromechanical exfoliation of
the graphite into single-layer graphene sheets by ultrasonication in organic solvents
[45] and chemical vapor deposition (CVD) method for large-scale production were
some of the many ways for the synthesis of graphene [46]. Currently, the most studied
graphene nanomaterials are graphene oxide (GO) and reduced graphene oxide (rGO)
[47]. GO possesses abundant oxygen-containing functional groups providing scope
for further modification, whereas rGO is obtained by removing these oxygen func-
tionalities through reduction routes [48]. Each atom of the single layer of graphene
has maximum exposure to the environment, thereby having the highest surface area
(2630 m2 g−1 ) among all the nanomaterials [49]. As such, graphene, GO, rGO, and
their composites can be effectively used for wide-ranged applications, particularly in
the biomedical field [50]. Graphene and its nanocomposite materials have bacterial
inactivation properties [51]. Graphene nanocomposites of polymer and metal/metal
oxides are found to be the most promising in disinfecting microbial contamination
in water treatments [52]. Traditionally, nanocomposite systems were employed to
kill bacterial cells or to inhibit cell division. Although graphene and graphene-based
composite materials are used by many researchers as sensing platforms, their use in
sensing and detection of biological contaminants is limited. Mostly, electrochemical
sensors designed from graphene and graphene-based nanocomposites are reported
for the detection of biological toxins. A few examples are discussed below.
Electrochemical sensors: Burrs et al. [53] illustrated the electrochemical biosensing
of Escherichia coli, a pathogenic bacterium using a graphene paper functionalized
with platinum nano-cauliflower. The paper is conductive with a high electroactive
surface area of 0.2970.13 cm2 which has a LOD of 4 CFU mL−1 and a response time
of 12 min for E. coli O157:H7. Another work on detecting a uropathogenic bacteria
E. coli UTI89 in aqueous and serum samples was reported by Jijie et al. using
gold electrodes modified with rGO/polyethyleneimine (PEI) [54]. The selectivity
was induced by changing the electrode surface covalently with anti-fimbrial E. coli
antibodies and additional modification with pyrene-polyethylene glycol moieties.
The LOD obtained was 10 CFU mL−1 . Fei et al. explored the detection of a food
8 Trending 2D Nanomaterial Composites in Detection and Sensing … 181

pathogen Salmonella pullorum (S. pullorum) by the electrochemical immunoassay

with gold nanoparticles coated graphene oxide (rGO/AuNPs) and the immunomag-
netic beads (IMB). Using differential pulse voltammetry (DPV), LOD was found
89 CFU mL−1 [55]. A fast, selective, and ultrasensitive detection of Staphylococcus
aureus (S. aureus) was reported by Hernández et al. using a potentiometric biosensor
based on chemically modified graphene and aptamers [56].

4.2 Transition Metal Dichalcogenides and Their Composites

The lack of an intrinsic bandgap in pure graphene and limited chemical modifica-
tion has prompted the scientific community to search for other 2D nanomaterials
with semiconducting properties. Transition metal dichalcogenides (TMCs) are a
group of inorganic materials of the general formula, MX2 , where M is a transi-
tion metal typically from groups 4–10, and X stands for chalcogen series (such as
S, Se, and Te) [57]. The structure of TMCs is like that of sandwiches wherein X–
M–X is stacked together by the covalent bonding of trilayers and monolayers along
the crystallographic c-axis (0, 0, 1) [58]. They have mainly three structural poly-
types; 2H (hexagonal symmetry), 3R (rhombohedral symmetry), and 1T (tetragonal
symmetry) [58, 59]. The symmetry of MX2 can either be trigonal prismatic (D3h ) or
anti-prismatic (D3d ) with a coordination number 6 [60]. The bandgap ranges from
0 to 2 eV for semimetal and semiconductor structures depending on the number
of layers, the presence or lack of doping atoms, and elemental composition [56,
61]. The underlying van der Waals interactions between the layers make TMCs a
unique material for interlayer diffusion susceptible to high charge mobility [58, 62].
The preparation of TMD monolayers requires mechanical exfoliation by ultrasonica-
tion, electrochemical exfoliation, hydrothermal method, CVD, etc. The exfoliation
process results in a higher degree of monolayers with high aspect ratios and a greater
number of monolayers in a polymer matrix [58, 63].
The high specific surface area, along with the possibility of surface treatment,
makes TMCs monolayer a suitable choice for designing different polymer composites
[64, 65]. Among the different TMCs, the group VI TMCs, MoS2, and MoSe2 show
excellent physicochemical properties and biocompatibility [66, 67]. There are several
reports of TMCs-based nanocomposites acting as electrochemical biosensors for
sensing various biological contaminants. Most of the detection techniques use the
strategy of fabricating aptamer-based-electrosensors because of the lack of cross-
reactivity, thereby high specificity toward the target analyte giving instant response
in the electrochemical signal. Following are some examples of detection of microbial
toxins by TMCs based on electrochemical techniques.
Electrochemical sensors: Among many bacterial toxins, Salmonella paratyphi is the
food-borne pathogen that causes paratyphoid A fever [68]. Mishra et al. designed a
MoSe2 -modified aptasensor to detect the Salmonella bacteria [69], where an aptamer
functionalized with amine, and specific to the bacteria was incorporated onto MoSe2
182 J. S. Boruah et al.

Fig. 3 Illustration of the electrochemical immunosensor for detection of ZEA in biofluids based
on MoS2 -Thi nanocomposites. Reproduced with permission from Ref. [74]

nanobroom-modified fluorine-doped tin oxide by cross-linking with glutaraldehyde.

The study showed good linearity of detection ranging from 10−2 to 10−10 CFU/mL
with a low LOD of 1 × 10−10 CFU mL−1 . Considering the detection of fungal
toxins, the most toxic aflatoxin, AFB1 [70], was detected by building an electrochem-
ical aptasensor based on tetrahedral DNA nanostructures (TDNs), immobilized on
macroporous MoS2 -AuNPs hybrids [71]. This hybrid was able to increase the immo-
bilization amount of TDNs, thereby also facilitating the mobility of electrons. The
aptasensor showed a LOD of 0.01 fg mL−1 . The system could detect AFB1 in grain
products such as wheat powder and rice samples.
Wang et al. fabricated a methylene blue (MB)-modified OTA (Ochratoxin A,
mycotoxin causing nephrotoxicity) aptamer on the MoS2 nanosheet/AuNP (MoS2 -
AuNP) nanocomposite that is surrounded by gold electrode via host–guest recog-
nition of β-cyclodextrin (β-CD) [72, 73]. The aptasensor possesses satisfactory
results with detection ranging from 0.1 to 50 nmol L−1 and sensitivity (LOD) of
0.06 nmol L−1 . Another mycotoxin produced by Fusarium, zearalenone (ZEA), was
detected by Jiang et al. by constructing an electrochemical immunosensor based on
thin-layer MoS2 and thionin (MoS2 -Thi) composites (as shown in Fig. 3) that were
used as electrochemical probes [74]. The MoS2 -Thi-based immunosensor showed
a linear range of 0.01–50 ng mL−1 , low LOD (0.005 ng mL−1 ZEA) carried out in
both urine and plasma.
Microcystins (MCs), a group of algal toxins, are associated with multiple
health issues, and their toxicity is evaluated from the Microcystin-LR (MC-LR)
content. Pang et al. constructed an enzyme-free electrochemical immunosensor
for detecting MC-LR using MoS2 nanosheets/BSA-stabilized gold nanocluster
(MoS2 /AuNCs) nanocomposites and Au core/Pt shell nanoparticles (Au@PtNPs)
[75]. The immunosensor exhibits LOD of 0.3 ng L−1 for MC-LR in various water
samples.
8 Trending 2D Nanomaterial Composites in Detection and Sensing … 183

4.3 Mxene Family

Another unique two-dimensional nanomaterial of layered morphology consists of

MXenes that include early transition metal carbides, nitrides, and carbonitrides.
MXenes are obtained from layered hexagonal MAX phases having a general formula,
Mn+1 AXn , where M is an early transition metal, A denotes elements of Group 13
and 14 of the periodic table, and X is either carbon or nitrogen [76]. The multilayer
structured MAX phase is composed of alternating layers of M and A consisting of a
strong mixed metallic-covalent (M–X) bond and weak M–A bond [76, 77]. Modula-
tion of layer A from the MAX phase emerges from highly stabilized closed packed
Mn+1 Xn Tx nanosheets, termed MXene [78]. Here, T stands for surface terminating
groups of etched MXenes such as –O, –F, –OH produced due to chemical etching.
As predicted by DFT calculations, the surface termination is the controller of surface
activating properties. The monolayer of MXene is said to be metallic with high
electron density [62].
Titanium carbide (Ti3 C2 ) is the most explored Mxene. It is prepared by exfoliation
of Ti3 AlC2 in 50% hydrogen fluoride (HF) at room temperature for 2 h. The aqueous
HF solution acts as an etching agent to remove the Al layer, followed by adding a
surface termination group to the exfoliated layers to finally form Ti3 C2 (OH)2 and/or
Ti3 C2 F2 [79]. Interestingly, one study showed higher antibacterial activity toward
both gram-negative (Escherichia coli) and gram-positive (Bacillus subtilis) compared
to that of graphene [80].
The non-toxic degradation by-products (CO2 , N2 ) of MXenes make them suitable
for environmental remediation applications [81]. The metallic character, tuneable
conductivity, and variety of functional groups make MXene an interesting 2D nano-
material for sensing applications. Their added advantage of hydrophilicity, biocom-
patibility, compared, and ease of functionalization with high intercalation capacity
[82] in comparison with the other 2D materials help in designing a sensor system to
be utilized at a commercial scale.
Although several works of MXenes as sensors have been used for the detection
of biomarkers, gases, and other environmental contaminants [83], the sensing of
biological contaminants/microbial toxins is not well-explored yet.
Electrochemical sensing: One report has found that MXene is used as an electro-
chemical immunosensor to detect gliotoxin, the most toxic mycotoxin produced by
Aspergillus fumigatus [85]. The biosensor was prepared by incorporating tetrahedral
DNA nanostructure (TDN) onto the surface of MXene nanosheets [84] (Fig. 4). The
presence of Ti on the MXene nanosheets provides an easy method for assembly via
a strong interaction between titanium and phosphate groups of TDNs, thereby elimi-
nating the requirement of complex chemical modification of TDNs generally required
for the immobilization of TDNs onto the electrode. The use of MXenes in designing
the sensor has helped enhance the sensitivity with the added benefit of providing
an ample surface area to incorporate a larger amount of TDN onto the electrode.
184 J. S. Boruah et al.

Fig. 4 Schematic representation of the TDN/MXene-based electrochemical sensors to detect

gliotoxin. Reproduced with permission from Ref. [84]

The biosensor exhibited a broad detection range to gliotoxin concentrations (5 pM–

10 nM) with a LOD of 5 pM. Such fabrication of MXene-based E-DNA biosensor
will open avenues for its applicability in detecting other biological contaminants.

4.4 Phosphorene Family

Phosphorene is another 2D layered semiconductor material and known for its unique
single-layer feature. It was first synthesized from black phosphorus using a scotch
tape-based micro-cleavage [86]. The resulting 2D material is layered dependent,
having a hinge-like structure, giving anisotropy in its structure, and behaves as a
quasi-one-dimensional excitonic nature that contrasts to those found in other 2D
nanomaterials [86–88]. 2D phosphorene, composed of sp3 hybridized phosphorus
atoms, represents layered orthorhombic crystal structure with space group Cmca [89].
It forms a honeycomb lattice structure with non-planarity in the form of structural
ridges [90].
The phosphorene monolayer reveals a tunable direct bandgap of the layers modu-
lating in the order of 1.51 eV for a single layer to 0.59 eV for a five-layer system [91].
This advantageous feature of phosphorene leads to high drain current modulation up
to 105 and charge mobility (~1000 cm2 V−1 s−1 ) [92]. The stacking of multiple 2D
8 Trending 2D Nanomaterial Composites in Detection and Sensing … 185

phosphorene is due to van der Waals interactions which form multilayers with an
interlayer distance of 5.5 Å [93].
The combination of the features like narrow bandgap, anisotropic electrical
conductance, and reactive edge structure makes 2D phosphorene suitable for an
application in electrically transduced sensing technologies [94]. Moreover, due to
its puckered honeycomb structure, it has high chemical adsorption energy offering
plentiful adsorption sites for interaction with analytes [94, 95]. The introduction
of structural ripples and dopants on the surface of black phosphorus (BP) helps in
improving sensitivity and charge transfer toward analytes [96].
Two-dimensional phosphorene has been used as electrochemical sensors for
the detection of gases, volatile compounds, different ions, and biomolecules
[97]. However, a few reports were found for electrochemical sensing biological
contaminants which are mentioned below.
Electrochemical sensors: A simple voltammetric method was reported for the sensing
of ochratoxin A (OTA) in food samples [98]. OTA is a fungal contaminant and is
categorized as Group 2B carcinogen by the International Agency for Research on
Cancer (IARC) [99]. It is known to be highly stable throughout the food chain,
imposing a threat to human beings. In this work, Xiang et al. fabricated a nanosensor
using BP nanosheets and functionalized it with Ag+ ions and employed the sensor to a
voltammetric analysis of OTA in food samples using DPV [98]. The detection of OTA
by an electrochemical sensing platform has a disadvantage of a strong fouling effect
on electrodes from the oxidation products of OTA [100]. However, functionalized BP
as an electro-sensor showed good stability, electrocatalytic ability, and strong anti-
fouling property toward OTA oxidation. The BP nanosensor can selectively detect
OTA in a linear way ranging from 0.3 to 10 μg/mL with a LOD of 0.18 μg/mL through
an irreversible electrochemical response with an adsorption-controlled process.
The easy functionalization and biocompatibility made this two-dimensional mate-
rial a promising transducer with an improved biosensor performance. This has
prompted the researchers to develop a unified apta-sensing system to detect okadaic
acid (OA, C44 H68 O13 ), a marine toxin produced by several species of dinoflagellates
known to accumulate in both sponges and shellfish, causing seafood poisonings.
Ramalingam et al. fabricated an electrochemical microfluidic biochip for detecting
OA by using a screen-printed carbon electrode (SPCE) [101] (Fig. 5). The SPCE
was designed with phosphorene-gold nanocomposite on which an OA specific to
an aptamer was immobilized and potassium ferro-ferricyanide was used as a redox
indicator.
Phosphorene when paired with AuNPs significantly enhanced the electrochemical
response and proved to be effective in creating the aptamer specific to OA without
flaking and displaying a LOD of 8 pmol L−1 . The electrochemical aptasensor has
excellent selectivity as it did not show any cross-reactivity with other types of food
toxins and is employed to detect OA in fresh mussel extracts. The results suggest
that the microfluidic electrochemical aptasensor can be applied as a POC device for
an on-field assay.
186 J. S. Boruah et al.

Fig. 5 a Graphical representation of the microfluidic chip to detect okadaic acid. b Schematic view
of the sensing process. Reproduced with permission from Ref. [101]

From all the work discussed above for the categories of 2D nanomaterials, it was
found that most of the reports are based on electrochemical sensing. A summary of
the 2D nanomaterial-based electrochemical sensors is tabulated, mentioning the type
of contaminant, the sensor element, and the respective LOD values (Table 1).

5 Other 2D Nanomaterials with Future Prospects

in Sensing of Biological Contaminants

The newer members of 2D nanomaterial; germanene and silicene family, boron

nitride and borophene family, tin, antimony, bismuth, tellurium family are still in
the nascent stage of the study. Different computational methods can be utilized to
study sensing through density-functional theory (DFT) which is a computational
quantum mechanical modeling method to investigate the electronic structure in atoms
or molecules. The ab initio DFT calculations (from first principles) predict the mate-
rial behavior following quantum mechanics avoiding the use of fundamental material
properties. Some theoretical functions are applied to the systems of interest to see the
properties. For instance, non-equilibrium Green’s function was recently employed to
study the anisotropic gas (CO, NO, NO2 and NH3 ) sensing properties of borophene
[102]. Although DFT-based studies have been reported for them, they need to be
supported by experiments to get correlated data. These newer 2D nanomaterials are
discussed in detail below.
8 Trending 2D Nanomaterial Composites in Detection and Sensing … 187

Table 1 2D nanomaterial-based electrochemical sensors

Detection Biological 2D LOD References
technique contaminant nanomaterial/nanocomposite
Electrochemical Escherichia Graphene paper 4 CFU mL−1 [53]
sensors coli functionalized with platinum
nano-cauliflower
Electrochemical Escherichia rGO/PEI 10 CFU mL−1 [54]
sensors coli
Electrochemical Salmonella rGO/AuNPs 89 CFU mL−1 [55]
sensors pullorum
Electrochemical Staphylococcus Graphene 1 CFU mL−1 [56]
sensors aureus
Electrochemical Salmonella MoSe2 1× [69]
sensors paratyphi 10−10 CFU mL−1
Electrochemical Aflatoxin, MoS2 -AuNPs 0.01 fg mL−1 [71]
sensors AFB1
Electrochemical Ochratoxin A MoS2 -AuNP 0.06 nmol L−1 [73]
sensors
Electrochemical Zearalenone MoS2-Thi 0.005 ng mL−1 [74]
sensors
Electrochemical Microcystins MoS2 /AuNCs and 0.3 ng L−1 [75]
sensors Au@PtNPs
Electrochemical Ochratoxin A BP nanosheets 0.18 μg/mL [99]
sensors
Electrochemical Okadaic acid Phosphorene-gold 8 pmol L−1 [102]
sensors nanocomposite
Electrochemical Gliotoxin MXene nanosheets 5 pM [86]
sensors

5.1 Silicene and Germanene Family

Silicene, an allotrope of silicon, is a 2D nanomaterial with a hexagonal honeycomb

structure like graphene. The stronger coupling between layers in silicene compared
to multilayered graphene contributes to its non-flatted structure. The hybridization
in silicene is sp2 -sp3 mixed hybridization [103]. In recent years, elemental sheets
of silicon (silicene) and germanium (germanene) are emerging as strong candidates
in the realm of 2D nanomaterials [104]. The greater binding affinity of common
contaminants than that for graphene is based on their hybridization. Moreover, both
the silicene and germanene with their buckled honeycomb structures possess higher
reactivity than graphene, showing sensitivity to various pollutants [105]. The silicene
synthesis has already been successfully carried out on different metal substrates
[92], while germanene was made on Pt (111) surface. The report of the multilayer
germanene exfoliated on SiO2 /Si surface is well-established [106]. As of now, no
188 J. S. Boruah et al.

such sensors (fluorescent, FET, electrochemical, colorimetric) have been developed

except for some density-functional theory (DFT)-based systems as discussed below.
Silicene and germanene have been investigated so far to detect toxic gases like
H2 S, CO2 , SO2 by incorporating defects into them, with the help of DFT [92, 107].
Theoretical studies suggest that doping with B, Al, N, and P could produce effec-
tive silicene over pristine one in terms of sensing. Another theoretical research on
these two systems revealed that biomolecules like DNA nucleobase, amino acid, and
heterocyclic molecules could be efficiently adsorbed. This suggests that they have
tremendous potential to work for other sensing materials [108]. However, this field
remains unexplored, with no report of the use of silicene and germanene in detecting
biological contaminants.

5.2 Boron Nitride and Borophene Family

Boron nitride (BN), with layered hexagonal microstructure, has recently received a
lot of attention owing to its unique properties like thermal stability, increased mechan-
ical strength, and oxidation resistance [109]. The C–C bonds in BN nanomaterials
(BNN) present a partial ionic character, and BNN has high electronegativity. This,
in turn, results in enhanced optical, electronic, and mechanical properties [110]. The
excellent biocompatibility of BNN has grasped the attention of scientists for their
possible application in the biological field [111]. Balmain in 1842, first demonstrated
the synthesis of BN [112]. Monodispersed 2D BNN can be synthesized via modified
solid-state metathesis reaction [113, 114].
However, BNN has played a significant role in the detection of biological contam-
inants. Yang et al. in 2019, synthesized graphene oxide and BN 2D nanomembrane
for the effective removal of antibiotics from water [115]. Chao et al. showed the
adsorption capacity of hexagonal BN (g-BN) for fluoroquinolone antibiotic gati-
floxacin (GTF) to be more than 90% [116]. Adsorption efficiency of g-BN increases
with higher temperature, indicating that adsorption is exothermic. The primary
removal mechanism was determined to be electrostatic interaction as the adsorp-
tion of GTF is inversely proportional to the ionic strength. BN nanosheets were
synthesized to demonstrate their efficiency for the pre-concentration of chlortetracy-
cline hydrochloride (CTC), tetracycline (TC), norfloxacin (NOR), and ciprofloxacin
(CIP) [117]. More aromatic rings in CTC and TC resulted in their higher sorption
by BN nanosheets. Recently, Zhi et al. demonstrated the immobilization of proteins
in BN nanotubes via electrostatic interactions and π–π interactions [118]. Lin et al.
also demonstrated that BN nanosheets in water displayed excellent affinity toward
proteins with an adsorption capacity of 312 mg/g at room temperature [119]. But the
2D BN nanomaterial is yet to be explored in the biosensor field.
Borophene is a new generation super material discovered in 2015 and the lightest
material to date [120]. It is a 2D boron nanosheet first fabricated on argentum (Ag)
substrate [121]. Many researchers have claimed their potential applications due to
8 Trending 2D Nanomaterial Composites in Detection and Sensing … 189

their excellent properties. Borophene has been used to develop sensors for formalde-
hyde [122], ethanol [123], and hydrogen cyanide [124]. Density-functional theory
(DFT) and non-equilibrium Green’s function (NEGF) methods were used to study
the electronic properties of borophene. The adsorption of ethanol molecules on the
surface of edge-hydrogenated 2D borophene caused an increment in the current
passing through it. In addition to this borophene, fullerene was also used as NO and
CO sensors [125].
However, the use of borophene in the detection and removal of biological contam-
inants were still to be explored. By determining the electron sensitivity and energy
of borophene to the purine and pyrimidine bases (A, T, G, and C), researchers have
found that borophene attached to different bases has different conductivities gener-
ating different electrical signals [126]. In addition, the sensitivity of borophene to
different bases was also measured (A > G > C > T). Hence, borophene nanosheets
could be the future material for biosensor devices [127].

5.3 Tin, Antimony, Bismuth, Tellurium Family

Another member of the 2D family, stanene, is formed from tin (Sn) hexagonal lattice
in buckled arrangement [128]. The first successful formation of stanene was achieved
in 2015 on a Bi2 Te3 substrate [129]. Its persistent room temperature conductivity is
another exciting property that could be explored further [130]. The stability of stanene
comes from low-buckling originating from σ-π bonding [131]. It shows sp2 -sp3
hybridization. Recently, stanene with monolayers and a few layers were successfully
synthesized on Bi2 Te3 (111), InSb (001), Au (111), and Sb (111) substrates [130,
132]. From its discovery, it has been employed in application in gas sensing purposes
(SO2 , H2 S, NO2 , O3 ) only through DFT [133]. The use of stanene as a sensor for
biological contaminants is yet to be explored.
Antimonene and bismuthene are also 2D layer materials of group V elements of Sb
and Bi. Antimonene was first experimentally synthesized in 2016 [134]. Antimonene
monolayer sheets consisting of sp3 hybridized antimony atoms possess a honeycomb-
like structure, unlike flat graphene. The stability comes from the puckered atoms,
held together by weak van der Waals forces. This material has significant properties
with good electrical conductivity (1.63104 Sm−1 ), tuneable bandgap (2.28 eV), and
so on [135]. Although there are few reports of toxic gas and reagents (like acetone,
dimethyl ether, and ethyl methyl ether) sensing by different forms of antimonene
[79, 136, 137], no application related to biological sensors has been reported to date.
Similarly, bismuthene has been limited to use only in voltammetric detection of ions
and sensing of toxic gases [138–140]. Sensing study for biological contaminants by
antimonene and bismuthene is still unexplored.
Tellurene, a highly anisotropic 2D nanostructure of tellurium (Te), has the most
stable α-phase for a few-layer tellurene and the tetragonal β-phase for a monolayer
tellurene [141]. It has a direct bandgap of nearly 0.33 eV in bulk and an indirect
190 J. S. Boruah et al.

monolayer bandgap of 0.92 eV [142]. Tellurene monolayer has been employed theo-
retically to act as a chemosensor for various toxic gases, solvents [143, 144] and as
a biosensor for DNA/RNA nucleobases and amino acids [145]. However, it is yet to
be explored to apply experimentally in actual samples.
From the above discussion, it is noted that these recently developed 2D nano-
materials are primarily involved in chemosensing and biosensing for toxic gases
and other bioactive molecules using computational study (like DFT). The properties
and bandgap tunability of such 2D nanomaterials give a probable scope to develop
sensors for biological contaminants.

6 Conclusion

Biological contaminants are considered prime contributors to environmental pollu-

tion as well as hazards to human health. Therefore, it is essential to find out ways to
eradicate such contaminants. Several 2D nanomaterials were effective in the sensing
of biological toxins contaminated in soil, water, air, food, etc. However, it was found
that primarily electrochemical sensors were used to serve the purpose as they offer
several advantages like easy miniaturization and operation, high sensitivity, repro-
ducibility, and suitable on-site analysis. Besides, most of the 2D nanomaterial systems
consist of electron-rich sites that aid in designing of these sensors. Modifying such
systems with aptamer, DNA, RNA, antibody is another strategy to enhance their
sensing properties toward microbial toxins. Bandgap tunability is one of the func-
tional advantages of 2D nanomaterials, and it can be achieved by attaching metal
nanoparticles with 2D nanostructures. Functional groups available on the surface of
such materials are also a leading factor for a selective and efficient sensing. Among
different 2D nanomaterials, graphene has been explored to a great extent. Transition
metal dichalcogenides-based platforms are used for the detection of many food-borne
pathogens and fungal toxins. It is interesting to note that composites of graphene or
other 2D nanomaterials are more promising in terms of their microbial decontam-
ination capacity, specifically in water. This is usually accomplished with the help
of metal and metal oxide. There is no report on the use of newer 2D nanomate-
rials, viz. borophene, stanene, antimonene, and bismuthene as sensors for biological
contaminants. Hence, there is a promising scope to develop sensors for biological
contaminants using these novel 2D nanomaterials.

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Chapter 9
Newly Emerged 2D Mesoporous Silica
Nanoparticles: Role in Target-Setting
Biomedicines

Prateek Srivastava, Sumit Kumar Hira, and Partha Pratim Manna

1 Introduction

A smart nanosystem behaves as a nanodevice which ameliorates the drug phar-

macokinetics and its biodistribution [1]. The physicochemical behavior of several
drugs remains unsupportive having less water solubility and fewer dissolution rates
which magnify in altered bioavailability and thereby lessens the treatment efficacy.
The contemporary administration routes of water-insoluble drugs require organic
solvents, mingling further with the catabolic steps of the blood elements which
can degrade the therapeutic peptide or proteins during injections. National Institute
of Health (NIH) has approved certain chemotherapeutic drugs like Doxorubicin,
Cisplatin, 5-Fluorouracil, 6-Mercaptopurine which are also featured in the World
health organization’s list of essential medicines for medicaments of cancer malig-
nancies. Despite the application of drugs to subdue the tumor growth, the non-specific
nature of many drugs could lead to deleterious off-target side effects with reduced
therapeutic efficacy. Thus, in order to magnify the solubility, stability, and tuning its
outcome toward the effector/inflamed sites, various nanosystem delivery mechanisms
have been laid out as a nanomedicine device for treating various ailments [2]. The
term nanomedicine manifests the biological/medical implementation of the nanoma-
terials for improved diagnosis and therapy against diseases, and thereby improving

P. Srivastava · P. P. Manna (B)

Immunobiology Laboratory, Department of Zoology, Banaras Hindu University, Varanasi, India
e-mail: [email protected]
P. Srivastava
e-mail: [email protected]
S. K. Hira
Cellular Immunology Laboratory, Department of Zoology, The University of Burdwan, Burdwan,
India
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 197
Z. Khanam et al. (eds.), 2D Nanomaterials for Energy and Environmental Sustainability,
Materials Horizons: From Nature to Nanomaterials,
https://doi.org/10.1007/978-981-16-8538-5_9
198 P. Srivastava et al.

the wellbeing of patients. These nanoscale materials bring in the multifaceted modi-
fications pertaining to tether/attach specific ligand targeted for the drug delivery and
imaging in the biological system [3]. For remedial benefits of nanomedicine in the
cancer therapy, the US Food and Drug Administration (FDA) has approved some
of them in clinical trial like Doxil, Abraxane, and Lipoplatin. Indeed, the results for
their application are superior than free drug administration and further open several
key parameters which need to be highlighted like enclose of the drug, release of
impetuous drug escaping from reticuloendothelial system (RES) during circulations,
cytotoxicity of the engineered nanomaterials, and cost-effectivity of the nanocarriers
[4].
Many efforts were made for the use of unique biocompatible and biodegrad-
able inorganic nanomaterials which offer great versatility for the expansion of
advanced drug delivery system. Inorganic 2D nanomaterials are considered as
the thinnest nanomaterials because they were composed of only few sheets
(nanoscale/macroscale dimension level). They have layered structure which is held
by weak van der Waals molecular interactions. Two-dimensional nanomaterials
like graphene offer brilliant molecular binding with the hydrophobic drugs via
supramolecular stacking and hydrophobic interactions because of special sp2 bond
of carbon atoms. Since then, new 2D materials have been emerged including transi-
tion metal dichalcogenides (MoS2 , TiS2 ), graphene, bismuth, tellurium, etc., having
varying energy band, electrical properties, used in the energy storage, photoelec-
tronics, and water splitting devices. The brilliant aspects of 2D material include
photodynamic and heat conversion properties and have gained many advantages in
the medical fields, like therapy, sensing, targeting, and imaging. The development
and appreciation of the smart drug delivery system have created numerous oppor-
tunities and some inevitable drawbacks in treatment schedule for cancer. The most
obvious demerit is the low drug loading capacity which reduces the efficacy during
multi-mode treatment. However, 2D materials offer plentiful performance in drug
loading. Owing to their lamellar structure, 2D nanomaterial ensures ambient surface
area for maximum drug loading.
Among various inorganic 2D nanomaterials, mesoporous silica nanoparticles
(MSNs) work as an excellent candidate for an efficacious delivery system, which
presents brilliant biocompatibility, functional groups employment, convenient pore
size, large storage capability for drugs, and vast surface area to accommodate desired
chemical modifications [5]. Silica in its amorphous (pyrogenic) form is currently
used in cosmetics and distinctive care products, additives in pharmaceutical and
nutraceutical industries and made it a safe and harmless agent certified by FDA [6].
Further, Wiesner group received FDA safety approval for the build out of the “Cornell
Dots” (core–shell silica nanoparticles) and the clinical first phase trial was successful
[7]. The silica nanomaterials became the most promising inorganic nanosystem for
biomedical applications. MSNs offer generous surface area and pore volumes which
are crucial parameters for substantial drug loading. The cargo inside the MSN such as
enzymes, drug molecules, therapeutic peptides, and oligonucleotides can be fastid-
iously encapsulated and protected from the harsh environments including stomach
before entering the target site. Further, the liberation of loaded guest molecules from
9 Newly Emerged 2D Mesoporous Silica Nanoparticles … 199

MSNs can be fine-tuned to the internal and external signal inputs which augment the
drug arm loading at the targeted area, thus bettering the overall therapeutic outcome.
The loading can be performed in normal phosphate buffer saline (PBS) and thus
exclude toxic organic solvents for drug loading. MSNs could act as an inorganic
support floorboard for the fabrication and evolution of various cap systems which
can be switched off/on via internal or external stimuli [8]. Thus, MSNs may have
increased opportunity for application in the precinct of nanomedicine including drug
delivery, targeting, and diagnosis on account of their modular design characteristics
[9]. Another aspect of silica inorganic nanomaterials in bioengineering process is to
generate 2D nanostructures which offer excellent platforms for many potential appli-
cations. Among the best 2D functional nanocomposites, 2D graphene sheet serves as
a template for the assembly or coating other 2D silica-based nanomaterials. Besides
that, versatile chemical properties can be doped on silica surfaces in order to achieve
multiple applications [10–12]. The present chapter discusses the role of emerging
2D MSNs in target-setting biomedicines. The different synthesis approaches along
with the mechanism of drug delivery using MSN have been presented in detail.

1.1 Focus on Nanopharmaceuticals

For the materials science advancement in nanoscale platform, NIH encourages

nanoscience-related research and development in the year 2000 under the National
Nanotechnology Initiative (NNI) program. The program aims to study, design, and
explore novel nanomaterials which may contribute significant progress in health
science-related research [13]. The term nanomedicine emerged by blending nanoma-
terial science with medicine following the wisdom of nanotechnology. Later, people
in the pharmaceutical field adopted the nanoscience terminology as “nanopharma-
ceuticals.” Nanopharmaceuticals are the deployment of the nanosized materials for
the transportation of drug/cargo of interest [14]. The colloidal system is a nanosystem,
explored as delivery agent 40 years ago. Certain examples include the encapsula-
tion of the anthracyclines (liposome) in 1970s [15] (Table 1). The entrapped drug
manifests shoot-up in anti-tumor effect with reduced cardiotoxicity. Yet, suitability
and performance of the construct faced several hurdles to purge the malignant cells.
There are some key features which are essential to generate nanodevice for the cancer
therapy: (a) high drug concentration at the tumor site, (b) loading capabilities, (c)
stimuli-responsive release, (d) stability of the drug from hydrolysis during circula-
tion, (e) congeniality and biodegradability, and (f) easily reproducible synthesis of
the nanocarrier [16]. Thus, it is critically important to pick up a nanocarrier which
inherits the above-mentioned important parameters.
200 P. Srivastava et al.

Table 1 Examples of approved cancer nanomedicines undergoing clinical trial

Nature of the Name Cancer target Status References
nanoparticle
Liposome Doxil Sarcoma Approved [17]
Liposome Marqibo Leukemia Approved [18]
Liposome Lipoplatin Pancreatic/head/malignant Phase I [19]
pleural effusion
Paclitaxel in Genexol® Passive targeting via EPR South Korea [20]
20–50 nm effect 2001 breast and
micelles pancreatic
cancer (IV)
Paclitaxel Opaxio® Passive targeting via EPR FDA 2012 [21]
covalently linked effect glioblastoma
to polyglutamate
nanoparticles
Albumin Abraxane® Passive targeting via EPR FDA 2005 breast [22]
conjugated effect cancer
paclitaxel
Source Author

2 Fabrication Methods of Nanoparticles

Nanostructures can be synthesized by two ways: one is the bottom-up and other is
top-down approach. In the bottom-up process, the particles are formed atom by
atom while the top-down process involves the exodus or re-clustering of atoms
to create the desired structure [23]. In the bottom-up system, atom, molecules
behave as constituent blocks for the formation of complex nanostructure materials.
Further, in the bottom-up approach, the nanosized structure can be finely tuned by
altering the dimensions of building blocks which can control their organization and
assembly. Hence, the bottom-up approach is highly controlled for complex chemical
synthesis. Among the different bottom-up approaches, sol–gel process is helpful in
terms of obtaining high chemical homogeneity, managing the size, and morphology
at moderate temperatures executed in aqueous solution [24]. The sol–gel process
consists of hydrolysis and condensation of a metal alkoxide (liquid precursor) to a
solid. The protocols for the sol–gel synthesis involve three steps: first, hydrolysis of
metal oxide, followed by the condensation between themselves and bring out water
molecules generating gel structures, and finally, the drying process [25] (Scheme 1).
The whole procedure can be set out by distinct steps (Scheme 1): formation of
steady solution of precursors (the sol); the sol reaction in basic medium at around
80 °C producing a porous network (the gel); bridged, rigid, surrounded by a contin-
uous liquid phase via gelation; drying (removal of liquid from the gel network);
densification; and breakdown of the gel at high temperature [26].
9 Newly Emerged 2D Mesoporous Silica Nanoparticles … 201

Scheme 1 Schematic view of sol–gel processing. Source Author

2.1 Synthesis of MSN

Ordered mesoporous materials can be synthesized with various pore dimensions

via utilization of specific surfactant and framework compositions. In the early 1990s
Mobil Oil Company first synthesized mesoporous silica, utilizing the cationic surfac-
tants as fabricating agents through which inorganic material can be deposited under-
going hydrolysis and condensation via sol–gel approach, creating a mesoscopically
ordered hybrid inorganic material [27, 28]. After thermal calcinations or chemical
extraction, the porous construct of inorganic silica materials was obtained. The
shaping of mesoporous materials was supervised by two crucial parameters, first
(a) casting of surfactant molecules to develop the micelle structure and secondly,
(b) potential of the inorganic oxide to undergo hydrolysis and condensation to bring
out thermally stable structure. Synthesis of mesoporous materials may involve a
self-assembly process, similar to the biological condition. Four major components
required for the assembly of silica nanoparticles includes the silicon source, surfac-
tants, solvent, and the base catalysis. The self-assembled liquid–crystal arrays of
surfactants direct the generation of MSN material. In the liquid–crystal templating
mechanism (LCT), when the surfactant was dissolved in the aqueous solution it
generates a liquid crystal. However, above the critical micelle concentration (CMC),
202 P. Srivastava et al.

Fig. 1 Development of mesoporous silica by structure-directing agents: a true liquid–crystal

template mechanism, b cooperative liquid–crystal template mechanism. Source Author

they form a micelle structure. The shape and size of the micelle depend upon the
surfactant type, pH, surfactant concentration, and temperature [29, 30]. In experi-
mental setup, the micelles aggregates to form supramolecular structure containing
hexagonal, cubic, or laminar geometry which determines the mesoporous frame-
work structure [31]. An alternative route was also proposed including allied connec-
tions between surfactant and the silica precursor for generating the final mesoporous
ordered material. MSN materials can also be generated when the surfactant concen-
tration is below CMC and present at lyotropic liquid-crystalline phase which acts as
a cooperative congregate of surfactant and tetraethyl orthosilicate (TEOS) [32]. In a
typical synthesis procedure, the surfactant-silica precursor interactions are optimized
under basic reaction condition. The silica precursors like tetramethyl orthosilicate
(TMOS) or tetraethyl orthosilicate (TEOS) are normally added in the basic reaction
mixture consisting of cationic surfactant cetyltrimethylammonium bromide (CTAB)
at around 60–80 °C (Fig. 1). The organization framework in MSN can be regulated
by the surfactant which was demonstrated by Stucky research group, utilizing the
block-copolymer surfactants [33]. Further, by altering the hydrocarbon chain length
of the surfactant molecules, the controllable pore size in MSN structure can be gener-
ated ranging from 2 to 30 nm [34]. The most familiar representatives of this class are
MCM-41 possessing 2D-hexagonal p6mm structure, MCM-48 with 3D-bicontinuous
cubic Ia3d structure and MCM-50 with lamellar p2 structure [35] (Fig. 2). According
to IUPAC, the porous materials, inherit the pore diameter ranging from 2 to 50 nm,
are termed as mesoporous material. Our work underpins on the generation of meso-
porous MCM-41 class of materials with well-defined pore size distribution, large
surface area (≥700 m2 /g), and pore diameter ranging from 1.5 to 10 nm.

2.2 Reaction Kinetics and Template Removal

The silica source and cationic surfactant interaction are the non-covalent interactions
including electrostatic and hydrogen-bonding among the head groups of surfactant
9 Newly Emerged 2D Mesoporous Silica Nanoparticles … 203

Fig. 2 Various structures of M41S materials: a MCM-41 (2D hexagonal with space group p6mm),
b MCM-48 (cubic shape with space group Ia3d), and c MCM-50 (lamellar form with space group
p2). Source Author

and silica precursor without phase separation. Most commonly used silica precur-
sors are alkoxysilanes, e.g., tetramethyl orthosilicate (TMOS), tetraethyl orthosili-
cate (TEOS), tetrapropyl orthosilicate (TPOS), and tetrabutyl orthosilicate (TBOS).
Different alkoxysilanes, particularly the branched, bulkier precursors exhibit reduced
hydrolysis rate, caused by the steric barrier and result in larger particle size [24].
Therefore, it is the basic condition which is generally adjusted to generate negatively
charged particles to avoid inter-particle aggregation. pH of the reaction mixture regu-
lates the MSN size, and lowering in pH increases the particle size [36]. The isoelectric
point of silica is 2, so raising pH from 6.0 to 9.0 could result in speedy condensa-
tion rates with fast association and growth of silica–surfactant nuclei [37]. Further,
the initial silicate and surfactant concentrations can be modulated for alteration in
size of the silica nanoparticles under diluted condition [38]. After the completion of
the reaction, the template was removed from the silica network to yield the porous
network structures. Majority of the conventional method used for template removal is
calcination. In this process, the silica nanoparticles are subjected to heat with heating
rates of 1 °C/min up to at least 550 °C, followed by isothermal heating for 4–8 h
[39]. However, this process influences the morphological framework of the silica
nanoparticles including surface area, pore size, and pore capacity. The heat treat-
ment could bring in contraction of silica structure which perhaps the fast magnitude
of condensation of silica network and may affect particle aggregation/agglomeration
in aqueous media [39]. An alternative template extraction method includes acid
treatment, liquid extraction, and supercritical fluid extraction, rooted in the synthesis
employed. The silica nanomaterials which are synthesized in basic condition, an ion
exchange process involving acids or cationic proton donors is essential to break the
non-covalent interactions between negatively charged silica network and the cationic
surfactant head groups. Other extraction methodology for MCM-41 type materials
involves drawing out using ethanolic solution of ammonium nitrate or acidic ethanol.
204 P. Srivastava et al.

Fig. 3 Functionalization procedures of MSN by a co-condensation method and b post-synthesis

grafting method. Source Author

2.3 Surface Functionalization of MSN

The notable advantages of using MSN material as delivery vehicle are the proficiency
to incorporate desired functional groups employment. Beneficial aspect of MSN
includes three functional domains—the silica framework, external particle surface,
and interior pore surfaces [40]. MSN provides a broad range of flexibility to modify
surfaces which generates wide varieties of silica-based hybrid materials that possess
specific functions for the delivery of drug. Commonly used organic precursors are
organotrialkoxysilanes [(R’O)3 SiR] or organotrichlorosilanes [Cl3 SiR]. There are
two popular classical pathways for the surface functionalization. In one method,
fusion of organosilanes with silica precursors results in the synthesis of MSN mate-
rials (“co-condensation”). The other pathway is to produce unfunctionalized MSN
materials first and later transform their surfaces with organosilanes (“grafting”) [41]
(Fig. 3).

2.4 Surfaces Functionalization by Co-condensation Method

Co-condensation is the direct process where the organosilanes are condensed besides
the silica precursors during the production of silica nanoparticles. This leads to
homogenous allocation of the organic groups to the mesostructure. Lin and coworkers
proposed that varying organosilanes, associates with the surfactant through non-
covalent bonds could result changes in the structural morphology. They showed
that the organosilanes with hydrophobic group interact with hydrophobic tail of
the surfactant molecules, stabilize the creation of long cylinder micelles, and mani-
fest rod-shaped silica [42]. Contrarily, the hydrophobic organosilanes inhibit the
9 Newly Emerged 2D Mesoporous Silica Nanoparticles … 205

micelle growth and results in spherical shaped particles. Thus, by using two organosi-
lanes with converse head group properties in varying ratios, the surface func-
tionality and the particle architecture of MSN can be tuned with co-condensation
method [43]. To preserve the structural parameters like pore and long-extend pore
ordering, the proportion of organosilanes incorporated following co-condensation
approach should not surpass 25% of the surface, assigned to the modification in
condensation rates among organosilanes and silica precursors (Fig. 3a). Multiple
efforts were made to incorporate various organic functional groups into the porous
samples through direct synthesis method in order to augment the hybridization
effectiveness. Recently, Xie et al. developed periodic mesoporous silica, functional-
ized with organic precursor via co-condensation using (R’O)3Si-H and (R’O)3Si-R
type terminal trialkoxyorganosilanes [44]. By using this synthetic route, they have
obtained materials with higher co-condensation having organic precursor. There are
some other methods which could offer the organic functionality to be incorporated
either on the pore surface or on the walls [45].

2.5 Surface Functionalization by Post-synthesis Grafting

Method

Post-synthetic tempering of mesoporous material is usually carried out after the

removal of surfactant via annexation of functional moiety on the exterior by chem-
ical conjugation (grafting), surface polymerization or by adsorption of the func-
tional groups [46]. In adjoining method, vast majority of the functionalization occur
between free silanol and the organic precursors. Majority of the open silanol groups
were present around the lateral surface and at the orifices, which heads to the gath-
ering of organic precursors on that specific area. Since organic grafting mostly occurs
at the lateral surface, it pertains better with pore structure against the co-condensed
material. However, the extent of functionalization by post-grafting procedure is low
compared with the co-condensation method because of the restricted number in free
surface silanol groups. There are reports which indicated that the functional groups
are preferentially affixed to the outer/external surface or the pore opening since free
silanol groups are most accessible there than the inner pore surface which suffers
from lower diffusion rates of organic precursors [47] (Fig. 3b). The surface function-
alization over the silica nanoparticles plays a pivotal role in biological and catalysis
process. The active targeting ligands like folic acid or hyaluronic acid can be attached
over the silica nanoparticles thus offering better drug entrapments inside the cancer
cells via receptor-mediated endocytosis. Further, some studies suggest amination
(charge) over the silica nanoparticles offers better uptake in cancer cells. The surface-
functionalized drug molecule or the PEGylation can help in better circulation time
and also offers zero premature release in the bloodstream. Functionalization (like
–COOH, –NH2 , –SH, =CH2 , etc.) over the silica offers a vast range of chemical
reactions. This can have diverse functions like development of novel cap system to
206 P. Srivastava et al.

entrap the drug inside and inherit specific linker which could be melted down when
met with suitable environment like pH or enzymes.

3 Biological Performance of MSN

3.1 Cellular Interaction and Uptake of MSN

The lipid bilayer system not only furnishes integrity to the cells but also plays
significant roles in cellular signaling events and molecular associations with
the biomolecules including nanoparticles. Nanoparticles entail to interweave the
cell membrane barrier to dispatch the cargo of interest. The physicochemical
possessions of nanoparticles, like its size, shape, outer surface charge, hydropho-
bicity/hydrophilicity and surface chemistry or functionality could affect the endo-
cytosis behavior of MSN [48, 49]. This relationship links the biological proper-
ties with the surface physicochemical nature of nanoparticles and contributes a
keystone feature in nanomedicine. Comprehending physicochemical nature of these
transported particle, various types of endocytosis pathways following internaliza-
tion, cargo properties, etc., may tune the cellular uptake mechanism pathways [50].
Recently, MSNs were used as a carrier system for the transport of chromobodies
inside the living cells for real-time visualization [51].

3.2 Effects of MSN Size

The particle size is a critical parameter which determine the success of a delivery
platform against desired tumor sites. Nanosized particles mimics with various
biomolecules or viruses in terms of size and other properties which can be endo-
cytosed in similar fashion. This molecular uptake can be energy-dependent or via
recruiting caveolin- or clathrin-coated pits or other pathways, independent of these
proteins. Lim et al. observed a brisk and elevated intracellular uptake of smaller MSN
compared with the larger ones [47, 52]. This effect was further corroborated by Mou
and coworkers which showed an optimal size of 50 nm MSN manifests the highest
cellular uptake [36]. Mou and coworkers have developed MSN with varying sizes
(between 30 and 280 nm) and point out that particle size was correlated to uptake
studies as the largest size represents least uptake by HeLa cells. Also, noticeable
endocytosis efficiencies were observed with spherical- and tubular-shaped MSNs.
These investigations permitted researchers to regulate the rate of drug delivery accu-
rately (Fig. 4). Not long ago, CT imaging and mathematical modeling helped in
better understanding of the route, MSN size, biodistribution, and removal kinetics in
rat model of pharmacokinetics study [53].
9 Newly Emerged 2D Mesoporous Silica Nanoparticles … 207

Fig. 4 Cellular internalization pathways for the nanoparticles: a larger nanoparticles were inter-
nalized via phagocytosis. Smaller particles are internalized through various mechanisms, such
as b clathrin-mediated endocytosis, c caveolae-mediated endocytosis, and d macropinocytosis-
dependent pathways. Source Author

3.3 Effects of MSN Surface Charge

Surface charge of the nanoparticles governs its molecular incitement with the cell.
Usually, the cellular uptake is elevated with the positive charged nanoparticles;
however, charge consistency and hydrophobicity of the particles are also signifi-
cant [54, 55]. Different studies demonstrated the surface charge-dependent uptake
mechanisms, but still no general procedure has been identified. Furthermore, posi-
tively charged nanosystems have the property of endosomal escape when internalized
inside the cells [56]. However, neutrally and negatively charged nanoparticles prefer
lysosomal co-localization. A plausible explanation for this phenomenon states that
excessive positive charges on the nanoparticles cause proton pumping into the endo-
some with ingress of chloride ions to conserve the neutral charge, which results
in increasing ionic strength within the endosome. This later condition manifests
osmotic swelling and physical fracture of the endosomal membrane, an event termed
as “proton-sponge” effect resulting in runoff the nanoparticles [57]. This behavior
brings in cytoplasmic emplacement of positively charged nanoparticles and enhances
drug accumulation throughout the nucleus. Slowing et al., have revealed that surface
functionalities govern the uptake of MSN in HeLa cells with positive zeta-potentials
which can be taken up more contrast to their counterparts with negative zeta-potential,
owing to exorbitant electrostatic affinity to negatively charged cell membranes [58]
(Fig. 5). The functional group charges on the MSN surface could affect release and
encapsulation efficiency of the drug which also affects cell response [59].

3.4 Effect of MSN Hydrophobicity and Surface Properties

Another crucial criterion for biomedical application of the nanoparticles is its surface
hydrophobicity. Nanoparticles require hydrophilicity for stable dispersion in aqueous
environment which also prevents opsonization after intravenous administration.
However, hydrophobicity of the nanoparticles also encourages cellular uptake. Under
in vitro condition, nanoparticles surface comes in direct association with the cell
208 P. Srivastava et al.

Fig. 5 Different charges on nanoparticles affect cellular uptake and intracellular distribution.
Source Author

membrane which bears alkyl lipids and cholesterol, imparting a partially hydrophobic
character. Thus, hydrophobic nanoparticles manifest upregulated cellular uptake,
compared with the hydrophilic particles. The surface of nanoparticles is impor-
tant for modification through electrostatic or hydrophilic/hydrophobic interactions.
Shastri and co-workers have illustrated that stabilizing both lipophilicity and charge
attributes lipid in high specificity toward the endothelial cells [60]. Recently, Desai
and her group have shown the difference in release profiles of hydrophobic and the
hydrophilic drugs in 2D and 3D cultures [61].

4 Biocompatibility and Biodistribution

In order to become a good drug delivery platform, an ideal nanocarrier should have
properties like efficient biodistribution, biocompatibility, and clearance from the
cellular systems [16]. The critical challenges for a nanocarrier are distribution of
drug to the appropriate locations with lesser after-effects compared to conventional
therapies. This also includes in vivo biodistribution for maximum benefits plus excre-
tion of vehicle like MSN. The studies suggest that MSN accumulates mainly in liver,
kidney, and urinary bladder following intravenous injection and partially excreted
through the renal route [62]. However, the biodistribution of MSN allying the tumor
and healthy mice is somewhat different as the MSN passively gathered in tumor,
owing to leaky blood vessel (EPR effect) and influence the overall biodistribution.
Hyeon and coworkers employed the florescent PEGylated MSNs (<100 nm size)
and observed their accretion in tumor cells after intravenous administration which is
responsible for the EPR effect [63]. At a dose below 200 mg kg−1 , no toxic effect
was perceived in experimental study and thus makes MSN a safe nanocarrier for
drug delivery. In their next study, the same group observed that when the PEGy-
lated MSNs (70 nm size) were passively targeted to xeno-implanted MCF-7 tumor,
some percentage of MSN was accumulated in the liver, lungs, and spleen due to
phagocytosis by mononuclear cells [64]. Similarly, results recorded by Lu et al. have
shown biocompatibility and biodistribution of MSN in human cancer xenografts and
9 Newly Emerged 2D Mesoporous Silica Nanoparticles … 209

Fig. 6 MSN as nanomedical multifunctional nanoplatforms. Source Author

observed that MSNs are well-tolerated up to 100 mg kg−1 dose and favored its accu-
mulation in tumor sites [65]. The surface modifications with protein, lipid bilayers,
and polymers over the MSN via electrostatic interactions with Si–OH (outer surface)
were reported to eliminate toxicity during in vivo studies [66]. Such physicochem-
ical factors (described above) and functional group over MSN impart effect on blood
circulation time, biodistribution, and biocompatibility of administered drug. There-
fore, detailed guidance on distinct surface functionalization, size, charge, etc., still
needs further investigation (Fig. 6).

4.1 Toxicity of Nanomaterials

Mesoporous silica nanomaterial when enters the body may come in close contact
with the immunocompetent cells and thereby induces immunotoxicity. The molec-
ular association of silica nanoparticles with the immune system manifests in varying
outcomes, mostly related to the morphologies and the characteristic of the construct.
The major effector cells like monocytes/macrophages and polymorphonuclear leuko-
cytes are involved in close encounter with the silica nanoparticles [67]. These particles
can be phagocytosed by the dendritic cells, macrophages (antigen-presenting cells),
or stimulate lymphocytes. The uptake of silica by these cells can be manifested by
the damage of the cell membrane, inducing apoptosis, and necrosis [68]. Further, the
210 P. Srivastava et al.

interaction can also influence the signaling pathways within the immune cells. These
nanoparticles influenced signaling events can be demonstrated by proinflammatory
responses, reactive oxygen species (ROS) generation, etc. Silica nanoparticles are
an important candidate for application in biomedical experiments owing to their
properties like large surface area, pore size, pore volume, and easy functional group
employment. There are reports which indicate that the amorphous silica offers better
safety features compared with the crystalline silica. During in vivo study, the silica
nanoparticles were observed in the lymphocytic infiltration, which induces gran-
uloma and hydropic degeneration in hepatocytes. When accumulated in spleen it
reduces the activation and proliferation of B and T cells. Some studies also suggest
that antibody levels of IgG and IgM increase which can cause histological changes
[69]. The main reason is the oxidative stress that generates immunotoxicity especially
the MAPK and NADPH oxidase pathways. The silica nanoparticle also induces toxic
mechanisms by autophagy dysfunction.

5 Barriers for Drug Delivery

In order to augment the therapeutic effectiveness, the nanodelivery system must

accumulate in the target cells in optimal concentration. However, the route taken by
a nanocarrier to the tumor sites is hindered by the physiological and biochemical
barriers. The physiological barriers for oral drug delivery include intestinal epithe-
lium, which is highly absorptive and is built with villi, covered with enterocytes,
goblet cells, and mucus layer [70]. When the drug-loaded nanocarrier was intra-
venously administered, it requires to overcome other obstacles and modulate other
physiological barriers such as opsonization, abrogation of reticuloendothelial system,
tumor microenvironment, and evasion from endosomal and lysosomal compart-
ments [71]. After the intravenous administration, nanoparticles undergo opsoniza-
tion, involving adsorption of serum albumin, apolipoproteins, complement factors
and immunoglobulins onto the surface, and uptake by inhabitant macrophages [72].
This heads to non-specific dispersal of the nanotherapeutics to healthy organs like
spleen and liver. Nanocarriers are passively accumulated in the tumor cells owing to
leaky tumor vasculature and poor lymphatic drainage with enhanced resident time
[73]. However, numerous barriers still exist, which hampers the nanoparticle’s effi-
cient extravasation. These incorporate the tumor interstitium barrier, physiological
elements such as low pH, low oxygenation, very dense extracellular matrix (various
architectural proteins) and raised interstitial fluid pressure in the tumor microenvi-
ronment [74]. Further, the cell membrane of tumor cells and intracellular organelles
represent extra barriers for the nanoparticles to conquer for effective intracellular
delivery of the cargo. For therapy in brain diseases, blood–brain barrier (BBB)
behaves as diffusion barrier, made up of tight junctions, which excludes influx of
elements from blood to brain [75]. Thus, to weather the storm, nanoparticle design
should possess the aptness to encapsulate and protect drugs in addition to deliver
them in a temporally or spatially controlled manner.
9 Newly Emerged 2D Mesoporous Silica Nanoparticles … 211

6 Endosomal Escape

Endocytosis is a vital mechanism for uptake and internalization of biological

constituents, such as DNA, siRNA, and proteins. Following endocytosis, these
biomolecules are escorted to the lysosome and are disintegrated by specific enzymes.
Thus, another intracellular barrier for the nanocarrier to release drug inside the
cytoplasm is the endosomal entrapment. Hence, different approaches were adopted
to promote endosomal escape and assure cytosolic drug availability [76]. For
example, bacteria and viruses use different penetrating pathways to escape the endo-
somal pathway. For carrier-mediated delivery, different approaches can be employed
to ensure this escape mechanism like pore generation using different peptides,
polyethylenimine (PEI) buffering effects and amalgamation with the lipid bilayer
of endosomes [77]. Of late, the MSNs were decorated with self-immolative linker
attached to polyvalent peptides which confer potency to deliver the nanoparticles in
the cytoplasm via endosomal escape [78].

7 MSN for On-Demand Drug Release

As mentioned earlier, the proficiency of functional group employment, enormous

surface area, pore size, large loading capacity and the superb biocompatibility makes
MSNs an ideal candidate for delivery system. On-demand stimuli-responsive drug
delivery systems (DDS) are convenient approach to reach drugs in spatial, temporal,
and dosage-managed fashions. Stimuli-responsive system could deliver on-board
cargo in site-selective and controlled release pattern upon encountering triggering
agents [79]. Thus, the stimuli-responsive systems are progressive and surpass persis-
tent drug release platforms. Among the distinct nanosystems, mesoporous silica
provides the prospect to introduce a cap/gate-like assemblies over the porous frame-
work to design the nanosystem for on-demand drug delivery. Fabrication and perfor-
mance of such system inherit two subunits: first a porous silica support system for
fill up with drug of interest and second zipping the pores reversibly by biological
elements or supramolecular entities which can govern the movement of cargo from
the pores.
In recent time, many investigators have made significant progress for the expan-
sion of MSN-based drug delivery procedure with stimuli-responsive release prop-
erties [80]. The intracellular drug delivery by number of regulating mechanisms
over the stimuli-responsive MSN has been postulated and confirmed their feasibility
with accurate location and timing. The triggers or stimuli release mechanism, built
on internal or external inputs, requires a pathway for application. Internal stimuli
are unique and specific with the targeted pathological condition like upregulated
glutathione level in cancer which permits the DDS to respond to the desired area
and release its cargo in a self-regulated fashion. External inputs such as non-ionizing
radiation [81], temperature [82], magnetic field, and ultrasounds [83] are noninvasive
212 P. Srivastava et al.

Fig. 7 Schematic representation of various gate opening mechanisms in mesoporous silica

nanocarrier. Source Author

and easy to perform techniques so that it could assist in localize drug release and
optimize its efficiency. Examples of triggers include pH [84], light [81], redox poten-
tial [85], temperature [82], enzymes [86], etc. Operational aspects of these triggering
stimuli were also presented in works, generated from our laboratory (Fig. 7).

8 Targeted Delivery Approach of MSN

Cell-specific targeting approach provides a basis that spontaneously distinguishes

the place of action to the diseased organ and thus reduces both drug administration
dosage and the side effects of the drug. The targeting module can be bifurcated into
two parts, passive and active targeting [87]. Both targeting designs are applied to
intensify drug bioavailability to the neoplastic cells.

8.1 Passive Routes

Passive accumulation of MSN at the tumor site is attributed by EPR effect, a hypoth-
esis predicated by Matsumura and Maeda in 1986 [88]. The tumor vasculature has
increased permeability because of large gaps between the endothelial cells; hence,
tumor vessels are more permeable to nanoparticles than the well-defined vasculature
observed in the normal tissue [89]. Effectiveness of EPR effect can be transpired with
the particle size, surface charge, or hydrophobicity. Tamanoi and coworkers illus-
trated that the fluorescently labeled MSNs were preferentially migrated and located
in tumor site of mice following intravenous injection [65].
9 Newly Emerged 2D Mesoporous Silica Nanoparticles … 213

8.2 Surface Decoration with Tumor Directed Ligands

Active targeting involves the attachment of specific targeting ligands/biomolecules

over the nanoparticle surface whose receptors are unique to, or upregulated in
dysplastic and pathologic tissues. Targeted with specific ligand enhances the effi-
cacy and reduces the toxicity of therapeutic agents. Anchoring a biological targeting
moiety toward nanoparticle surface manifests enhanced internalization of the
nanoparticles in targeted sites which contains overexpressed receptors [90]. Active
targeting strategy does not intensify the tumor localization rather it accelerates the
particle attachment and uptake through receptor-mediated endocytosis [91]. Certain
efforts have demonstrated the nimble effect of the ligands for escalated cellular
uptake when adhered to the nanoparticle surface. One such ligand is folic acid [92],
whose receptors (folate receptor) are overexpressed in many different types of human
neoplasia including breast, endometrial, ovarian, colorectal, and lung. Folic acid-
tagged MSN (FA-MSN) upregulates cellular uptake by HeLa cells [93]. Besides
that, other small nutrient biomolecules such as mannose [94] also function in similar
fashion, resulted in improved uptake of MSN by MCF-7 breast cancer cells. Another
targeting ligand, the RGD peptide, abbreviation for arginine–glycine–aspartic acid
also shown to interact with overexpressed αν β3 integrin receptor in metastatic cancers.

8.3 Enzyme-Responsive Drug Release

We have designed a novel methodology to deliver doxorubicin using biomolecules of

known specificity. One such interaction in biological world is the dynamic interaction
between bovine serum albumin (BSA) and bilirubin [95]. Bilirubin was attached
over the nanoparticle’s (MSNP-NH2) surface through an amide bond. Bilirubin is
a potent antioxidant and shows strong anti-tumor effect besides inheriting strong
molecular interactions with BSA molecules. Availing protein–ligand interaction for
covering the pores, we have employed bilirubin-BSA complex as anew capping
agent in protease-responsive drug release from MSN. Bilirubin-BSA complex was
designed and explored as a biocompatible cap system with the protease-responsive
pore opening for treatment against colon carcinoma. Bilirubin was tagged to the
amine-terminated silica nanoparticles which were filled with doxorubicin (DOX),
and the pores were sealed via molecular interactions between BSA and Bilirubin.
DOX loaded MSN shows good colloidal stability and offers impressive tumoricidal
property. Doxorubicin is a key drug of NCI-approved chemotherapeutic regimen
R-CHOP. Doxorubicin hydrochloride (trade name Adriamycin) normally acts as a
topoisomerase II poison [96]. Besides that, doxorubicin also induces cellular response
like the adduct formation with DNA. The adduct formation occurs in association with
endogenous formaldehyde and forms an activated Schiff base creating aminal (N–C–
N) linkages with the exocyclic amino group of guanine residues [97]. Doxorubicin-
loaded nano-formulation (MSNP-BR-BSA) significantly affects human (HCT-116)
214 P. Srivastava et al.

Fig. 8 Targeted delivery of chemotherapeutic drugs from silica nanoparticle employing various
platforms. Source Author

and murine (MC-38) colon carcinoma cells by inhibiting the amplification of cell
number and inducing apoptosis (Fig. 8).
In our next study, we focused on upregulated enzymes associated with cancer
malignancies as therapeutic target. Cancer cells are manifested with uncontrolled and
rigorous cell division, obliged with actively functional telomerase enzyme. Telom-
erase enzyme is absent in the normal somatic cells which cause ageing effects as
the cell undergo cycles of division. Search for novel triggering strategies specific to
cancer prompted us to design telomerase-specific oligomer consisting of murine
telomerase complementary repeat sequences and the telomerase-specific primer
sequences. These specific oligonucleotide sequences sealed the pores of DOX-
loaded aminated MSN via electrostatic interactions. Telomerase enzyme elongates
the oligonucleotide sequences which resulted in the formation of rigid hairpin struc-
ture which subsequently leaves the MSN surface and release DOX from the pores
[98]. Treatment of telomerase-responsive Dalton’s lymphoma (DL) bearing mice
with the newly fabricated oligo-wrapped nanoprobe, specific to mouse telomerase,
significantly augmented the life span and improved the histopathological parame-
ters. Besides that, treatment with this new probe-induced dramatic reduction in tumor
foci across the tissue section in spleen and liver. Treatment with this nano-probe also
restored the normal tissue architecture of deep vascularized organs and prevents
metastasis (Fig. 8).
More than 80% of all cancers are solid tumors that grow as a lump of tissue in
particular organ, or gland. The common sites are breast, lung, prostate, and colon,
and other examples include brain, uterus, pancreas, skin, and liver. Examples of solid
tumors are sarcomas, carcinomas, and lymphomas. Nanocarrier, when target the
9 Newly Emerged 2D Mesoporous Silica Nanoparticles … 215

solid tumor, the activity was hampered by the existence of tough extracellular matrix
(ECM) which is fabricated by the architectural proteins, thus reducing the overall
therapeutic efficacy. Further, poor and heterogeneously developed vascular network
in solid tumor limits the oxygen supply and other crucial nutrients which lead to
generation of acidic metabolites. Pepsin is a protease which is idle at physiological pH
and becomes vibrant in acidic condition. Low pH in the tumor microenvironment can
be an ideal condition for the pepsin activity. The pepsin biomolecules were attached
to the doxorubicin-loaded mesoporous silica nanoparticles [99]. Pepsin decorated
MSN demonstrated an enhanced diffusion inside the tumor mass. The tumor cells
(extracted from the inner cores) over the HOPG surface manifest approximately three
times more silica content compared with the non-protease attached nanoconstruct.
Thus, this design enhances drug biodistribution homogenously throughout the length
and breadth of the solid tumor (Fig. 8).

8.4 pH-Responsive Drug Release

Chemoresistance is a phenomenon by virtue of which cancer cells reduces the killing

efficiency of a particular drug. Cancer cells develop multidrug resistance receptor
proteins (P-glycoprotein 1) which can pump drug outside the neoplastic cells and
thus reduces desired therapeutic potential of the nanoconstruct. One way to reckon
with this problem is receptor-mediated targeting. ATP is a biomolecule which has the
tendency to bind the P2X7 receptors, expressed in transformed cells. These receptors
are non-specific ion channels which could guide the influx of the biomolecules or
nanoparticles, functionalized with ATP [100]. Further, the influx of ions like calcium
brings alteration in cancer cells biomechanics leading to necrosis, membrane bleb-
bing, and apoptosis. Based on these keystone information’s, MSNs were garnished
with ATP molecules and loaded with doxorubicin inside the pores. However, the
design pertains to some pitfalls like the hasty drug release during circulation. There
are reports where ATP acts as a stabilizer in generating the amorphous calcium
carbonate nanoparticles. Thus, ATP molecules provided the organic phosphorous
source for efficient calcium carbonate mediated biomineralization over the silica
surface which seals the pores. The formed nanohybrid material was stable at phys-
iological pH; however, when it encountered low pH in tumor microenvironment,
calcium carbonate was leached out the surface, thus unmasking the ATP to clenched
P2X7 receptor. This novel formulation augments the cellular uptake and demon-
strated significant anti-tumor function against DL and doxorubicin-resistant DL cells
(DLR) with large-scale growth inhibition and induction of apoptosis (Fig. 8).
216 P. Srivastava et al.

8.5 Redox-Responsive Drug Release

In another study, we have adopted a combination drug approach using clinically active
drugs with non-overlapping toxicity contributed by incorporating varying triggering
mechanisms leading to synergistic or additive effects. We employed MSN as an effec-
tive delivery platform for 5-fluoro-2-deoxyuridine (5FUdr) and doxorubicin against
DL. The construct was made by attaching cysteine molecules via S–S bonds which
inherit glutathione sensitivity [101]. Both the amine and carboxyl group terminated
MSN-Cysteine offer the site for 5FUdr attachment via ester bond and folic acid
(FA) to the amine groups. DOX was loaded inside, and the pores were sealed by
using boronic ester bond using beta-cyclodextrin. FA selectively accumulates drug
at the vicinity of tumor cells, and the particles can deliver both the drugs when met
with respective triggering agent. This multifunctional nanoconstruct was designed
for triple stimuli-responsive drug release that inherits sensitivity toward low pH,
glucose molecules, and glutathione enzyme (Fig. 8).

9 Conclusions and Future Prospects

Two-dimensional nanomaterials are now important components in cutting edge

applied research at the interface of environmental and biological interactions. Current
development in this field enabled application of biomedical and environment tech-
nologies in improving human health. Extensive diversity of 2D nanomaterials with
reference to their chemical and physical forms could offer numerous opportunities for
researchers in broad areas of interest. However, it also poses substantial challenges
for any comprehensive assessment in health effects. Studies on 2D nanomaterials
come in various forms like nanosheets (sheet-like silicates), large lateral dimension
(41 mm) sheets with variable effects in application. The key issue for the applica-
tion of these 2D nanomaterials is affiliated to their long-term bio-persistence which is
also closely related to the toxicity. This includes adverse biological responses via cell
membrane compromisation and damage, phagocytosis by cells, impaired lung clear-
ance, and lysosomal damages. These effects are critical which could be overcome by
designing new thin sheet structures, interacting with the membranes, and subcellular
organelles. In order to eliminate these serious limitations, high-priority research areas
are required to be selected which may include several issues like release and expo-
sure kinetics, phase transformation in medium and cellular response to chemical and
physical forms. Besides that, other critical issues like degradation, bio-persistence,
safety associated aspects for nanosheets and its by-product needs to be considered.
Development of analytical and in-silico methods to ascertain the dissolution, transfor-
mation, and redox reactions of wide spectrum 2D nanomaterials in cellular environ-
ment are also significantly important. Clearly, maximum emphasis should be given
to inevitable inflammatory reactions following absorption of the sheet-shaped silica
materials in in vivo settings. Exposure to such materials could initiate plethora of
9 Newly Emerged 2D Mesoporous Silica Nanoparticles … 217

activities including phagocytosis, translocation to membrane, and interference in lung

clearance, etc. It is highly probable that these biological nanosheets could be game
changer in future medicine and offer significant opportunities for future research
for the realization of its potential application. On a precautionary note, emerging 2D
nanomaterial research requires better engineering methodology and control for fabri-
cation and synthesis which could limit the exposure and avoid toxicity. These issues
plus other concerns are required to be addressed for safe and beneficial application
of 2D nanomaterials.

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Chapter 10
Futuristic 2D Nanomaterial Composites
Agro-Formulations for Sustainable
Agriculture

Poonam Gogoi Konwar

1 Introduction

Global hunger is on the rise impacting 9.9% people around the world which means
811 million people go hungry every single day. There are 161 million people cate-
gorized as undernourished severely influenced by the change in climate and the
current Covid-19 pandemic situation. Ironically, 39% are overweight and 13% are
obese out of the world’s adult population in 2016 as per World Health Organization
(WHO). Evidently, there is more than enough food to feed the world’s population
but there is not a uniform distribution of food around the world. Many reasons could
be responsible, for instance, overpopulation, poverty, increased cost of living and
climate changes. A significant change in dietary patterns is also a reason which
seems to be associated with environmental and societal instabilities due to incom-
petent/insufficient policies in the sector of agriculture and environment. Traditional
agricultural breeding practices are not capable to deal with the changing climatic
conditions, plants succumbing to unknown diseases and other related issues. In this
situation, primary objective of all the brilliant minds is the development of agriculture
in an imperishable manner and at the same time to do away with the current situation.
A growing movement towards sustainable agriculture that integrates three aspects;
environment, economy and social equity offers innovative alternatives to protect the
ecosystem in the long run. One such alternative is the use of nanotechnology for the
advancement of agriculture and food industry.
Nanomaterials (NMs) and their formulations are designed to cope with the enor-
mous agricultural challenges such as abrupt climate change, soil fertility decline,
infestation by pests and weeds, disease eruption, lack of nutrients as well as low
post-harvest nutritional value of agricultural products [1, 2]. Nanotechnology-based
approaches bring incredible nanotools with the capacity to rapidly diagnose plant

P. G. Konwar (B)
Department of Soil Science, Assam Agricultural University, Jorhat, Assam 785013, India
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 223
Z. Khanam et al. (eds.), 2D Nanomaterials for Energy and Environmental Sustainability,
Materials Horizons: From Nature to Nanomaterials,
https://doi.org/10.1007/978-981-16-8538-5_10
224 P. G. Konwar

diseases, enhance nutrient absorption in plants and fight the changing climate among
others. The common practice of using different NMs as nanofertilizers and nanopes-
ticides for crop development is very well documented in literature [3–7]. Nano-
mediated sensors for identification and detection of diseases and agrochemical
residues in plants and to monitor the quality of agricultural soil have also gained popu-
larity in recent times. Genetic engineers are also very fascinated with this novel tech-
nique for developing nanodevices for evolving genetically modified plants having
distinctive and improved characteristics [8]. Naturally, NMs have been present on
earth since a billion years in its native state having particular characteristics, however,
due to unintentional anthropogenic involvement at various levels, it acquired some
changes in its basic nature and properties resulting in the evolution of incidental NMs,
which got distributed worldwide. In recent advances, mindful approaches to achieve
a better understanding of their nature and formulating them for specific applications
to achieve maximum benefits have led to the development of engineered NMs [9].
The utilization of wide palette of engineered NMs in site specific delivery of fertil-
izers and pesticides, effective detection of plant diseases, minimum usage of inputs,
reducing loss and contamination of the ecosystem has led to the revolutionalizing
agriculture and food industry [10]. Consequently, the repertoire of NMs has brought
about a paradigm shift associated with the way the scientific world has conceived
the future of nanoscience in agriculture.
One billionth of a metre, as derived from Greek word ‘dwarf’ is a nanometre.
Owing to its smaller size, NMs have very large surface area to volume ratio and
thus are highly reactive [11]. The NMs in form of nanoparticles (NPs), nanowires
(NWs), nanotubes (NTs), nanosheets (NSs), nanoplatelets (NPts) and nanocompos-
ites (NCs) are known to boost the overall efficacy by contributing quick response,
superior sensitivity and stronger limit of detection on account of novel physic-
ochemical, electrical and chemical properties [12]. 2D NMs, at the forefront of
nanotechnology, can be incorporated into agricultural formulations in different forms
like nanoflakes/nanosheets, nanowalls, nanodisks/nanopaltelets and layered mate-
rials forming junctions [13]. Their existing achievements have manifested important
significance as a plant growth stimulator and component of fertilizers [14] thereby
improving agricultural productivity resulting in revolutionization of the precision
farming techniques and sustainable agriculture development [15]; in nanoencapsula-
tion for smart and slow delivery systems [16]; as an antibacterial and antifungal agent
[17] demonstrating its potential application in food packaging [18, 19]; improvement
of soil quality by acting as nanocarriers for micro-and macronutrients [20–22]; in
water treatment and ultrafiltration [23]; for pesticide and insecticide quantitation
[24] and as biosensors for sensing, monitoring, quantification and restoration of
biotic and abiotic stresses for in-situ soil application [25–28]. These advancements
of 2D NMs are credited to their extraordinary properties like high surface area, small
size, excellent variety in surface functionalization and high reactivity [29, 30].
However, it is easily debatable that the application of NMs in the field
agrochemical-formulations for a sustainable agriculture is very limited and scat-
tered. This chapter aims to bring together the research done in this regard to shed a
light on the potential of 2D NMs and composites in the field of agriculture.
10 Futuristic 2D Nanomaterial Composites … 225

2 Preparation of 2D NMs-based agro-formulations

The methods of green synthesis are believed to safeguard the application of 2D NMs
in the field of agriculture. Greener tools and techniques for the synthesis of NMs
and their release with active components at different target sites have resulted in
better soil health, effective control of pest and weed and improved nutrient uptake
and crop nutrition [31]. Different approaches of top-down and bottom-up methods
of synthesis involve additional step of surface functionalization to improve their
properties, stability, cargo loading and biocompatibility. The preparation strategies of
various types of 2D NMs- based formulations that are popularly used for agricultural
applications are discussed here.

2.1 Graphene

Graphene is a 2D packed honeycomb like lattice of single or multiple layers of C-

atoms which is considered as one of the most versatile 2D NMs. It has outstanding
range of properties, viz., chemical, electrical, thermal, optical, mechanical and struc-
tural [32]. Additionally, graphene can be derived into different forms by tuning
its size and surface chemistry such as graphene oxide (GO), reduced GO (rGO),
multi-layered graphene (MLG) and graphene flakes.
Hummer’s or modified Hummer’s method is the most common for the prepa-
ration of GO which involves oxidation followed by exfoliation of natural graphite
powder [20]. A common practice of packing agrochemicals onto GO through π-π
interactions is known to increase its performance. This can be simply achieved by
mixing of all ingredients to form solution followed by separation and washing step.
A functionalized GO/Fe composite was synthesized as a carrier of phosphate ions to
enhance nutrient delivery in plants. A homogenized solution of GO was prepared by
sonication in deionized water and then vigorously mixing with a solution of FeCl3 in
1:1 mass ratio. Overnight drying of the supernatant obtained from the centrifugation
process resulted in GO–Fe nanocomposite which was physically loaded with potas-
sium dihydrogen phosphate (KH2 PO4 ). In comparison to commercial monoammo-
nium phosphate (MAP) fertilizer, the application of GO–Fe nanocomposite loaded
with phosphate has shown slower release of phosphate ions [16].
Polymer coatings are found to improve porosity and flexibility of GO NMs.
Poly-dopamine (PDA) and chitosan are some of the commonly used polymers for
the purpose. Simple polymerization of PDA to prepare a coating on GO encap-
sulated with Hymexazol pesticide is shown by Tong et al. [33]. Most commonly
used fertilizer, potassium nitrate was coated with chitosan-GO nanocomposites for
enhanced porosity [22]. Furthermore, introducing oxygen-functionalized metal ions
to graphene are known to increase surface area resulting in higher loading of micronu-
trients. For instance, Cu–GO and Zn–GO nanocomposites were prepared by the addi-
tion of CuSO4 .5H2 O and ZnSO4 .7H2 O salts in GO solution, respectively, and were
226 P. G. Konwar

used as solid fertilizers with their pH maintained at 4.5 and 6. In another method,
a coating of KNO3 pellets with GO films through ion-mediated thermal reduction
method produced K+ ions encapsulated rGO films with reduced toxicity [34].

2.2 Transition Metal Dichalcogenides (TMDs)

TMDs consist of hexagonal layers of transition metal atoms (M) that are sandwiched
between chalcogen atoms (X) in a MX2 stoichiometry [35]. There are 40 different
types of TMDs owing to the various combinations of transition metal (Ti, W, Hf, Nb,
Re, Mo, Ta, etc.) and chalcogen (S, Se or Te). TMDs have implemented their appli-
cations in many important agricultural studies such as detection of fenitrothion and
pesticide residues in plants and their parts, nitrogen fixing in the soil and regulating
physiological and biochemical behaviours in rice.
The method of synthesis for TMDs is very similar to graphene which includes
mechanical cleavage, chemical vapour deposition (CVD) and chemical synthesis.
Ultra-thin TMD nanosheets with strong absorption and fluorescence in the visible
region were prepared by using a simple kitchen-blender to exfoliate MoSe2 , MoS2 ,
WSe2 and WS2 . These TMD nanosheets were used as a label-free and highly sensi-
tive colorimetric sensor for the detection of single strand DNA based on van der
Waal’s interaction between them in dispersed state [36]. Another example is the use
of Vanadium selenide as an electrochemical sensor in agriculture (V2 Se9 ) which
was prepared by a facile hydrothermal process and ultrasonic treatment with rGO
[37]. There are also examples of the use of polymers such as poly (ethylene glycol)
diacrylate (PEG) with TMDs to prepare composite nanocarriers for the loading of
agri-active component [38].

2.3 MXenes

MXenes with a typical formula of M2 X, M3 X2 and M4 X3 are considered as one

of the biggest families of 2D NMs [39]. They have layered structures stacked with
thick sheets of transition metal nitrides, carbides or carbonitrides contributing to
their unique combination of ceramic and metallic properties. This achieved by selec-
tively removing aluminium from MAX which are basically layered ternary carbides,
Mn+1 AXn (n = 1, 2 or 3), where M refers to early d-block transition metals (Ti, V,
Cr, Nb, etc.), A refers to main group 3 and 14 elements (Al, Si, Sn, In, etc.) and
X refers to either C or N atoms [35]. The transition metal carbides and nitrides are
known to provide amazing metallic conductive characteristic to MXenes with addi-
tional advantages, for instance, high ion transport, low diffusion barrier properties,
large surface area and hydrophilicity. For instance, the use Ti3 C2 nanocarrier for the
efficient delivery of pesticide, avermectin (AV). HF (40%) etching of MAX phase
10 Futuristic 2D Nanomaterial Composites … 227

bulk Ti3 AlC2 powder followed by ultrasonic exfoliation resulted in Ti3 C2 nanocar-
rier which was then loaded with. AV@Ti3 C2 exhibited excellent water solubility,
photostability with a pH responsive release of AV with enhanced anti-pest activity
[40].
Mxene-polymer nanocomposites offer excellent conductivity, affordability and
mechanical flexibility with surface functionalities for multiple applications [41].
One such example is their state-of-the-art preparation as a sensor for ammonia which
involves 3-stage process. Stage 1 is the synthesis of MXenes through techniques such
as selective etching, CVD, chemical transformations [42]. Stage 2 is the synthesis
of MXenes nanocomposites through in-situ or ex-situ approaches, wherein in-situ
involves synthesis of both precursor or one precursor (Mxene) in the presence of
other (polymers) and ex-situ involves blending together pre-synthesized precursors
[42]. Stage 3 is the fabrication of chemiresistor by fabrication of a sensing film over
a substrate through techniques such as electrospinning, drop-casting, inkjet printing
and dip-coating. The substrate could be a glass, indium-tin-oxide (ITO), polyethylene
terephthalate (PET), etc. [43].

3 Applications of 2D NMs in Agriculture

Nano-based technologies aim at improving the efficiency and availability of all essen-
tial agrochemical and biological agents to regulate the releasing concentration of
agro-active ingredients. It also aids in slow degradation by increasing their stability
which increase their shelf life, consequently, achieving sustainable agriculture. NPs
have a large surface area which facilitates quick and higher loading attachment of
agro-active ingredients [35]. 2D NMs and their nanocomposites have attracted their
application in such process of absorption, encapsulation and controlled delivery of
agrochemical which are shown in Fig. 1.
In this section, the different roles of 2D NMs and their nanocomposites in
promoting sustainable agricultural practices are discussed in detail.

3.1 Boosting Seed Germination, Seedling Growth and Plant

Development

2D NMs regulate the productivity of food crop plants as well as the industrial plants.
Interestingly, the impact of graphene during the initial stages of the plant (germina-
tion and seedling development) is dependent upon the size and concentration of the
nanomaterial. Graphene exhibited a positive effect on germination of tomato seeds,
reason being its ability to penetrate seed husk facilitating water uptake resulting in
speedy germination and higher percentage of germination rates [44]. A remarkable
improvement in the number and surface area of leaves, increased root length and
228 P. G. Konwar

Fig. 1 Different modes of entry and roles of 2D NMs in plants

rate of formation of flower buds has been observed simply by the application of
graphene oxide to the culture medium of Arabidopsis thaliana. In the same way,
graphene oxide increased the perimeter, contrived the ripeness and sugar content in
watermelon. We believe that graphene oxide may be used as a strategy for enabling
the acceleration of both plant growth and the fruit ripening process [20]. GO assisted
in expediting the germination of spinach and chive plants when applied at the rate
of 50, 200 μg mL–1 and 50 μg mL–1 , respectively, due to its ability to absorb water
more efficiently [45]. The spray application of graphene nanosheets in solanaceous
crops such as eggplants and pepper @ 0.1, 0.2 and 0.3 GNS g L−1 triggered the
activities of enzymes, viz., ascorbate peroxidase, catalase, glutathione peroxidase
and glutathione-S-transferase, thereby enhancing their overall physiological traits
and yield parameters [46]. Similarly, in cotton and Catharanthus, soil application
of graphene resulted in enhanced seed germination, better pollination, early flower
production, increased flower bud number, and improved tolerance to salt and water
deficit stress [47]. Therefore, graphene-based 2D nanocomposites have great poten-
tial in the field of crop improvement through enhanced plant growth and faster process
of fruit ripening.
As the plant grows, its response towards graphene becomes highly dependent on
concentration, length of exposure and the plant type as well. When applied at appro-
priate concentration, it facilitates growth and development in plant, and at higher
levels, it impedes it. Low concentration (25–50 mg L−1 ) of graphene on seedling
growth of afforestation species such as Larix olgensis had a positive impact showing
10 Futuristic 2D Nanomaterial Composites … 229

an increased root, stem and leaf biomass. A higher concentration (100–500 mg L−1 ),
however, was found to reduce all these enhancements over a period of time. Also, the
seedling survival rates followed a decrease trend with an increase in graphene concen-
tration due to oxidative stress created at different stages in the seedlings [48]. Silver
decorated graphene oxide (Ag-GO) administered radish plants appeared to have a
better root elongation and improved shoot growth, whereas in alfalfa and cucumber
the treatment inhibited the same [49]. A delayed seed germination, growth of radicle
and plumule, length of root and stem, fresh weight of above and below ground parts,
adventitious roots were observed at higher concentrations (5 mg/L) of graphene as
compared to lower ones (100 and 200 mg/L) in rice seedlings [50]. However, the
same treatment in tomato was adequate in inducting their growth. A 285% and 30%
increase in the fresh weight of root and shoot system, respectively, was obtained.
Similarly, in the dry weight 128% increase for shoot system and 480% for the root
system was obtained [51].
Another parameter of 2D NMs that can affect the production and quality, and
impact different molecular pathways in plants is their particle size and surface chem-
istry. Graphene oxide (GO), reduced GO (rGO) and GO quantum dots (GOQDs) can
be translocated from the stems of wheat to grains resulting in the formation of large
aggregates of graphene nanoparticles. These NMs caused a decrease in the concen-
tration of prolamin, globulin, amylopectin and amylose and contents by 11–25%,
8–28%, 23–37% and 5–34%, respectively. A decrease in the levels of minerals with a
19–36% increase in the concentration of soluble sugar in wheat grains was reported.
rGO cause a more downregulated levels of proteins possessing nutrient reservoir
activity in comparison to GO. The decrease in the concentration of mineral element
in presence of rGO and GOQD was much higher than as detected with GO which
could be due to calmodulin upregulation facilitated by ABC transporters. GOQD and
rGO were found to change the metabolomic and proteomic profiles more effectively
than GO. This clearly suggests that the small size and low oxidation content in a
graphene nanocomposite is more detrimental to the quality of grain [52].

3.2 Nurturing Plant Nutrition

The use of fertilizers is a very common practice to increase the productivity of crops.
Fertilizers provide the ultimate food to the developing crops and thus, it is a major
challenge to maintain the quality and efficacy of these fertilizers. Also, different
coating materials such as sulphur and polymers are extensively used, however, the
severe lack of controlled release of agro-ingredients is a major issue that also hampers
the soil pH. An alternative to conventional fertilizers, nanofertilizers have been
designed with an aim to slowly deploy nutrients into plants and to increase their
nutrient efficiency through binding to nano-adsorbents. The use of nanotechnology
where nanoparticles are encapsulated with the nutrients can provide the necessary
thrust to develop advanced revolution for improving agricultural production in a
230 P. G. Konwar

sustainable manner. Notably, NMs based application of agricultural inputs (fertil-

izers, pesticides and herbicides) are known to increase their efficiency by delivering
a desirably slow release of large quantity of macro- and micronutrients to the soil and
plants, and therefore, enhances the crop productivity and at the same time ensures a
minimum usage of the inputs delivering lower cost of cultivation and less wastage
as compared to that of commercial fertilizer granules. With a single or multiple
coating of NMs, a controlled nutrient release can be achieved, although the role
of coating material and the applied method are critical. Broadly, there are three
major categories into which nanofertilizers are divided; nanoscale fertilizers which
are NMs containing the nutrients, nanoscale coatings which are NMs coated on the
conventional fertilizers and nanoscale additives which are the conventional fertilizers
containing some nanoscale additives. The first ever record of GO-based as a slow-
release fertilizer was an enhanced uptake of micronutrients, Zn and Cu in the form
of Zn–GO and Cu–GO nanofertilizers by the plants [53]. Graphene and GO were
used as additives in the fertilizer monoammonium phosphate (MAP) to study their
effect on its physical properties. Sheets of graphene and GO were co-granulated in a
very dose (0.05–0.5%) with MAP. 0.5% graphene sheet co-granulation (MAP-GN)
resulted in 18 times higher mechanical strength. On the other hand, same % addition
of GO in MAP (MAP-GO) resulted in a lesser 8 times improvement. There was also
an improved resistance in MAP granules to abrasion (> 70%) and to impact resistance
(> 75%). There was also enhancement in physical properties on heating MAP-GO at
50 °C which otherwise dried in the ambient conditions. These exciting advantages
of graphene and GO as additives was attributed to their nano-matrix as a superior
filler, larger specific area, and most importantly, their wrinkled 2D nanostructure that
contributes to the great ability of adhesion or interloacking. These findings confirmed
the potential use of graphene or GO in making fertilizers that are physical more stable
in a soil environment [54].
Graphene and its derivatives have been employed as coating agent for the release
of NPK fertilizers, but lack from controlled release, porosity, and flexibility [16].
A chitosan polymer-based GO nanocomposite was prepared by a cross-linking
reaction between the amino groups of chitosan and epoxy group of GO. This
GO/chitosan nanocomposite showed increase in the mechanical strength of coating
with a controlled release of agro-active ingredients for a week [22]. Remarkably,
such nanocomposites can be synthesized with green methods on a very large scale at
reasonable costs. As encapsulation exhibits a biphasic dissolution behaviour, it can
enhance the uptake of Zn and Cu compared to soluble fertilizers that are commercially
available [18].
In recent years, several new composites have been designed by using graphene
and GO to enhance the mechanical properties of reinforcement materials such as
polymers, alloys and metalloids, fertilizer granules and cementitious materials. Such
an improvement in mechanical properties due to graphene is attributed to its high
Young’s modulus, high surface area and high intrinsic strength. However, there are
several other parameters that can also influence the mechanical properties of the
final nanocomposites. The physiochemical properties and concentration along with
the chemical interactions of graphene-based nanomaterials with the matrix can also
10 Futuristic 2D Nanomaterial Composites … 231

influence the mechanical properties of composites [28]. GO modified polyacrylate

polymers were used as an excellent coating material with improved mechanical
strength due to a crosslinked network between them that rendered controlled release
of fertilizers and increased water resistance. For instance, a reduction from 87.25
to 59.71% in the cumulative nutrient release for 28 days was obtained. A delayed
release in urea was also shown at 0.3% addition of GO that improved the coating
strength. This study has great advantage in delivery water-borne controlled release
of fertilizers through GO-polymer nanocomposites [55].
In a pesticide carrier system, it is necessary to achieve their effective use without
any loss. One example of that is the synthesis of GO and poly-dopamine (PDA)
nanocomposite as a stimuli-responsive adhesive. GO with a PDA layer resulted in
higher loading capacity of hymexazol (Hy) with a NIR laser- and pH-dependent
release. A stimulate rain-wash experiment on adhesion-performance revealed that
Hy-GO@PDA had more stable persistence and more residual Hy with a concentrated
surfactant as compared to Hy solution only. It also showed an inhibited bioactivity
for Fusarium oxysporum f. sp. Cucumeberium. GO@PDA has the potential to be
successfully used as a pesticide carrier resolving issues of low-utilization and wash-
off, in particular with water-soluble pesticides [56].

3.3 Diagnosing and Controlling Biotic Stresses (Pest

and Diseases)

An interesting advancement in the use of nanoparticle happened as a pesticide agent

which could be an alternative to chemically synthesized pesticides [57]. Graphene-
based NMs are cheap and easily produced at large scale, thus can be a great and
safe alternative to ditch the traditional use of pesticides and nematicides. More-
over, they can act as good additives for soil. Inoculation of root-rot pathogens, viz.,
Meloidogyne incognita and Macrophomina haseolina, and their subsequent applica-
tion in lentil plant with GO at 250 ppm and 125 ppm caused a significant reduction
in root noduling, nematode multiplication and root-rot index as compared to the
non-inoculated treatments. The total dry matter weight of the lentil plant was also
more than the untreated ones [58]. There was a reduction in number of nematode
galls (94%) and total egg mass (99%) by treating it with rGO in tomato plant. Also,
a treatment of rGO in soil infested with Meloidogyne incognita, ensured a higher
mortality rate of the nematode against the traditional nematicide [51].
The antimicrobial properties possessed by graphene, GO and rGO against many
multi-resistant bacterial, fungal and nematicidal phytopathogens act as a powerful
tool in controlling various crop diseases [59, 60]. In this regard, GO and rGO has
better antimicrobial properties than graphene. GO and rGO have the capacity of
deactivating bacterial cell by causing oxidative stress and disrupting phosholipid
cell membrane. An improved antibacterial activity against MRSA and E. coli was
seen in an injectable hydrogel incorporated with GO due to high conductivity and
232 P. G. Konwar

photothermal activity. A very low concentration of GO @ 250 μg/mL inhibited

and suppressed the bacterial infection in rice caused by Xanthomonas oryzae pv.
oryzae with mortality rate of 94.48% by inducing severe oxidative damage in the
bacterial cells and thereby, showcasing its superior lethal efficacy as compared to
bactericide bismerthiazol. The unique and extreme sharp edges of GO can injure
the cell membrane of a bacteria rendering it as a valuable antibacterial agent against
pathogens with multidrug resistance [61]. However, the antimicrobial activity of
graphene, GO and rGO is somewhat controversial. A study showed no such inheri-
tance of antibacterial properties in graphene and credited its reported behaviours as
a result of impurities.
At varying concentrations, graphene and its oxides (GO and rGO) have the ability
to check the fungal populations by curbing the mycellar growth, inhibiting spore
formation and crimping the biomass [62]. Combination of nanocomposites also have
profound detrimental effects on spores and hyphae of these fungal pathogens and
thus, pose as a strong antifungal agent to curb the heavy yield losses in agriculture.
For instance, silver NPs nanocomposites are used against Fusarium graminearum
for controlling leaf spot disease in plants [63, 64], GO–Fe3 O4 nanocomposite, when
applied to the leaf discs in grapes plants, helped in controlling the downy mildew
disease caused due to Plasmopara viticola by inhibiting their spore formation [65,
66], rGO-CuO nanocomposites caused cell death of the fungal pathogen by creating
various pits and pores in the cell membranes. 1 mg/L of the nanocomposite was
sufficient to reduce the Fusarium wilt, reduce the severity of root-rot diseases below
5% in tomato and pepper without causing any phytotoxicity for ~ 70 days. Usually,
2.5 g/L of Kocide is used to get ~ 30% reduction in disease in both the plants [67].
Transition metal dichalcogenides (TMDs) are also known to damage the cell
membrane by releasing reactive oxygen species (ROS). Some recent studies on MoS2
and WS2 have shown them to be non-toxic and used as antimicrobials. MoS2 gener-
ates superoxide anions that slips through the membrane and bind to the peptide
backbones. WS2 , on the other hand, can rupture the cell membrane [68]. Various
other 2D NMs have the potential to be used as antimicrobial agent but is limited
by the research. An antibacterial activity against gram-positive and gram-negative
bacteria was demonstrated in MXenes NSs, viz., Ti3 C2 Tx and indium (III) selenide
(In2 Se3 ). The sharp edges of NSs help in cellular degradation and the photothermal
activity of In2 Se3 increases the efficacy of antimicrobial activity [68]. An interesting
use of clay nanosheets as a non-toxic and biodegradable NM is achieved in the topical
RNAi delivery to achieve protection against the plant viruses [62]. The global crop
production is severely hit by deadly viral pathogens [69–71], among which bego-
movirus species stand as one of the most prominent pant viruses. The incorporation
of 2D NMs for such a viral-pathogen eradication can change the way we manage
crop production in the world.
10 Futuristic 2D Nanomaterial Composites … 233

3.4 Combating Abiotic Stresses (Salinity and Drought)

Abiotic stresses such as salinity, drought, heat, flooding, freezing, nutrient deficiency,
ultraviolet radiation, etc. have posed a major threat to agro-ecosystem by negatively
altering the morphological, biochemical, physiological and cellular aspects of plants,
thereby hampering crop growth and production. Abiotic stresses are known to cause
oxidative stress in plants [72] resulting in cell damage. In field conditions, plants
are exposed to various combinations of stress such as drought and salinity, salinity
and heat etc. accelerating the intensity and severity of different stresses. There is
a strong relation between drought, greenhouse emissions and the climate changes
which is leading to an increase in arid land mass causing severe damages to agriculture
[73]. Therefore, mitigation of these stresses by implementing modern technologies
like nano-based techniques is the need of the hour [74]. NMs help in minimizing
the damage through enhancing their defence mechanisms by involving antioxidant
enzymes such as superoxide dismutase, peroxidase and catalase [75], supplying
more efficient and less toxic fertilizers, etc. However, NMs at higher concentration
can cause toxicity [14, 76] aggravating the accumulation of free radicals and reactive
species of oxygen and nitrogen leading to a damage in the structure of nucleic acids,
proteins and cell membrane resulting in oxidative injury in plants [77]. The damage
is caused by inducing malondialdehyde, hydrogen peroxide and proline contents
and decrease in antioxidant enzyme activity resulting in post-harvest yield reduction
[78]. Therefore, it is essential to maintain a balanced application of NMs at different
stages of plant growth.
An improved tolerance towards salinity stress was observed after the foliar appli-
cation of GO by the pearl millet (Pennisetum glaucum L.), a fodder plant as a result of
modifying its biophysical and morphological traits. Furthermore, modified GO when
applied at 20 mg L−1 , a higher growth and yield in its green and dry form was achieved
suggesting a boost in photosynthetic efficiency, chlorophyll content, total protein
content and thus, biomass accumulation of the fodder plant [79]. It was observed that
GO alleviated the damage caused due to salinity and also improved the morpholog-
ical, physiological and biochemical characteristics of Milk thistle, a herbal plant [80].
Improved germination rate was also observed in Sorghum and Switch grass, bioen-
ergy crops, under salt stress conditions when treated with graphene [81]. GO consists
of hydrophilic oxygen-containing groups acting as an effective water retention agent
and thus, prevents evaporation of soil water [82]. Therefore, under drought condition,
a higher photosynthesis rate, lignin biosynthesis, increased activity by antioxidant
enzymes, lowered residual toxicity by reactive oxygen species and glyoxylate and
dicarboxylate metabolism were observed in Paeonia ostii, a hardy shrub [83]. More-
over, a prolonged exposure of GO brought about an increase in flowering and plant
survival rate in Catharanthus, an ornamental plant and total fibre production in case
of cotton plant by subduing the harmful effects of severe drought conditions [47].
234 P. G. Konwar

Interestingly, 2D metal nanosheets and graphene NMs can act as nanoenzyme

by mimicking activities of various enzymes, such as catalase, superoxide dismu-
tase, peroxidase and oxidase [84]. Therefore, there is a high probability of engi-
neering 2D NMs exhibiting antioxidant activities by preparing 2D NMs filled with
different molecular antioxidants, for instance, flavonoids, carotenoids and vitamins,
and 2D nanocomposites possessing radical scavenging like properties [85]. These
approaches will reduce the oxidative stress and also increase the tolerance towards
different kinds of stress in plants.

3.5 Sensing and Restoring the Ecosystem

The rapid pressure on agriculture to meet the food supply demand of the ever-
increasing population has posed a severe threat of environmental pollution in the
form of contaminations caused by inorganic or organic compounds, heavy metal
residue, soil degradation, poisonous gases etc. [86]. The extensive usage of chemical
fertilizers and pesticides over the last six decades has resulted in heavy contam-
ination of soil and water which ultimately harm the other members of the food
chain [87]. The introduction of nanotechnology in the field of monitoring, sensing,
catalyzing, imaging and prevention has been very promising in dealing with the
emerging damage to the ecosystem owing to their distinctive novel material proper-
ties. viz., large surface to volume ratio, excellent chemical strength, easy functional-
ization, high thermal and mechanical stability, great electrical conductivity and mass
production [88, 89].
NMs have enormous potential in augmenting the productivity of crops through
deployment of genetic materials and drug molecules into the intracellular levels of
plants [90–92]. The specific use of 2D NMs can be beneficial in tackling food inse-
curity through managing soil and water quality which will minimize the dependence
on pesticides and fertilizers. Also, biosensors could become valuable for the inte-
grated management of pest in crops and livestock by constant monitoring and/or
early detection of any diseases to avoid potential outbreaks [93]. The very first
step towards that would be to monitor the toxic chemical hazards present in the
environment. Scientists have developed different sensors having unique characteris-
tics, particular target and specific mode of operation such as phenols/phenoxy acids
[94], halogenated pesticides [95] and inorganic substances, e.g. Hg [96]. Graphene-
based nanocomposites are often used in the detection of nitrate and nitrite in water.
Graphen/MWCNTs/FeNPs nanocomposites were developed by combining graphene
with metal nanocomposites to develop glassy carbon electrode (GCE) for facili-
tating nitrate and nitrite ions detection in water [97]. Similarly, GO nanosheets and
poly (3,4-ethylenedioxythiophene) (PEDOT) nanofibers were together fabricated
to appraise the level of nitrate in the soil by immobilizing the nitrate reductase
enzymes [98]. An array of GO-based nanocomposites was administered for electro-
chemical sensing of major environmental pollutants, viz., 4-Nitrophenol, TNP, TNT,
HQ, APh and o-NPh [99]. GO-based nanocomposite was able to detect thallium
10 Futuristic 2D Nanomaterial Composites … 235

ions in cereals [100], which is detrimental for human health. Similarly, AuNPs-rGO
composite formed from L-cysteine, gold nanoparticles and reduced graphene oxide
was used for the determination of Cu2+ ions in the soil samples [101].
Graphene nanocomposite based sensors have played a promising role in ultrasensi-
tive detection of phytohormones [102, 103], flavonoids [104, 105], growth regulators
[106, 107] and pesticides/herbicides in soil [108, 109], fruits [110] and vegetables
[111]. A fabricated sensing film based on self-assemblage of phosphotungstic acid-
GO nanohybrid on graphite electrode was able to detect minute concentration of
plant hormone methyl jasmonate [112]. Similarly, sensor made up of platinum NP
and loaded with graphene nanosheet was used to detect Oxalic acid (OA) is naturally
present in plants, fruits and vegetables [113]. A graphene-based magnetic nanocom-
posite was found to be successful in detecting and extracting seven types of triazole
fungicides (tebuconazole, paclobutrazol, diniconazole, triadimefon, myclobutanil,
hexaconazole and propiconazole) in cucumber, cabbage and tomato [114].
Poly(safranine T)-rGO nanocomposite based disposable electrochemical sensor
was able to detect indole 3-acetic acid (IAA) hormones even in low levels in
plant leaves [115]. Graphene nanosheets were fabricated as sensors to quantify
quercetin in onion and apple [116]. A graphene nanosheets hydroxyapatite modi-
fied glassy carbon electrodes can detect concentrations of flavonoid luteolin in
peanut hulls [117]. Graphene-like tungsten disulphide (WS2 ) nanosheets on poly(3,4-
ethoxylenedioxythiophene) (PEDOT), a porous and conductive polymer was devel-
oped to detect concentration of quercetin in lotus leaves [118]. Excitingly, a
chemiresistance-based hybrid gas sensor prepared from hybrid films of polyaniline
(PANI)/Ti3 C2 Tx was found to be capable to monitor the volatilization of ammonia
in the agricultural fields [119]. A nanocomposite designed from graphene ribbon
and AgNPs were found effective in the detection of organophosphorus pesticide
methyl parathion in fruits and vegetables [120]. There are also photocatalysts based
on WO3 nanosheets/nanorods and grafts of α-CD, β-CD and γ-CD on the nanocom-
posites of MoS2 /g-C3 N4 (CDs/MoS2 /g-C3 N4 ) which can be used for the removal
of toxic pesticides such as bromacil, chlorfenvinphos [121] and glyphosate from
agricultural runoff, respectively [122]. The performance and multitude of function-
alities designed for the nanosystems essentially rely on numerous parameters like
sensitivity, specificity, facile operation, precision and detection limit.

4 Future Challenges and Conclusion

In recent years, research and innovations revolving around nanotechnology have

emerged as a powerful potential tool in combating the major issues of hunger among
the rising population Nano-based agricultural strategies improve food production
in a sustainable manner without causing any harm to the limited natural resources.
Bowing to the outstanding properties governed by 2D NMs, it is now possible to
improve rate of seed germination, achieve great seedling and enhanced crop perfor-
mance and growth. This can be successfully achieved by providing slow and target
236 P. G. Konwar

oriented delivery of macro- and micronutrients to the developing plants enhancing

their uptake and absorption for proper utilization. At the same time, 2D NMs
enhanced pesticides, herbicides and nematicides achieve better protection, improved
tolerance against biotic as well as abiotic stress with less residual effects. These
nanoformulations also ensure a reduced loss of agricultural inputs and thus mini-
mizing the cost of production. When 2D NMs are combined with any other material,
the formulation will have more space for the reactions because of higher surface
area providing energy storage or generation more efficiently. The smart packaging
technique in the form of nanofilms aids in minimizing post-harvest loss of perishable
food items such as flowers, fruits and vegetables during storage and transportation
by protracting their shelf life. Researchers believe that NM might help in harvesting
energy from the environment from various sources; however, it will require devel-
oping new NM and notions. Therefore, 2D NMs possess limitless potential that can
achieve the goal of food sustainability for the future generations. While nanotech-
nologies can offer several innovative prospects, their use in food and agriculture
fields has raised issues related to environment, safety, human health, ethics and
regulations. Some associated factors such as toxicity of NMs, production cost and
stability criteria in external environments require serious and thorough investigations.
Keeping in mind that a substantial amount of research is already being conducted, it
may be anticipated that society and environment will significantly benefit from 2D
NMs driven technology advancement in the near future.

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Chapter 11
Fate of 2D Nanomaterials and Their
Toxic Effects on the Environment
and Human Health
Achyut Konwar, Jayanta Sarmah Boruah, Kabyashree Phukan,
and Sazzadur Rahman

1 Introduction

The importance of nanomaterials has increased tremendously in the market with

people consuming them every day. It was noted that about 1814 nanomaterial-
containing products have been used by consumers till March 2015 which keep on
increasing manifolds. One-third of those materials belong to personal care items
related to health and fitness. [1] Among different groups of nanomaterials, two-
dimensional (2D) nanomaterials are gaining much focus for their versatile use in
sensing, [2, 3] drug delivery, [4] energy storage, [5–7] water purification, [8] catal-
ysis, synthesis of nanocomposites, [9] etc. Graphene, graphene oxide, nanoclay, black
phosphorus and transition metal dichalcogenides (TMDs) are the most commonly
used 2D nanomaterials. Because of their wide industrial applications, their impact
on the environment and evaluation of toxicity causing risk to biodiversity, living
organism, including human have become major concerns for the environmental
safety (Fig. 1). It is found that globally about 66,000 metric tons of engineered nano-
materials (ENMs) are released into the surface water. [10] Therefore, it has become

A. Konwar (B)
Central Institute of Plastic Engineering and Technology, Institute of Plastic Technology,
Bhubaneswar, B/25, CNIC, Patia, Bhubaneswar, Odisha 751024, India
e-mail: [email protected]
J. S. Boruah · K. Phukan · S. Rahman
Material Nanochemistry Laboratory, Institute of Advanced Study in Science and Technology,
Guwahati 781035, India
e-mail: [email protected]
K. Phukan
e-mail: [email protected]
S. Rahman
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 243
Z. Khanam et al. (eds.), 2D Nanomaterials for Energy and Environmental Sustainability,
Materials Horizons: From Nature to Nanomaterials,
https://doi.org/10.1007/978-981-16-8538-5_11
244 A. Konwar et al.

Fig. 1 Chart showing various factors that govern the toxicity of 2D nanomaterials

utmost importance to evaluate their interaction mechanism with the environment and
biological samples to get a clear understanding of their level of toxicity.
This chapter brings out the toxicological effect of common as well as most recently
developed 2D nanomaterials. It includes a detailed review on the toxicological study
of different 2D nanomaterials carried out by various research groups. A discussion
on the probable mechanism of toxicity of 2D nanomaterials causing adversity to
environment and human health and some possible measures of remediation is also
included.

2 Fate of Nanomaterials in the Environment and Human

Body

Nanomaterials can enter the environment through any natural and/or manmade path-
ways [11]. Apart from the natural phenomenon like volcanic activities, weathering,
soil erosion, forest fires, clay minerals and dust storms, the nanomaterials could enter
into the environment through various human activities such as automobile traffic,
11 Fate of 2D Nanomaterials and Their Toxic Effects … 245

burning fossil fuels and mining/demolition [11, 12]. The fate of nanomaterials in
the environment is controlled by the physicochemical properties as well as their
ability to interact with other pollutants. The major concern is related to the engi-
neered nanomaterials. These are a group of nanomaterials intentionally produced
in large quantities for various applications and can directly encounter human beings
through different consumer products [13]. These engineered nanomaterials produced
in industries or laboratories ultimately find their easiest way to the environment
through waste systems. Degradation of nanoparticle (NP) incorporated products also
causes the release of nanomaterials. Once discharged, the nanomaterials accumulate
into different matrices of the environment, viz. air, water and soil (Fig. 2) [14].
Atmospheric nanomaterials exposed to sunlight and UV radiation at a significantly
higher degree compared to the nanomaterials released into the other components of
environment. This exposure is likely to cause various physio-chemical changes of the
nanomaterial [15]. They may also change in size by interacting with other volatile

Industry and Laboratory

Soil
2D
nanomaterials Water

Plant Sea Weeds/Algae

Atmosphere

Terrestrial Animals Aquatic Organisms

Human

Fig. 2 Scheme of possible pathways of 2D nanomaterials in ecosystems

246 A. Konwar et al.

compounds present in the atmosphere. Gravitational settling of the nanomaterials

from the atmosphere depends upon their size and density [16, 17].
Similarly, various processes, for example, aggregation, diffusion, accumulation,
interaction with other components, biological degradation, etc., affect the destiny
of nanomaterials in the aquatic system [18]. Aggregation of nanomaterials by inter-
acting with other compounds or particles may cause sedimentation. The degree of
aggregation generally depends on the characteristics of the particles (i.e., type, size
and surface properties) and of the environmental system (i.e., pH, ionic strength and
dissolved organic carbon content). Moreover, the interaction may lead to change in
the nanomaterial’s surface properties and reactivity [19, 20].
Several variables (e.g., nanoparticle’s physical–chemical properties, character-
istics of the soil and environment and interactions of nanomaterials with natural
colloidal material) influence the mobility of nanomaterials released into the soil.
Previous studies have also reported that plants can take up and translocate nanoma-
terials from the soil, which may influence germination rate and plant growth. Nano-
materials may be responsible for adverse effects on the diversity of microorganism
communities present in soil [21–24].
Transformation of nanomaterials’ properties after releasing into the environment
makes the situation more complicated. Most studies on the effect of environment on
nanomaterials are based on their short-term effects. Whereas the transformation of
nanomaterials’ properties is a factor of retention time as well as the components of
the environment. Hence, the dynamics of the environment introduces an uncertainty
toward the fate of the nanomaterials [25, 26].

3 Nanotoxicity: Effect of Physicochemical Properties

of Nanomaterials Toward Human Health

Nanotoxicity is a moderately new branch of toxicology that addresses the gap in

knowledge of toxicity induced by nanomaterials. This branch includes the basic
understanding of the physicochemical effects of nanomaterials and their routes of
exposure/uptake mechanisms for toxicity assessment in humans and the environ-
ment. Toxicity of nanomaterials greatly depends on their shape, size, surface and
physicochemical properties. A slight variation of their properties may have a great
impact on their toxicity [25–27].
There are three ways of toxicity assessment viz., in vivo, in vitro and in silico assay.
In in vitro study, different cell lines are exposed to several potential toxic substances
and left for incubation for definite time intervals. The proliferation and the cellular
metabolism of these exposed cells are measured using different assays (MTT, WST-
8, etc.). The MTT {3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide}
is a colorimetric assay for cell’s viability by measuring it’s metabolic activity. It
is based on the reduction of mitochondrial NADPH-dependent cellular oxidore-
ductase enzymes which reduce tetrazolium dye (MTT) and gives insoluble purple
11 Fate of 2D Nanomaterials and Their Toxic Effects … 247

color formazan. Through the process of endocytosis cells taken up MTT and after
reduction by mitochondrial enzymes it is transported back to the cell surfaces in
the form of needle like insoluble formazans. The water-insoluble formazan can
be dissolved in cell by adding DMSO (sodium dodecyl sulfate) into the treated
96 well plate and absorbance can be measured at a wavelength 570 nm (usually
between 500 and 600 nm) by a spectrophotometer [28]. There are some limitations
in the application of tetrazolium salt due to low solubility of formazan. To over-
come such problems, several water-soluble tetrazolium salts (WST), which include
WST-1, WST-3 and WST-8 [2-(2-methoxy-4-nitrophenyl)-3-(4-nitrophenyl)-5-(2,4-
disulfophenyl)-2H-tetrazolium, monosodium salt], have been synthesized. In the
presence of an electron mediator, such as 1-methoxy-5-methylphenazium methylsul-
fate (1-mPMS), WST is readily reduced by NAD(P)H to produce a formazan product,
and the absorbance can be measured in the range 430–550 nm. Similarly, WST is
also colorimetric assay that shows efficacy for various qualitative and quantitative
applications [29].
In in vivo technique, a small dosage of the toxic substance is administered
inside the body of model animals such as mice. The cellular uptake, distribution,
metabolism and removal pathway can be studied through this technique. However,
compared to in vivo assessments, in vitro testing methods are fast, low cost and
do not involve ethical issues of animal testing. In silico method is one of the rela-
tively novel approaches compared to the conventional in vitro and in vivo assessment
techniques. This technique is faster and cost-effective. It utilizes several theoretical
models to predict the physicochemical properties of the molecules. The toxicity
of any molecular compound is predicted using the available experimental data and
further interpolating using mathematical models [27].
To determine the toxicity of 2D nanomaterials, many different parameters are
studied such as disruption of metabolic activity, oxidative stress and cell membrane
disintegration [30]. There are many in vitro tests that can be done to determine
the generation of toxicity which are grouped into two categories, namely viability
tests and functional assays. In cell viability test, various cellular properties such as
membrane integrity, structure and mitochondrial activity can be measured by specific
assays to determine cell damage caused upon exposure of cells to 2D nanomate-
rials [31]. For example, MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium
bromide) and WST-8 (water-soluble tetrazolium salt) assays assess mitochondrial
activity. In metabolically active cells, the colored product formazan dye gradually
increases (which indicates more viable cells as the color intensity increases) with
decreasing the tetrazolium reagent [32, 33]. On the other hand, functional assays
give more emphasis on the mechanism of toxicity via various cellular processes. For
example, comet assay [34] where cell DNA damage can be identified by the ratio of
fluorescence intensity emitted from damaged DNA to intact DNA where the value
measures the level of DNA damage as a result of exposure of nanomaterials [35].
The other cellular indicators namely oxidative stress where by inducing stress, cells
generate more intracellular reactive oxygen species (ROS) such as hydroxyl radicals,
peroxy radicals and hydrogen peroxide [36]. Quantification of amount of ROS can
be done by 2 ,7 -dichlorodihydrofluorescein diacetate (DCFDA) [37–39].
248 A. Konwar et al.

4 Toxicity Assessment of 2D Nanomaterials in Human

Health

4.1 Toxicity of Graphene Family Nanomaterials

Graphene is one of the most widely used 2D nanomaterials for advanced applica-
tions. Nearly, all fields (electronics to biological) are associated with graphene or its
derivatives. Although it has shown its superiority in many ways, it has shown toxi-
city issues toward humans and environment. The variability in their toxicity level
stems from lateral dimensions (size), shape, dispersity, surface structure and charge or
functionalization. The exact mechanism responsible for graphene toxicity is not clear
yet. Physical interactions could be one of the major causes of graphene toxicity and
antimicrobial property [40]. Graphene can bind with α-helical structures of peptides
and is observed to cause an abnormal stretching of the cell membrane of RAW 264.7
cells (a type of macrophage cell line) by largely adhering to the membrane surfaces
at a concentration above 75 μg/mL [41, 42]. 2D nanostructure of graphene materials
also can provide sharpened edges, which can act like a ‘blade’, causing damage to
bacterial cell membranes [43]. However, such a damage to the cell wall by physical
contact with graphene can be minimized by coating with different macromolecules
like PEG [44].
The oxidized form of graphene, i.e., GO can lead to the generation of exces-
sive reactive oxygen species (ROS) on interaction with cells. Increasing levels of
ROS can overwhelm the activity of antioxidant enzymes, including catalase, SOD
or glutathione peroxidase, thereby producing oxidative stress within the cell. It is
noted that many diseases are accompanied by a high rate of oxidative stress. It was
found that the cytochrome c/H2 O2 system played a key role in nanotoxicity under
stress. GO offers electron transfer from cytochrome c available on the surface of
mitochondria to H2 O2 , which subsequently increases the ROS production leading to
higher cytotoxicity which is not possible in normal physiological conditions [45].
This oxidative stress generation is also responsible for GO-induced acute lung injury
[46]. ROS generation can be the first step in the mechanisms of carcinogenesis, aging
and mutagenesis. ROS has a significant role in cellular macromolecular damage, such
as membrane lipid breakdown, protein denaturation, DNA fragmentation and mito-
chondrial dysfunction, affecting cell metabolism and signaling [47–49]. Exposer to
GO may reduce the activity of superoxide dismutase and glutathione peroxidase
[50–52].
Liao and coworker investigated the impact of graphene and graphene oxide on
erythrocytes and human skin fibroblasts, considering the particle size, exfoliation
method and the extent of oxidation. It was noticed that treatment of smaller GO
particles showed more hemolysis than that of the aggregated or larger ones. Further,
modification of GO surface with chitosan eliminates the hemolytic activity of GO
[51].
GO could cause mutagenesis in mice after intravenous injection of GO at a signifi-
cantly lower dose compared to cyclophosphamide, a classic mutagen [53]. GO cannot
11 Fate of 2D Nanomaterials and Their Toxic Effects … 249

enter into the cell nucleus although it gets the opportunity to interact with DNA during
mitosis [54–57]. The π-stacking interaction between the graphene carbon rings can
severely deform the hydrophobic end base pairs of DNA which potentially increases
the genotoxicity [58]. DNA damage not only leads to cancer development, but also
increases health risk of the next generation if the mutagenic potential of GO arises
in reproductive cells impacting fertility and health of the offspring [53, 59].
Intratracheal instillation or intravenous administration of graphene nanomate-
rials at high doses can cause significant inflammatory response including inflamma-
tory cell infiltration, pulmonary edema and granuloma formation [46, 60]. Figure 3
shows the effect of GO with different concentration and incubation time of human
erythrocytes. Here, phosphate buffer saline (PBS) was used as control. The optical
microscope images in Fig. 3a, b indicate the intact of erythrocyte morphology in

Fig. 3 Impact of concentration and exposure time of GO on the morphological of human erythro-
cytes. Exposures of erythrocytes to a PBS for 1 h, b PBS for 4 h, c GO 10 μg mL−1 for 1 h, d
GO 10 μg mL−1 for 4 h, e GO 80 μg mL−1 for 1 h, f GO 80 μg mL−1 for 4 h. Scale bar =
50 μm (Reprinted from ‘Distribution and biocompatibility studies of graphene oxide in mice after
intravenous administration’, 49, [60])
250 A. Konwar et al.

PBS. However, the GO suspension ruptures the erythrocytes at higher concentration

(80 μg mL−1 ) with more exposure time (4 h). But lower concentration of GO (10 μg
mL−1 ) could not show such destruction.
A study has revealed that 21 days of subcutaneous injection of GO cause inflam-
mation followed by a secretion of various cytokines including IL-6, IL-12, TNF-α,
MCP-1 and IFN-g [61, 62]. Nanomaterials composed of graphene can elicit inflam-
mation and tissue injury by triggering the release of whole Th1/Th2 cytokines and
other chemokines which promote the engagement of circulating monocytes into the
injured or damaged tissues [63, 64]. Some other graphene nanomaterials such as pris-
tine graphene [64] and rGO [65] activate the NF-κB signaling pathway by binding
to toll-like receptors (TLRs). This signaling cascade is stimulated by various pro-
inflammatory cytokines such as IL-1 and TNF-α and toll-like receptors. This results in
the shifting of NF-κB from cytoplasm to the nucleus and binding to IκB which acts as
a transcription factor followed by the synthesis of different types of pro-inflammatory
cytokines [66].

4.2 Toxicity of Transition Metal Dichalcogenides (TMD)

Since 1960, people have been working on TMDs, and it was observed that based
on the properties of transition metal and chalcogen, they may show insulating,
semiconducting, metallic and superconducting behaviors. TMDs include inorganic
compounds like MoS2 , WS2 , MoSe2 , WSe2 , MoTe2 , etc. Two-dimensional TMDs
have emerged as promising materials for catalysis, energy storage, biosensing, photo-
electronic devices, photodynamic therapy, drug and gene delivery, due to various
unique mechanical, optical, electronic and chemical properties. The increasing appli-
cations of 2D TMDs have increased their environmental accumulation and the possi-
bilities of human exposures [67–69]. Like graphene, the toxicity of TMDs varies
depending on the particle shape, size and surface chemistry. It is noted that the
toxicological characteristic of TMDs is still not well-explored.
2D TMDs generally have low toxicity in their bulk form. The toxicity of these
materials has, however, been shown to be influenced by the parameters used in the
production processes such as exfoliation conditions, as well as defect density and
chemical composition [70]. Consequently, it is still difficult to draw conclusions
about the toxicity of the entire class of 2D TMDs. In vitro cell viability assays such
as MTT and WST-8 assays, which measure cellular reduction, have been used for
assessing the toxicity of semiconducting 2D TMDs such as MoS2 , WS2 and WSe2
[71]. It is observed that while MoS2 and MoSe2 did not show appreciable toxicity
to lung cancer cells, WSe2 induced significant toxicity, although its toxicity was
lower than that observed for graphene oxide and graphene. It is also observed that
decreasing the number of layers in 2D MoS2 can increase the toxicity, which is
attributed to the enhanced surface area, defects and edges [70]. Some other studies
using human pulmonary epithelial cells demonstrate a low health risk of 2D WS2 and
MoS2 [72]. Cell viability measurement for 2D TMDs without surface modification,
11 Fate of 2D Nanomaterials and Their Toxic Effects … 251

carried out by Teo et al., showed a big difference between MoS2 , WS2 and WSe2
nanosheets. The degree of cytotoxicity can be ranked in the order of WS2 < MoS2 <
WSe2 . The higher toxicity of WSe2 can be attributed to the Se. Chalcogens mainly
being located at the exterior of each 2D TMDs layer can have more interaction with
cells compared to the transition metal [71].
In addition to chemical composition, surface modification also influences in vitro
cytotoxicity of 2D TMDs. Chitosan-functionalized MoS2 and PEGylated WS2 exhib-
ited negligible cytotoxicity while testing with different kinds of human cells [73, 74].
Thickness is also another factor playing a critical role in 2D TMDs induced toxicity.
The effect of exposure to human lung cells with MoS2 nanosheets of three different
thicknesses by different exfoliation methods was compared. Tert-butyllithium and
n-butyllithium exfoliated MoS2 nanosheets were found to be more cytotoxic than
methyllithium exfoliated MoS2 . Tert-butyllithium and n-butyllithium provided more
efficient exfoliation than methyllithium reducing the final thickness of MoS2 . Hence,
smaller the nanosheet thickness, stronger their cytotoxic influence [70]. The increase
in active edge sites and surface area caused by thickness reduction might contribute
to the increased cytotoxicity [75].
2D TMDs also exhibit antimicrobial activity. Unlike graphene, 2D TMDs cannot
disrupt the cell membrane by cutting like a blade with sharp edges. The mechanism
of antimicrobial activity of MoS2 was studied against E. coli, and it was observed that
killing ability was higher for the exfoliated nanosheets. The exfoliated MoS2 could
kill more than 90% of the total bacterial cells, while the unexfoliated one could kill
only 40%. Cell death occurs due to both ROS generation as well as ROS independent
oxidative stress [76, 77].

4.3 Toxicity of Phosphorene

2D black phosphorus or phosphorene has attracted researchers for its promising

properties like high carrier mobility and tunable electronic band gap making it a
suitable candidate for various applications in optoelectronics, biosensing, nanoelec-
tronics, rechargeable batteries, photocatalysis, and biomedical imaging. Phospho-
rene shows low toxicity, good biocompatibility, and biodegradability. A very few
reports are available on the toxicity study of phosphorene. However, the application
of phosphorene is not entirely safe [78].
Latiff et al. investigated the cytotoxicity effects of layered black phosphorus (BP)
against human lung epithelial cells using WST-8 and MTT assays. Black phos-
phorous exhibited a dose-dependent response on A549 cells with a toxicity level
intermediate between graphene oxide and TMDs such as WS2 and MoS2 [78]. Lee
and his coworkers fabricated black phosphorus-based nanodots using an exfoliation
method. These BP-Nanodots were stable in aqueous medium [79]. After in vitro
cytotoxicity assessment in CHO-K1, HeLa and COS-7 cell lines, no or little cyto-
toxic effect was observed for HeLa, COS-7 cells at 1.0 mg mL−1 concentration of
nanodots and only 10% cell death for CHO-K1 cells at 3.0 mg mL−1 of nanodots.
252 A. Konwar et al.

Fig. 4 Treatment of L-929 cells with BP (10 μg/mL) for 12 h. a Percentage of live cells present
after exposed to BP, b optical microscope images of L-929 fibroblasts in the presence of BP at 0
and 12 h. The scale bars = 100 μm ([80] Reproduced from the Ref. under CC BY 4.0 licensing
from the MDPI publisher) https://creativecommons.org/licenses/by/4.0/

Song et al. investigated the cytotoxicity of black phosphorus nanosheets (BPNSs) by

subjecting with different fibroblast cell lines, viz. NIH3T3, nHDF and HT1080. A
dose and time-dependent cytotoxicity was observed for all the cell lines. The investi-
gation revealed that the nanosheets were more toxic to cancerous HT1080 cells when
compared to their toxic response to normal cells. Cytotoxic effects of layered BPs are
proven to be because of both oxidative stress-mediated enzyme activity reduction
and membrane disruption. Notably, layered BPs did not show significant toxicity
at concentrations below 4 μg/mL [80]. But, at higher concentration (10 μg/mL),
it was found to induce apoptosis of L-929 fibroblast cells on keeping exposed for
longer time (12 h) as shown in Fig. 4. The percentage of live cells got reduced conse-
quently (Fig. 4a), and the quantity of apoptotic cells (red colored) increased with
time (Fig. 4b).

4.4 Toxicity of MXenes

MXenes, a dynamic class of 2D nanostructures consisting of early transition metal

carbides, nitrides and carbonitrides, can tune their crystal structure to apply in
multiple fields [81]. It has a general formula, Mn+1 Xn Tz , where M is an early tran-
sition metal, X is carbon and/or nitrogen, n = 1, 2, or 3; Tz stands for the surface
terminal functional groups (e.g., –OH, = O, –F) [82]. Since its discovery in 2011, its
use has been rapidly expanded to cover tremendous applications [83]. Development
of many theoretical and experimental results on it comes to a pose while discussing
its safety measures as no such in-depth study has been taken place so far. The avail-
able literature discusses mostly the toxicity of Ti-based Mxenes. It is observed that
the toxicity of MXenes is also influenced by their stoichiometry (i.e., Ti2 C or Ti3 C2 ).
11 Fate of 2D Nanomaterials and Their Toxic Effects … 253

An investigation by Rasool et al. [84] indicated that Ti3 C2 MXene exhibited bacte-
ricidal properties against Escherichia coli and Bacillus subtilis strains, while the
study of Jastrz˛ebska et al. [85] showed the lack of toxicity of Ti2 C MXene toward
Staphylococcus aureus, Bacillus sp. and Sarcina bacteria.
Another study of Jastrz˛ebska et al. [86] revealed varying toxicity levels of Ti3 C2
MXenes for different cell lines. They also found that the toxicity was higher for
cancerous cells compared to that for normal cells. The mechanism of action is
assumed to be ROS-induced oxidative stress, which varies for varying cell lines.
Furthermore, another report showed the possibility to ‘tune’ the cytotoxicity of
the Ti3 C2 Tz flakes using simple, inexpensive, post-delamination treatments, such
as ultrasonication or mild thermal oxidation. Sonication of Ti3 C2 Tz flakes or soni-
cation followed by mild oxidation in the water at 60 °C could change their toxic
effect selectively toward cancer cells as compared to non-malignant ones. Post-
treatment methods sufficiently change the surface properties of the Ti3 C2 Tz flakes,
which significantly influence their toxicity. The most important features responsible
for the toxicological properties are related to the presence of transition metal oxides
Mx Oy and lithium atoms on the surface [87].

4.5 Toxicity of Hexagonal Boron Nitrides (hBN)

Hexagonal boron nitride (hBN) has a crystalline structure similar to graphite, except
that the carbon atoms are replaced by boron and nitrogen atoms. hBN has self-
lubricating ability and is used in many different applications like cosmetics, as addi-
tive in plastics and ceramics, lances, coatings, paints, etc. [88] hBN also has the
potential to be used in different biomedical applications. Hence, it is important to
have a knowledge about their toxicological effect. However, a very few reports are
available on the toxicity study of hBN. Boron nitride (BN) does not show any toxicity
at a low concentration although it has some adverse effects at a higher concentration.
The size of BN nanomaterials is another factor governing its toxicology. For example,
in vivo study of hBN nanoparticles having 30–60 nm radius and 1.6 nm thickness
did not show any physiological change when injected into mice. The concentration
used in this study was 20 μg/mL [89]. BN nanoparticles having a size 100–250 nm
with concentration 30 μg/mL showed a negative effect on the viability/metabolism
of osteoblast cells [90]. hBN with 75 nm size at doses 250 μg/mL even did not
show any significant change in the cell morphology [91]. However, PEG-coated
BN nanoparticle having a size 20 nm at a concentration 300 μg/mL was found to
have some toxic effect upon in vivo testing in mice [91–93]. Investigation by Kar
et al. demonstrated no significant changes in any important acute hematological or
biochemical function at low doses after 24 h of intravenous injection of different
doses of hBN NPs. At higher doses, i.e., 1600 and 3200 μg/kg, some adverse effects
were observed. Histological detections also indicated that 1600 and 3200 μg/kg hBN
NPs treatment could induce significant damage in the liver, kidney, heart, spleen and
pancreas. The results of the study show that hBN NPs of 121 nm diameter could be
254 A. Konwar et al.

promising for biomedical applications where low doses between 50 and 800 μg/kg
are not toxic [94].

4.6 Toxicity of Silicene and Germanene

Silicene and germanene are allotropes of silicon and germanium, respectively.

Both silicene and germanene are 2D materials in a honeycomb structure similar
to graphene [95]. Unlike graphene which has a planar like structure, both silicene
and germanene have buckled sheets type arrangements. They exhibit almost similar
properties to graphene, but there is some restriction in their application in electronics
due to the presence of negligible bandgap. Also, both silicene and germanene are
thermodynamically less stable. Hence, to improve their stability and to increase
their bandgap, different modifications have been carried out. The reported modi-
fied silicene and germanenes are siloxene (Si6 H3 (OH)3 ), germanane (Ge6 H6 ) or
methylgermanane (Ge6 (CH3 )6 ), etc. [96]. Modified forms of silicene and germanene
are also formed during their synthesis. These materials have a high potential to be
used in different fields of application. Germanane is reported to show photocatalytic
properties which can generate hydrogen through water splitting and can hydrolyze
ammonia-boron or borazine complex [97]. Methylgermanane has been reported as
photocatalysts for the generation of hydrogen and also used as a fluorescence marker
on nanographene-platinum microrobots [98].
Before large-scale usage of new materials, it is crucial to study their toxicity.
As of now, only one report is available on the toxicology study of silicene and
germanene derivatives. Toxicity of siloxene, germanane and methylgermanane was
studied on the cell lines obtained from various parts of a human body, such as lung
carcinoma (A549), breast carcinoma (MCF7), kidney (HEK293) and liver carcinoma
(HepG2) cell. The cytotoxicity was assessed by exposing an increasing concentration
of the respective material to the cell followed by evaluating the cell viability by cell
counting kit8 (CCK8). The result obtained from this study revealed that siloxene
has less toxicity toward all cell lines. Germanane and methylgermanane were found
to show dose-dependent toxicity on cells. Germanane was found to be more toxic
than methylgermanane, particularly in low concentrations (6.25 and 12.5 μg mL−1 ).
Furthermore, both germanane and methylgermanane were more toxic toward liver
cells and more compatible toward breast cells [99].

4.7 Toxicity of 2D Ceramic Nanomaterials

Nanoclays are layered silicates that form platelets with nanosized thickness stacked
together by van der Waals forces. Among many ceramic materials available in the
market, 2D ceramic nanomaterials have a significance in terms of its widespread use.
11 Fate of 2D Nanomaterials and Their Toxic Effects … 255

Nanoclay is one of the most popular members of this family with tunable characteris-
tics. Naturally occurring nanoclays, such as montmorillonite, bentonite, kaolin, and
halloysite, have been employed in many industrial applications such as nanosized
fillers, as fillers for polymer composites, anticorrosion and flame-retardant protective
coatings. Nanoclay–polymer composites have potential for many biomedical applica-
tions, antimicrobial coatings, drug delivery, bone healing implants, paper-mimicking
sheets, pesticide carriers, cosmetic formulations, etc. [100].
An investigation by Marina Kryuchkova et al., using a protozoan model organism
P. caudatum, revealed lower cytotoxicity of some most popularly used nanoclays
compared to a similar sized silica or graphene oxide nanomaterial. Different types
of nanoclays were used, and the order of safety was found as halloysite > kaolin >
montmorillonite > silica > bentonite > graphene oxide, where halloysite was found
to be the safest against the used protozoan model. However, this study was carried
out using a high concentration of nanomaterials (up to 10 mg mL−1 ) [100]. Lordan
et al. [101] determined the cytotoxicity of two different nanoclays: the unmodified
nanoclay, Cloisite Na+® and the organically modified nanoclay, Cloisite 93A® , in
human hepatoma HepG2 cells. Their study showed a high level of toxicity by both
these nanoclay inducing necrosis, an acute form of cell death. High amount of ROS
generation was observed in the presence of Cloisite Na+® which was the cause
of damage to the cell membrane. Both the nanoclays showed a dose-dependent
toxicity starting from 1 to 1000 μg/mL. However, contradictory results were also
found for similar studies. A study carried out by Maisanaba et al. did not find any
toxicological effect by Cloisite Na+® although organoclay Cloisite 30B® showed
some toxicity against hepatic cell line HepG2 [102]. Nanoclays in their natural form
are aggregated and stacked together due to the electrostatic interaction and van der
Waals force to form cluster. Different types of organic modifiers are used to modify
the surface properties of the nanoclay which helps to have good compatibility with
the matrix in a composite. Tertiary ammonium cation-based modifiers are generally
used for modification of nanoclay through an ion-exchange method. These organic
modifiers are primarily responsible for enhanced toxicity of organoclays. Janer et al.
in their study observed that after the removal of organic modifiers by washing with
methanol or ethanol, the toxicity of organoclays decreases. [103] The most widely
used nanoclay, i.e., montmorillonite (MMT) in its pristine form shows toxicity only at
high doses and on long-time exposure. When tested against normal human intestinal
cells, the cell membrane damage was observed at MMT concentration 1000 μg/mL
and exposure time of 48–72 h. Significant ROS generation was also found in the cells
incubated with above 50 μg/mL MMT after 48–72 h; however, it did not produce ROS
within 24 h at practical biological concentration of below 500 μg/mL. MMT could
be absorbed into the body within 2 h, but it did not significantly accumulate in any
specific organ [104]. Since MMT is widely tested by researchers as a component in
drug delivery vessels, a detailed study of its toxicological properties is very important.
256 A. Konwar et al.

5 Effect of 2D Nanomaterials in the Environment

Apart from the toxicological effect on human health, 2D nanomaterials also have
serious environmental effects. After their release from industries, laboratories or
consumer products, nanomaterials are mostly accumulated in water bodies, so there
is a great chance of serious environmental damage to aquatic organisms, which is yet
to be extensively evaluated. Hu and his coworkers analyzed the effect of graphene
oxide (GO) on the green microalgae Chlorella Vulgaris, after administration of GO
[39]. Their study revealed enveloping of algal cells by GO nanosheets forming blister-
like nanostructures. GO could damage cell organelles especially via plasmolysis and
an increase in the starch grain number after entering into the cells. Reduction of cell
division was also observed along with the aggregation of chromatin and damage to
the chloroplast structure. GO also inhibited cell growth, enhanced ROS generation
and disrupted antioxidant enzymes. Furthermore, GO penetration into the cell caused
metabolic disturbances linked to key biological processes. Similarly, the growth of
Triticum Aestivum was inhibited as a result of graphene absorption [105]. Thus, it has
been proved that graphene has a negative impact on the growth and/or alteration of
photosynthesis resulting in a disproportion of nutrient homeostasis depicted through
a decrease in the shoot biomass, number of root hairs, reduced PSII activity and
chlorophyll content. The phytotoxicity has been evaluated on C. Vulgaris by incor-
porating GO with carboxyl single-walled carbon nanotubes (C-SWCNTs), where
even at a concentration of 1 mgL−1 DNA replication gets inhibited [106]. Begum
and her colleagues [107] investigated the GO effects in terrestrial plants such as
tomato, red spinach and cabbage. They found that after 20 days exposure to GO,
particles accumulated on the surface of the roots at a concentration of 1000 mgL−1
causing cell death and injury to the leaves. The phytotoxic effect varies with concen-
tration, time and also the plant species. Although GO has many adverse effects on
plant cells, an investigation by Ming Zhang revealed that GO at a concentration level
40 μg mL−1 could promote the germination of tomato seeds by increasing their water
absorption capability. However, the seedling growth was hampered by the presence
of GO, indicated by a lower accumulation of biomass. Lower seedling growth may
hamper the growth of the plant in its later stages [108]. Similarly, a positive effect
on germination and growth of rice has been seen at a concentration of 5 μg mL−1 .
Although it shows inhibitory effects at a concentration of 50 μg mL−1 [109]. Another
formulation of sulfonated graphene NPs stimulated growth (plant height, root, and
shoot biomass) at a low concentration (50 mg L−1 ) in maize seedlings, and on the
other hand, at a high dosage (500 mg L−1 ), it exhibited a strong inhibitory effect
through Ca2+ signaling and possessed ROS production and lipid peroxidation [29].
Similarly, at a high dosage of GO (2000 mg L−1 ), wheat seed shows germination but
with a slight reduction in root elongation. However, in such concentration of GO,
the chromosomal aberrations and mitotic abnormalities increase which stipulate the
clastogenic and aneugenic effect of GO in wheat root meristem [110]. The toxi-
city of particles depends upon the environmental air conditions. After exposure to
11 Fate of 2D Nanomaterials and Their Toxic Effects … 257

abiotic factors such as sunlight, water, humidity etc., their physicochemical proper-
ties changes and ultimately reduces the toxicological effect of GO [111]. Incorpora-
tion of 2D nanomaterials into water, soil and air ultimately affects the food chain. GO
shows serious toxic effects beyond a concentration of 1.2 mg L−1 in Phanerocheate
chrysosporium, a white-rot fungus [112]. Toxicity of GO has also been seen in
aquatic environment. In Euglena Gracilis, the growth inhibits at a concentration of
GO exceeding 2.5 mgL−1 which might be due to the coating of cell membrane by
GO resulting in a decrease in light utilization [113]. Planktonic Crustacean Daphnia
magna plays a chief role in the freshwater food chain. Carbon-14 tracking was used to
investigate the toxicity of GO in the planktonic organism, where graphene was found
nearly about 1% of the mass at a maximum concentration of 250 μg L−1 for 24 h
[114]. Further graphene was found in the brood pouch of gravid organisms where
a few-layer graphene (FLG) with horseradish peroxidase was introduced to prevent
the gathering of graphene [115]. As compared to the unmodified particles, modified
FLG shows reduced toxicity. To reduce the toxicity in zebrafish, humic acid (HA)
is incorporated to modify GO surface [116]. Thus, surface modification or coating
may help to reduce the adverse environmental effects of GO. Direct administration
of GO often causes harmful effects in living organisms. At concentrations of 0.01–
100 mg L−1 , GO found to be hardly attached to the chorion surface that hinders the
oxygen supply by blocking the pores. This hypoxic chorionic environment results in
delayed hatching, ischemia, and malformation of the embryo. On the other hand, an
incorporation of HA causes detachment of GO from the chorion results in a marked
increase in physiological oxygen concentration leading to healthy embryos. Another
positive effect of inducing HA is that it enhances negative charge on the surface of
the material which minimizes contact of particles with the embryo. Whereas, free
GO causes alteration in protein secondary structures from which the chorionic sac is
made of. The level of toxicity also depends on the environment. Zebra fish in cultured
water secretes various small organic molecules, proteins, mucopolysaccharides and
nucleotides. These biological secretions along with the GO nanosheets (GOBS) cause
extensive cell deaths [115]. The probable mechanism of toxicity is the tight adhesion
of GOBS on embryonic surfaces attributed to the increase in the functional group
on GO surfaces. This phenomenon ultimately inhibits oxygen and ion exchange
causing a metabolic imbalance in the cell. Apart from GO nanosheets, black phos-
phorus nanosheets (BPNSs) also show some toxic effect on environmental organisms.
Depending upon the concentration, the toxicity of BPNSs varies. The 120 h expo-
sure of BPNSs stimulates the growth of Chlorella vulgaris (C. vulgaris) at 1 mgL−1 ,
and on the other hand, at high concentrations (5 and 10 mgL−1 ), BPNSs retard the
growth. Studies revealed that BPNSs caused a remarkable reduction of antioxidant
agents such as glutathione (GSH) and glutathione disulfide (GSSG) in C. Vulgaris.
Higher concentration of BPNSs leads to an increase amount of reactive oxygen
species (ROS), and reduced superoxide dismutase results in high oxidative stress
which is accompanied by the gentle release of dissolved phosphate ions, including
PO2 3− , PO3 3− and PO4 3− and causes disturbance in the growth of C. vulgaris
[117]. Likewise, natural and modified nanoclays also exhibited some toxic effects
in aquatic organisms. Robinson et al. [118] investigated the role of natural nanoclay
258 A. Konwar et al.

and found that it inhibited the growth and reproduction rate of Daphnia Magna by
clotting the gut [118]. Another study by Blake [119] reported that nanoclays in an
aggregated form present in solution show nominal toxic effects on D. magna, due to
rapid settlement of sediment which minimizes the exposure time or interaction time
to nanoclays in the water [119]. The toxicity of GO was also revealed in the zebrafish
model [120]. The effect of GO on head skeleton and cardiac function of zebrafish
is shown in Fig. 5. It was observed that the head skeleton formation in zebrafish
decreased when treated with GO (Fig. 5b) compared to control (Fig. 5a) as indicated
in the red box. Similarly, erythrocyte detection in the cardiac section of zebrafish
in the presence of GO (Fig. 5d) was reduced significantly by 87.18% compared to
control (Fig. 5c). The quantity of erythrocyte is the indication of the cardiac output
in zebrafish embryos.

A B

C D

Fig. 5 Study on skeletal and cardiac development of zebrafish larvae treated with GO. Head
skeleton of zebrafish larvae stained with alcian blue/alizarin red S at 7 dpf (days post fertilization)
as a control, absence of GO, b 100 μg/L GO. Erythrocyte number (as cardiac output) in zebrafish
embryos at 48 hpf (hour post fertilization) in, c control, absence of GO and d 100 μg/L GO. The
scale bar = 20 μm. mk = Meckel’s cartilage; ps = parasphenoid (Reprinted with permission from
{Ref. [121]}. Copyright {2017} American Chemical Society)
11 Fate of 2D Nanomaterials and Their Toxic Effects … 259

6 Precautionary Measures for Handling of 2D

Nanomaterials

2D nanomaterials are emerging advanced materials for future technologies. Their

applications and production are increasing progressively. In the future, there is
a high chance of new members to add in this family. Therefore, it is of utmost
importance to take necessary precautionary measures for handling and use of such
nanomaterials to avoid a toxic environment and nature’s imbalance. Realizing the
underlying risk of nanomaterials because of their growing applications, different
precautionary guidelines have been started on industrial as well as research level.
Different regulatory bodies across the globe have been formed to underline the safety
issue of nanomaterials. Mainly, World Health Organization (WHO), Organization for
Economic Co-operation and Development (OECD) and the International Organiza-
tion for Standardization (ISO) are some of the international organizations which have
been involved to issue various standard guidelines to be applicable for the safe use
of nanomaterials considering all the possible impact and risk assessment. Till 2017,
OECD published 58 relevant reports, and ISO provided 55 standards based on the
health and safety issues of nanomaterials including safe handling in the workplace,
coordination with the WHO recommendations [121–123]. The basic framework of
guidelines is summarized below [27].
i. Before going for a large-scale production of new nanomaterials, a thorough
study on their toxicological effect must be carried out.
ii. The risk factor should be minimized with a proper approach. For example, a
surface functionalization or coating generally helps to reduce their toxic effect.
However, sometimes this approach may affect the most required property of
a nanomaterial. It is reported that GO after coating with polyethylene glycol
(PEG) exhibits lower toxicity compared to the pristine one.
iii. Proper analysis of a tolerable exposure limit of a particular nanomaterial in
the environment and hence control of their production and application.
iv. Spreading awareness about nanomaterial toxicity among public and a proper
management of waste of nanomaterial-based products.
v. Proper surveillance of exposure level of nanomaterial in the environment.
vi. Proper protocol should be employed to prevent exposure and any accident.
vii. Workers or employees of nanomaterial production industry or laboratory
should have proper training.

7 Conclusions

Discovery of most of the 2D nanomaterials is very recent, and hence, toxicology of

this family of nanomaterials is not well studied. Except for graphene or graphene
oxide, reports on toxicological study of other nanomaterials are very few. The actual
mechanism of toxicity of these nanomaterials is also not very clear. Few contradictory
260 A. Konwar et al.

results have also been observed in studies carried out by different groups. Hence,
an uncertainty rules on their exposure limit in the environment. Moreover, the most
challenging part is that the exposure limit varies for different organisms. Although
in some cases, these nanomaterials show a positive effect, but in other cases, at the
same concentration, they show adverse effects. Until and unless we have detailed
information about their toxicity, we must limit the production and application of
nanomaterials.

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Chapter 12
Prospective on 2D Nanomaterials
for Energy and Environment:
Challenges, Commercial Aspect,
and the Future Research Endeavor

Zeba Khanam, Neelam Gogoi, and Divesh Narayan Srivastava

1 The Rise of 2D Nanomaterials

Two-dimensional (2D) nanomaterials ignited a surge of unprecedented research

interest since the discovery of a stable atomic carbon nanosheet ‘graphene’ in 2004
as a breakthrough in nanoscience and technology [1, 2]. The astonishing optoelec-
tronic properties of pioneer graphene and its technological advances encouraged
the scientific community to extensively explore the new 2D layered atomic crys-
tals. Layered materials endow unique appealing features when scaled down to single
or few atomically thin nanosheets. For instance, they possess large specific surface
area which significantly increases their physical and chemical reactivity and influ-
ences the 2D wave function through quantum confinement effects. Modification
in the bandgap structure with layer thickness occurs upon 2D confinement [1–
3]. Henceforth, these ultrathin 2D nanomaterials present unique mechanical, elec-
trical, photonic, magnetic, and catalytic properties that differ from those of their
bulk counterparts. Due to their outstanding attributes, viz tailored surface chem-
istry, highly exposed active edge sites, greater flexibility, more versatility, biocom-
patibility, better functionality, excellent mechanical strength, etc., 2D nanomaterials

Z. Khanam (B)
School of Materials Science and Engineering, Harbin Institute of Technology, Shenzhen 518055,
China
e-mail: [email protected]
N. Gogoi
School of Life and Environmental Sciences, School of Chemistry, University of Sydney, Sydney,
NSW 2006, Australia
e-mail: [email protected]
D. N. Srivastava
Analytical and Environmental Science Division & CIF, CSIR-Central Salt & Marine Chemicals
Research Institute, Bhavnagar, Gujarat 364002, India
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 267
Z. Khanam et al. (eds.), 2D Nanomaterials for Energy and Environmental Sustainability,
Materials Horizons: From Nature to Nanomaterials,
https://doi.org/10.1007/978-981-16-8538-5_12
268 Z. Khanam et al.

could be promising for diversified applications from electronics, energy, environment

to biomedicines, and agriculture [1–4].
A plethora of 2D nanomaterials have been designed and developed through top-
down exfoliation from bulk crystals or bottom-up approaches from small molecule
precursors [1–5]. Interestingly, the library of 2D nanomaterials is expanding enor-
mously and featuring more than 150 exotic members so far. In general, 2D nano-
materials are categorized as metals, semi-metals, superconductors, semiconductors,
or insulators depending on their atomically thin structural configurations and varied
chemical compositions [1–7]. These include-
• Transition metal dichalcogenides (TMDs) such as MoS2 , WS2 , MoSe2 , and WSe2 .
• Transition metal halides (TMHs) such as PbI2 , and MgBr2 .
• Transition metal oxides (TMOs) such as MnO2 , and MoO3 .
• Transition metal carbides/nitrides (MXenes) such as Ti3 C2 Tx .
• Mono-elemental 2D analogs (Xenes) such as
– group III elements-borophene,
– group IV elements-graphene, silicene, germanene, and stanene,
– group V elements-phosphorene, arsenene, antimonene, and bismuthene,
– group VI elements-selenene and tellurene.
• 2D nitrides—such as hexagonal boron nitride (h-BN, also known as “white
graphene”) and graphitic carbon nitride (g-C3 N4 ).
• Layered perovskites—such as Oxide pervoskites-K2 Ln2 Ti3 O10 , RbLnTa2 O7 , etc.,
and Halide perovskites—Cs2 PbI2 Cl2 , etc.,
• Layered double hydroxides (LDHs), Silicates or aluminosilicates or 2D nanoclay,
• 2D Metal organic frameworks (MOF), 2D Covalent organic frameworks (COF)
and 2D polypeptoid
• Metallenes—such as 2D iron, 2D copper, 2D rhodium, 2D platinum, and 2D
gold nanosheets.
A brief overview on the rapidly emerging 2D nanomaterials along with their
properties and various synthetic approaches has been already addressed in Chap. 1.
The present chapter outlines the key technological challenges of 2D nanomaterials
for energy and environmental applications. In addition, the future developments,
prospects, and opportunities that could be offered are also discussed.

2 Challenges Associated with the Production Methods

Layered structures are characterized by strong in-plane bonds but weak interlayer
bonding. This allows them to be isolated into individual atomically thin nanosheets.
The micromechanical cleavage using “Scotch-tape” was originally used to prepare
highly crystalline graphene from bulk layered graphite crystals [8, 9]. Since then,
12 Prospective on 2D Nanomaterials for Energy … 269

there are probably a dozen methods that have been developed to prepare 2D nanoma-
terials with desired structure composition (thickness and size), quality (crystal phase,
defect, and surface property), and optimized optical/electronic properties [8–14].
Major approaches for the state-of-the-art production are-
• Top-down: This approach includes mechanical force-assisted cleavage and liquid
exfoliation such as oxidation-assisted liquid exfoliation, ion exchange-assisted
liquid exfoliation, ion intercalation-assisted liquid exfoliation, and selective
etching-assisted liquid exfoliation [2, 5, 8–12].
• Bottom-up: This approach includes chemical vapor deposition method (CVD),
wet-chemical synthesis (hydrothermal or solvothermal), and epitaxial growth
synthesis [12–16].
According to remarkable advancements in recent years, exfoliation approaches
have become popular as one of the mainstream methods for the preparation of
solution-processable 2D nanomaterials with advantages of straightforward and cost
effectiveness. 2D nanomaterials are obtained in the form of dispersions that can
be used directly [5, 8–12]. On the other hand, CVD can produce high-purity 2D
nanomaterials with controlled thickness and size [15, 16]. Even though a variety of
preparation strategies continues to emerge, several challenges remain unaddressed.
Therefore, the following critical points should be carefully considered for the future
studies-
1. Sustainable production: Significant progress is needed to advance the sustain-
able and scalable synthesis of 2D nanomaterials. Efforts must be dedicated to
push the limits to high structural integrity, high phase purity, and precise func-
tionalization. For the application-driven researches, the majorly concerned areas
are scalability and production costs while providing a balance between ease of
fabrication and final material quality with tailoring of on-demand properties [8–
11, 17]. The lack of an explicit understanding of the structural design-application
mechanism adds up to the continued list of challenges. Unfortunately, exfolia-
tion methods suffer from some drawbacks such as poor throughput and low yield,
rendering it difficult to produce 2D nanosheets in bulk quantities. The applied
mechanical force in exfoliation process determines not only the production rate,
but also the quantity and purity of resulting 2D nanomaterials. For example, the
pioneer mechanical cleavage (Scotch-tape adhesion) approach is not scalable
though it can easily produce high-quality monolayers. Similarly, liquid-phase
exfoliation (using ultrasonic waves, shear forces, or electrochemical exfoliation)
is associated with long processing times, limited production yield, low through-
puts, and induced oxidation. However, the modified Hummer’s method (chem-
ical oxidation) is readily scalable, but the products are found to be heavily defec-
tive. The exfoliation process involves many factors, such as applied mechanical
forces, type of exfoliants/intercalants/stabilizers and their feeding concentra-
tions, power supplies, and several other operational conditions. The develop-
ment of new exfoliation strategies depended on the tedious cycle of trial and
error. Therefore, systematic studies on the regulation of these parameters are
270 Z. Khanam et al.

extremely critical. The combination of two or more methods, such as electro-

chemical exfoliation with shear mixing, ball milling, or thermal shock could
be a better alternative to boost the production yield and to further reduce the
nanosheet thickness. It shall focus on the technical innovation such as contin-
uous feed, nonstop production, automatic separation, purification, and recy-
cling [8–11]. On the other hand, the bottom-up approaches (for instance, CVD)
involve complex and costly procedures requiring high temperatures and high
vacuum conditions along with difficulties in transferring the product onto target
substrates that may introduce residues or defects into the 2D structure [8–11,
15, 16]. These drawbacks limit the processing of 2D nanomaterials beyond
laboratory scale. Hence, a significant understanding is required to drift this
research domain toward the development of novel, efficient, economic proto-
cols for upscaling the production of 2D nanomaterials with better control over
desired product characteristics.
2. Pursuit of greener approaches: To further advance research in this field, an
environmentally benign method for the scalable production of 2D nanomate-
rials would be worthwhile and will open new avenues for commercial imple-
mentation. The conventional material synthesis approaches are dominated by
the excessive use of toxic chemicals and harsh conditions posing serious health
and environmental concerns. Research advances must promote the concepts
of green chemistry and sustainability both in academia and industry. Substi-
tuting toxic chemicals with supercritical fluids, biocompatible materials, etc.,
can assure a greener way of preparing 2D nanomaterials [10, 11, 18–20].
3. Controlling Defects and morphology: There is still much to learn about control-
ling defects, understanding the impact of substrate, developing means for
controlled doping and controlled morphology, which underpin future research
[3]. The undesired alteration of pristine properties of 2D nanomaterials, due
to inevitable oxidation or insufficient intercalation or surface defects, during
preparation is a serious issue. The multiple physio-chemical reactions during
synthesis may lead to inhomogeneous oxygen content, defect density, and
surface functionalities [5, 8]. In order to prevent the destruction of 2D lattice,
a proper selection of starting materials such as solvents or exfoliants or other
processing conditions along with their easy removal post-processing is essen-
tial. Another hurdle is to achieve 2D nanomaterials with controlled sizes and
layer thicknesses. The effective preparation strategies giving more control over
morphology and surface modification without compromising the inherent prop-
erties are required to advance the development of 2D nanomaterials for practical
applications [5, 8–11].
4. Sorting and Separation: Looking ahead, the generic approaches produce 2D
nanomaterials with a wide distribution of layer numbers and lateral sizes. It is
yet another difficult task to further sort and separate the product according to its
lateral dimensions and thicknesses. Also, it is extremely difficult to transfer the
obtained product to target substrates. Therefore, significant progress is required
for well-constructed separation and transfer techniques [5, 9–11].
12 Prospective on 2D Nanomaterials for Energy … 271

5. Storage and Stability: The storage and stability requirements of prepared prod-
ucts is another roadblock on the way to commercialization [18]. For example,
MXenes require sub-zero temperatures for their storage. It is extremely impor-
tant to develop an effective method for long-term storage of 2D nanomaterials
without undergoing oxidation or irreversible aggregation at ambient conditions.
6. Computational Modelling and Theoretical predictions: There is an urgent
necessity for steadfast computational methods to address the gap between
theoretical predictions and experimental confirmations. Material’s informatics
combining computational, statistical, and machine learning approaches should
be adopted to predict and establish practical design rules for accelerating the
creation of next-generation 2D nanomaterials with new compositions and prop-
erties [1, 3, 19]. These data-driven approaches can then be integrated to the
resulting data sets to develop an understanding of the underlying structure–
property–performance relationships [19, 21–23]. Furthermore, the collaboration
between characterization techniques and theoretical modeling will be beneficial
for an in-depth understanding of the fundamental mechanism and providing a
comprehensive perspective on materials’ structure and function [3, 8]. This is a
challenging direction but would make breakthrough in the nanoscience research.

3 2D Nanomaterials for Sustainable Future

The emergence of numerous 2D nanomaterials puts forward a giant step toward the
development of sustainable technologies in the field of energy and environment.
The cutting-edge attributes of 2D nanomaterials, in particular (a) in-plane electro-
conductivity with charge density waves, (b) asymmetric out-of-plane flexibility, (c)
reduction/oxidation ability with gap tunability, and (d) exceptional large surface area
with superior chemical reactivity, hold extensive implications in different fields [4],
for instance:
• Energy storage and conversion,
• Photocatalytic degradation,
• Adsorption removal,
• Desalination and membrane filtration,
• Detection and sensing,
• Drug delivery and healthcare applications,
• Agricultural practices.
In spite of the substantial research garnered so far, there are still many topical and
foreknown challenges and future directions which need to be considered to facilitate
the commercial application of 2D nanomaterials.
272 Z. Khanam et al.

3.1 Energy Storage and Conversion: Challenges

and the Future

2D nanomaterials certainly show a great potential as next-generation electrode mate-

rials for huge application in energy. As suggested, high specific surface area, varied
surface functionality, reversible transport of ion and mass, and good mechanical
robustness are proven to be crucial foe systems of energy storage and conversion [4,
24, 25]. The recent progress on various 2D nanomaterials for solar cells, electrochem-
ical water splitting, piezo and thermoelectric devices, batteries, and supercapacitors
is discussed in Chaps. 2 and 3, respectively. There are still many opportunities to
explore and expand the research in this field, like creation of porous structures,
effects of functional groups, intercalation of ions, new hybrid device configuration,
etc. [24–26], as summarized below-
1. Restacking and porous structure: 2D nanomaterials have acquired importance
as electrochemically active electrode materials for energy storage devices, for
instance, supercapacitors and batteries [6]. As known, the specific capacitance
of device depends on the surface area of active electrode material. Due to the
tendency of 2D nanomaterials to irreversibly aggregate and restack, it may
significantly decrease their surface area, and ion diffusion rate thereby may
reduce their charge-storage capacity. Therefore, in order to exploit the full poten-
tial of 2D nanomaterials in energy storage, the research should focus to prevent
restacking of 2D nanosheets and maximize the accessible surface area. One
way to achieve this is to increase the active sites or enlarge the interlayer space
through intercalation with guest molecules [27, 28]. The inclusion of conductive
interlayer spacers may create adequate interlayer separations by introducing
additional electron-conductive pathways. This promotes an easy access and
swift transport of ions resulting in a better electrochemical performance of
2D nanomaterial-based electrodes [25]. Furthermore, the aggregation of 2D
nanosheets can be prevented by fabricating porous microstructures that can also
stimulate pathways for efficient charge transport. The porous microstructure
opens 2D channels and effectively shortens the diffusion paths of ions [27, 28].
It can provide more sites for charge storage along with maintaining structure
stability during charge–discharge cycles [6].
2. Doping, tunable functionality, and Hybrid configurations: For further
improving the electrochemical performance, approaches like defect/vacancy
creation, heteroatom doping, heterostructure construction, and surface/interface
modification could provide excellent opportunities [28]. 2D transition metal
compounds, such as TMDs, TMOs, and TMHs, are being widely studied as
active faradaic materials in electrochemical energy storage devices due to
their large theoretical capacities, compatibility with electrolytes, and chem-
ical stability. They show multiple oxidation states where the charge storage
mainly arises from the pseudo-capacitance caused by rich redox reactions on
their surfaces [28]. For instance, MoS2 exhibits large pseudo-capacitance due
to varied oxidation states of Mo (+2 to + 6), while electrical double layer
12 Prospective on 2D Nanomaterials for Energy … 273

(EDL) capacitance occurs due to its stacked-sheet-like structure [6]. However,

the inherently poor electronic conductivity, low-rate capability, poor cycling
stability, and large structural changes during metal-ion insertion/extraction
along with high cost of manufacture are major challenges that require further
investigation to commercially exploit these materials [29]. On the other hand,
non-faradaic materials like graphene or phosphorene-based electrodes mainly
store charge through the formation of EDL, exhibiting high power density but
low specific capacitance. Combining pseudocapacitive-type materials (TMOs
or TMHs) with EDL capacitive-type material (say graphene) is a viable
approach to overcome limitations of each component, generating hybrid elec-
trodes with enhanced performance. Further, these impediments can be over-
come by implanting vacancies or defects/holes, doping with additional metallic
elements, and/or integrating with a conductive matrix [28]. For instance,
introducing redox pseudo-capacitances by heterogeneous atomic doping of
redox quinone/hydroquinone molecules into the EDL capacitive-type phos-
phorene or graphene could be an alternative choice [26]. Next, compositing
or hybridizing TMDs and MXenes with different materials, such as conduc-
tive polymers, or other transition metal compounds like TMOs, or 2D nitrides,
needs more attention. Besides, systematic investigations on the interfacial inter-
actions of various 2D nanomaterials with other polymeric materials should be
explored. Such polymer 2D nanocomposites are expected to accelerate the
electrons/ions conduction at electrode–electrolyte interface, achieving high-
performance energy storage devices. A detailed electrochemical characteriza-
tion of such composites will provide important insights that will contribute
to future electrochemical applications of 2D nanomaterials [24, 25]. Further-
more, the emerging conductive organic frameworks—MOFs and COFs with
stacked p-conjugated 2D layers, controllable pore size, high specific surface
area, tunable porous structure, and surface functionality are also appealing elec-
trode materials for future energy devices. The high porosity from organic molec-
ular assembly is beneficial to generate EDL capacitance, and the heteroatoms (B,
N, O, and S) on the precise locations of frameworks may exhibit redox activity
for the pseudo-capacitance [28]. Apart from this, the intercalation of various
cations (Li, Na, K, Al) into the 2D nanomaterial interlayers (graphene, phospho-
rene, MXenes, etc.) could show promising potential for hybrid battery-capacitor
devices or metal-ion capacitors [25, 30, 31]. The device configuration involving
the hybrid/composite electrodes or the asymmetric assembly design in which
positive and negative electrodes consisting of different active materials (specif-
ically, pseudocapacitive-type electrode at one side and EDL capacitive-type
electrode at the other) shows superior overall performance. Hence, designing
new hybrid device configurations with high specific capacitances and wide elec-
trochemical voltage windows represents an interesting future research direction
[28].
3. Fabrication technologies: The energy application of 2D nanomaterials is mainly
hindered by the lack of feasible electrode fabrication technologies [28]. In addi-
tion to it, the potential problems associated with 2D nanomaterials synthesis
274 Z. Khanam et al.

such as low production yield, uncontrolled morphology, inductive defects, and

arbitrary functionalities overshadow their real performance. For instance, an
acid-free synthesis of MXenes is a key challenge to leverage their intrinsic
performance as electrode materials [24]. In general, the electrode material can
be directly synthesized on the patterned current collectors using CVD, laser
scribing, pyrolysis, and electrolytic deposition, or the electrodes can be fabri-
cated using existing 2D nanomaterials dispersions/powders by means of inkjet
printing, drop casting, spin coating, spray coating, layer-by-layer assembly,
electrophoretic deposition, vacuum filtration, painting, filling, and rolled-up
technologies [28]. A deeper understanding of different techniques or their
combination is needed to realize the commercial value of energy devices.
4. Properties and Performance relationships: As observed in literature, syner-
gistic effects account for enhanced performances of energy device, but the
rational factors responsible for it are still unexplored. To leverage the optimum
performances, understanding the interface relationships that govern the physio-
chemical properties of 2D nanomaterials is critically important. How do the
interface atoms adjust their orientation, crystalline structure, and layer number
to exhibit high synergistic effects are the unresolved issues [24]. Few studies
suggested that vertically orient 2D nanomaterials directly grown on interdigital
current collectors could be advantageous to attaining low interfacial resistance
and expediting the ion transport [28]. Besides, the layer number/thickness may
play a decisive role in the performance. The scientist community must find
the most appropriate layer number/thickness of 2D nanomaterials for high-
performance energy storage/conversion devices. There are rarely any studies
engaged in regulating the orientations or layer thickness of 2D nanomaterials
and their corresponding electrocatalytic, electrochemical, piezo, or thermoelec-
tric behaviors [26]. Moreover, the principles of interface chemistry and the
binding mechanism of 2D nanomaterials with interacting materials influencing
the overall performance should be explored. Detailed advanced studies inte-
grated with in-situ characterizations and data mining techniques are required
to unravel the fundamentals of 2D interfaces parameters to leverage the best
materials performance [24].
6. Novel electrolytes: Apart from electrode optimization, the electrolyte compat-
ibility is also of paramount interest in electrochemical energy storage devices.
The aqueous/non-aqueous electrolytes known so far are becoming obsolete with
newly emerged 2D nanomaterials due to their superior surface chemistries and
physio-chemical properties. Hence, a parallel effort is needed to design safe,
compatible electrolytes such as polymer electrolytes together with the fabrica-
tion of novel 2D nanomaterials-based electrodes. To this, the electrode–elec-
trolyte interfacial reactions occurring during electrochemical tests require a
deeper investigation [24–33].
7. Stability: The intrinsic instability issues of 2D nanomaterials may further
hamper their applications. For instance, MXenes electrodes are susceptible
to oxidize in varied electrolytes which may cause decay in capacitance and
increase in internal resistance during electrochemical cycling stability tests
12 Prospective on 2D Nanomaterials for Energy … 275

[24]. 2D nanomaterial-based electrodes often encounter degradation or struc-

tural collapse under ambient conditions, and thus, an inert atmosphere is mostly
preferred for device assembling. This is one of the major limitations in manufac-
turing 2D nanomaterial-based energy devices that should be analyzed seriously.
The plausible strategies to alleviate the stability issues could be surface modifi-
cation or coatings or proper encapsulation of 2D nanomaterials while preserving
their electrochemical entity [24, 26, 28]. For instance, in-situ deposition of a
proper passivated layer on the electrode surface could suppress the reactive
activities and forbid the volume change during cycling. Another possible way
would be creating 2D nanomaterials heterostructures through layer-by-layer
assembly that can instigate strong synergistic effects to improve the stability
performances [26].
8. Other unexplored materials: Energy-related investigations can be expanded to
predict and discover novel 2D nanomaterials. Catalysts based on 2D nanoma-
terials such as MoS2 and CN show high catalytic activity, particularly toward
HER; however, their semiconducting nature limits the charge transfer capabili-
ties. In addition, the catalytic active sites are mostly confined to the edges with
catalytically inert in-plane atoms in these 2D nanomaterials. Theoretical analysis
demonstrated that MXenes could be exceptional candidates for electrochemical
water splitting, but very few experimental evidences is presented. 2D nanomate-
rials based on earth-abundant elements with superior electrocatalytic activities
and electrochemical properties are always in huge demand. The prospects of
newly discovered elemental 2D nanomaterials (such as silicene, germanene, and
tellurene) toward OER, HER, EDL, or pseudo-capacitive processes are mostly
unidentified [25, 28].

3.2 Treatment and Removal of Pollutants: Challenges

and the Future

2D nanomaterials and their functional composites are gaining tremendous research

attention in treatment and monitoring of environmental contaminants due to their
ultrafast processing and ultrahigh treatment efficiency. Through control over their
structural morphology and highly anisotropic physicochemical properties, 2D nano-
materials have preceded the innovation and advancement of smart treatment systems
equipped with remarkable catalytic, adsorptive, filtration, and sensing performance
[21]. They have been used as an ultrafast visible light photocatalyst, high-efficiency
absorbents, filtration membranes, and sensing platforms for removing environmental
pollutants, including dyes, heavy metals ions, antibiotics, and even toxic gases. We
outlined the recent progress of 2D nanomaterials in environmental remediation appli-
cations, starting with photocatalysis in Chap. 4, adsorption in Chap. 5, desalination
and membrane filtration in Chap. 6, with the extension to electrochemical sensors for
detecting toxic gases, water pollutants, and other biological contaminants in Chaps. 7
and 8, respectively. The rich chemical diversity of 2D nanomaterials offers myriad
276 Z. Khanam et al.

opportunities in treatment and removal technologies; however, for achieving best

performance, prediction of their complex physicochemical response is quite chal-
lenging. In spite of immense advancements at laboratory scale, to date only few have
paved the way to market [21]. This chapter seeks to highlight the practical barriers
and challenges allied with industrial implementation of 2D nanomaterials and the
future directions needed to be prioritized in respective treatment technologies, as
discussed below.

(a) Photocatalytic degradation of organic contaminants

Photocatalytic technology is a promising sustainable approach for environmental

remediation. Typically, it involves the use of semiconductors as a photocatalyst
to initiate the photoreactions under suitable light irradiation to degrade recalci-
trant organic pollutants with minimal energy input, low operating cost and oper-
able under ambient conditions (including pressure and temperature) [34, 35]. During
the photocatalytic reaction, the free electrons get excited to conduction band (CB)
while leaving holes in valence band (VB), and such electron–hole pairs take part
in photocatalytic applications which can include water splitting, CO2 reduction,
and degradation of pollutants. 2D nanomaterials and their composites are consid-
ered as promising candidates as photocatalysts providing crucial features such as
diverse host–guest species, large specific surface areas, surface-rich active sites, and
porous structures. Many 2D nanomaterials including graphene, phosphorene, metal
oxides, carbon nitride, MXenes, and TMDs have been evaluated as photocatalysts
or co-catalysts. [21]. These 2D nanomaterial-based photocatalysts still have certain
bottlenecks to move from experimental to industrial level [36].
1. Hybrid Photocatalysts: The redox potentials of photogenerated electron–hole
pairs rely upon the 2D bandgap structure; hence, it should be carefully adjusted
for the development of effective photocatalysts. Several strategies such as
hetero-structuring, size controlling, and element doping could be exploited
to modulate the bandgap structure of 2D nanosheets in the desired wave-
length range [21]. For instance, an atomic level investigation should be made
on the variation of electronic structure in MXenes after metal doping to
enhance the photocatalytic process. Engineering 2D nanomaterial hybrids or
heterostructures with superior redox capability, improved interfacial arrange-
ments, enhanced photon adsorption and charge-carrier transportation could
produce efficient and broad-spectrum photocatalysts [34]. Thus, an extensive
research effort should be devoted to design efficacious hybrid 2D nanomaterials
photocatalysts in order to extend their commercial applications [36].
2. Uncontrolled aggregation and Recombination: The photocatalytic perfor-
mance is greatly affected due to undesirable aggregation of 2D nanomaterials
which reduce their specific surface area. Also, the excited photogenerated charge
carriers lack stability and are easy to recombine, which usually leads to low
conversion efficiency. The stirring of the reaction mixture may prevent aggre-
gation, but not accessible in practice. The judicious design of particle interaction,
surface engineering of photocatalysts like self-assembly, or the charge hopping,
12 Prospective on 2D Nanomaterials for Energy … 277

and wise selection of ligands could be promising approaches to mitigate these

issues [21].
3. Effectiveness of light irradiation: Photocatalysis often suffers low conversion
efficacy of light irradiation mainly during degradation of persistent organic
pollutants. There are rare reports signifying the potent strategies to enhance the
usage of light energy [36].
4. Practical implementation: Photocatalytic degradation is mostly performed in a
model solution, while real aqueous environment is more complex. For decon-
taminating pollutants in rivers, lakes, or oceans, the photocatalytic performances
are unignorably influenced by several environmental factors such as ionic
strength, pH, and interference of other entities. A systematic investigation should
be performed to discern these factors to exploit the practical implementation of
2D nanomaterial photocatalysts [36].
5. Recycling and toxicity: Reportedly, 2D nanomaterial photocatalysts are unable
to satisfy the demand of repetitive usage, and at the same time, their residual
contamination can impose severe environmental and human health risks. Hence,
it is imperative to readily and fully separate the 2D nanomaterial photocatalysts
for ideal recycling as well as purifying the aqueous system completely. This
could be probably resolved by hybridizing them with magnetic nanoparticles
or loading on to the porous materials, or creating macroscopic 3D architecture
assembly. Moreover, some of the intermediates generating during photocatalytic
degradation are more harmful than the original contaminant which should be
precisely studied. Few reports acclaimed that applying hybrid photocatalysts
could prevent the generation of toxic intermediates [36]. Overall, it is extremely
important to thoroughly investigate 2D nanomaterial photocatalysts for any
toxic impacts to the environment and human health.
6. Stability: The instability issue of 2D nanomaterials may hinder their technolog-
ical applications in environmental remediation. The comprehensive knowledge
of their oxidation in various solvent systems, subsequent lattice change of 2D
nanomaterials, and their long-term stability requires in-depth analysis [34].
(b) Adsorption of toxic gases and water pollutants
Adsorption-based removal of pollutants like heavy metal ions, organic dyes, and
toxic volatile compounds is another promising method for environmental mitigation
due to its minimal capital expense and simplicity [21]. 2D nanomaterials mani-
fest exceptionally higher adsorptive capacity and selectivity as compared to other
dimensional regime materials. With the attributes of large surface area, abundant-
active sites, and rapid mass transport, 2D nanomaterials bestow high levels of
surface/interface interactions, favorable for adsorption which is essentially an inter-
facial process [21, 37]. The plausible mechanisms of selective adsorptions or interac-
tions are hydrogen bonding, π-π stacking, ion/ligand exchange, hydrophobic inter-
action, Lewis acid/base, and electrostatic interaction [21]. In spite of the impressive
promises of 2D nanomaterials as the new-found generation of adsorbents for the
treatment and removal of pollutants, there exist numerous challenges and baffling
matters to be further inspected [37].
278 Z. Khanam et al.

1. Production: Low yield and high material cost of adsorbents based on 2D nano-
materials limit an industrial-scale production. Henceforth, the exploration of
cost-effective, environmentally-benign and upscale methods is of great signif-
icance. More research should direct toward hybrid 2D nanomaterials that have
the potential for the advancement of remediation technologies for environment
[34, 37].
2. Aggregation: The inevitable aggregation of 2D nanomaterials in aqueous
medium may reduce the specific surface area and adsorption active sites
thereby lowering their adsorptive capacity [37]. For the development of high-
performance 2D nanomaterials adsorbents, the rate of terminal sedimenta-
tion must be prudently considered, because fast sedimentation can lead to the
removal of adsorbents prior to an effective decontamination process, while an
ultra-slow sedimentation may contribute to the recovery cost in the separa-
tion process of used adsorbents from the wastewater. The judicious design to
understand surface interactions and nanosheet behavior in aqueous phase is also
important. Besides the colloidal stability of 2D nanomaterials, adsorbents are
crucial for their practical application in offshore conditions or lakes wherein
homogeneous stirring is inaccessible [21].
3. Mechanism studies: 2D nanomaterials possess a very diverse chemical and
physical attributes. Therefore, there is a need to precisely understand different
molecular levels and tuning of their surface chemistries to have a better control
over their adsorption behaviors [21]. Several factors including nature of pollu-
tants, solution/gas chemistry, and adsorbent characteristics such as distribution
of functional groups, porosity, and even defects density have significant influ-
ence on the adsorption process [35, 37]. These must be explored in detail using
experimental as well as computational methods to completely understand the
adsorptive removal mechanism.
4. Secondary contamination and separation: Recycling of 2D nanomaterials
adsorbents after adsorption process is a daunting challenge. Although magnetic
separation, centrifugation, and membrane filtration could be employed, they are
not feasible at an industrial scale. Moreover, inadequate separation may pose a
risk of secondary contamination and toxicity to environment and human health,
and therefore, it requires comprehensive investigations [37].
5. Stability: The lack of stability is another critical concern that influences the
overall lifespan of 2D nanomaterials adsorbents and severely restricts their
practical applications. The future work should consider on reinforcing 2D nano-
materials adsorbents for their successful utilization in aqueous environment
[34, 37].
(c) Desalination and membrane filtration
Over the years, desalination and membrane filtration have been established as most
potential technology for water remediation [35]. Filtration membranes can provide a
physical barrier that is designed to separate the pollutants from wastewater depending
upon their size or permeability [21]. The membrane separation process can be cate-
gorized into microfiltration, nanofiltration, ultrafiltration, and reverse osmosis. The
12 Prospective on 2D Nanomaterials for Energy … 279

process of desalination and membrane filtration is advantageous in terms of high

removal efficiency, ease of cleaning, minimal usage of toxic chemicals, and negli-
gible carbon footprint contribution [35]. In recent times, 2D nanomaterials have
shown extremely high capabilities as efficient functional membranes for application
in desalination and membrane filtration. However, there are still many challenges
that should be tackled to extensively make use of their remarkable properties in
desalination and membrane filtration [18].
1. Permeability and selectivity: The development of efficient functional
membranes with high selectivity and permeability faces great challenges due
to the typical trade-off that exists between selectivity and permeability. As
membrane thickness is inversely proportional to permeability, designing 2D
nanomaterial-based membranes with controlled atomically thin structure can
allow the selective molecules to pass through [21]. Theoretical studies such
as density functional theory (DFT) could be used to predict superior features
of different 2D nanomaterials for their possible application in water desali-
nation and membrane filtration [18]. Proper experimentation is required to
develop next-generation 2D nanomaterial-based functional membranes that
can maintain quite high permeation without sacrificing separation selectivity
[18, 21].
2. Fouling: Fouling is a common issue associated with filtration membranes.
It prevents their long-term operation due to high energy consumption and
reduced water recovery from the desalination processes. To alleviate the
fouling/biofouling phenomenon, incorporation of other antibacterial nanoma-
terials (such as silver nanoparticles) into 2D nanomaterial-based functional
membranes seems to be a beneficial approach that ensures easy inactivation of
bacterial growth. Additionally, self-repair and self-cleaning designs may facil-
itate the use of 2D nanomaterial membranes for practical applications in water
desalination and membrane filtration [21].
3. Water flux: The control of water flux is correlated directly to the material flake
size. Hence, experimental and theoretical approaches are extremely necessary
to perceive an optimum flux rate accompanied with a high salt rejection rate
and further revealing the underlying mechanism [34].
4. Fabrication and Stability: More research should be directed toward the scalable
fabrication of 2D nanomaterial membranes with long-term stability [21]. These
membranes prone to swell or collapse easily, causing ion rejection and thereby
may result in poor separation selectivity. Engineering of interlayers by tuning
of d-spacing of nanosheets can prevent swelling and/or structural collapse of
the membranes [34].

(d) Detection and sensing of contaminants

The sensing techniques offer advanced environmental monitoring that can quantita-
tively determine the effectiveness of treatment. 2D nanomaterials are very well-suited
for sensing applications, as their high surface-to-volume ratio, an extremely high
density of active surface sites, and atomic thinness contribute to a strong response
280 Z. Khanam et al.

toward external stimuli [21]. Additionally, 2D nanomaterials have a broad optical

spectrum with tunable band structure and favorable electronic properties. These
amazing properties make 2D nanomaterials a strong candidate suitable for designing
of a range of sensor modalities. They mainly include fluorescent sensors, colori-
metric sensors, field-effect transistor sensors, and electrochemical sensors [2, 12, 21,
38–40]. Among them, many studies are reported for electrochemical sensors that
have extreme potential to detect the amount of target analytes per unit area with
a rapid response and recovery, and low power consumptions [38–40]. Typically,
electrochemical sensing of pollutants relies on the principle of detecting electrodes
capable of producing a measurable electrical signal as a response to electrochemical
adsorption or reaction with an analyte. The sensing probe–analyte interactions are
either non-covalent (electrostatic force) or covalent linkages that mainly depends
upon the nature of pollutant. The pollutants, if present, can induce a change in poten-
tial, current, capacitance, or resistance, which can be easily recorded and analyzed
[21]. With great progresses made in this flourishing field, broader prospects with
more breakthroughs in 2D nanomaterials-based sensing applications are expected.
It still needs in-depth examination to understand the interactions between newly
emerged 2D nanomaterials sensing platforms and target analytes to further realize
their commercial use.
1. Fabrication: The critical challenge in developing any 2D nanomaterial-based
sensors is lack of controlled synthesis of 2D nanomaterials with desired morpho-
logical characteristics and surface chemistries. Nevertheless, the production
rate, quantity, and quality of 2D nanomaterials are limited with existing
methods. For instance, the existing 2D nanomaterials’ synthesis via CVD
method involving high-temperature processing is incompatible with flexible
polymeric substrates and is typically grown on a metal substrate which is then
transferred on target polymeric substrates. However, such transfer methods end
up creating wrinkles and/or defects, making the device fabrication extremely
challenging. Achieving uniformity in material properties is necessary for their
implementation in industries beyond fundamental science research. Therefore,
a smart research objective should be either cost-effective scalable synthesis with
ease of transfer methods or enabling the low-temperature yet direct synthesis
onto the final substrate to avoid transfer step [2, 12, 21, 38–40].
2. Selectivity and sensitivity: Fabricating a reliable, robust, and more functional
sensing probe interface is an interesting research direction. Nevertheless, each
2D nanomaterial has its own peculiar characteristics and shortcomings that
could affect the sensing performance. Moreover, the synthesis process or the
precursors used may also introduce impurities which could influence the perfor-
mances of 2D nanomaterials as sensing signal probes. Research should be
emphasized toward resolving the issues of lower detection limit, poor selectivity,
instability, complicated separation, and unwanted impurities/contamination that
could degrade the sensor performances [41]. This can be partly tackled by regu-
lating the properties of 2D nanomaterials and their composites in a desirable
and controlled manner. Proper tailoring or altering the surface chemistries of
12 Prospective on 2D Nanomaterials for Energy … 281

2D nanomaterials through functionalization or defect engineering like creating

heterostructures/composites or hybridization with other materials and molec-
ular/chemical doping will offer more room to design the signal probes with
selective recognition of specific pollutant and high sensitivity [12]. For instance,
metal dopants can improve the detection limit and enhance the selectivity as
they facilitate better interaction between modified sensing probes and the target
analyte due to effective charge transfer [41]. Further, determining the impact of
target analytes on the integral properties of 2D nanomaterials and the associated
sensing mechanism will be helpful to recognize the selectivity and sensitivity
relationship. An attempt should be made to unravel the recognition events occur-
ring at the interface. Understanding of interfacial interaction mechanisms of 2D
nanomaterial-based sensing probe with environmental pollutants is crucial to
maximize the sensor performance. Considerable research effort should be made
toward combination of theoretical data (e.g., DFT calculation) and experimental
analysis to develop the improved sensing probes [12, 41].
3. Stability: Another challenge of 2D nanomaterial-based sensors is to
maintain their long-term stability. Their tendency of aggregation, oxida-
tion/decomposition, or structural collapse during storage and application or reac-
tion is duly responsible for relatively low chemical and physical stability. Struc-
tural deformities arising during synthesis of 2D nanomaterials can affect their
electronic properties and hence influencing their sensing performance. Stabi-
lizing these 2D nanomaterials during the synthesis process is equally important
as their storage in ambient conditions. Moreover, the performance of sensors
may degrade over a short period of time while interacting with complex envi-
ronment/media in practice leading to structural disfigurements, material decay,
and thermal hazards. Surface functionalization, doping of other elements, and
polymer coating can improve their stability to a great extent. Nevertheless, the
stability issue should be solved without sabotaging the sensitivity and selectivity
of the device which needs in-depth investigation [41].
4. Toxicity: A parallel attempt should begin for understanding various interactions
of 2D nanomaterials with biological or environmental entities to facilitate their
applications in these domains ensuring human health and environment safety
[42]. It is extremely crucial that 2D nanomaterials do not introduce new impu-
rities and maintain their chemical stability while comes in contact with testing
media/environment [43]. Studies on the assessment of potential toxic effects
and long-term safety of 2D nanomaterial sensing platforms are still limited.
Modifying surface properties of 2D nanomaterials could remarkably improve
their stability, recyclability, biocompatibility, and help in reducing toxicity. It
is necessary to systematically investigate the impact of surface functionaliza-
tion and properties of 2D nanomaterials composites on the environment, human
health, and other organisms.
282 Z. Khanam et al.

3.3 Biomedicines and Healthcare: Challenges and the Future

The amazing physio-chemical properties of 2D nanomaterials attracted researchers

to realize their application in biomedical fields that mainly include drug delivery,
bioimaging, antibacterial, biosensing, clinical diagnosis, tissue engineering, and
other therapeutic uses [44]. We provided a thorough discussion of newly emerged 2D
mesoporous silica nanomaterials applications in biomedicines in Chap. 9. Progress
in this field is continuing to push forward to take advantage of these ultrathin 2D
nanostructures. Herein, we present an insight on various research opportunities and
critical challenges that could be explored for investigation of next-generation 2D
nanomaterials with biomedical applications at their core [45].
1. Fabrication: Most of the preparation strategies of 2D nanomaterial introduce
impurities, involve toxic reagents, and have insufficient control over exper-
iments and products that are highly unfeasible for their bio-medicinal use.
Therefore, more efforts should be made to explore advanced, scalable, low
cost, eco-friendly synthesis methods, and to manufacture tunable structure with
desired properties [44]. Scalable production of 2D nanomaterials with precise
control over size, surface terminations, and morphology is very crucial for clin-
ical trials [19, 45]. Combination of superior opto-electro-magnetic properties
together with the ease of surface functionalization would open new directions
in clinical diagnosis and therapy. Noting that hybridization of 2D nanomaterials
will not only result in combination of advantages but also a combination of
drawbacks, which is a problem worth considering [44].
2. Biocompatibility and safety: For real-life biomedical applications, the safety
assessment of 2D nanomaterials which includes their biocompatibility, cellular
uptake mechanisms, cell toxicity, and intracellular or in vivo metabolic path-
ways is an important prospect [46]. There are a few reports demonstrating the
short-term in vitro biocompatibility of 2D nanomaterials, but the long-term
in vivo biosafety of targeted tissues and organs are almost unknown [19]. It is
known that the cytotoxicity is majorly influenced by nanomaterial properties
such as synthesis method, surface chemistry, and morphology. [45]. A system-
atic study on the effect of 2D nanomaterials and their various composites on
the environment and human health with a clear mechanistic reason for toxicity
is not well-reported [43]. Hence, research efforts should be put into the investi-
gation of long-term safety, toxicology, biocompatibility, pharmacokinetics, and
biodistribution of 2D nanomaterials [44]. The toxicity of 2D nanomaterials to
vital systems like nervous system, reproductive system, and immune system
should be critically assessed in small as well as large animal models [19, 44].
3. Mechanism: The understanding of different mechanisms involved in various
healthcare applications such as drug delivery, cancer treatment, or disease detec-
tion should be thoroughly investigated with the help of computational modeling
and theoretical studies [44].
4. Possible developments: 2D nanomaterials can offer overarching opportunities in
developing advanced, smart, compatible healthcare devices. 2D nanoplatforms
12 Prospective on 2D Nanomaterials for Energy … 283

could be integrated into textiles for quick monitoring of health and fitness. 2D
electronic tattoos as a part of virtual/augmented reality systems can efficiently
monitor and respond to user’s state of motion/physiology. 2D nanomaterial-
based sensors for in vitro diagnostics of nucleic acids could enable highly
sensitive, label-free, rapid, and early detection of various diseases [45]. Further-
more, advancement and realization of many such nanotechnologies hinge upon
smart academic research collaborated with budding industrial partners. More
applications of 2D nanomaterials could be explored in biomedical fields such
as acoustic dynamics therapy, acoustic power bio-implants, or acoustic sensing
[44, 47]. 2D nanomaterials have the potential to serve as the next-generation
technology in personalized health monitoring [44–46].

3.4 Agricultural Practices: Challenges and the Future

The application of nano-enabled technologies in agricultural practices has undoubt-

edly delivered very covenant outcomes in achieving and boosting sustainable agri-
culture by facilitating proper and less damaging management strategies for limited
natural resources for land, water, and energy. How and at what concentration nanoma-
terial will respond in a positive manner is firmly and critically dictated by their prop-
erties, interactions, and reactions with the plant and soil constituents. It is because of
their excellent physicochemical properties that they have magical effects in farming
system [48]. However, it is very important to understand that everything comes at a
cost. Besides having multiple remarkable applications, the benefit of using nanotech-
nology is often succeeded by negative effects which can cause harm to the health
of environment and human population in the long run. Investigations regarding the
applications, uptake, mobility, fate, toxicity, loss, and remediation of nanoparticle is
still sparse and for the most part limited to laboratory research studies only. It might
take a long time to reach from laboratory to field for general farm practices. A brief
discussion on potential of 2D nanomaterials in improving quality as well as quantity
of agricultural produce has been made in Chap. 10. Recognizing the high influences
of these 2D nanomaterials in opening new avenues in agrarian sector, this section
will endeavor to address profuse innovation opportunities and different challenges
before their market implementation for general use.
1. Residual effects in plants: The introduction of engineered 2D nanomaterials
have helped in achieving an improved overall effect different from what caused
by natural nanoparticles, but they might result in some residual effects which
may cause harm to environment [49]. The risks of overuse of nanofertilizers
carefully request examination before its general use in farming system for
revamping dose–response equations [50]. It is necessary to develop sustainable
conduct to upscale the manufacturing of environmentally-safe nanomaterials
and in designing green nanoparticles for the controlled release and increased
284 Z. Khanam et al.

rate in nutrient uptake [50]. The European Union is considering various regu-
latory guidelines to address safety issues for the use of nanomaterials in agri-
culture [51]. But the complexity involved in the agricultural systems such as
multiple organisms (plants, humans, and pests), microbiomes (soil, plant), vari-
ability in climatic conditions, soil structures, compositions, design of NMs,
and societal engagement [52] are major bottlenecks. Therefore, this field needs
more thoughtful understanding about their ambiguous physical and chemical
characteristics.
2. Toxicity in human and animals: The rapid utilization of 2D nanomaterials in
each prospect of growing food from soil to post-harvest application and food
packaging is bringing their direct or indirect contact with one and all. Also, it
is not known very clearly that how it gets infiltrated into the bodies of humans
and animals and cause health hazards. Graphene could follow an entry route
in humans through intracheal instillation [53], oral intravenous injection [54],
administration [55], subcutaneous injection [56], and intraperitoneal injection
[57]. There are also reports of exposure to graphene in occupational situations
with potential toxicity to researchers and workers [58]. In animal or cell modules,
nanomaterials exert numerous levels of toxicity with distinct administration
routes [59]. Thus, NMs may have mysterious consequences and call for in-
depth study and research regarding their mode of action for their standardized
use.
3. Ease of application: Development of handy and easy to use 2D nanomaterial-
based sensors and techniques for rapid and real-time analysis of plants, soil,
water, and pesticides is necessary. Also, designing 2D nanomaterial compos-
ites in a way that they can exhibit multifunctional properties such as acting as
both fertilizers and pesticides will reduce the amount of used nanomaterials to
a greater extent. This will consequently reduce a number of issues associated
with nanomaterials in agriculture [60].
4. Incomplete knowledge: Although experts have the opinion that 2D nanomate-
rials in agriculture are safe but scientific gaps are still needed to be filled in by
conducting thorough assessments on the impact of life cycle of the 2D nanoma-
terial on environment and human health. Extensive studies are urgently required
to increase the awareness of their mechanism, toxicity, impacts, and build-up
strategies to assess and deal with any risks that they may arise [61].
5. Societal issues: Nanoscience has an ambiguous outlook in agriculture due to
the fear of the unknown generated in public from, for example, unconstructive
response toward genetically modified (GM) crops, lack of serious legislation
and regulatory guidelines, and new-fangled nanotechnologies. A quick action
to slash down the existing ragged outlines among the society and budding
scientific notions is needed in order to overcome the societal barrier toward
implementation of nanotechnology in real-world agriculture [62].
12 Prospective on 2D Nanomaterials for Energy … 285

4 Commercial Aspect of 2D Nanomaterials: Highlights

on Patented Research

Moving ahead, to kick in the 2D nanomaterials commercialization, the validation and

standardization of proof-of-concept prototypes are critical. In recent times, a large
number of patents on 2D nanomaterials have been reported in the field of energy,
environment, agriculture, and biomedicines, and some of them are summarized in
Table 1. Nevertheless, it still needs a sustained collaboration, data sharing, system-
atic frameworks, and cooperation between the academic laboratories, the suppliers,
the industries, as well as the governing ministry to make their way to the market. In
addition, the industry and the academic collaborators should seek to design innova-
tive 2D nanomaterial appliances or products from the consumers’ point-of-view to
increase the end-user productivity.

5 Conclusions

In conclusion, we have briefly outlined the technological challenges, future oppor-

tunities, and commercial aspect of 2D nanomaterials in the field of energy and envi-
ronment in this chapter. As realized, criteria such as high-throughput, low-cost, and
controlled manufacturing of stable 2D nanomaterials with desired structural features
are critical for specific applications. Furthermore, to improve the properties and
performance of the 2D nanomaterials for different applications, crystal phase engi-
neering, surface engineering including hybridization, doping and defect engineering,
creating heterostructures/composites remain the topic of interest. The stability of
2D nanomaterials is also essential that should be sustained not only during their
processing and storage but also in applications. Most of the 2D nanomaterials are
prone to oxidize or collapse in ambient conditions or during the chemical reaction
in applications which may lead to material loss, structural degradation, or secondary
contamination. The fabrication routes should also make sure to minimize the use of
hazardous chemicals and should not have any negative influence on ecosystems or
the life forms. Therefore, biocompatibility, safety assessment, and toxicity evalua-
tion of 2D nanomaterials have to be taken into account to avoid any possible health
risks. Another promising future direction is to identify the most suitable 2D nano-
material for a specific application. It is extremely important to build a fundamental
structure-properties-performance relationship using innovative theoretical studies,
data-driven approaches, and computational modelling. Current research on newly
emerging members of 2D family such as MOF, COF, 2D polypeptoid, and other
mono-elemental 2D nanomaterials (silicene, germanene, phosphorene, etc.) is still
at their preliminary stage and should be evaluated for unexplored applications. For
instance, adsorption of pollutants using phosphorene and electrochemical detection
of toxic gases using TMDs are rarely reported. At last, efforts should be made toward
developing an advanced multifunctional 2D nanomaterial-based devices/assemblies
Table 1 Highlights on patents related to 2D nanomaterials/composites-based devices/products for energy, environment, agriculture, and biomedical applications
286

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Graphene US8226801B2 [63]
Mass production of pristine nano-graphene
materials
Graphene US20170225233A1 [64]
Chemical-free production of graphene
reinforced inorganic matrix composites
Graphene US9236197B2 [65]
Graphene hybrid materials, apparatuses,
systems, and methods
Graphene US20190292671A1 [66]
Metal matrix nanocomposite containing oriented
graphene sheets and production process
Graphene CN103700513B [67]
A kind of graphene paper and its preparation
method and application
Graphene CN107555424A [68]
A kind of preparation method of porous class
graphene active carbon material and products
thereof and application
Graphene US8834959B2 [69]
Method for the preparation of doped single
graphene sheets
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Graphene CN105514450B [70]
Nitrogen-doped graphene/difunctional VPO
catalysts of ferronickel houghite and its
preparation method and application
TMDs EP2869348B1 [71]
Two-dimensional chalcogenide-based materials,
methods of forming the same, and devices
including the two-dimensional
chalcogenide-based materials
TMDs US20160181516A1 [72]
Phase transformation in transition metal
dichalcogenides
12 Prospective on 2D Nanomaterials for Energy …

MoS2 US20160093491A1 [73]

Large scale and thickness-modulated MoS2
nanosheets
MXenes US10720644B2 [74]
Two-dimensional, ordered, double transition
metals carbides having a nominal unit cell
composition M 2M nXn + 1
MXenes US9415570B2 [75]
Compositions comprising free-standing
two-dimensional nanocrystals
(continued)
287
Table 1 (continued)
288

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
MXenes US20200176619A1 [76]
Physical forms of MXene materials exhibiting
novel electrical and optical characteristics
MXenes CN107159286A [77]
A kind of Ti3C2/TiO2The preparation method
of two-dimensional material
MXenes CN107117616B [78]
A method of stratiform MXenes material is
prepared using ternary MAX material
MXenes CN107777688B [79]
Preparation method of sheet-like MXene sheet
material
Phosphorene US9461125B2 [80]
Method of preparing monoatomic layer black
phosphorous by irradiating ultrasound
Phosphorene US10906811B2 [81]
Composition comprising optically and
electronically active phosphorene
Phosphorene US10676357B1 [82]
Bipolar exfoliation of black phosphorous into
phosphorene
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Phosphorene AU2021104425A4 [83]
Liquid-phase exfoliation method for producing
black phosphorus nanoribbons or phosphorene
nanoribbons
Phosphorene KR20170125677A [84]
Method for preparing bulk phosphorene using
spark plasma sintering and bulk phosphorene
prepared thereby
Silicene US10600644B2 [85]
Mono- and multilayer silicene prepared by
plasma-enhanced chemical vapor deposition
Tellurene US20200247671A1 [86]
12 Prospective on 2D Nanomaterials for Energy …

Substrate-free crystalline 2D nanomaterials

Layered perovskite JP6270183B2 [87]
Organic/layered perovskite compound and
method for producing organic/inorganic layered
perovskite compound
MOF US10201803B2 [88]
Polymer-metal organic framework materials and
methods of using the same
TMDs, TMHs, phosphorene, perovskite, many other layered materials US10309027B2 [89]
Method for producing dispersions of nanosheets
(continued)
289
Table 1 (continued)
290

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Energy storage and conversion
Supercapacitor Graphene US9017756B2 [90]
Continuous process for producing
spacer-modified nano-graphene electrodes for
supercapacitors
Supercapacitor Graphene US9053870B2 [91]
Supercapacitor with a mesoporous
nano-graphene electrode
Supercapacitor Graphene US20090092747A1 [92]
Process for producing nano-scaled graphene
platelet nanocomposite electrodes for
supercapacitors
Supercapacitor Graphene WO2018013254A1 [93]
Supercritical fluid production of graphene-based
supercapacitor electrode from coke or coal
Batteries Graphene JP2019522868A [[94]
Chemical-free production of graphene-filled
electrode active material particles for battery
applications
Batteries Graphene US11081691B2 [95]
Carbon nanotubes—graphene hybrid structures
for separator-free silicon-sulfur batteries
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Fuel cells Graphene CN104959134B [96]
A kind of Heteroatom doping porous graphene
electro-catalyst and preparation and application
and device
Thermoelectric device Graphene ES2660904T3 [97]
Thermoelectric materials and devices
comprising graphene
Solar cells Graphene CN109659138A [98]
A kind of hollow carbon sphere/nickel sulfide of
N doping/graphene ternary active
multilayer/multi-factor structure composite
material and preparation method for
dye-sensitized solar cells
12 Prospective on 2D Nanomaterials for Energy …

Solar cells Graphene CN109423068A [99]

Super-hydrophobic wear-resisting graphene
composite coating and the solar energy heat
collection pipe for applying it
Photovoltaic cells Graphene CN111541398A [100]
Preparation method of functionalized graphene
roll-up photovoltaic PN junction
(continued)
291
Table 1 (continued)
292

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Photovoltaic cells Graphene US10839974B2 [101]
High optical transparent two-dimensional
electronic conducting system and process for
generating same
Photovoltaic Cells TMDs US20170179314A1 [102]
Photovoltaic cells
Photovoltaic devices Graphene/TMDs US10692977B2 [103]
Heterostructures and electronic devices derived
therefrom
Solar-thermal fuel cells TMDs/TMOs US20120325200A1 [104]
Nano-templated energy storage materials
Supercapacitors TMDs US20190139713A1 [105]
Two-dimensional transition metal
dichalcogenide micro-supercapacitors
Na-battery TMDs (MoS2 )/graphene US20190081320A1 [106]
Robust MoS2 /graphene composite paper based
electrodes for Na + battery applications
Li-battery TMDs (MoS2 )/graphene CN102683648B [107]
Preparation method of few-layer MoS2 /graphene
electrochemical storage lithium composite
electrode
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Li-battery TMDs (MoS2 )/graphene CN102142537B [108]
Graphene/MoS2 compound nanomaterial
lithium ion battery electrode and preparation
method thereof
Zn-battery TMOs (MnO2 ) CN106571461A [109]
Chargeable–dischargeable Zn–MnO2 battery
with long service life and applications thereof
Capacitor electrode TMOs (MnO2 ) JPWO2012086697A1 [110]
Nanoporous ceramic composite metal
Ultracapacitor MnO2 /porous carbon film/nickel composite CN105551813A [111]
Preparation method of MnO2 /porous carbon
film/nickel composite material
12 Prospective on 2D Nanomaterials for Energy …

Fuel cell TMOs (MnO2 ) ES2683360T3 [112]

Reversible fuel cell and reversible fuel cell
system
Al-battery MXenes US20180309125A1 [113]
Electrochemical systems comprising MXenes
and max phase compositions and methods of
using the same
(continued)
293
Table 1 (continued)
294

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Li–S battery MXenes CN106450205B [114]
Two-dimensional transition group metal
carbon/nitride and nano-sulfur particle
composite material and preparation and
application thereof
Li-battery MXenes CN107706372B [115]
MXene-coated composite electrode material and
preparation method thereof
Li-battery or MXenes WO2021042456A1 [116]
Na-battery Rapid preparation method for few-layer MXenes
and application
Supercapacitor MXene CN109003836A [117]
A kind of preparation method based on MXene
flexible fabric electrode and its application in
supercapacitor
Supercapacitor MXene CN106430195A [118]
MXene material and preparation method and
application thereof
Battery MXene CN109671949A [119]
A kind of MXene-based flexible compound
negative electrode material and preparation
method thereof
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Semiconductor device Phosphorene JP6477315B2 [120]
Phosphorene film forming method and
semiconductor device manufacturing method
Li-battery Phosphorene CN106711408B [121]
Flexible lithium ion battery black phosphorus
nanometer sheet-graphene composite film
cathode and preparation
Li-battery Silicene US20150364754A1 [122]
Silicene nanocomposite anode for lithium ion
battery
Photovoltaic cell hBN US9859034B2 [123]
Functionalized boron nitride materials and
12 Prospective on 2D Nanomaterials for Energy …

methods for their preparation and use

Solar cell Layered perovskite CN108365102B [124]
Stable and efficient two-dimensional layered
perovskite solar cell and preparation method
thereof
Photovoltaic device Layered perovskite CA3079471C [125]
Quasi two-dimensional layered perovskite
material, related devices and methods for
manufacturing the same
(continued)
295
Table 1 (continued)
296

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Piezoelectric device Layered perovskite JP4419232B2 [126]
Crystalline oriented bismuth layered perovskite
type porcelain composition and method for
producing the same
OER Layered perovskite CN108039495B [127]
Non-metal element modified layered perovskite
oxide oxygen reduction electrode material
OER Layered perovskite CN108579751B [128]
Layered perovskite oxide, preparation method
and application thereof in oxygen evolution
reaction electrocatalysis
Fuel cell Layered perovskite CN105449227A [129]
Layered perovskite cathode material for fuel cell
and preparation method of layered perovskite
cathode material
Battery LDH JP6001198B2 [130]
Batteries using layered double hydroxides
Zn-battery MOF CN110492069A [131]
A kind of synthetic method of Zn@metal organic
framework combination electrode material
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Zn-battery MOF CN107887603B [132]
Preparation method of metal organic framework
MOF-5 as zinc ion battery positive electrode
material
Redox battery MOF CN105789668B [133]
The preparation method of metal organic
framework materials/polymer composite proton
exchange membrane
Solar cell Halide perovskite US10403708B2 [134]
MOF Graded bandgap perovskite solar cell
2D polymer
hBN
TMD
12 Prospective on 2D Nanomaterials for Energy …

MXene
Photocatalytic degradation of pollutants
Organic pollutant degradation Graphene CN104001504A [135]
Preparation method for silver and graphene
co-modified TiO2 nanowire and application of
silver and graphene co-modified TiO2 nanowire
in photocatalytic degradation of pollutants in
wastewater
(continued)
297
Table 1 (continued)
298

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
(rhodamine B) dye degradation Graphene CN103480398B [136]
Micronano-structured and graphene-based
composite visible light catalytic material and
preparing method thereof
Organic pollutant degradation Graphene CN103691420A [137]
Mesoporous niobium pentoxide/graphene
compound photocatalyst prepared by one-step
self-assembly method
Organic pollutant degradation Graphene CN106378158A [138]
Preparation method of bismuth sulfide/titanium
dioxide/graphene compound with high-catalysis
degradation activity under visible light
Organic pollutant degradation Graphene CN104258857A [139]
Silver chromate-graphene oxide composite
photocatalytic material and preparation method
thereof
Integrated photocatalytic-capacitive Graphene CN104829019A [140]
deionization of pollutant Photo-electric organic wastewater co-processing
method based on graphene material and device
thereof
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Organic dye degradation TMDs CN105148947A [141]
Preparation and application of TiO2 @MoS2
composite
Organic dye degradation TMDs CN106268875A [142]
A kind of MoS2 for efficient degradation
wastewater from dyestuff photocatalyst and
preparation method thereof
Organic dye degradation TMDs CN109465037A [143]
The magnetic CDs-MoS of micropollutants in a
kind of degradation water2-Fe3 O4 . The green
synthesis method of catalysis material
Organic dye degradation TMDs CN106964370B [144]
12 Prospective on 2D Nanomaterials for Energy …

A kind of oxidation silver

nano-grain/molybdenum sulfide nanometer
sheet heterojunction structure ultrasound near
infrared light catalyst and preparation method
Heavy metal and dye degradation TMDs CN109225273A [145]
A kind of copper sulfide/tungsten sulfide
composite photocatalyst and preparation method
thereof
(continued)
299
Table 1 (continued)
300

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Pathogen (Bacteria, viruses) degradation TMDs KR20180055860A [146]
Molybdenum disulfide and related substances
for water treatment
Organic pollutant degradation TMDs CN108355679A [147]
A kind of Fe3 O4 /MoS2 /BiVO4 preparation
method, product, and its application of material
Methylene blue dye degradation g-C3 N4 CN103193785B [148]
Graphene-like C3N4 material, as well as
preparation method and use thereof
Organic pollutant degradation MXenes CN111715250B [149]
Preparation method and application of supported
transition metal carbide Fenton-like
nano-catalyst
Organic pollutant degradation MXenes CN113134375A [150]
MXene-based two-dimensional silver compound
and preparation method and application thereof
Organic dye (rhodamine B) degradation MXenes CN111822028A [151]
Bismuth-based photocatalytic composite film
based on MXene and preparation method thereof
Organic dye degradation MXenes CN110560164A [152]
Polydopamine-coated C3 N4 /MXene composite
material and preparation method thereof
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
NH3 , H2 S and other organic pollutants MXenes CN111545230A [153]
degradation Preparation method, product and application of
nano-titanium dioxide/MXene composite
membrane
Organic pollutant degradation MXenes CN109794281A [154]
One kind preparing the nitrogen co-doped
nano-TiO of carbon based on MXene material2
the method of photochemical catalyst
Synchronous adsorption of phenol and lead MXenes CN112121855B [155]
ions in water and photocatalytic phenol Preparation method of photocatalytic thiourea
reduction modified two-dimensional MXene material
Organic dye degradation Phosphorene CN106586987B [156]
12 Prospective on 2D Nanomaterials for Energy …

A kind of preparation method of the black

phosphorus nanoscale twins for photocatalytic
degradation of dye wastewater
Organic dye degradation Phosphorene/g-C3 N4 CN108355696B [157]
Black phosphorus/g-C3 N4 composite visible
light photocatalytic material and preparation
method and application thereof
(continued)
301
Table 1 (continued)
302

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Organic dye degradation Phosphorene CN112076769A [158]
Spherical bismuth vanadate/black phosphorus
composite photocatalyst and preparation method
thereof
Photocatalytic treatment of toxic gases Phosphorene-g-C3 N4 -MOF CN108745404B [159]
Carbon nitride film composite material based on
black phosphorus/metal organic framework
modification, preparation method thereof and
application thereof in waste gas treatment
Photocatalytic treatment of toxic gases Phosphorene CN109529898B [160]
Black phosphorus/bismuth tungstate
nanocomposite and preparation method thereof
and application of black phosphorus/bismuth
tungstate nanocomposite in waste gas treatment
Bisphenol-A degradation MOF CN106927535B [161]
Method for photocatalytic degradation of
phenolic pollutants based on stable porphyrin
metal organic framework material
Heavy metal and dye degradation MOF CN107617447B [162]
Ag @ MOFs/TiO2 . Preparation method and
application of photocatalyst
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Organic dye degradation Layered double oxide CN102151577B [163]
Ag3PO4/Mg–Al layered double oxide (LDO)
visible light composite photocatalyst,
preparation, and application thereof
Adsorption-based removal of pollutants
Organic pollutant adsorption Graphene CN103570009A [164]
Graphene capable of efficiently adsorbing
organic substances and regeneration method
thereof
Groundwater remediation Graphene WO2018078427A1 [165]
Graphene-based filtering element and uses
thereof
12 Prospective on 2D Nanomaterials for Energy …

Non-polar contaminants such as oil Graphene US20210024378A1 [166]

adsorption Graphene reinforced polystyrene composite for
separation of non-polar compounds from water
Gaseous contaminants adsorption Graphene WO2018006745A1 [167]
Air filtration device utilizing graphene coating,
and system
NH3 adsorption Graphene US10994241B1 [168]
Sorbent system for removing ammonia and
organic compounds from a gaseous environment
(continued)
303
Table 1 (continued)
304

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Toxic gas and water pollutants adsorption Graphene CN203916677U [169]
A kind of water and gas dual-purpose graphene
absorption and reclaim equipment
Heavy metals. nitrates, phosphates removal Graphene US20210060522A1 [170]
Graphene-based materials for the efficient
removal of pollutants from water
Radioactive pollutants removal Graphene US20170151548A1 [171]
Sorption And Separation of Various Materials by
Graphene Oxides
Pesticide removal Graphene CN110420619A [172]
A method of recycling graphene-based
adsorbent material processing pesticide sewage
Heavy metal, organic dye adsorption TMDs/Graphene US10493426B2 [173]
Graphene-metal chalcogenide porous material
Mercury adsorption TMDs USRE44124E1 [174]
Regenerable high capacity sorbent for removal
of mercury from flue gas
Heavy metal adsorption TMDs US20190144305A1 [175]
Adsorption and removal of heavy metal ions
from water by transition metal dichalcogenides
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Heavy metal adsorption TMDs US8070959B2 [176]
Chalcogenide compounds with a clay-like
cation-exchange capacity and methods of use
Organic dye adsorption TMDs CN108383169A [177]
A kind of preparation method and applications of
ternary layered transitionmetal dichalcogenide
Atrazine removal MXenes CN113181947A [178]
CuO-Fe2 O3 /MXene composite material for
water treatment and purification and preparation
method and application thereof
Heavy metal adsorption MXenes US11053138B2 [179]
Method of removing arsenic from a liquid
12 Prospective on 2D Nanomaterials for Energy …

Heavy metal adsorption MXenes CN104587947A [180]

Method for preparing two-dimensional
nano-adsorbent titanium carbide for effectively
adsorbing hexavalent chromium ions
Organic dye (Methylene blue) adsorption MXenes CN107694510B [181]
Method for removing methylene blue in printing
and dyeing wastewater by two-dimensional
magnetic MXene
(continued)
305
Table 1 (continued)
306

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Organic dye (Eosin Y and methylene blue) MXenes CN108774343A [182]
adsorption Composite aerogel and preparation method
thereof and composite hydrogel and preparation
method thereof
Organic dyes, heavy metals adsorption MXenes CN106268610A [183]
A kind of preparation method of two dimension
titanium carbide adsorbing material
Organic dyes, heavy metals adsorption hBN/GO CN103480329B [184]
Hexagonal boron nitride/graphene oxide
composite adsorption material and preparation
method thereof
SOx removal Layered double hydroxide US5114898A [185]
Layered double hydroxide sorbents for the
removal of SOx from flue gas and other gas
streams
CO2 adsorption MOF CN105056895B [186]
A kind of preparation method and applications
of metal organic framework mesopore silicon
oxide composite
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Heavy metal adsorption MOF CN112973638A [187]
Preparation method and application of modified
MIL-125 (Ti) material for removing
micro-polluted mercury in water body
Organic pollutant adsorption MOF CN105481043A [188]
Method for adsorbing organic pollutants in
water environment with porous carbon obtained
by carbonizing metal organic framework
material as adsorbent
Antibiotic adsorption MOF CN108201878B [189]
Preparation method of carbon-point-modified
metal organic framework adsorption material
and application of carbon-point-modified metal
12 Prospective on 2D Nanomaterials for Energy …

organic framework adsorption material in

treatment of water pollutants
Desalination and membrane filtration
Desalination and membrane filtration Graphene US10456754B2 [190]
High-performance membranes for water
reclamation using polymeric and nanomaterials
Deionization or desalination Graphene US9475709B2 [191]
Perforated graphene deionization or desalination
(continued)
307
Table 1 (continued)
308

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Desalination Graphene CN108636141B [192]
Preparation method of graphene desalination
film
Desalination Graphene CN207361918U [193]
A kind of porous graphene desalination plant
Desalination Graphene US20180333685A1 [194]
Method for making a polygraphene membrane
for water desalination
Deionization Graphene US20130240355A1 [195]
Functionalization of graphene holes for
deionization
Gas separation membrane Graphene US9610546B2 [196]
Separation membranes formed from perforated
graphene and methods for use thereof
Integrated photovolataiv-desalination device Graphene CN111204828A [197]
Preparation method of
graphene-aluminum-based layer-by-layer
assembled photovoltaic and seawater
desalination device functional area
Integrated desalination-energy storage MnO2 AU2016203645B2 [198]
device Redox desalination system for clean water
production and energy storage
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Desalination TMDs US20190039028A1 [199]
porous membranes comprising nanosheets and
fabrication thereof
Desalination TMDs CN110015722A [200]
The preparation method of molybdenum
disulfide@graphite paper integral capacitance
type desalination electrode
Membrane filtration TMDs EP3140028A2 [201]
Stacked two-dimensional materials and methods
for producing structures incorporating same
Adsorption of petroleum waste and MXenes US20200254396A1 [202]
desalination Precise Fabrication of
12 Prospective on 2D Nanomaterials for Energy …

Activated-Hydrophilic-Hydrophobic
MXenes-based Multidimensional Nanosystems
for Efficient and Prompt Water Purification from
Petroleum Wastes and Desalination Process
under Ambient Conditions
Capacitive deionization and desalination MXenes/graphene CN107633954B [203]
graphene/MXene composite electrode material
and application thereof
(continued)
309
Table 1 (continued)
310

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Membrane filtration MXenes CN106178979B [204]
High-performance two-dimensional stratiform
Ti3C2- MXene film and preparation method
thereof and the application in water process
Membrane filtration MXenes WO2018205290A1 [205]
MXene-based composite nanofiltration
membrane and preparation method therefor
Desalination MXenes US20180169591A1 [206]
Two-dimensional metal carbide desalination
membrane
Forward osmosis MXenes CN113398777A [207]
Three-layer structure composite forward
osmosis membrane with MXene drainage layer
and preparation method thereof
Forward osmosis MXenes CN112473372A [208]
Conductive forward osmosis membrane and
preparation method thereof
Desalination MXenes CN109569319A [209]
A kind of application of the two dimension
self-crosslinking MXene film in ion isolation
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Desalination MXenes CN110342601B [210]
Based on CuInSe2 seawater desalination
structure of/MXene nano-composite material
Sea water desalination, sewage purification, MXenes/GO CN110090603A [211]
water–oil separation A kind of MXene and graphene oxide composite
aerogel and its preparation method and
application
Photo-thermal desalination MXenes CN107537323B [212]
MXene nanowire composite electrospun fiber
membrane for photo-thermal desalination
Gas separation membrane, MOF CN111282405A [213]
Desalination Modified metal organic framework nanosheet
12 Prospective on 2D Nanomaterials for Energy …

and preparation method thereof

Membrane filtration, desalination MOF EP3774001A1 [214]
Membranes comprising a layer of metal organic
framework particles
Detection and sensing of pollutants
Heavy metal detection Graphene CN105717174B [215]
The electrochemical detection method of
modified graphene oxide composite modified
electrode trace heavy metal ion in water body is
detected
(continued)
311
Table 1 (continued)
312

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Heavy metal detection Graphene CN106483184A [216]
Heavy metal analysis device and method based
on graphene sensor
Heavy metal detection Graphene CN104391030B [217]
A kind of heavy metal ion Cd built based on
alginic acid functionalization graphene 2+, Pb
2+, and Cu 2+ the preparation method of sensor
and application
Pesticide detection Graphene CN101995402B [218]
Preparation and application of
electrochemiluminescence sensor for detecting
trace pesticide residue
Catechol, hydroquinone, and resorcinol Graphene CN102980928A [219]
detection Tungsten sulfide-graphene electrochemical
sensor as well as preparation method and
application of sensor
Gas sensor Graphene CN102680527B [220]
Method for preparing graphene gas sensors in
batches based on nano soft lithography
Gas sensor Graphene Amperometric electrochemical gas sensing [221]
apparatus and method for measuring oxidizing
gases
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Gas sensor Graphene US9869651B2 [222]
Enhanced sensitivity of graphene gas sensors
using molecular doping
VOCs sensor TMDs US9063063B2 [223]
Low-dimensional material chemical vapor
sensors
NO2 gas sensor TMDs CN109825816A [224]
A kind of molybdenum disulfide film gas
sensitive and preparation method and application
Pesticide detection MXenes CN113390943A [225]
Electrochemical sensor for detecting
organophosphorus pesticide and preparation
12 Prospective on 2D Nanomaterials for Energy …

method thereof
Antibiotic detection MXenes CN109115850A [226]
A kind of chemically modified electrode and the
preparation method and application thereof of
sensitive detection fortimicin
Phenol, catechol, bisphenol-A detection MXenes CN110057882A [227]
A kind of electrochemical biological sensor and
its application based on two-dimensional
titanium carbon compound
(continued)
313
Table 1 (continued)
314

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Nitroaromatic explosives detection MXenes CN109406611B [228]
Nano-palladium/carbon nanotube-MXene
composite material and application thereof in
detection of nitroaromatic explosives
H2 O2 detection MXenes CN109675608A [229]
A kind of PB complex nanomaterial and its
preparation method and application
Gas sensor MXenes WO2019124625A1 [230]
Chemiresistor gas sensor using MXene, and
manufacturing method therefor
Gas sensor MXenes CN109799267B [231]
Planar humidity and ammonia gas sensor based
on alkalized organ-shaped MXene sensitive
material and preparation method thereof
NH3 gas sensor Phosphorene CN105116034A [232]
Sensor based on black phosphorus electrode and
preparation method of sensor
NO2 gas sensor Phosphorene US10648959B2 [233]
Black phosphorus gas sensor
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Gas sensor MOF US10274421B2 [234]
Sensor devices comprising a metal organic
framework material and methods of making and
using the same
H2 O2 detection MOF CN109270140B [235]
Preparation method and application of
electrochemical sensor made of high-dispersion
graphene/Zn-based metal organic framework
composite material
Biomedical and Healthcare applications
Drug delivery Graphene US20150283239A1 [236]
Graphene derivative-based composition for drug
12 Prospective on 2D Nanomaterials for Energy …

delivery and preparation method thereof

Drug delivery Graphene CN104436210A [237]
Malignant-tumor-resistant graphene oxide
nano-drug delivery system and preparation
method thereof
Drug delivery Graphene CN108379461A [238]
A kind of graphene blood pressure lowering
patch and preparation method thereof
Drug delivery Graphene Method of manufacturing graphene aerogels for [239]
drug delivery
(continued)
315
Table 1 (continued)
316

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Magnetic thermal therapy, Graphene CN104758930A [240]
drug delivery Preparation method of in-situ gel based on
magnetic graphene oxide and application thereof
Drug delivery Graphene KR101618556B1 [241]
Mesoporous silica-coated graphene oxide hybrid
structure and development of drug delivery
system using phase change material and drug
delivery system using thereof
Cancer detection Graphene CN110819717A [242]
Graphene oxide-containing amplification system
and application thereof in colorectal cancer
marker detection
Rare cell detection Graphene US10935550B2 [243]
Functionalized graphene oxide system for
detecting rare cells
Tumor cells detection Graphene CN108330054B [244]
Graphene chip for specific capture of circulating
tumor cells in whole blood and preparation
method and application thereof
Medicinal sterilizer and applicator Graphene CN110013601B [245]
Graphene pesticide applicator and pesticide
application method
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Bioelectronic device Graphene WO2016200105A2 [246]
Graphene bioelectronic device, treatment and
diagnosis nanoparticle, and endoscope system
Drug carrier TMDs CN103705928A [247]
Single-layer MoS2 nano-chip, preparation
method, and nano-drug carrier
CT imaging and phototherapy TMDs CN106512002A [248]
Multifunctional nanometer hybrid integrated CT
imaging and phototherapy and preparing method
of multifunctional nanometer hybrid
Photo-thermal therapy for cancer treatment TMDs CN107802836B [249]
Tumor targeted photo-thermal medicament,
12 Prospective on 2D Nanomaterials for Energy …

preparation method and application

Drug carrier, phototherapy TMDs CN106563130A [250]
Stripping preparation method of molybdenum
disulfide nanosheet and applications of
molybdenum disulfide nanosheet
Drug carrier, phototherapy TMDs CN107375928A [251]
A kind of preparation method and application of
cancer target photo-thermal therapy nano-carrier
(continued)
317
Table 1 (continued)
318

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Drug carrier MXenes CN108245682B [252]
Acidity and photo-thermal response type
mesoporous MXene nanosheet drug carrier and
preparation method thereof
Cancer therapy MXenes CN108273058B [253]
Sustained-release preparation for tumor targeted
therapy and preparation method thereof
Drug carrier MXenes CN111110913A [254]
Porous MXene membrane for drug loading and
application thereof
Cancer diagnosis MXenes CN108159438A [255]
A kind of photo-acoustic imaging contrast
medium of cancer diagnosis and its preparation
method and application
Photo-thermal therapy for cancer treatment Phosphorene CN106267201B [256]
A kind of black phosphorus of polymer wrapped
and preparation method and application
Photo-thermal therapy and photo-acoustic Phosphorene CN105535971B [257]
imaging for cancer treatment A kind of black phosphorus nanoparticle and its
preparation method and application with
biocompatibility
(continued)
Z. Khanam et al.
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Photo-thermal therapy for cancer treatment Phosphorene CN106335885B [258]
A kind of black phosphorus nanometer sheet and
preparation method and application
Photo-thermal therapy for cancer treatment Phosphorene CN106366121B [259]
Through ligand modified black phosphorus of
titanium and preparation method and application
Agriculture applications
Nano-fertilizer Graphene US11040918B2 [260]
Graphene for fertilizer applications
Nano-fertilizer Graphene US20190308916A1 [261]
Controlled release of fertilizer compositions and
uses thereof
12 Prospective on 2D Nanomaterials for Energy …

Nano-fertilizer Graphene CN104829340B [262]

A kind of micro-capsule graphene composite
material controlled release fertilizer granules
and preparation method thereof
Nano-fertilizer Graphene CN111285729A [263]
Carbon-based mica fertilizer, preparation
method, and application thereof
(continued)
319
Table 1 (continued)
320

Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Soil restoration Graphene CN108085010B [264]
A kind of complex repairation agent and its
application for heavy metal pollution of soil
Medium for improving plant growth Graphene JP2019527057A [265]
Graphene-based growth medium and method
Regulating compost for plant growth Graphene CN105891269A [266]
Method for regulating lawn compost substrate
and bioavailability using carbon nanomaterial
Nano-pesticide Graphene CN108684706A [267]
A kind of graphene pesticide compound and
preparation method thereof
Nano-pesticide Graphene CN112293419A [268]
Graphene oxide-containing pesticide
composition
Nano-pesticide Graphene CN108064844A [269]
A kind of cyclodextrin modified
graphene-houghite pesticide slow-releasing
agent and preparation method thereof
Nano-pesticide-fertilizer Graphene CN106577644A [270]
Medical fertilizer containing graphene
nanomaterial and preparation method of medical
fertilizer
Nano-pesticide-fertilizer Graphene CN104829340A [271]
Microcapsule graphene composite material
controlled-release pesticide-fertilizer granules
and preparation method
Z. Khanam et al.

(continued)
Table 1 (continued)
Synthesis/fabrication/preparation methods
2D nanomaterials Patent References
Nano-pesticide-fertilizer Graphene CN109053289A [272]
A kind of compound controlled release fertilizer
granules of graphene and preparation method
thereof
12 Prospective on 2D Nanomaterials for Energy …
321
322 Z. Khanam et al.

that are intelligent, adaptive, selective, and programmable. An example could be

combining membrane separation technologies with photocatalysts that can enable
photocatalytic degradation of organic foulants, alleviating the fouling issues. Next,
energy storage devices could be integrated with capacitive deionization or electro-
chemical sensing, which would simultaneously remove the redox water pollutants
and reutilize it for charge storage. It not only requires innovations in material prop-
erty, but also calls for fundamental understanding of underlying physics, chemistry,
and associated mechanism of these diverse and multidisciplinary processes. Never-
theless, massive efforts are still needed to gain the commercial success of these
exciting materials for future sustainability.

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328 Z. Khanam et al.

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