nanomaterials

Review
A Review of Plant-Mediated ZnO Nanoparticles for
Photodegradation and Antibacterial Applications
Dorcas Mutukwa 1 , Raymond Tichaona Taziwa 2, * and Lindiwe Khotseng 1, *

1 Department of Chemistry, University of the Western Cape, Robert Sobukwe Rd., Private Bag X17,
Bellville 7535, South Africa; [email protected]
2 Department of Applied Science, Faculty of Science Engineering and Technology, Walter Sisulu University,
Old King William Town Road, Potsdam Site, East London 5200, South Africa
* Correspondence: [email protected] (R.T.T.); [email protected] (L.K.)

Abstract: This review focuses on the synthesis of plant-mediated zinc oxide nanoparticles (ZnO NPs)
and their applications for antibacterial and photocatalytic degradation of dyes, thereby addressing the
need for sustainable and eco-friendly methods for the preparation of NPs. Driven by the significant
rise in antibiotic resistance and environmental pollution from dye pollution, there is a need for more
effective antibacterial agents and photocatalysts. Therefore, this review explores the synthesis of plant-
mediated ZnO NPs, and the influence of reaction parameters such as pH, annealing temperature,
plant extract concentration, etc. Additionally, it also looks at the application of plant-mediated ZnO
NPs for antibacterial and photodegradation of dyes, focusing on the influence of the properties of the
plant-mediated ZnO NPs such as size, shape, and bandgap on the antibacterial and photocatalytic
activity. The findings suggest that properties such as shape and size are influenced by reaction
parameters and these properties also influence the antibacterial and photocatalytic activity of plant-
mediated ZnO NPs. This review concludes that plant-mediated ZnO NPs have the potential to
advance green and sustainable materials in antibacterial and photocatalysis applications.

Keywords: plant extracts; biosynthesis; green synthesis; photocatalysis; dye treatment; wastewater
treatment; antibacterial agents; immobilisation; hydrogels; supports
Citation: Mutukwa, D.; Taziwa, R.T.;
Khotseng, L. A Review of
Plant-Mediated ZnO Nanoparticles
for Photodegradation and
Antibacterial Applications. 1. Introduction
Nanomaterials 2024, 14, 1182. Over the years, there has been a global upsurge in the interest in environmentally
https://doi.org/10.3390/ friendly and sustainable nano-synthesis approaches. These synthesis approaches fall
nano14141182 under green synthesis and their key focus is on reducing and eliminating the need for
Academic Editors: Rui A. Lima, hazardous and harmful chemicals in nanoparticle (NP) production. One such approach
Diana Pinho and Beatriz D. Cardoso that has gained significant interest in the scientific community is green synthesis using
plant materials. Its attractiveness stems from its simplicity, environmental friendliness, and
Received: 18 June 2024 cost-effectiveness. Moreover, plant-mediated nano-synthesis produces biocompatible NPs
Revised: 3 July 2024
that can be employed for a wide range of applications [1]. Therefore, it is a viable alternative
Accepted: 8 July 2024
to chemical and physical nano-synthesis methods such as pulsed laser deposition, infrared
Published: 11 July 2024
irradiation, sputtering, chemical vapour deposition, etc. Even though some of these
chemical and physical nano-synthesis methods are widely used, they face drawbacks
which include the use of hazardous chemicals, the need for pressure and temperature
Copyright: © 2024 by the authors.
control, high energy consumption, high cost, and time constraints, which impact the
Licensee MDPI, Basel, Switzerland. environment negatively [2]. Table 1 shows some of the advantages and disadvantages of
This article is an open access article green synthesis of ZnO NPs [3].
distributed under the terms and Plant-mediated ZnO NPs have been extensively studied owing to their remarkable
conditions of the Creative Commons performance in various applications. Plants such as Pluchea indica [4], Cnidoscolus aconi-
Attribution (CC BY) license (https:// tifolius [5], Mucuna pruriens [6], Scoparia Dulcis [7], Tilia Tomentosa [8], Azadirachta indica
creativecommons.org/licenses/by/ (A. indica) [9,10], Zingiber Officinale (Z. officinale) [11] etc., have been successfully used to
4.0/). prepare ZnO NPs for various applications including antibacterial, anticancer, antioxidant,

Nanomaterials 2024, 14, 1182. https://doi.org/10.3390/nano14141182 https://www.mdpi.com/journal/nanomaterials

Nanomaterials 2024, 14, 1182 2 of 37

supercapacitors, photodegradation of dyes, agriculture, gas sensing, glucose sensing, solar

cells, and sunscreen. Among the many applications of plant-mediated ZnO NPs appli-
cations, photocatalytic degradation of dyes and antibacterial applications are the most
explored and this is owing to their outstanding performance that has been well documented
in the literature [12,13]. Dyes are used in many industries such as fabric, pharmaceutical,
food, tanneries, leather, cosmetics, etc., and large amounts of these dyes make up part of
industrial wastewater. Conventional wastewater treatment technologies are used to treat
industrial wastewater; however, one of the major drawbacks of some of these technologies
is their failure to treat dye wastewater adequately [14]. This is a major concern because dis-
charging untreated or inadequately treated dye effluents into waterbodies poses a serious
threat to human lives, aquatic lives, and the environment. Photodegradation of dyes using
semiconductor metal oxides such as ZnO NPs offers an alternative remedy that is consistent,
secure, and capable of degrading dyes even at low concentrations [12,15]. Additionally,
there has been a global surge in antibiotic drug resistance, posing a threat to the health of
animals and humans, as well as food production [16]. Therefore, new technologies must be
developed to combat this threat. Plant-mediated ZnO NPs have demonstrated outstanding
antibacterial activity against a wide range of bacteria and, therefore, are a potential remedy
to combat antibiotic drug resistance [17].

Table 1. The advantages and disadvantages of green synthesis of ZnO NPs.

Advantages Disadvantages
Cost-effective Reproducibility issues
Biocompatible Relatively less stable NPs
Low energy consumption Difficult to control morphology
Avoids hazardous chemicals -
Does not require expensive equipment -

In light of these, this review delves into the synthesis of ZnO NPs using plant materials
and their applications in the photocatalytic degradation of organic dyes and antibacterial
activity against a wide spectrum of bacteria. The review will highlight the influence of
synthesis parameters such as pH, annealing temperature, reaction temperature, plant
extract, and Zn salt precursor concentrations on the properties of plant-mediated ZnO NPs
such as crystallite size, morphology, and optical bandgap. The influence of properties of
plant-mediated ZnO NPs and reaction parameters such as initial pH, catalyst dosage, and
initial dye concentration on the photodegradation efficiency will be discussed in detail.
Additionally, the antibacterial mode of action of plant-mediated ZnO NPs will be analysed.
Lastly, conclusions and recommendations will be given.

2. ZnO NPs Properties and Their Importance

In recent years, ZnO NPs have sparked major research and industrial interest owing
to their numerous properties which allow their applications in various industries. For
instance, ZnO NPs have been explored for gas sensing owing to their high chemical
sensitivity, high electron mobility of 200 cm2 /V.s, and high thermal stability [18]. Their
high exciton-binding energy of 60 meV has led to their use in photonic devices such as
light-emitting devices (LEDs), photodiodes, and phototransistors [19]. The properties
of ZnO NPs like transparency, low adhesiveness, and ability to absorb ultraviolet (UV)
light have allowed their use in cosmetics [20]. ZnO NPs absorb electromagnetic radiation
and exhibit photoluminescence, resulting in their application in field emission display
devices. In the rubber industry, ZnO NPs are used as additives to enhance the properties of
rubber such as strength, antiaging, and toughness, while their wide bandgap of 3.37 eV
at room temperature (RT) results in their applications in optoelectronic devices such as
supercapacitors [21,22]. Table 2 shows some of the physiochemical properties of ZnO
NPs [23,24].
Nanomaterials 2024, 14, 1182 3 of 37

Table 2. ZnO properties.

Property Value
Appearance White solid
Odour Odourless
Molecular weight 81.38 g/mol
Density 5.6 g/cm3
Coordination geometry Tetrahedral
Crystal structure Hexagonal wurtzite
Melting point 1975 ◦ C (decomposes)
Flash point 1436 ◦ C
Toxicity hazards None
Refractive index 2.0041
Bandgap Direct and 3.37 eV at RT
Electrical conductivity Semiconductor
Hole effective mass 0.59
Electron effective mass 0.24
Exciton binding energy 60 meV
Bohr radius 2.34 nm
Luminescence Luminescent in UV and visible light

Additionally, ZnO NPs possess antibacterial, anticancer, antioxidant, and anti-

inflammatory properties in addition to being non-toxic and biocompatible, thus mak-
ing ZnO NPs one of the sought-after metal oxides in the biomedical field [25]. Moreover,
their ability to absorb UV light and generate electron–hole pairs has led to their applications
as photocatalysts for the photodegradation of organic dyes and hydrogen gas production
through water-splitting [26,27].

3. Synthesis of ZnO NPs

Several synthesis methods for the preparation of ZnO NPs have been reported in the
literature [28,29]. Generally, these methods can be divided into top-down and bottom-up
approaches. The top-down approach involves the physical or chemical breakdown of bulk
materials to NPs, while the bottom-up approach utilises smaller particles such as atoms,
ions, and molecules to build up the NPs [30]. Figure 1 shows the contrast between
Nanomaterials 2024, 14, x FOR PEER REVIEW 4 of 40 the
top-down and bottom-up approaches of synthesising NPs [31].

Figure 1.
Figure 1. Contrast
Contrastbetween
betweenthe
thetop-down
top-downand bottom-up
and synthesis
bottom-up approaches.
synthesis approaches.

The approaches
The approaches can
canbe
befurther
furthersubdivided into
subdivided three
into categories,
three which
categories, are physical,
which are physical,
chemical, and biological/green synthesis methods, as shown in Figure
chemical, and biological/green synthesis methods, as shown in Figure 2.2.
 Figure 1. Contrast between the top-down and bottom-up synthesis approaches.

Nanomaterials 2024, 14, 1182

The approaches can be further subdivided into three categories, which are physical,4 of 37
chemical, and biological/green synthesis methods, as shown in Figure 2.

Figure 2.
Figure 2. An
Anoverview
overviewofofZnO
ZnOnanoparticle
nanoparticlesynthesis methods.
synthesis methods.

3.1. PhysicalSynthesis
3.1. Physical SynthesisMethods
Methodsof of
ZnOZnO NPs
NPs
Physical methods
Physical methods suchsuchasas laser ablation,
laser ball milling,
ablation, thermal
ball milling, evaporation,
thermal sputtering,
evaporation,
arc discharge, and molecular beam epitaxy are some of the synthesis
sputtering, arc discharge, and molecular beam epitaxy are some of the synthesis methods methods that have
been employed
that have to fabricate
been employed toZnO NPs ZnO
fabricate [32,33].
NPs These methods
[32,33]. These are ideal for
methods arethe preparation
ideal for the of
preparation
ZnO NPs onof anZnO NPs on
industrial scaleanowing
industrial scale
to their owing
high to theirrates.
production high However,
productionthe rates.
physical
However, methods
synthesis the physicalforsynthesis
NPs are methods
hampered forby
NPstheare hampered
need by the exposure
for vacuum, need for vacuum,
to radiation,
exposure
and high to radiation,
operating and high operating
temperatures temperatures
which require cooling which require
systems cooling
[34]. systems
This consequently
[34]. This
leads consequently
to high costs due leads
to theto high
needcosts
for due to the need
specialised for specialised
equipment equipment
and the need for and
skilled
the need for
personnel forskilled personnel
the operation of for
the the operationSome
equipment. of theofequipment.
the physical Some of thethat
methods physical
have been
methodsfor
utilised that have
the been utilised
preparation for the
of ZnO NPs preparation
are discussedof ZnO NPs are discussed below.
below.
Laser ablation is a physical synthesis method
Laser ablation is a physical synthesis method that involves that involves targeting a laser
targeting on the
a laser on the
surface of precursor material in a liquid or gaseous environment.
surface of precursor material in a liquid or gaseous environment. When the precursor When the precursor
material isis heated
material heatedby bythethelaser,
laser,ablation
ablation occurs
occursleading
leadingto vapour
to vapouror plasma formation,
or plasma formation,
depending on the intensity of the laser beam. The NPs are formed from the rapid cooling
and condensing of the vapour or plasma. The process can occur using a continuous laser
(laser ablation) or pulsed laser (pulsed laser ablation) [35]. The advantages of the laser
ablation method include not requiring harsh and toxic solvents, being safe, and producing
NPs with narrow particle sizes. However, it faces several challenges such as high cost,
low yield, and difficulties in controlling the morphology and structure of the NPs [36,37].
Ismail et al. [38] prepared high-purity colloidal ZnO NPs using Nd:YAG laser ablation at
RT by targeting Zn metal in water. The laser energy density (laser fluence) influenced the
properties of the synthesised ZnO NPs such as optical and particle size, with particle size
increasing with an increase in laser energy density.
High ball milling is a physical synthesis method that is commonly used for the syn-
thesis of ZnO NPs. The method is based on targeting bulk material with high-energy
balls, which transfers the kinetic energy from the balls to the bulk material, leading to the
breaking down of bonds in the bulk material. This results in smaller particles breaking
away with newer surfaces from the bulk material [39]. While ball milling is a convenient
and efficient method used to produce NPs even on an industrial scale, it is hampered by
high energy demands and lengthy synthesis times. Salah et al. [40] prepared spherical ZnO
NPs using the high-energy ball milling method. The results from transmission electron
microscopy (TEM) revealed that ZnO NPs produced after 50 h of milling had particle sizes
of about 30 nm. These results were in agreement with the scanning electron microscopy
(SEM) results. The particle size of the synthesised ZnO NPs decreased with an increase in
milling time. Additionally, the obtained ZnO NPs were reported to be ideal for antibacterial
applications due to their structural and optical properties.
Nanomaterials 2024, 14, 1182 5 of 37

Sputtering is an efficient physical method used to produce thin-film nanostructures by

targeting a solid surface with high-energy gas or plasma particles [41]. The bombardment
of the solid surface using high-energy gaseous ions causes the physical ejection of clusters
of atoms [42,43]. Generally, the sputtering process can be summarised in four steps. The
first step involves the formation of the positively charged gaseous ions followed by the
bombardment of the cathode target by the positively charged gaseous ions due to electric
field acceleration. The third step involves the ejection of particles from the cathode target
and finally formation of a thin film on the substrate due to condensation. The sputtering
process can be achieved using three different power sources or a combination of the three,
which are magnetron, radio-frequency (RF) diodes, and direct current (DC) diodes [44,45].
Gridchin and associates [46] utilised the RF magnetron sputtering method for the
preparation of ZnO thin films. The deposition was conducted in Ar/O2 plasma gas with
varying O2 compositions and growth temperatures. The authors observed that the ZnO
thin films synthesised in the absence of O2 with pure Ar plasma gas were porous, while
the thin films synthesised at 200–300 ◦ C were textured and polycrystalline. The sputtering
deposition method can be utilised for a wide selection of materials, e.g., metals, metal oxides,
insulators, semiconductors, and organic compounds. However, some of its drawbacks
include the need for a larger target, the high cost of the target and equipment, and low
purity [47]. Table 3 gives some advantages and disadvantages of some physical synthesis
methods used to prepare ZnO NPs.

Table 3. The advantages and disadvantages of some physical synthesis methods.

Synthesis Method Advantages Disadvantages References

Efficient and ideal for Lengthy processing
Ball milling [39]
large-scale production. times.
Poor coverage due to
Thermal evaporation High deposition rates. [48]
low vacuum.
High production
Physical vapour Simple and relatively
costs and low [49]
deposition low-temperature method.
productivity.
High operational cost
Molecular beam Produces high-purity
and expensive [48]
epitaxy materials.
equipment.
The nature of sputtering gas
High cost of target
Sputtering may affect the properties of [47,48]
and low purity.
the thin films.

3.2. Chemical Synthesis Methods of ZnO NPs

Chemical methods such as sol–gel, solvothermal, hydrothermal, microemulsion, and
chemical vapour deposition are some of the synthesis methods that have been utilised for
the preparation of ZnO NPs. Wet chemical synthesis methods are the most studied and
reported synthesis methods for the preparation of NPs. However, the chemical synthesis
methods are associated with problems with agglomeration of NPs during synthesis. To
address this problem, capping agents or stabilisers are added to prevent agglomeration
as well as to control the particle size [32]. Capping agents such as polyvinylpyrroli-
done (PVP), cetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG), and
sodium dodecylbenzene sulfonate (SDS) are used in several wet chemical synthesis meth-
ods. The major drawback associated with the use of some of the capping agents is their
non-biodegradability and toxicity [50]. The use of chemical methods enables the prepara-
tion of ZnO NPs with diverse properties and applications, and some of the methods are
discussed below.
Sol–gel is an attractive and versatile method that is used for the preparation of metal
oxide NPs. Decades ago, the sol–gel method was used in ceramic and glass material
production; it was later adopted for NP synthesis. It involves the formation of solid particles
in a liquid called ‘sols’ followed by the formation of a network of particles enclosed in
Nanomaterials 2024, 14, 1182 6 of 37

a liquid called ‘gels’ through crosslinking of the sols. Sol–gel occurs through two main
processes, which are hydrolysis and condensation, as shown in Equations (1) and (2) [37,51].

Hydrolysis : M − OR + HOH → M − OH + R − OH (1)

Condensation : M − OH + XO − M → M − O − M + XOH (2)

where M is a metal, R is an alkyl group, and X is H or an alkyl group.
The hydrolysis process occurs in water or alcohol using precursors such as metal
alkoxides and metal salts, which leads to the formation of a sol. This is followed by
condensation which involves the formation of metal–hydroxy–metal bond (M − OH) and
metal–oxo–metal bond (M − O − M) bridges through olation and oxolation processes,
respectively [52]. The condensation process is followed by ageing, drying to remove water
and alcohol from the gel, and lastly, calcination to obtain the NPs. Reaction parameters,
such as pH, hydrolysis time, type of precursor used, ageing time, and water-to-precursor
ratio, have an impact on the structure, particle size, morphology, and other properties of
the synthesised NPs [53]. Therefore, controlling these parameters during synthesis can help
tailor the properties of the NPs for specific applications.
For instance, ZnO NPs were prepared by the sol–gel method under acidic conditions
using Zn(NO3 )2 ·6H2 O as the precursor, isopropyl alcohol as a solvent, and glycerine as
a stabiliser. The reaction was carried out at 70 ◦ C for 2 h and dried at 70 ◦ C for 24 h. The
obtained gel was calcined at varying temperatures, at 500, 700, and 900 ◦ C. The synthesised
ZnO NPs were observed to be of irregular morphology and with particle sizes ranging from
50 to 100 nm based on the field emission scanning microscopy (FESEM) results. The authors
also observed that particle size increased as the calcination temperature increased [54]. In
another study, ZnO NPs were prepared by the sol–gel method under acidic conditions using
zinc acetate dihydrate, sodium hydroxide, and PEG as precursors and calcined at 800 ◦ C.
The obtained ZnO NPs were observed to be spherical with a particle size distribution
between 50 and 70 nm from the TEM images [55].
Another chemical method that has been widely utilised for the synthesis of NPs is the
hydrothermal synthesis method. It involves the interaction of an aqueous solvent with the
precursor usually metal salts at medium to high temperature and pressure in an autoclave.
When the process takes place in a non-aqueous environment, with a non-aqueous solvent, it
is called solvothermal [56,57]. The synthesis parameters of the hydrothermal/solvothermal
method influence the structure, particle size, and morphology which results in different
properties of the synthesised NPs [58,59]. However, difficulties in controlling the particle
size of NPs during synthesis and issues with reproducibility are some of the limitations of
hydrothermal methods [60]. Wang et al. [61] utilised the solvothermal method for the prepa-
ration of ZnO NPs for the photodegradation of methyl orange (MO) and p-nitrophenol. The
ZnO NPs were synthesised using zinc acetate dihydrate, sodium hydroxide, and ethanol.
The reaction mixture was heated at 80 ◦ C for 2 h and transferred to an autoclave for 12 h
at 180 ◦ C. The prepared ZnO NPs were observed to be near-spherical with a particle size
diameter of about 25–40 nm from the SEM images.
The chemical reduction synthesis method has been widely studied in research labora-
tories for the preparation of a wide range of NPs. This is due to its ability to produce NPs
of various properties and morphologies. The technique involves the reduction of metal
salt precursors such as nitrates, sulphates, and chlorides using reducing agents such as
sodium triethyl borohydride, sodium borate, toluene, sodium hydroxide, and hydrazine.
The reduction process leads to the formation of metallic atoms or metal oxide in the form of
a precipitate. The NPs can be stabilised using capping agents to prevent aggregation [62].
For instance, ZnO NPs were prepared by the chemical reduction of zinc nitrate hexahydrate
using sodium hydroxide and starch as the stabilisation agent. The synthesised ZnO NPs
were analysed using TEM and SEM. The ZnO NPs were revealed to have an average
particle size of 48 nm and spherical with a few hexagonal particles, respectively [63]. The
chemical reduction method has several drawbacks which limit its application, and these
Nanomaterials 2024, 14, 1182 7 of 37

include toxicity of some of the reducing agents, relative costliness, issues with impurities,
and poor reduction [64]. Table 4 depicts some of the advantages and disadvantages of some
chemical synthesis methods of ZnO NPs.

Table 4. Advantages and disadvantages of some chemical synthesis methods.

Synthesis Method Advantages Disadvantages Reference

Easy and
Utilises chemical agents and
Sol–gel low-temperature [65]
metal alkoxides are expensive
synthesis.
A simple method that Requires an autoclave, and
Hydrothermal produces high-yield and high temperatures. Risk of [66]
uniform NPs. explosion from the autoclave.
Utilises hazardous agents and
It is cost-effective and has
Chemical reduction the formation of toxic [67]
a good production rate.
by-products.
Chemical vapour Produces high-purity Operates at high temperatures
[68]
deposition NPs. and utilises chemical agents.
Difficult to scale up and
Microemulsion No energy requirements. requires large amounts of [65]
surfactants.

3.3. Green Synthesis

Green chemistry has been defined by the United States Environmental Protection
Agency (EPA) as “an area of chemistry, chemical engineering or/and related fields fo-
cused on the designing of chemical/products and/or processes, which reduce/decreases
or remove the utilisation and/or creation of dangerous/toxic substances” [69]. The green
synthesis of NPs using plants, algae, and microbes is a green chemistry technology as it
eliminates the need for toxic raw materials and minimises the production of toxic products.
Therefore, it lessens the negative impacts of chemical synthesis technologies on the environ-
ment and human health. Additionally, green synthesis of NPs reduces energy consumption
and is a cost-effective method [70]. It is an alternative method to the conventional synthesis
methods that has been receiving attention in recent years. Green synthesis can be divided
into microbes, plants, and algae, with bacteria, yeast, and fungi falling under microbes.
Biomolecules such as enzymes, proteins, and carbohydrates from or in microbes are
capable of reacting with metallic ions via reduction or oxidation to produce NPs [71].
These biomolecules remove the need for toxic reducing agents and capping agents as they
act as reducing and stabilising agents. The microbes interact with the metallic ions via
several pathways which can affect the size and morphology of the NPs. Moreover, the
size and morphology can be manipulated by controlling synthesis conditions such as pH
and temperature [72]. The reactions can be intracellular or extracellular, with intracellular
requiring extra costly purification processes to obtain the synthesised NPs from the cells.
Bacteria are microorganisms that are abundantly found in the environment, water, soil,
and land. They are capable of thriving even under severe conditions and reproducing,
making them suitable candidates for NP production [73]. Bacteria are known to produce
biomolecules such as enzymes, carbohydrates, proteins, and amino acids through various
metabolic pathways. These biomolecules play an essential role in the growth, reproduction,
and adaptability of the bacteria to the environment. Recently, the biomolecules from
bacteria have found use in the fabrication of NPs. The biomolecules are capable of reducing
metal ions to generate NPs and act as stabilising agents that can prevent aggregation during
the synthesis process [74].
Barani et al. [75] utilised two bacteria strains isolated from water and shrimp (Mari-
nobacter sp. 2C8 and Vibrio sp. VLA) for the synthesis of ZnO NPs using zinc sulphate
monohydrate as the Zn salt precursor. The obtained bacteria strains from the isolation
process were incubated at 30 ◦ C for 72 h in broth media to obtain bacterial biomass. The
biomass was incubated at 30 ◦ C for 48 h and centrifuged to collect the supernatant that
Nanomaterials 2024, 14, 1182 8 of 37

was utilised for the synthesis of ZnO NPs. The TEM results revealed that the fabricated ZnO
NPs were roughly spherical with average particle size diameters of 10.23 and 20.26 nm for
Marinobacter sp. 2C8-mediated ZnO NPs and Vibrio sp. VLA-mediated ZnO NPs, respectively.
Amongst microorganisms used for the green synthesis of NPs, fungi-mediated syn-
thesis has been reported to exhibit better performance. This is owing to the presence of a
variety of intracellular biomolecules and biomolecules on the surface of the cells. Moreover,
fungi are capable of producing larger amounts of NPs compared to bacteria, and this makes
fungi-mediated synthesis more ideal for the large-scale production of NPs [76,77]. Kalpana
and co-workers [78] successfully synthesised ZnO NPs using Aspergillus niger fungi and
zinc nitrate at 32 ◦ C for 48 h with shaking; the authors observed a colour change from
light yellow to colourless. The morphology of the synthesised ZnO NPs was studied using
SEM and reported to be spherical with an average particle size of 61 nm. Additionally,
the authors confirmed the presence of ZnO NPs and the functional groups such as car-
boxylic and aromatic groups on the surface of the synthesised ZnO NPs using Fourier
transform infrared spectroscopy (FTIR). The functional groups were attributed to be from
the fungi biomolecules.
NPs of different morphologies and sizes have been successfully synthesised using
microorganisms. This synthesis technique is a green synthesis route that avoids the use
of toxic chemicals and synthesises NPs in an eco-friendly manner. However, the method
is limited by the need for screening, long incubation periods, the need for high aseptic
conditions, and complex maintenance [79]. Additionally, there is a risk of contamination
of the synthesised NPs with the microorganisms posing a threat to human health. Green
synthesis of NPs using plants offers a more favourable option and has been explored for
producing ZnO NPs with excellent results.

3.4. Plant-Mediated Synthesis

Plants are abundant and easily accessible natural resources that are “chemical factories”
and have a vast majority of applications. For instance, they are employed in environmental
remediation to eliminate heavy metals and other pollutants from the environment through
processes like detoxification, accumulation, or phytoremediation. Plants require little
maintenance as compared to microbe-mediated green synthesis, and similar to microbes,
plants possess biomolecules which can be used to fabricate NPs. Moreover, the reaction
kinetics during plant-mediated synthesis is comparable to chemical synthesis methods [80].
This makes plant-mediated synthesis of NPs a viable option for the environmentally
friendly and sustainable nano-synthesis of NPs.
Plant parts such as leaves, roots, stems, flowers, and fruits produce large quantities
of biomolecules via various metabolic pathways that can be used to fabricate NPs. The
biomolecules have free radical-scavenging capabilities and are rich in antioxidant activ-
ity [81]. The biomolecules include vitamins, proteins, terpenoids, reducing sugars, polyphe-
nols, polyols, etc., which can be utilised to reduce metal salts to NPs and stabilise the NPs.
Green synthesis of NPs using plant materials has been extensively studied and reported
owing to its ability to be easily scaled up for large-scale production, cost-effectiveness,
and environmentally friendly nature [82]. Even though plant-mediated synthesis of NPs
has several advantages over chemicals and microbe-mediated synthesis, research is still
required to better control the size and morphology of the NPs.

Plant-Mediated Synthesis of ZnO NPs

ZnO NPs have been synthesised using different plants and plant parts, with different
zinc salts such as nitrates, chlorides, sulphates, and acetates as the Zn precursors. The syn-
thesis process can be divided into three steps: plant collection and treatment, biomolecule
extraction, and synthesis. The process begins with the collection of fresh plant material
which is followed by washing of the plant material to remove dirt and debris. The washed
plant material is dried or used in its fresh form. The drying process can be achieved using
different drying techniques like sun-drying, oven-drying, and freeze-drying. Typically,
Nanomaterials 2024, 14, 1182 9 of 37

drying is preferred as it eliminates moisture and stops any metabolic processes, which in
turn aids in the reproducibility of the synthesis process. After drying, the plant material is
ground to powder to increase the interaction with the solvent during the extract process.
The next step is the biomolecule extraction step which involves the extraction of the
biomolecules from the dried powder or small pieces of fresh plant material, typically using
non-toxic solvents such as water and ethanol. The extraction is usually carried out at low
temperatures (RT to 80 ◦ C) using conventional extraction methods such as maceration,
decoction, and Soxhlet extraction. In some cases, non-conventional extraction methods
such as microwave-assisted, ultrasound-assisted, autoclave-assisted extraction, etc., are
utilised for the extraction of biomolecules from plant material. Chennimalai et al. [83]
utilised a combination of maceration and heat-assisted extraction to extract biomolecules
from Opuntia humifusa (O. humifusa) fruit. The extraction process entailed adding
Nanomaterials 2024, 14, x FOR PEER REVIEW
100 mL
10 of 40
of distilled water to 20 g O. humifusa fruit powder, shaking the mixture for 24 h and
heating the mixture in an oven at 60 ◦ C. The qualitative analysis of the extract yielded
saponins, polyphenols, tannins, flavonoids, terpenoids, carbohydrates, and proteins. These
proteins. These biomolecules have been reported to take part in the plant-mediated
biomolecules have been reported to take part in the plant-mediated synthesis of ZnO NPs.
synthesis of ZnO NPs.
After obtaining the plant extract, it can be mixed with the Zn salt precursor and
After obtaining the plant extract, it can be mixed with the Zn salt precursor and
heated at low temperatures (usually from RT to 100 ◦ C), which is one of the appeals of
heated at low temperatures (usually from RT to 100 ℃), which is one of the appeals of
plant-mediated synthesis.The
plant-mediated synthesis. The reduction
reduction of of
thethe
ZnZnsaltsalt precursors
precursors and and the stabilisation
the stabilisation of of
the synthesised ZnO NPs by the plant biomolecules occurs in this step and
the synthesised ZnO NPs by the plant biomolecules occurs in this step and the mechanism the mechanism
will be discussed
will be discussedinindetail
detailinin later
later sections.
sections. Typically,
Typically, thethe plant-mediated
plant-mediated synthesis
synthesis of ZnOof ZnO
NPs has followed
NPs has followedtwotwocommon
common approaches:
approaches: co-precipitation
co-precipitation and and direct
direct reduction.
reduction. In co-In co-
precipitation, twoprecursors
precipitation, two precursorsare areused,
used, hydroxides
hydroxides likelike sodium
sodium hydroxide
hydroxide and potassium
and potassium
hydroxide
hydroxide andand the
the Zn
Znsalt
saltprecursors.
precursors.In In comparison,
comparison, the the direct
direct reduction
reduction approach
approach
involves the reduction
involves the reductionofofthe
theZnZnsalt
saltprecursors
precursors using
using thethe plant
plant extract.
extract. A summary
A summary of of
plant-mediated synthesisofofZnO
plant-mediated synthesis ZnONPsNPsis is depicted
depicted in Figure
in Figure 3. 3.

Figure 3.
3. Summary
Summaryofofplant-mediated
plant-mediatedsynthesis of ZnO
synthesis NPs.
of ZnO NPs.

Sathappan and associates

Sathappan associates [84]
[84]successfully
successfullysynthesised
synthesisedZnO ZnONPs with
NPs Cissus
with quadran-
Cissus
gularis (C. quadrangularis)
quadrangularis stem extract
(C. quadrangularis) and zinc
stem extract andacetate dihydrate.
zinc acetate The method
dihydrate. The methodinvolved
mixing
involved1 mL of C.1 quadrangularis
mixing extract with
mL of C. quadrangularis 50 mL
extract of 0.02
with 50 mLM ofzinc acetate
0.02 dihydrate
M zinc acetate and
dihydrate the
adjusting andpHadjusting the pH
to 12 using 2M to sodium
12 usinghydroxide.
2 M sodium hydroxide.
The mixture wasThe mixture
allowed wasto stand
allowed
for to stand
2 h, and for 2precipitate
a white h, and a white
was precipitate was obtained,and
obtained, centrifuged, centrifuged,
washed withand washed
ethanol. To
with ethanol.
obtain the ZnOTo obtain
NPs, thethe white
ZnO NPs, the white
precipitate precipitate
was dried inwas
thedried
oveninatthe
60oven at 60 ℃ In
◦ C overnight.
overnight.
another In another
study, study, Hertia
Hertia intermedia intermedia (H.
(H. intermedia) intermedia)
extract extracttowas
was utilised utilised
fabricate ZnOto NPs.
fabricate
The ZnO NPs.
procedure The procedure
involved adding 10 involved
mL ofadding 10 mL of
H. intermedia H. intermedia
extract to 100 extract
mL of to0.1100
M zinc
mL of 0.1 and
sulphate M zinc sulphate and
maintaining themaintaining
pH at 8. The themixture
pH at 8.was
The heated
mixtureatwas60 heated ath60to℃
◦ C for 6 obtain
a yellowish-brown mixture. The mixture was centrifuged and washed with washed
for 6 h to obtain a yellowish-brown mixture. The mixture was centrifuged and ethanol and
with ethanol and dried at 50 ℃ in the oven [85]. Donga and Chanda [86] successfully
prepared ZnO NPs using 50 mL of Caesalpinia crista (C. crista) seed extract and 5 g of zinc
nitrate hexahydrate at 80 ℃. The mixture was heated until the formation of a deep yellow-
coloured paste. The paste was annealed at 400 ℃ for 2 h in a Muffle furnace to obtain the
ZnO NPs.
In some instances, the synthesis can be microwave-assisted, ultrasound-assisted, or
Nanomaterials 2024, 14, 1182 10 of 37

dried at 50 ◦ C in the oven [85]. Donga and Chanda [86] successfully prepared ZnO NPs
using 50 mL of Caesalpinia crista (C. crista) seed extract and 5 g of zinc nitrate hexahydrate
at 80 ◦ C. The mixture was heated until the formation of a deep yellow-coloured paste. The
paste was annealed at 400 ◦ C for 2 h in a Muffle furnace to obtain the ZnO NPs.
In some instances, the synthesis can be microwave-assisted, ultrasound-assisted, or
autoclave-assisted. Algarni and associates [87] successfully synthesised ZnO NPs for
photodegradation application using 5 g zinc nitrate hexahydrate, 18 mL sodium hydroxide,
and 30 mL Rosmarinus officinalis leaf extract in a steel autoclave at 80 ◦ C and 180 ◦ C.
Sonication was utilised for the preparation of Thymus vulgaris (T. vulgaris)-mediated ZnO
NPs. The method involved adding T. vulgaris to 0.1 M zinc nitrate hexahydrate in a 4:1 ratio
and sonication for 1 h to obtain a white-coloured precipitate. The precipitate was washed
with ethanol and deionised water, dried in the oven at 50 ◦ C, and annealed in the furnace
at 400 ◦ C [69]. In another study, a microwave-assisted method was used for the synthesis
of ZnO NPs using Rumex dentatus (R. dentatus) leaf extract. The method involved adding
100 mL of 0.1 M zinc nitrate hexahydrate to 100 mL of R. dentatus extract on a hotplate at
60–70 ◦ C with stirring. This was followed by microwave treatment of the reaction mixture
at 500 W for 5 min in a domestic microwave. The mixture was separated and washed, and
the obtained paste was dried in the oven at 50 ◦ C for 4 h [88].
A few studies have used solution combustion to prepare plant-mediated ZnO NPs.
This approach involves heating a mixture of the plant extract and the Zn salt precursor in a
furnace. Surendra et al. [89] prepared Lantana camara (L. camara) leaf-mediated ZnO NPs
by adding 8.99 g of zinc nitrate hexahydrate to 5 mL of L. camara extract and heating the
mixture at 80 ◦ C for 10 min on a heating mantle. The mixture was then subjected to 500 ◦ C
(combustion) to obtain the ZnO NPs in a furnace.

3.5. Influence of Synthesis Parameters on the Formation and the Properties of Plant-Mediated
ZnO NPs
This section will discuss the influence of synthesis parameters on the formation and
properties of plant-mediated ZnO NPs. The synthesis parameters such as pH, reaction
time, precursor salt concentration, temperature, type of Zn salt precursor, and the influence
of the type of biomolecules present in the extract and plant extract concentrations play a
role in the formation of plant-mediated ZnO NPs and hence their properties [90].
The concentration of salt precursor is known to influence the properties of NPs during
synthesis. Generally, increasing the Zn precursor concentration to a certain point (optimum)
results in increased particle rate growth, which leads to the formation of smaller parti-
cles. However, any further increase in Zn precursor concentration beyond the optimum
precursor concentration leads to agglomeration, resulting in larger particles [91]. This
trend was observed by Abdol Aziz and co-workers [92] for ZnO NPs prepared with Musa
acuminata (banana) peel extract and varying concentrations of zinc acetate dihydrate (0.01,
0.05, and 0.1 M). The authors observed that the crystallite size decreased with an increase
in precursor concentration from 0.01 to 0.05 M (25.78 to 14.93 nm, respectively) from the
X-ray powder diffraction (XRD) results. Nevertheless, a further increase in precursor con-
centration to 0.1 M increased the crystallite size to 15.23 nm. Additionally, increasing the
Zn salt precursor concentration resulted in a decrease in the calculated bandgap from 3.54
to 3.44 eV. Thus, the calculated bandgap red-shifted towards lower energy values with
a decrease in crystallite sizes. However, increasing the Zn salt precursor concentration
beyond 0.05 M resulted in an increase in the bandgap to 3.58 eV. As a result of quantum
confinement effects, the bandgap is expected to blue shift towards higher energy values
with a decrease in crystallite size. However, in the case of banana peel-mediated ZnO
NPs, the crystallite sizes exceed the exciton Bohr diameter of ZnO; therefore, the quantum
confinement effects are less prominent [93].
In another study, the influence of different salt precursor concentrations (5, 10, and
50 mmol kg−1 ) on the size and morphology of aloe vera-mediated ZnO NPs was investi-
gated. The XRD results revealed that increasing the Zn salt precursor resulted in a slight
Nanomaterials 2024, 14, 1182 11 of 37

increase in crystallite size, while the TEM results showed that varying the precursor salt
concentration affected the shape and particle size of the aloe vera-mediated ZnO NPs.
The aloe vera-mediated ZnO NPs synthesised with 5, 10, and 50 mmol kg−1 exhibited
hexagonal, spherical and hexagonal, and cuboidal/rod-shaped particles, respectively. The
average particle sizes were 63 nm, 65 nm and 60–180 nm, and 40–45 nm, respectively [94].
These findings demonstrate that Zn precursor salt concentration influences the formation
and properties of plant-mediated ZnO NPs. They also highlight that the Zn salt precursor
concentration can be used to manipulate and control properties such as the shape and size
of plant-mediated ZnO NPs, which can lead to diverse applications of the plant-mediated
ZnO NPs.
The use of different Zn salt precursors has been reported to influence the properties
of plant-mediated ZnO NPs. This is supported by the investigations by Fakhari and
associates [95] who utilised Laurus nobilis (L. nobilis) leaf extract and zinc acetate and zinc
nitrate precursors to prepare ZnO NPs. From the SEM images, the authors observed that
the ZnO NPs from the zinc acetate precursor were spherical like bullets, whereas the ZnO
NPs from the zinc nitrate precursor were nano-flowers. The spherical ZnO NPs had a
smaller particle size (21.26 nm) compared to the nano-flowers (25.49 nm). In a similar study,
Abdullah and co-workers [96] assessed the influence of different Zn salt precursors on the
properties of Phoenix dactylifera (P. dactylifera)-mediated ZnO NPs. The authors observed
that the choice of Zn salt precursor resulted in different particle sizes and shapes of the
synthesised ZnO NPs from the SEM and TEM results, with the different morphologies
observed given in Table 5.

Table 5. Different morphologies of P. dactylifera-mediated ZnO NPs synthesised using different types
of Zn salt precursors.

Type of Zn Salt Precursor Morphology

Mixture of random, conglomerated, packed, clustered, and
Zinc chloride anhydrous rod-shaped NPs with face-centred rhombohedral, spherical,
hexagonal, and cubic-like structures
Needle-shaped nanorods, thinner nanoplates, and
Zinc acetate dihydrate
flower-like nanolayers
Nanorods, flower-like, nanolayered, and some
Zinc nitrate hexahydrate
cubic structures
Nanorods, nanoplate flower-like nanolayered, and
Zinc sulphate monohydrate
hollow spherical

These investigations show that the type of Zn salt precursor used can influence the
size and shape of plant-mediated ZnO NPs. Therefore, Zn salt precursors can be a tool to
control and tailor the morphology of plant-mediated NPs for specific applications.
pH is an important parameter in nano-synthesis, and this also applies to plant-
mediated synthesis of ZnO NPs. However, the influence of pH on the synthesis and
properties of plant-mediated ZnO NPs has not been extensively investigated at the present
moment. Among the few studies that have investigated the influence of pH on the syn-
thesis and properties of plant-mediated ZnO NPs, several of the studies have proposed
pH 12 as the ideal pH for the synthesis of ZnO NPs. Abdullah et al. [97] investigated the
influence of pH on the crystallite size and morphology of M. acuminata peel-mediated
ZnO NPs. The ZnO NPs were synthesised at varying alkaline pHs of 8, 9, 10, 11, and
12. The SEM results (Figure 4) revealed that the ZnO NPs synthesised at pH 8, 9, 10, 11,
and 12 were granulated and crumbled, flaked and sheet-like, leaf-like, triangular-like, and
triangular-like with tapered tips, respectively. From the XRD results, the authors observed
that the M. acuminata–ZnO NPs synthesised at pH 8, 9, and 10 were wurtzite in structure
with some zinc hydroxide impurities, whereas those synthesised at pH 11 and 12 were
high-purity ZnO NPs with a wurtzite structure.
Nanomaterials 2024, 14, 1182
Nanomaterials 2024, 14, x FOR PEER REVIEW 12 of 37 13 of 40

Figure
Figure 4. SEM images 4. SEM
of M. images peel
acuminata of M.extract-mediated
acuminata peel extract-mediated ZnO NPs synthesised
ZnO NPs synthesised at pH.
at different different pH.
Adapted
Adapted from Ref. [97]. from Ref. [97].

The crystallite size Thedecreased

crystallite size decreased from
significantly significantly
79.9 tofrom
30.279.9
nm to 30.2an
with nmincrease
with an increase
in in
pH from 8 to 12. The authors proposed pH 12 as the optimum pH for the synthesis of M.
pH from 8 to 12. The authors proposed pH 12 as the optimum pH for the synthesis of
acuminata-mediated ZnO NPs. Similarly, Gupta [98] and associates optimised the pH for
M. acuminata-mediated ZnO NPs. Similarly, Gupta [98] and associates optimised the pH
the synthesis of ZnO NPs using Catharanthus roseus (C. roseus) extract using UV-Vis. The
for the synthesis authors
of ZnOreported
NPs using that Catharanthus
C. roseus-mediated roseusZnO roseus)
(C. NPs extract using
synthesised at pHUV-Vis.
12 exhibited an
The authors reported that C. roseus-mediated ZnO NPs synthesised
absorption peak at 366 nm, whereas no peaks were observed for those at pH 12 exhibited
prepared an at pH 8,
absorption peak at 366 nm, whereas no peaks were observed for those prepared
10, and 14. These findings suggest that the ideal pH for synthesising C. roseus-mediated at pH 8, 10,
and 14. These findings
ZnO NPs suggest
was pH that12.theThis
idealcanpH befor to the C.
synthesising
attributed roseus-mediated
presence of the optimum ZnO ratio of
hydroxyl ions to hydrogen ions at pH 12 which promotes
NPs was pH 12. This can be attributed to the presence of the optimum ratio of hydroxyl the formation of the Zn–O bond
ions to hydrogen ions at pH 12 which promotes the formation of the Zn–O bond as ahydroxyl
as a result of the attraction between the positively charged zinc (II) ions and the
ions. Therefore,
result of the attraction between the at low pH, therecharged
positively are insufficient
zinc (II)hydroxyl
ions and ions
thetohydroxyl
facilitate the
ions.formation
Therefore, at low pH, there are insufficient hydroxyl ions to facilitate the formation of the in the
of the Zn–O bond, whereas at higher pH, there are excess hydroxyl ions resulting
Zn–O bond formation [99]. Hence, pH 12 has been utilised in several reports for the
Zn–O bond, whereas at higher pH, there are excess hydroxyl ions resulting in the Zn–O
synthesis of ZnO NPs using plant extracts.
bond formation [99]. Hence, pH 12 has been utilised in several reports for the synthesis of
However, some studies have reported pH 8 as the ideal pH for the synthesis of ZnO
ZnO NPs using plant extracts.
NPs using plant materials. Gherbi et al. [100] synthesised ZnO NPs using Portulaca oleracea
However, some studiesleaf
(P. oleracea) have reported
extract pH 8pHs
at different as the ideal
(4, 6, pH 11)
9.5, and for by
theadding
synthesis
sodiumof ZnO
borohydride.
NPs using plant materials.
The authors Gherbi
reported et al.
that[100] synthesised
the XRD calculationsZnO NPs using
showed Portulaca
an increase oleracea
in the crystallite size
(P. oleracea) leaf extract
of ZnOatNPs different
(25.38 pHs (4, nm)
to 26.04 6, 9.5, andthe
when 11)pH by increased
adding sodiumfrom pH borohydride.
4 to 6. In contrast, a
The authors reported that in
decrease the XRD calculations
crystallite showed
size (25 to 22.17 nm) anwasincrease
observed ininthe
thecrystallite size of under
ZnO NPs prepared
ZnO NPs (25.38 toalkaline
26.04 nm)pH when
conditions,
the pH from pH 9.5 and
increased from11. pHMoreover,
4 to 6. In the XRD results
contrast, revealed the
a decrease
in crystallite size presence of impurities
(25 to 22.17 nm) wasinobserved
the ZnO NPs synthesised
in the ZnO NPs at prepared
pH 4 and 11. Therefore,
under alkaline the authors
pH conditions, from proposed
pH 9.5 thatandpH 11.
8 was the ideal pH
Moreover, thefor the preparation
XRD of P. oleracea-mediated
results revealed the presence ofZnO NPs
impurities in the of ZnOhigh purity and smaller sizes.
NPs synthesised at pH 4 and 11. Therefore, the authors proposed
In another study, Mohammadi and Ghasemi [101] synthesised ZnO NPs at pH 4, 6,
that pH 8 was the ideal pH for the preparation of P. oleracea-mediated ZnO NPs of high
7, 8, and 10 using cherry extract. The results from the UV-Vis analysis revealed that no
purity and smaller sizes.
absorption peak was observed for cherry-mediated ZnO NPs at pH 4. The absorption
In another study,
peaks Mohammadi
red-shifted towards and Ghasemi [101] synthesised
higher wavelengths as the pHZnO NPs at
increased pH44,to6,8 due to
from
7, 8, and 10 usinglarger
cherry extract. The results from the UV-Vis analysis
particles, while a further increase in pH from 8 to 10 exhibited a blue revealed thatshift
no towards
absorption peak lowerwas observed for cherry-mediated ZnO NPs at pH 4. The
wavelengths due to smaller particles. The authors concluded that the optimum pH absorption
peaks red-shifted fortowards higherofwavelengths
the synthesis ZnO NPs using as cherry
the pHextract
increased
was 8.from
It has4been
to 8 suggested
due to larger that alkaline
particles, while a conditions influence
further increase indeprotonation
pH from 8 toand activation of
10 exhibited biomolecules
a blue which lower
shift towards increases their
wavelengths duereducing
to smaller andparticles.
stabilising Thepower. On theconcluded
authors other hand, thatacidictheconditions
optimum havepH beenforreported
to influence protonation, which reduces the
the synthesis of ZnO NPs using cherry extract was 8. It has been suggested that alkalinereducing and stabilising power of
biomolecules present in plant extracts [102].
conditions influence deprotonation and activation of biomolecules which increases their
However, pH has been reported to affect the electrical charges of the biomolecules
reducing and stabilising power. On the other hand, acidic conditions have been reported to
present in the plant extracts, which in turn affects their power to reduce and stabilise the
influence protonation, which reduces the reducing and stabilising power of biomolecules
NPs and hence the growth of the NPs [103]. Therefore, the ideal pH for preparing plant-
present in plant extracts [102].
However, pH has been reported to affect the electrical charges of the biomolecules
present in the plant extracts, which in turn affects their power to reduce and stabilise
the NPs and hence the growth of the NPs [103]. Therefore, the ideal pH for preparing
plant-mediated ZnO NPs should depend on the type of biomolecules present in the plant
extracts. Padalia and co-workers [104] investigated the influence of pH 5 and 8 on the
Nanomaterials 2024, 14, 1182 13 of 37

particle size of Salvadora oleoides (S. oleoides)-mediated ZnO NPs. The study revealed
that the S. oleoides-mediated ZnO NPs synthesised at pH 5 had smaller particle sizes
(average 26.62 nm) with spherical particles compared to those synthesised at pH 8 (average
38.62 nm), with irregular morphology from the TEM images. In another study, Sarillana
and co-workers [105] synthesised ZnO NPs at pH 7, 8, and 9 using Theobroma cacao L.
(T. cacao) pod husks. The UV-Vis spectra revealed that the absorption peaks of the T. cacao-
mediated ZnO NPs blue-shifted with a decrease in pH, indicating the formation of smaller
particles with a decrease in pH. Therefore, the ideal pH for the synthesis of ZnO NPs using
T. cacao pod husk extracts was pH 7. These findings demonstrate the influence of pH on the
formation of ZnO NPs using plant extracts and therefore, there is a need to optimise the
pH as the ideal pH for the synthesis of ZnO NPs using plant extracts might be dependent
on the type of biomolecules present in the plant extract. However, only a few studies have
investigated the influence of pH on the formation and properties of plant-mediated ZnO
NPs and therefore, more studies are required to better understand the influence of pH.
This would lead to the development of better plant-mediated ZnO NPs that are suitable for
various applications. Additionally, some studies have highlighted the influence of pH on
the particle size of plant-mediated ZnO NPs. Therefore, pH can be used as a tool to tune or
control the properties of plant-mediated ZnO NPs, leading to plant-mediated ZnO NPs of
various properties that are suitable for various applications.
Plant extract concentration has been reported to influence the properties of plant-
mediated ZnO NPs. Nithya and associates [106] investigated the effect of varying the
volume of Cardiospermum halicacabum (C. halicacabum) extract from 0.2 to 0.6 mL on the
properties of the synthesised ZnO NPs. The authors reported that increasing the volume
of C. halicacabum extract resulted in a significant reduction in crystallite size from 62 to
48 nm of the synthesised ZnO NPs from the XRD studies. This was in agreement with the
observed dynamic light scattering (DLS) results; the particle size also decreased with an
increase in C. halicacabum extract volume. This is similar to observations by Soto-Robles and
associates [107] for different Hibiscus sabdariffa (H. sabdariffa) plant extract concentrations
used for the synthesis of ZnO NPs. The authors observed from the TEM images that the
particle size decreased as the H. sabdariffa concentration increased from 1% (20–40 nm)
to 8% (5–12 nm). The TEM images and the size distribution are given in Figure 5. The
calculated bandgap from the UV-Vis results revealed that the bandgap decreased (2.96 to
Nanomaterials 2024, 14, x FOR PEER REVIEW 15 of 40
2.77 eV) with an increase in H. sabdariffa concentration.

Figure 5. The TEM images of H. sabdariffa-mediated ZnO NPs synthesised using (A) 1%, (B) 4%, and
Figure 5. The (C)
TEM8%. images
Particle size H. sabdariffa-mediated
ofdistribution ZnO ZnO
of H. sabdariffa-mediated NPsNPs
synthesised using
synthesised using (D) (A) 1%, (B) 4%,
1%, (E)
and (C) 8%. Particle
4%, andsize distribution
(F) 8%. Adapted fromof H.[107].
Ref. sabdariffa-mediated ZnO NPs synthesised using (D) 1%,
(E) 4%, and (F) 8%. Adapted from Ref. [107].
Similar to the influence of Zn salt precursor concentration, studies have revealed that
increasing the plant extract concentration beyond the optimum leads to an increase in size.
This was reported for ZnO NPs synthesised using varying volumes of Solanum nigrum (S.
nigrum) leaf extract. It was observed from the XRD studies that the crystallite decreased
from 2.53 to 2.07 nm with an increase in S. nigrum volume from 5 to 15 mL. On the
contrary, a further increase in S. nigrum extract to 20 mL sizes led to an increase in
crystallite size to 2.70 nm [108]. At lower plant concentrations, the biomolecules present
Nanomaterials 2024, 14, 1182 14 of 37

Similar to the influence of Zn salt precursor concentration, studies have revealed

that increasing the plant extract concentration beyond the optimum leads to an increase
in size. This was reported for ZnO NPs synthesised using varying volumes of Solanum
nigrum (S. nigrum) leaf extract. It was observed from the XRD studies that the crystallite
decreased from 2.53 to 2.07 nm with an increase in S. nigrum volume from 5 to 15 mL. On
the contrary, a further increase in S. nigrum extract to 20 mL sizes led to an increase in
crystallite size to 2.70 nm [108]. At lower plant concentrations, the biomolecules present
in the extract are insufficient to reduce and stabilise the synthesised NPs which leads to
aggregation and larger particles. On the other hand, excess biomolecules in extracts can
affect the nucleation step, also resulting in larger particles. These findings highlight the
influence of plant extract volume or concentration on the properties of plant-mediated
ZnO NPs. Plant extract concentration can be utilised as a tool for controlling the properties
of plant-mediated ZnO NPs as varying this parameter results in varying properties of
plant-mediated ZnO NPs.
Temperature is also an important parameter during the synthesis of NPs. The general
trend is that increasing reaction temperature decreases the particle size, and this is due
to nucleation being favoured over particle growth at high temperatures, which leads to
smaller particles. This is because, at high temperatures, the molecules interact with the
precursor faster due to their increased kinetic energy, which results in nuclei formation
instead of particle growth. However, at low temperatures, the kinetic energy is low, which
leads to particle growth due to the Oswald ripening thermal effect. It should be noted that
when the temperature is too high, the surface activity of the nuclei increases, which leads
to collisions and agglomeration, resulting in increased particle sizes [109]. On the contrary,
Basri et al. [110] reported a smaller particle size diameter of pineapple peel-mediated
ZnO NPs synthesised at 28 ◦ C (at RT) (8–45 nm) which were a mixture of spherical and
nanorods compared to those synthesised at 60 ◦ C (73–123 nm), which were flower rod-
shaped. Another study reported an increase in particle sizes of cherry-mediated ZnO
NPs with an increase in reaction temperature from RT to 90 ◦ C from the SEM results. The
authors attributed these observations to the reduction in stability of biomolecules present
in the cherry extract as the temperature increased [101]. This resulted in the cherry extract
losing its reducing and stabilising power as temperature increased.
Similar to the reaction temperature, annealing temperature has also been reported
to influence the size, morphology, and optical bandgap of ZnO NPs. Doan Thi and asso-
ciates [111] studied the influence of different annealing temperatures (unannealed and 300
to 900 ◦ C) on the crystallite size of orange peel-mediated ZnO NPs. From the XRD results,
the unannealed ZnO NPs exhibited the smallest crystallite size (12 nm), whereas the ZnO
NPs annealed at 300 and 900 ◦ C had crystallite sizes of 22 and 95 nm, respectively. The
crystallite size increased with an increase in annealing temperature. The authors attributed
this to the re-orientation of particles as a result of an increase in thermal energy, which leads
to a reduction in the number of defects in grain boundaries. Additionally, the TEM results
revealed that the particle size also increased with an increase in annealing temperature
(10–20 nm, 35–60 nm, 70–100 nm, and 200–230 nm for as-prepared ZnO NPs, ZnO NPs
annealed at 400, 700, and 900 ◦ C, respectively).
Similar observations were reported by Álvarez-Chimal and associates [112] for Dys-
phania ambrosioides (D. ambrosioides)-mediated ZnO NPs annealed at 200, 400, 600, and
800 ◦ C. From the SEM analysis, the authors observed that the particle size increased with
an increase in annealing temperature, with average particle sizes of 7 and 14 nm for ZnO
NPs annealed at 200 and 400 ◦ C, respectively. The D. ambrosioides-mediated ZnO NPs were
observed to be quasi-spherical from 200 to 400 ◦ C. However, quasi-spherical and hexagonal
prisms were observed from 600 to 800 ◦ C with average particle sizes of 22 and 130 nm for
quasi-spherical particles and 70 and 90 nm for hexagonal prisms, respectively.
Karthik et al. [113] investigated the influence of different annealing temperatures (100,
300, and 600 ◦ C) on ZnO NPs synthesised using Acalypha indica (A. indica) leaf extract. From
the XRD results, the authors observed that the A. indica-mediated ZnO NPs annealed at
Nanomaterials 2024, 14, 1182 15 of 37

100 ◦ C were amorphous and therefore did not exhibit any diffraction peaks. However,
the A. indica-mediated ZnO NPs annealed at 300 and 400 ◦ C were crystalline, and their
crystallite sizes increased with an increase in annealing temperature (39.34 and 43.63 nm,
respectively). The TEM results revealed that the A. indica-mediated ZnO NPs annealed
at 100 and 300 ◦ C were aggregated and of irregular shape, while the A. indica-mediated
ZnO NPs synthesised at 600 ◦ C were spherical. The particle sizes also increased with an
increase in annealing temperature, and crystallinity was also enhanced at 600 ◦ C. The
increase in particle size with an increase in annealing temperature can be attributed to
agglomeration, which happens at higher temperatures, and the Oswald ripening effect.
The higher the annealing temperature, the higher the activation energy for diffusion,
which leads to crystalline grain growth, resulting in larger particles [114]. These studies
highlight the influence of annealing temperature on the properties of plant-mediated ZnO
NPs, and annealing temperature can be used as a parameter that can be manipulated to
control the properties of plant-mediated ZnO NPs. This will lead to the development of
better-performing plant-mediated ZnO NPs in their various applications.
The use of different plants or plant parts for the synthesis of ZnO NPs also results in
varying properties of the synthesised NPs. Kebede Urge et al. [115] synthesised ZnO NPs
under the same reaction conditions using Z. officinale root and Allium sativum (A. sativum)
bulb extracts. The UV-Vis results revealed that the absorption peak of Z. officinale-mediated
ZnO NPs was blue-shifted towards shorter wavelengths compared to A. sativum-mediated
ZnO NPs. Both synthesised ZnO NPs were revealed to be wurtzite in structure and of
high and good crystallinity from the XRD analysis. The crystallite sizes of the Z. officinale-
mediated ZnO NPs and A. sativum-mediated ZnO NPs were 19.8 and 21.94 nm, respectively.
This report clearly shows that the use of different extracts influences the size and different
properties of ZnO NPs. In another study, Naseer and associates [116] synthesised ZnO
NPs under the same conditions using Cassia fistula (C. fistula) and Melia azadarach (M.
azadarach) extracts. The DLS results revealed that the M. azadarach-mediated ZnO NPs had
smaller particle sizes (3.62 nm) compared to C. fistula-mediated ZnO NPs (68.1 nm). The
authors attributed the differences in particle size to differences in biomolecules present in
the two plant extracts. The biomolecules present in the M. azadarach extract had a better-
reducing ability compared to the biomolecules present in the C. fistula extract. These studies
demonstrate that the properties of plant-mediated ZnO NPs are dependent on the type of
biomolecules present in the extract, which is also mostly dependent on the type of plant or
plant parts. Therefore, utilising different plant extracts to prepare plant-mediated ZnO NPs
can help tailor properties such as the size and shape of the synthesised NPs for different
applications. Table 6 gives some properties and applications of plant-mediated ZnO NPs
that have been reported.
Green synthesis of ZnO NPs has successfully been achieved using various plants
and plant parts. Furthermore, synthesis parameters such as precursor concentration, pH,
reaction temperature, and so on influence the formation and properties of plant-mediated
ZnO NPs. However, the influence of these synthesis parameters on the formation and
properties of plant-mediated ZnO NPs has not been extensively reported. There is a need
for more research that focuses on manipulating and tailoring plant-mediated ZnO NPs
using synthesis parameters such as pH, reaction temperature, annealing temperature, type
of Zn salt precursor, plant concentration, and Zn salt precursor concentration. This will lead
to the development of high-performing plant-mediated ZnO NPs that can be suitable for
various applications. However, understanding the mechanism of formation is also essential
in controlling the properties of plant-mediated ZnO NPs. The mechanism of formation of
plant-mediated ZnO NPs will be discussed in the section below. Additionally, studies are
needed that focus on reproducibility and scalability of the synthesis processes.
Nanomaterials 2024, 14, 1182 16 of 37

Table 6. Properties and applications of some plant-mediated ZnO NPs.

Plant XRD Particle Size Shape Application Ref.

30 nm
Leaf-like, triangular-like,
M. acuminata 33.3 nm - Photocatalysis [97]
triangular with tapered tips
40.0 nm
62–94 nm SEM
C. roseus Average 36.83 nm Spherical Antimicrobial [98]
50–92 nm TEM
Cherry 20.18 nm 87.5–116 nm Spherical - [101]
8.71 nm
5–12 nm
H. sabdariffa 9.05 nm Spherical Photocatalysis [107]
20–40 nm TEM
38.63 nm
Antibacterial
S. nigrum Average 2.07 nm Average 49 nm DLS Spherical Antioxidant [108]
Photocatalysis
M. acuminata Average 14.93 nm Average 74.19 nm BET - - [92]
25.39 nm Average size
P. oleracea Spherical and oval Photocatalysis [100]
26.04 nm distribution 70 nm
Antibacterial
T. cacao - Average 81 nm TEM Irregular [105]
Photocatalysis
C. halicacabum Average 48 nm Average 48 nm DLS Hexagonal quartzite Antibacterial [107]
nanorods, nanoplate
flower-like, and hollow
spherical; needle-shaped
nanorods, thinner nanoplate,
and flower-like; nanorods,
P. dactylifera 9.3–22.6 nm 3.7–10.2 nm TEM Antioxidant [96]
flower-like, and some cubic;
clustered and rod-shaped NPs
with face-centred
rhombohedral, spherical,
hexagonal, and cubic-like
UV protection
Average 39.34 nm 53.39 nm TEM
A. indica Spherical and irregular Antibacterial [113]
43.63 nm 65.13 nm
Water repellent
Average 7, 14, 22, Quasi-spherical and
D. ambrosioides - Antibacterial [112]
70 nm FESEM hexagonal prisms
26.62 and 38.62 nm
S. oleoides - Irregular, spherical and round Antibacterial [104]
TEM

3.6. Mechanism of Formation of ZnO NPs

Plant extracts have been known to contain biomolecules such as alkaloids, flavonoids,
saponins, phenols, terpenoids, tannins, etc. These biomolecules play a significant role in the
reduction and stabilisation of ZnO NPs [79]. These biomolecules are also known for their
antioxidant properties, which make them ideal for the reduction of Zn salt precursor to ZnO
NPs and stabilisation of the ZnO NPs [28]. Del Buono et al. [117] successfully synthesised
ZnO NPs using Lemna minor (L. minor) extract. The phenolic profiles of the L. minor
extract were screened using ultra-high-pressure liquid chromatography quadrupole time
of flight mass spectrometry (UHPLC-ESI/QTOF-MS). The screening yielded tyrosols and
alkylphenols as the major phenolic compounds. Phenolic acids such as hydroxycinnamic,
ferulic, caffeic, and coumaric acids were also observed. Additionally, the L. minor extract
had a high flavonoid content including several glycosylated forms of kaempferol and
quercetin, peonidin, and delphinidin derivatives. The authors attributed the synthesis of
ZnO NPs using L. minor to the presence of these phenolic metabolites with antioxidant
properties, which were able to reduce and stabilise the ZnO NPs. The mechanism they
proposed was based on flavonoid and quercetin and is given in Figure 6.
 observed. Additionally, the L. minor extract had a high flavonoid content including several
glycosylated forms of kaempferol and quercetin, peonidin, and delphinidin derivatives.
The authors attributed the synthesis of ZnO NPs using L. minor to the presence of these
phenolic metabolites with antioxidant properties, which were able to reduce and stabilise
Nanomaterials 2024, 14, 1182 the ZnO NPs. The mechanism they proposed was based on flavonoid and quercetin and17 of 37
is given in Figure 6.

Figure
Figure 6.
6.Proposed
Proposedmechanism
mechanismof of
ZnO NPNP
ZnO formation using
formation L. minor.
using Adapted
L. minor. from from
Adapted Ref. [117].
Ref. [117].

Theproposed
The proposedmechanism
mechanism involves
involves thethe formation
formation of aof a complex
complex between
between the Zn the
(II)Zn (II)
ions
ions from
from the
the Zn
Znsalt
saltprecursor
precursorand andthethe
hydroxyl
hydroxyl groups
groupsfrom the the
from quercetin. This This
quercetin. is is
followed
followedbybybonding
bondingbetween
between thethe
OHOH group
groupof the biomolecule
of the biomolecule to form Zn(OH)
to form 2 and and
Zn(OH) 2
decomposition
decompositionofofthe
theZn(OH)
Zn(OH) 2 to to
2 thethe
ZnOZnONPsNPsviavia
calcination. ThisThis
calcination. mechanism
mechanismwas also
was also
Nanomaterials 2024, 14, x FOR PEER REVIEW 19 of 40
proposed
proposedby byChemingui
Cheminguietet al.al.
[118] forfor
[118] thethe
formation
formationof ZnO NPsNPs
of ZnO usingusing
L. nobilis extract.
L. nobilis extract.
The
The authors
authorsproposed
proposedthat
thatthe
thephenolic
phenolicbiomolecules
biomolecules were responsible
were for the
responsible forreduction
the reduction
and stabilisation of ZnO NPs via the formation of a complex between the Zn (II) ions and
and stabilisation of ZnO NPs via the formation of a complex between the Zn (II) ions and
the hydroxyl groups from the phenolic biomolecules. This was followed by hydrolysis of
the hydroxyl groups from the phenolic biomolecules. This was followed by hydrolysis of
the complex by the hydroxyl from the phenolic biomolecules. Thereafter, the formation
the complex by the hydroxyl from the phenolic biomolecules. Thereafter, the formation of
of Zn(OH)2 and its decomposition via calcination to produce biomolecule-capped ZnO
Zn(OH)2 and its decomposition via calcination to produce biomolecule-capped ZnO NPs.
NPs. Additionally, Aziz et al. [119] proposed the same mechanism involving the formation
Additionally, Aziz et al. [119] proposed the same mechanism involving the formation of
of a complex between Zn (II) ions and diisobutyl phthalate or dibutyl phthalate and
a complex between Zn (II) ions and diisobutyl phthalate or dibutyl phthalate and
hexahydrofarnesyl acetone,which
hexahydrofarnesyl acetone, whichare
are found
found in in essential
essential oilsoils of the
of the aerial
aerial partsparts of Anchusa
of Anchusa
italica
italica extract. The authors proposed that the complex was formed via the carbonyl groupgroup
extract. The authors proposed that the complex was formed via the carbonyl
of
of these molecules,as
these molecules, asgiven
givenininFigure
Figure7. 7.

Figure 7.
Figure 7. Proposed
Proposedmechanism
mechanismofof
formation of of
formation ZnO NPs
ZnO using
NPs A. italica.
using Adapted
A. italica. fromfrom
Adapted Ref. [119.].
Ref. [119].

Moreover,
Moreover, theytheysuggested
suggestedthatthatthe biomolecules
the biomolecules were responsible
were responsiblefor capping and and
for capping
stabilising the
stabilising the ZnO
ZnO NPsNPs andandpreventing
preventingagglomeration.
agglomeration.The Theinvolvement
involvement of of
biomolecules
biomolecules in
in the
the synthesis
synthesis of of
A. A. italica-mediated
italica-mediated ZnO
ZnO NPs
NPs was was supportedby
supported byFTIR
FTIRanalysis
analysisofofthe
theA.
A.italica
italica extract and A. italica-mediated ZnO NPs. The authors observed a
extract and A. italica-mediated ZnO NPs. The authors observed a shift in peak positions and shift in peak
positions between
intensity and intensity between
the FTIR the FTIR
results of A. results of A. italica
italica extract and extract and A. italica-mediated
A. italica-mediated ZnO NPs. The
ZnO NPs. The shift in peaks was attributed to the involvement
shift in peaks was attributed to the involvement of the functional groups of the functional groups
from biomolecules
from biomolecules in the A. italica extract in the reduction and stabilisation of A. italica-
in the A. italica extract in the reduction and stabilisation of A. italica-mediated ZnO NPs.
mediated ZnO NPs. The absorption bands of A. italica extract were 3422, 2943, 1727, 1451,
The absorption bands of A. italica extract were 3422, 2943, 1727, 1451, and 1053 cm−1 , which
and 1053 cm−1, which were shifted to 3352, 2929, 1729, 1411, and 1037 cm −1, respectively,
were shifted to 3352, 2929, 1729, 1411, and 1037 cm−1 , respectively, which were attributed
which were attributed to contributions from diisobutyl phthalate, hexahydrofarnesyl
to contributions from diisobutyl phthalate, hexahydrofarnesyl acetone, tannins, saponins,
acetone, tannins, saponins, and flavonoids, with functional groups of carboxylic acid,
and flavonoids, with functional groups of carboxylic acid, carbonyl, and alcohols, in the
carbonyl, and alcohols, in the formation and stabilisation of ZnO NPs [119]. Moreover, the
formation and stabilisation of ZnO NPs [119]. Moreover, the presence of biomolecules on
presence of biomolecules on the surface of the synthesised ZnO NPs even after calcination
the
proved thatof
surface thethe synthesisedare
biomolecules ZnO NPs even
involved in theafter calcination
capping of the proved that ZnO
synthesised the biomolecules
NPs.
are involved in the capping of the synthesised ZnO NPs.
A different mechanism of formation of ZnO NPs from plant extracts has been
proposed. The mechanism involves the direct reduction of Zn (II) ions from the precursor
salt to Zn by the biomolecules from the plant extracts. The reduction is then followed by
oxidation of the Zn by oxygen to form the capped ZnO NPs during calcination.
Mohammadi et al. [120] proposed a reduction mechanism for the formation of ZnO NPs
from Euphorbia petiolate (E. petiolate) extract. The mechanism involves the reduction of the
 Nanomaterials 2024, 14, 1182 18 of 37

A different mechanism of formation of ZnO NPs from plant extracts has been proposed.
The mechanism involves the direct reduction of Zn (II) ions from the precursor salt to Zn
by the biomolecules from the plant extracts. The reduction is then followed by oxidation of
the Zn by oxygen to form the capped ZnO NPs during calcination. Mohammadi et al. [120]
proposed a reduction mechanism for the formation of ZnO NPs from Euphorbia petiolate
(E. petiolate) extract. The mechanism involves the reduction of the Zn (II) from the precursor
salt by antioxidant phenolic biomolecules from the E. petiolate extract to form zero-valent
Nanomaterials 2024, 14, x FOR PEER REVIEW 20 of 40
Zn NPs, which is followed by growth of the Zn NPs and finally oxidation to ZnO NPs via
calcination, as shown in Figure 8 below.

Figure
Figure8.8.Proposed
Proposedmechanism
mechanism of
of formation of ZnO
ZnO NPs
NPsusing
usingE.E.petiolate
petiolateextract.
extract.Adapted
Adaptedfrom
from
Ref.
Ref.[120].
[120].

Thesame
The samemechanism
mechanism was was proposed by by Bhuyan
Bhuyan and andassociates
associates[121] [121]for
forZnO
ZnONPs NPs
synthesisedusing
synthesised usingA. A. indica
indica extract.
extract. The
The authors
authors proposed
proposedthat thatthe
thealdehyde
aldehydegroupsgroupsfrom
from
thebiomolecules
the biomoleculespresentpresent in in the
the A.A. indica
indica extract
extract were
wereresponsible
responsiblefor forthe
thereduction
reductionofofZnZn
(II) ions to ZnO NPs. The authors also mentioned the presence of terpenoids,flavanones,
(II) ions to ZnO NPs. The authors also mentioned the presence of terpenoids, flavanones,
andreducing
and reducingsugarssugarsas as some
some ofof the
the major
major constituents
constituentsof ofA.
A.indica
indicawhich
whichare areinvolved
involvedinin
the stabilisation of the synthesised ZnO NPs. The stabilisation of ZnO NPs is evident from
the stabilisation of the synthesised ZnO NPs. The stabilisation of ZnO NPs is evident from
the presence of several functional groups reported from the FTIR spectrum of A. indica-
the presence of several functional groups reported from the FTIR spectrum of A. indica-
mediated ZnO NPs. The authors observed bands at 2987 cm−1 and 3197 cm−1 , which were
mediated ZnO NPs. The authors observed bands at 2987 cm−1 and 3197 cm−1, which were
attributed to linkages between amino acids from protein residues, stretching vibrations of
attributed to linkages between amino acids from protein residues, stretching vibrations of
amide II, and atmospheric CO2 . The bands at 1081 cm−1 and 1038 cm−1 were attributed
amide II, and atmospheric CO 2. The bands at 1081 cm−1 and 1038 cm−1 were attributed to
to C–N stretching vibrations of aliphatic, aromatic amides and aliphatic amines, alcohol
C–N
and stretching vibrations
phenolic groups, andof aliphatic,vibrations
stretching aromatic of amides and aliphatic
secondary amines,
amines [121]. Thealcohol
presenceand
phenolic
of these functional groups from the biomolecules in the A. indica on the surface of the A.of
groups, and stretching vibrations of secondary amines [121]. The presence
these functional ZnO
indica-mediated groups NPsfrom the biomolecules
supports the capping ofinZnO the NPs
A. indica
usingon theextracts.
plant surface of the A.
indica-mediated
The two proposed mechanisms of formation of ZnO NPs using plant extracts.
ZnO NPs supports the capping of ZnO NPs using plant extracts can be
The
summarised two using
proposed mechanisms
Equations of formation
(3)–(6). The mechanism of of
ZnO NPs using
formation plant the
involving extracts can be
formation
summarised using Equations
of the Zn–biomolecule complex (3)–(6).
(EquationsThe(3)mechanism
and (4)) is more of formation
plausible and involving
has been the
formation
proposed by of the Zn–biomolecule
several complexto(Equations
researchers compared the mechanism (3) and (4)) is more
of formation plausible
involving and
direct
reduction
has (Equations
been proposed by(5)several
and (6)). However,compared
researchers it should be to noted that the mechanism
the mechanism of formationof
formation of ZnO NPs using plant extracts is not fully understood
involving direct reduction (Equations (5) and (6)). However, it should be noted that the at the present moment.
This is due of
mechanism to the presence
formation ofofZnO
a large
NPsvariety
using of biomolecules
plant extracts isinnotthe fully
plantunderstood
extracts as more
at the
than one
present type ofThis
moment. biomolecule
is due to may be involved
the presence of a in the variety
large reduction and stabilisation
of biomolecules of plant
in the the
ZnO NPs. Hence, research efforts should also focus on investigating
extracts as more than one type of biomolecule may be involved in the reduction and the mechanism of
formation of ZnO NPs using plant extracts to best understand the
stabilisation of the ZnO NPs. Hence, research efforts should also focus on investigating process and establish
large-scale production.
the mechanism of formation of ZnO NPs using plant extracts to best understand the
process and establish Zn2large-scale
+ production.
+ Biomolecule → Zn − Biomolecule(complex) (3)
Zn + Biomolecule → Zn − Biomolecule complex (3)

∆
Zn − Biomolecule complex → ZnO NPs (4)
Nanomaterials 2024, 14, 1182 19 of 37

∆
Zn − Biomolecule(complex) → ZnONPs (4)

Nanomaterials 2024, 14, x FOR PEER REVIEW

Zn2+ + Biomolecule → Zn + Biomolecule (oxidised) 21 of 40
(5)
∆
Zn + O2 (air) → ZnONPs (6)

4. Applications
Applications
4.1. Photocatalysis
Photocatalysis
4.1.1. Dyesand
4.1.1. Dyes andWastewater
Wastewater Treatment
Treatment Technologies
Technologies
Dyesare
Dyes aredefined
defined as coloured
as coloured organic
organic substances
substances made upmade up of chromophores
of chromophores and their and
their fixed property
fixed property of acidicoforacidic or basic
basic groups thatgroups that of
are capable areimparting
capable colour
of imparting colour to
to substrates
substrates
[122]. Dyes [122].
can beDyes can be as
categorised categorised as shown
shown in Figure 9. in Figure 9.

Figure Dyeclassification.
9. Dye
Figure 9. classification. Adapted
Adapted from
from Ref.Ref. [122].
[122].

The release
The release of of untreated
untreated ororinadequately
inadequatelytreatedtreatedindustrial
industrialwastewater
wastewaterinto intowater-
bodies is detrimental
waterbodies is detrimentalto thetoenvironment,
the environment,aquatic life, life,
aquatic and andhumanhuman health. ThisThis
health. is because
is
dyes
becauseare dyes
highly arecarcinogenic and mutagenic,
highly carcinogenic toxic, and toxic,
and mutagenic, highlyandresistant
highlytoresistant
biodegradation.
to
Moreover,
biodegradation. they Moreover,
can degrade theythecan
aesthetic
degradequality of waterbodies,
the aesthetic which increases
quality of waterbodies, whichthe bio-
chemical andbiochemical
increases the chemical oxygen demand,
and chemical thus limiting
oxygen demand,photosynthesis and hence the
thus limiting photosynthesis growth
and
of aquatic
hence life. There
the growth is a need
of aquatic life. to adequately
There is a needtreat industrialtreat
to adequately wastewater
industrialdue to the global
wastewater
due to the
decline in global
freshwaterdecline in freshwater
resources. Thisresources.
is due to This is due
a rapid to a rapid
increase increase
in global in global and
population
population and industrialisation,
industrialisation, which has putwhich pressurehas on
putfreshwater
pressure on freshwater
resources. resources.
The removalThe of dyes
removal of dyes from industrial wastewater is challenging since organic dyes
from industrial wastewater is challenging since organic dyes are resistant to heat, light, oxi- are resistant
to heat,and
dation, light, oxidation, and
biodegradation. Thisbiodegradation.
makes conventionalThis makes
wastewaterconventional
treatment wastewater
methods such
treatment methods such as aerobic and anaerobic treatment
as aerobic and anaerobic treatment inadequate in the removal of the dyes from inadequate in the removal of
wastewater.
the dyes from wastewater. Thus, other wastewater treatment
Thus, other wastewater treatment methods have been developed for the removal of dyes methods have been
developed
from for theeffluent.
industrial removal of dyes from industrial effluent.
Due
Due to the increaseduse
to the increased useofofdyes byby
dyes industries
industriesandandthe the
toxictoxic
nature of dyes
nature to aquatic
of dyes to aquatic
life and human health, there is a need to develop effective
life and human health, there is a need to develop effective industrial effluentindustrial effluent treatment
treatment
techniques. Therefore, various effluent treatment techniques have been assessed for the
techniques. Therefore, various effluent treatment techniques have been assessed for the
removal of dyes from industrial effluents. There have been several dye removal
removal of dyes from industrial effluents. There have been several dye removal tech-
technologies that have been proposed and studied and are currently in use. Conventional
nologies that have been proposed and studied and are currently in use. Conventional
methods such as adsorption, coagulation–flocculation, reverse osmosis, ultrafiltration,
and ion exchange have been utilised to treat dye effluents. Dye removal technologies such
as coagulation–flocculation, and adsorption generally transfer concentrated pollutants
Nanomaterials 2024, 14, 1182 20 of 37

methods such as adsorption, coagulation–flocculation, reverse osmosis, ultrafiltration, and

ion exchange have been utilised to treat dye effluents. Dye removal technologies such
as coagulation–flocculation, and adsorption generally transfer concentrated pollutants
without degradation from one phase to another [123]. Physical methods such as reverse
osmosis, ion exchange, and filtration (e.g., ultrafiltration, microfiltration, and nanofiltration)
that are currently utilised for the treatment of dye effluents have been associated with
various problems such as sludge generation, membrane fouling, disposal issues, handling,
and other technical issues [124]. Biological methods which utilise microorganisms and
enzymes are an environmentally friendly approach that is used for the treatment of dye
effluents; however, the processes are time-consuming and ineffective at treating some dyes,
which limits their applications [125]. Chemical methods including oxidation, electrochem-
ical, photolysis, and coagulation–flocculation have been reported to exhibit better dye
removal efficiencies on a range of dyes, with removal efficiencies around 88–99%. These
methods have been reported to be relatively more costly compared to the physical and
biological methods [126]. Additionally, methods such as sedimentation, filtration, chemical,
and membrane technologies are hampered by high operation costs and high maintenance
costs [127].
Due to the shortfalls of the methods mentioned above, research has focused on het-
erogeneous photocatalysis, which is an AOP. Photocatalysis has garnered more interest,
and this is owing to its non-toxic nature, relative cost-effectiveness, and non-energy in-
tensiveness since operations can take place in ambient conditions. Moreover, there are no
secondary pollution concerns because the technique is capable of decomposing organic
dyes into harmless compounds [128,129]. The method involves using photocatalysts to
generate charge carriers via the absorption of energy that is equal to or greater than the
bandgap energy of the photocatalyst. The charge carriers that are generated migrate to
the surface where redox reactions take place or recombine, which is termed recombina-
tion. ZnO NPs have been utilised extensively for the photocatalytic degradation of dyes
due to their properties such as having a low cost, high photostability, high chemical sta-
bility, high photoactivity in the UV region, high biological stability, and environmental
friendliness [130].

4.1.2. Photocatalytic Mechanism of Zn NPs

When ZnO NPs are irradiated with energy greater or equal to their bandgap energy,
the free electrons (e− ) in the valence band (VB) absorb the energy and become excited
to the free conduction band (CB). This leaves holes (h+ ) in the VB, and the electrons
and holes (charge carriers) migrate to the surface of the ZnO NPs. At the surface, the
holes react with the water and hydroxyl ion to form hydroxyl (·OH) radicals, whereas the
electrons react with the adsorbed oxygen to produce superoxide anion (·O2 − ) radicals,
which will result in the formation of hydrogen peroxide. The hydrogen peroxide reacts
further with ·O2 − radicals to produce more ·OH radicals. The ·OH radicals are potent
ROS and react with the adsorbed organic dyes on the surface of the ZnO NPs, resulting in
less harmful products: water and carbon dioxide. The photocatalytic reactions are given
from Equations (7)–(16) [90,131], whereas Figure 10 shows a schematic diagram of the
photocatalytic degradation mechanism of dyes using ZnO NPs.

hv
ZnO → ZnO (h+ ) + (e− ) (7)

ZnO h+ + H2 O → ZnO + H+ + ·OH

(8)
ZnO h+ + OH− → ZnO + ·OH


(9)
ZnO e− + O2 → ZnO + ·O2−


(10)
·O2− +
+ H → ·HO2 (11)
·HO2 + ·HO2 → H2 O2 + O2 (12)
 Nanomaterials 2024, 14, x FOR PEER REVIEW 23 of 40

Nanomaterials 2024, 14, 1182 21 of 37

ZnO (e ) + H O → ∙ OH + OH (13)
− −


ZnO e + H2 O2 → ·OH + OH (13)
H O + ∙ O → ∙ OH + OH + O (14)
H2 O2 + ·O2− −
→ ·OH + OH + O2 (14)
H O + hv → 2 ∙ OH (15)
H2 O2 + hv → 2·OH (15)
∙ OH++organic
·OH dyes →
organic dyes → mineral
mineralacids
acids++
COCO
+2H+OH2 O (16) (16)

Figure 10.
Figure 10. Schematic
Schematicdiagram
diagramofofthe
thephotocatalytic
photocatalyticdegradation mechanism
degradation of dyes
mechanism using
of dyes ZnOZnO NPs.
using
NPs.
The photocatalytic activity can be assessed using the percentage of degradation (effi-
Thewhich
ciency), photocatalytic
indicatesactivity can of
the degree bedye
assessed using the atpercentage
decomposition any givenof degradation
time. It is achieved
(efficiency),
by measuringwhich indicates the
the maximum degree of or
absorbance dye decomposition
concentration of at
theany
dyegiven time. time
at a given It is and
achieved by measuring the maximum
can be represented using Equation (17).absorbance or concentration of the dye at a given
time and can be represented using Equation (17).
A −𝐴At
𝐴0− C0 − Ct
% 𝑑𝑒𝑔𝑟𝑎𝑑𝑎𝑡𝑖𝑜𝑛
% f f iciency =
degradation e𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 100 =𝐶 − 𝐶 ×
×100 100
100 (17) (17)
A
𝐴0 𝐶C0
where the initial
where A00 is the initial absorbance
absorbance ofof the
the dye
dye before
before photodegradation
photodegradationand andAA t is
t isthe
the ab-
absorbance of the dye at time t, while C is the initial dye concentration and C
sorbance of the dye at time t, while C0 is the initial dye concentration and Ct is the dye
0 t is the dye
concentration at
concentration attime
timet.t.
Kinetics
Kinetics modelsare
models areused
usedtoto
describe
describe and predict
and thethe
predict mechanism and and
mechanism performance
performance of of
photocatalysts during the degradation process. The most commonly used
photocatalysts during the degradation process. The most commonly used kinetics modelkinetics model
in heterogeneous
in heterogeneous photocatalytic
photocatalytic degradation
degradation of dyes is the
of dyes Langmuir–Hinshelwood
is the Langmuir–Hinshelwood (L- (L-
H), which follows the pseudo-first-order model [132]. The L-H model is described
H), which follows the pseudo-first-order model [132]. The L-H model is described using using
Equations (18)–(20)
Equations (18)–(20)[133].
[133].
According
According to the L-H
to the L-H model,
model, when
whenthe theinitial
initialdye
dyeconcentration
concentrationisisvery
verysmall,
small,thenthen the
the following rate equation is used:
following rate equation is used:
𝑑𝐶 𝑘 𝐾𝐶
𝑟 − dC 𝑘 𝑞 kr KC (18)
r = −𝑑𝑡 = kr q x1 − 𝐾𝐶 (18)
where the degradation rate (r) is proportional dt to the1 −t KC
surface coverage of catalyst (qx)
coveredthe
where the dye, kr is the
by degradation reaction
rate constant, C is the
(r) is proportional concentration
to the of dye at time
t surface coverage t, and (qx )
of catalyst
K is the adsorption
covered by the dye,constant
kr is theofreaction
the dyeconstant,
molecule Catisthe
thesurface of the catalyst.
concentration of dye at time t, and K
is theEquation (18)constant
adsorption can be rewritten as follows:
of the dye molecule at the surface of the catalyst.
1 + 𝑘𝐶
Equation (18) can be rewritten as follows:
𝑑𝑡 𝑑𝐶 (19)
𝑘 𝐾𝐶
1 + kC
dt = dC (19)
kr KC
Nanomaterials 2024, 14, 1182 22 of 37

At a low C0 initial dye concentration, the second part of Equation (19) is negligible;
therefore, Equation (19) will become the following:
 
C0
In = k1 t (20)
Ct

Plotting a graph of In(C0 /Ct ) vs. t gives the pseudo-first-order constant, k1 t.

4.1.3. Photocatalysis Activity of Plant-Mediated ZnO NPs

The particle size of nano-photocatalysts is one of the major factors that influence the
photocatalytic activity of NPs. When the particle size of a nano-photocatalyst is small, there
is a high surface area-to-volume ratio, which means increased active sites for the adsorption
of surface oxygen and dye molecules, thus leading to better photoactivity [134]. The
bandgap energy of a nano-photocatalyst is also crucial in their photocatalytic degradation
activities. When the bandgap energy of a nano-photocatalyst is small, it means less energy
is required to create charge carriers, and it enables them to absorb a greater portion of the
electromagnetic radiation, which promotes the generation of the hydroxyl radicals and
leads to enhanced degradation. However, a balance is needed because when the bandgap
energy is too narrow, recombination of created charge carriers occurs, which reduces
the generation of the hydroxyl radicals, resulting in decreased photodegradation [135].
Additionally, the shape of NPs has been reported to influence the photoactivity of the
nano-photocatalysts.
Waseem et al. [15] studied the photocatalytic degradation of Methylene blue (MB)
dye using Citrus jambhiri lushi (C. jambhiri lushi) leaf-mediated ZnO NPs under UV light
irradiation for 120 min. The authors reported that the highest degradation efficiency was
exhibited by the C. jambhiri lushi-mediated ZnO NPs with a smaller bandgap compared
to those with a larger bandgap. Maro and associates [136] conducted photodegradation
studies of MB, MO, and Rhodamine B (RhB) dyes using Peumus boldus (P. boldus)-mediated
ZnO NPs with varying bandgaps. The degradation efficiencies increased with a decrease in
the bandgap of the synthesised ZnO NPs. The authors revealed that P. boldus-mediated ZnO
NPs with the smallest bandgap (2.80 eV) had the highest degradation efficiency against
MO (92% in 180 min) compared to 42 and 47% for P. boldus-mediated with bandgaps of 3.00
and 3.10 eV, respectively. The same trend was reported for the degradation efficiency of
P. boldus-mediated against MB and RhB dyes. This is because lower bandgaps allow the
generation of more charge carriers, which are responsible for the production of hydroxyl
radicals that are responsible for the degradation of dyes, resulting in better photoactivity.
A study compared the photocatalytic activity of nano-flowered ZnO NPs prepared
with Withania coagulans (W. coagulans) fruit extract and chemical methods against MB dye
under sunlight irradiation in 120 min. The authors reported that the degradation efficiency
of W. coagulans-mediated ZnO NPs (90%) was higher than the chemical-mediated ZnO
(78%). The difference was attributed to the smaller crystallite size and reduced bandgap of
W. coagulans-mediated ZnO NPs (25 nm and 3.35 eV, respectively) compared to chemical-
mediated ZnO NPs (30 nm and 3.44 eV, respectively) [137]. Bekele and co-workers [138]
compared the photocatalytic activity of ZnO NPs prepared using varying ratios of Acanthus
sennii leaf extract to Zn salt precursor volume (1:1, 2:3, and 3:2) against Acid orange 88 dye
in 120 min under UV light irradiation. Based on the XRD results, the authors revealed that
the 1:1-mediated ZnO NPs had the smallest crystallite (19.55 nm), which resulted in their
better degradation efficiency (62.6%) despite having a higher bandgap (3.31 eV) than 2:3-
and 3:2-mediated ZnO NPs with 3.28 and 3.25 eV, respectively. The efficiencies of 2:3- and
3:2-mediated with crystallite sizes of 34.19 and 23.07 nm in degradation of Acid orange dye
were reported to be 57.25 and 34.45%, respectively. The difference in photodegradation
performances was attributed to the greater surface area-to-volume ratio due to the smaller
size of 1:1 ZnO NPs and the presence of biomolecules on the surface.
In another study, Rafique et al. [139] investigated the photoactivity of ZnO NPs syn-
thesised with varying Citrus reticulata (C. reticulata) volumes (10, 20, and 30 mL) against
Nanomaterials 2024, 14, 1182 23 of 37

RhB dye under UV light irradiation in 160 min. The study reported that the photocatalytic
activity increased (60, 75.78, and 85.97%, respectively) with an increase in C. reticulata
volume owing to the decrease in particle sizes (40–80, 30–70, and 20–30 nm, respectively).
Additionally, the differences in the shape of the synthesised ZnO NPs could have con-
tributed to the differences in degradation efficiencies as the shapes of C. reticulata-mediated
ZnO NPs were observed to be irregular, spherical/flowers, and flowers, respectively.
Shanavas et al. [140] investigated the difference in photocatalytic activity of plant-
mediated ZnO NPs synthesised using different plants against RhB dye under UV exposure
for 180 min. The authors synthesised ZnO NPs using Artabotrys hexapetalu (A. hexapetalu)
and Bambusa vulgaris (B. vulgaris) leaf extracts. Based on the XRD results and bandgap
energy calculations, the crystallite sizes were 29 and 19 nm, respectively, and the bandgaps
were 3.06 and 3.12 eV, respectively. A. hexapetalu-mediated ZnO NPs exhibited 92% and
1.4 × 10−2 min−1 degradation efficiency and rate constant, respectively, which was slightly
above B. vulgaris-mediated ZnO NPs, with degradation efficiency and rate constant of
88% and 1.21 × 10−2 min−1 , respectively. The authors attributed the slight difference in
degradation performance to biomolecules on the surface of the A. hexapetalu-mediated
ZnO NPs that can aid in dye molecule adsorption, thus bringing the dye molecules to the
catalytic surface [140]. Additionally, the slight difference in their photoactivity could also
be related to the smaller bandgap energy of A. hexapetalu-mediated ZnO NPs compared
to B. vulgaris-mediated ZnO NPs. Therefore, more studies are needed to understand the
photocatalytic activity of NPs.
Alharthi et al. [141] investigated the photocatalytic degradation of MB dye using
Salvadora Persica-mediated ZnO NPs with different morphologies. The Salvadora Persica-
mediated ZnO NPs with some nanorods exhibited significantly better degradation efficiency
(95% in 150 min) than the Salvadora Persica-mediated ZnO NPs with some spherical particles
(75 in 150 min). The authors attributed this difference to the varying morphologies of the
synthesised NPs, the presence of the nanocavities and the nanorods offered a higher surface
area for degradation to take place. In another study, the photodegradation of MB dye was
carried out using Heliotropium indicum-mediated ZnO NPs of different morphologies. The
authors reported that the spherical ZnO NPs exhibited a higher degradation efficiency than
flower-shaped ZnO NPs under visible light irradiation [142].
All these observations validate the influence of properties of plant-mediated ZnO NPs
on degradation efficiency. However, it should be noted that photocatalytic degradation
is a complex process and does not only depend on the properties like size, bandgap, and
shape of the NPs. There are other factors such as surface defects and crystallinity of the
plant-mediated ZnO NPs that also come into play. Therefore, a better understanding of
the process will help synthesise plant-mediated ZnO NPs that are tailored for the effective
degradation of dyes. For example, the bandgap of the plant-mediated ZnO NPs can be
tailored by doping and coupling the NPs with semiconductors [143].
In addition to the properties of plant-mediated ZnO NPs influencing the photodegra-
dation processes, reaction parameters are also crucial during photodegradation, and there
is a need to optimise these parameters for effective photocatalytic activity. Parameters, such
as initial pH, catalyst dosage, and initial dye concentration are some of the parameters that
have been studied during photodegradation processes. The photodegradation efficiency
has been reported to increase with an increase in catalyst dosage. This is due to the presence
of a greater number of active sites for the generation of ROS, thereby increasing the de-
composition of the dyes until an optimal dosage is reached. Increasing the catalyst dosage
beyond the optimum threshold is associated with a decrease in the photodegradation
efficiency. This may be due to particle agglomeration, which reduces the uniformity of
the suspension and light scattering as a result of solution turbidity, thereby resulting in
reduced active sites [144].
In heterogeneous catalysis, when the initial concentration of the dye is increased
beyond the optimum concentration while other parameters remain constant, the pho-
todegradation efficiency is reduced. This can be attributed to the decrease in the ratio
Nanomaterials 2024, 14, 1182 24 of 37

of active sites to dye molecules and the ratio of hydroxyl radicals to dye molecules. The
adsorption of hydroxyl radicals will decrease, while the adsorption of the dye molecules
increases, which in turn decreases the rate of formation of the hydroxyl radicals. Addition-
ally, there is a reduction in photons of light reaching the ZnO NP surface due to increased
absorption of light by the dye concentration as the concentration increases, resulting in a
reduction in degradation efficiency [145].
pH plays an important role in photodegradation performance. It influences several
factors during the degradation process which include the surface charge of ZnO, the
charge of the dye molecules, the concentration of the hydroxyl radicals, and the adsorption
of the dye molecules on the ZnO NP surface. The surface charge of ZnO NPs can be
explained using the point of zero charge (pHpcz ), which is the pH where the concentration
of protonated and deprotonated groups is the same. The pHpcz of ZnO is estimated to be 9,
and at a pH lower than 9, the surface is protonated (positively charged), whereas, at a pH
greater than 9, the surface is deprotonated (negatively charged) as a result of the adsorbed
hydroxyl ions. A high concentration of hydroxyl ions on the surface of ZnO and in solution
may promote the formation of the hydroxyl radical responsible for the degradation of dyes,
thereby increasing the degradation efficiency [146].
The effect of pH on the photocatalytic degradation process can also be explained by
electrostatic interactions between charged surfaces, ions, and molecules. In some instances,
the electrostatic repulsion between the negatively charged ZnO and hydroxyl ions can
reduce the degradation efficiency in alkaline conditions. Additionally, the charge of the
dye molecules also affects their interaction with the charged surface of ZnO, thus affecting
the adsorption process. Under acidic conditions, anionic dyes are strongly adsorbed, while
cationic dyes are strongly adsorbed under basic conditions. It should be noted that ZnO
is an amphoteric metal oxide that dissolves at pH < 3 and pH > 11, which affects the
degradation efficiency [147]. Considering these factors, it is important to optimise the pH
of the photodegradation process to maximise the degradation activity.
The influence of photodegradation parameters was investigated by Nethravathi
et al. [148] for the degradation of MB dye by Garcinia xanthochymus-mediated ZnO NPs.
The process involved varying the initial dye concentrations (5 to 20 ppm), pH of the re-
action mixture (2 to 12), and G. xanthochymus-mediated ZnO NP dosage (50 to 200 mg).
The optimum conditions were reported to be 5 ppm, 200 mg, and pH 4, respectively. The
researchers reported that the degradation increased with an increase in pH; however, a
further increase beyond pH 4 resulted in a decrease in efficiency. They attributed this
observation to the presence of positively charged ZnO NPs at acidic pH, which facilitates
the attraction of the negatively charged MB dye molecules, thereby increasing efficiency.
As the pH is increased further, the ZnO NPs become negatively charged owing to the
adsorption of hydroxyl ions. The effect of nano-photocatalyst dosage was studied using
Ficus racemose (F. racemose)-mediated ZnO NPs for the photodegradation of RhB dye. The
degradation efficiency was revealed to increase with an increase in F. racemose-mediated
ZnO NPs loading from 20 to 60 mg. However, further increase of the F. racemose-mediated
ZnO NPs loading beyond 60 mg, resulted in a reduction in the degradation efficiency. The
authors suggested 60 mg as the optimum dosage for the degradation of RhB dye using F.
racemose-mediated ZnO NPs [149]. In another study, the effect of photodegradation param-
eters in the photodegradation of Congo red (CR) and Malachite green (MG) using Morinda
umbellate (M. umbellate)-mediated ZnO NPs was investigated. The authors investigated
the effect of initial dye concentration from 10 to 50 ppm and reported that at low dye
concentrations, the rate was proportional to the dye concentrations. However, at higher
dye concentrations, the degradation efficiency decreased with an increase in the initial dye
concentration. The authors suggested that the decrease in efficiencies for both dyes at high
initial dye concentrations was a result of the reduced number of active NPs due to the
increased adsorption of dyes, limited light penetration, and reduced ROS generation. The
optimum parameters for degradation of CR dye using M. umbellate-mediated ZnO NPs
were deduced as 10 ppm CR concentration, 0.125 g M. umbellate-mediated ZnO NPs, and
Nanomaterials 2024, 14, 1182 25 of 37

pH 6, whereas the optimum parameters for MG were 20 ppm dye concentration and 0.1 g
M. umbellate-mediated ZnO NPs. However, the degradation efficiency of the cationic MG
increased in all the pHs (3–10) [150].
All the above observations suggest that plant-mediated ZnO NPs have potential as
alternatives to chemical and physically synthesised ZnO NPs for photocatalytic degradation
of organic dyes. It should however be noted that the properties of plant-mediated ZnO
NPs such as particle size, optical bandgap, and shape influence their photoactivity. These
properties can be controlled and manipulated during the synthesis of the plant-mediated
ZnO NPs, leading to better photoactivity. The photocatalytic degradation process is very
complex in nature and can be influenced by several factors at the same time. Therefore,
a better understanding of the photodegradation process will lead to the development of
high-performing photocatalysts.
The reusability of nano-photocatalysts is an important factor in photodegradation
studies due to its correlation with the cost-effectiveness and sustainability of the process,
which is important in large-scale applications. Reusability studies conducted on Borreria
hispida-mediated ZnO NPs in the degradation of Malachite Red (MR) dye revealed the
photostability of plant-mediated ZnO NPs, evident from the reduction in efficiency from
94.24 to 84.8% after five cycles [151]. Bopape et al. [152] reported a significant reduction in
the degradation efficiency of MB dye from 81 to 37% after four cycles of degradation using
Commelina benghalensis-mediated ZnO NPs under UV light irradiation. They attributed this
reduction to the loss of catalyst, catalyst poisoning, catalyst coverage, etc. Similarly, the
photodegradation of Alizarin Yellow R dye using Serratula coronate-mediated ZnO NPs
as a photocatalyst reduced from 98.96 to 55% after six degradation cycles. The authors
suggested that the reduction in efficiency was a result of the deactivation of the active
sites [153].
Several studies have proposed and explored remedies to improve the reusability of
nano-photocatalysts during photodegradation processes. Some of these include immobil-
ising the NPs on supports to improve their reusability to facilitate easy separation of the
nano-photocatalysts from the reaction media. NPs can be immobilised on different sup-
port materials such as activated carbon, glass, cellulose, plant fibres, metals, clay, zeolites,
polymers, hydrogels, etc. [154]. To the best of our knowledge, there are no reports in the
literature about the embedding of plant-mediated ZnO NPs on supports to facilitate ease
of recovering the NPs in large-scale degradation settings. Therefore, some research efforts
can be focused on exploring this avenue.
Herein, we discuss some of the support materials that have been used with chemical-
mediated ZnO NPs. Hydrogels made from carboxymethyl cellulose (CMC) and sodium
alginate (SA) have been used as supports of NPs for the photodegradation of pollutants.
CMC and SA are naturally polysaccharides that are used to produce hydrogels through
hydrogen bonding that are eco-friendly, with good mechanical, thermal, and chemical
stability. Hydrogels have high adsorption capacity and can adsorb dye molecules, which
facilitates the degradation of the dye molecules by the embedded ZnO NPs, thereby
improving photodegradation activity. Ramadhani and Helmiyati [155] synthesised ZnO
NPs and embedded the NPs in a CMC–alginate hydrogel that was crosslinked using Ba (II)
ions. They reported that the hydrogel–ZnO composite exhibited a remarkable degradation
efficiency of 90.12% in 110 min for the degradation of CR dye under visible light irradiation.
The reusability experiments revealed that the efficiency decreased from 90.12 to 69.63%
in three cycles. ZnO NPs have also been embedded in Kaolinite (KL), a highly abundant
material that has a rigid structure and high chemical stability. The ZnO/KL composite was
utilised for the photodegradation of 2-chlorophenol, and the authors reported complete
degradation of the 2-chlorophenol in 180 min. The reusability tests revealed that the
ZnO/KL composite was easy to recover and photostable as evidenced by the excellent
stability of the degradation efficiency after five consecutive cycles [156].
Bel Hadjltaief et al. [157] immobilised ZnO NPs on Tunisian natural clay (TNC) support
and utilised the composite for photodegradation of MG and CR dyes under solar and UV
Nanomaterials 2024, 14, 1182 26 of 37

irradiation. The ZnO-TNC composite was reported to exhibit remarkable degradation

efficiencies for both dyes under solar compared to UV irradiation. The reusability test
revealed that the efficiencies were stable up to the fourth cycle for both dyes, and a slight
reduction was observed on the fifth cycle. These findings demonstrate that immobilising
ZnO NPs on supports can enhance their photocatalytic activity and also improve their
photostability, thus promoting their reusability potential. Additionally, it provides a means
for easy separation and recovery of NPs that is relatively cost-effective. Therefore, there is
a need to investigate the immobilisation of plant-mediated ZnO NPs on supports.

4.2. Antibacterial
Antibiotics are “magic bullets” of the 20th century that are used as antibacterial
agents to combat infections caused by bacteria. Even though antibiotics have helped fight
infections for years, their use and misuse have given rise to antibiotic-resistant infections.
The increase in antibiotic resistance in bacteria is a global threat to both humans and
animals, especially in developing countries, as it results in hundreds of thousands of deaths
per year [158]. Therefore, there is a need to develop antibacterial agents that are affordable,
safe, and capable of combatting antibiotic-resistant infections. Several strategies have been
proposed to overcome antibiotic-resistant infections and amongst them, the use of NPs
as non-traditional antibacterial agents has been investigated. Plant-mediated ZnO NPs
have been investigated as potential antibacterial agents, and they have shown exceptional
antibacterial activity.
Several methods evaluating the antibacterial activity of ZnO NPs in vitro have been
reported and the most common methods include agar dilution, broth dilution, and disc
diffusion. The disc diffusion or agar well diffusion method involves inoculating agar plates
with a standardised concentration of bacteria. This is followed by adding filter paper or
making wells containing the desired concentration of the antibacterial agent on the agar
plate and incubating the Petri dish under suitable conditions. The antibacterial agents
will diffuse through the agar and inhibit bacterial growth. This can be observed as discs
called inhibition zones which can be measured, and the antibacterial activity can be given
as inhibition zone diameter (ZOI) expressed in millimetres (mm) [159]. The agar dilution
and broth dilution methods are used to quantitatively measure the in vitro antibacterial
activity. Generally, the agar dilution method involves making varying concentrations of
antibacterial agents using two-fold serial dilution and adding them to the agar medium
(agar dilution) or liquid medium (broth) in plates or tubes. The inoculum is then incubated
at suitable conditions and the antibacterial activity is given as the minimum inhibition
concentration (MIC), which is the smallest concentration of the antimicrobial agent that
completely inhibits bacteria growth [160].

4.2.1. Antibacterial Mechanism of ZnO NPs

To the best of our knowledge, five antibacterial mechanisms of ZnO NPs have been
proposed, which are (1) ROS generation through photocatalytic activity; (2) induction
of oxidative stress; (3) attachment of the ZnO NPs to the bacteria cell walls; (4); release
of Zn (II) ions; and (5) genotoxicity [161]. The most accepted antibacterial mechanisms
involve the generation of ROS in the presence of light. The mechanism is similar to the
ROS generation for photocatalysis discussed in the sections above. The hydroxyl and
superoxide radicals interact with the surface of the cell membrane, thereby destroying the
cell membrane, while hydrogen peroxide enters the cells, causing damage and destruction
of DNA and proteins, which leads to the death of the bacteria [162]. However, a study
by Jiang et al. [163] reported that the hydroxyl radicals rather than the superoxide and
the hydrogen peroxide are responsible for the death of bacteria cells due to their higher
reactivity compared to the superoxides. Other studies have reported the induction of
oxidative stress through the generation of ROS in the absence of light. Defects can occur
on the surface of ZnO NPs, and these defects can be sites for generating ROS, which is
 superoxide radicals interact with the surface of the cell membrane, thereby destroying the
cell membrane, while hydrogen peroxide enters the cells, causing damage and destruction
of DNA and proteins, which leads to the death of the bacteria [162]. However, a study by
Jiang et al. [163] reported that the hydroxyl radicals rather than the superoxide and the
Nanomaterials 2024, 14, 1182 hydrogen peroxide are responsible for the death of bacteria cells due to their higher 27 of 37
reactivity compared to the superoxides. Other studies have reported the induction of
oxidative stress through the generation of ROS in the absence of light. Defects can occur
on the surface
responsible forofthe
ZnO NPs, andof
destruction these defects
bacteria cellcan be sites forHowever,
membranes. generatingthis
ROS, which is has
mechanism
responsible for the destruction of bacteria cell membranes. However,
been reported to be less efficient compared to the photocatalytic generation of ROS this mechanism has [164].
beenThereported to be less efficient compared to the photocatalytic generation
third mechanism that has been proposed involves the interaction of ZnO NPs of ROS [164].
with Thethe third mechanism
bacteria, that the
destroying has surface
been proposed involves the
of the bacteria. Theinteraction of occurs
interaction ZnO NPs due to
with the bacteria, destroying the surface of the bacteria. The interaction
physical interaction such as electrostatic interactions between the positively charged occurs due to ZnO
physical
NPs and interaction
the negativelysuchcharged
as electrostatic
bacteriainteractions between theofpositively
cells. The interaction ZnO NPscharged
with theZnOsurface
NPs and the negatively charged bacteria cells. The interaction of ZnO NPs
of the cell membrane also increases its permeability, thus allowing ZnO NPs to enter the with the surface
of the cell membrane also increases its permeability, thus allowing ZnO NPs to enter the
cell. Moreover, particles that are less than 10 nm can also penetrate the cell. Inside, the
cell. Moreover, particles that are less than 10 nm can also penetrate the cell. Inside, the
ZnO NPs inhibit metabolic reactions, resulting in cell death [165]. Another mechanism that
ZnO NPs inhibit metabolic reactions, resulting in cell death [165]. Another mechanism
has been proposed involves the penetration of Zn (II) ions from the dissolution of ZnO
that has been proposed involves the penetration of Zn (II) ions from the dissolution of
NPs. The Zn (II) ions can be adsorbed on the surface of the bacteria and interact with the
ZnO NPs. The Zn (II) ions can be adsorbed on the surface of the bacteria and interact with
surface, resulting in increased permeability. This allows the Zn (II) ions to enter the cell
the surface, resulting in increased permeability. This allows the Zn (II) ions to enter the
and inhibit cell activities such as glycolysis, proton transport system, and acid tolerance,
cell and inhibit cell activities such as glycolysis, proton transport system, and acid
leading
tolerance,to leading
cell death [166].
to cell The[166].
death final mechanism that has been
The final mechanism that hasproposed is genotoxicity,
been proposed is
and it occurs through the interaction of the metal ions from the NPs
genotoxicity, and it occurs through the interaction of the metal ions from the NPs with with the phosphoric
the
residues
phosphoric andresidues
proteins from
and the bacteria
proteins from theDNA. ThisDNA.
bacteria interaction can resultcan
This interaction in the inhibition
result in
of
the inhibition of DNA processes such as cell replication and division [161]. Figure 11of the
DNA processes such as cell replication and division [161]. Figure 11 shows some
proposed
shows some antibacterial mechanisms
of the proposed using
antibacterial ZnO NPs. using ZnO NPs.
mechanisms

Figure 11.
Figure 11. ZnO
ZnONPs’
NPs’antibacterial
antibacterialmechanisms.
mechanisms.Adapted from
Adapted Ref.Ref.
from [165].
[165].

The mechanism
mechanismofofantibacterial
antibacterial activity of of
activity NPsNPsis not fully
is not understood
fully understoodat the
atpresent
the present
moment. Therefore,
moment. Therefore,further
furtherstudies
studies are needed
are needed to to
understand
understand the the
mechanism,
mechanism, which will will
which
result in the realisation of the full potential of the NPs as antibacterial
result in the realisation of the full potential of the NPs as antibacterial agents. Understand- agents.
Understanding
ing the mechanismthe mechanism of antibacterial
of antibacterial action of action of plant-mediated
plant-mediated ZnO NPs ZnO is NPs
veryisimportant
very
important for public health, environmental safety, and industrial
for public health, environmental safety, and industrial advancement. Understanding the advancement.
Understanding
mechanism the mechanism
of antibacterial of antibacterial
action action ofZnO
of plant-mediated plant-mediated
NPs can help ZnOdevelop
NPs canmore
help develop more effective antibacterial agents that can combat antibiotic
effective antibacterial agents that can combat antibiotic resistance and design better resistance and an-
design better antibacterial coatings to help fight infections to safeguard public
tibacterial coatings to help fight infections to safeguard public health [167]. Additionally, health
it can result in the development of more effective antibacterial agents for use in the food
and food packaging industry to help prolong the shelf-life of food and prevent bacterial
contamination. Foodborne illness as a result of bacterial contamination is a major threat to
global health [168,169].

4.2.2. Antibacterial Activity of Plant-Mediated ZnO NPs

The antibacterial activity of plant-mediated ZnO NPs has been extensively reported in
the literature owing to their biocompatibility and non-toxicity. Additionally, it has been
reported that plant-mediated ZnO NPs exhibit a higher degree of antibacterial activity
compared to chemical-mediated ZnO NPs. This can be attributed to synergic efforts
Nanomaterials 2024, 14, 1182 28 of 37

from the ZnO NPs and the biomolecule capping agents on the surface of the NPs. For
example, Ravbar et al. [170] conducted a study that revealed that plant-mediated ZnO
NPs have better antibacterial activity compared to chemical-mediated ZnO NPs. The
antibacterial activity of the Japanese knotweed root-mediated ZnO NPs was significantly
greater compared to chemical-mediated ZnO NPs against Campylobacter jejuni and S. aureus
bacteria. This was evident from the lower MICs (62.5 and 500 mg/L, respectively) for
biosynthesised ZnO NPs compared to chemical-mediated ZnO NPs (500 and 2000 mg/L).
Similar findings were reported by Muthuvel and co-workers [108] using S. nigrum-mediated
ZnO NPs and chemical-mediated ZnO NPs against five bacteria (Bacillus subtilis (B. subtilis),
Staphylococcus saprophyticus (S. saprophyticus), Eschechiria coli (E. coli), and Pseudomonas
aeruginosa (P. aeruginosa)). The authors observed that the ZOIs at a 50 µL ZnO NP dosage
were 11, 8, 12, and 9 mm, respectively, for the biosynthesised ZnO NPs, which were
significantly higher than chemical-mediated ZnO NPs at the same concentration (no activity,
1, 2, and 1 mm, respectively).
In another study, Mahalakshmi et al. [171] conducted a comparative investigation
of the antibacterial activity of Sesbania grandiflora (S. grandiflora)-mediated ZnO NPs and
chemical-mediated ZnO NPs against S. aureus and P. aeruginosa. The authors reported
better antibacterial performance of S. grandiflora-mediated ZnO NPs compared to chemical-
mediated ZnO NPs. In another study, the antibacterial activity of A. indica-mediated
ZnO NPs was compared to chemical-mediated ZnO NPs. A. indica-mediated ZnO NPs
recorded significantly greater antibacterial activity against five bacteria compared to the
chemical-mediated ZnO NPs. The measured ZOIs for A. indica-mediated ZnO NPs were
23.3, 22.1, 21.3, 20.0, and 20.6 mm and 14.3, 9.6, 7.6, 9.3, and 9.8 mm for S. aureus, B. subtilis,
P. aeruginosa, Proteus mirabilis (P. mirabilis), and E. coli, respectively. The greater performance
of A. indica-mediated ZnO NPs compared to chemical-mediated ZnO NPs was attributed
to the smaller particle size of A. indica-mediated ZnO NPs, which resulted in higher surface
area and better interaction of the NPs with the bacteria [172]. Additionally, the significantly
better antibacterial potency of plant-mediated ZnO NPs against bacteria compared to
chemical-mediated ZnO NPs can be attributed to the synergic efforts of the ZnO NPs and
the biomolecules capped on the surface of the NPs. For example, polyphenols from plants
have been reported to possess antibacterial properties, and they interact with their proteins,
cell walls, damage to DNA, etc., ultimately leading to the destruction of the bacteria [173].
Bacteria can be divided into two major groups, Gram-positive (G+) and Gram-negative
(G−) bacteria, based on the structure of their cell walls, which provide support and help
protect the bacteria from physical stress. The G− bacteria are surrounded by an outer
membrane made up of two lipid bilayers that are separated by a thin peptidoglycan layer
of about 3–8 nm in thickness, whereas G+ bacteria consist of a thicker peptidoglycan layer
that has a thickness of about 20–30 nm but lacks the lipid bilayer [174]. Due to these
structural differences, some studies have reported a difference in the antibacterial activity
of ZnO NPs against the G+ and G− bacteria. For instance, Imade et al. [175] investigated
the antibacterial activity of plantain peel-mediated ZnO NPs against two G+ and two G−
bacteria. Significantly higher activity was reported for G+ S. aureus bacteria compared to
the G− Salmonella enterica, evident from the ZOIs of 27.67 mm and 10.67 mm, respectively.
The authors attributed this difference to the presence of the lipid bilayer in G− bacteria
that is harder for the ZnO NPs to penetrate.
However, other studies have reported a higher degree of antibacterial efficacy of
plant-mediated ZnO NPs against G− bacteria than G+. Rambabu and co-workers [176]
investigated the antibacterial activity of Phoenix dactylifera-mediated ZnO NPs against
two G+ and two G− bacteria. The authors observed that the antibacterial activity of the
prepared ZnO NPs at a 100 µg/mL dosage was relatively higher against G− bacteria
(Streptococcus pyogenes) with a ZOI of 14.5 mm compared to G+ (Proteus mirabilis) with a
ZOI of 18.7 mm. The authors attributed these observations to a thin peptidoglycan cell
wall that is easier to penetrate in G− bacteria. Contrary to these findings, some studies
have reported no significant differences in the antibacterial activity of plant-mediated ZnO
Nanomaterials 2024, 14, 1182 29 of 37

NPs on both G− and G+ bacteria. Archana et al. [177] studied the antibacterial activity
of Cucumis melo (C.melo)-mediated ZnO NPs against two G− and two G+ bacteria. The
authors reported that there was no significant difference in the antibacterial efficacy of C.
melo-mediated ZnO NPs at a 150 µL dosage for both G+ and G− bacteria as supported by
the ZOIs of 9.50, 9.85, 8.90, and 9.25 mm for G+ (S. aureus and B. subtilis) and G− (E. coli,
and P. aeruginosa) bacteria.
Similar to the photodegradation of dyes, the antibacterial activity of plant-mediated
ZnO NPs can be influenced by the properties of the synthesised ZnO NPs, such as size
and morphology. This was demonstrated in a study by Alnehia and associates [178]. The
study investigated the antibacterial efficacy of 200 mg/L pomegranate peel-mediated ZnO
NPs against E. coli. The authors noted that smaller pomegranate peel-mediated ZnO NP
particles (18.53 and 20 nm) exhibited better antibacterial efficacy than larger ones (30.34 nm).
This was evident from the measured ZOIs of 27, 25, and 17 mm, respectively. Additionally,
the authors reported that the pomegranate-mediated ZnO exhibited better efficacy on G+
than G− bacteria. In a similar study, A. indica-mediated ZnO NPs of different particle
sizes were investigated for antibacterial activity against S. aureus and E. coli. The particles
annealed at 600 ◦ C had a smaller particle size (20 nm) compared to those annealed at 100
and 300 ◦ C (107 and 87 nm, respectively). Therefore, the particles annealed at 600 ◦ C were
reported to exhibit significantly greater antibacterial activity than the particles annealed at
100 and 300 ◦ C [113]. Smaller particles exhibit better antibacterial efficacy due to having
a larger surface area than larger particles, which aids in the generation of ROS, thereby
leading to better antibacterial activity. Additionally, smaller particles can penetrate the
bacteria cells, unlike larger particles, and cause oxidative stress, leading to the death of the
bacteria cells [179].
In another study, Darvishi and co-workers [180] found that spherical-shaped Juglans
regia (J. regia) leaf-mediated ZnO NPs with particle sizes ranging between 45 and 65 nm had
significantly higher antibacterial potency than the flower-shaped ones, with particle sizes
ranging between 95 and 150 nm against infection-causing bacteria (E. coli, P. aeruginosa, and
Acinetobacter baumannii). The authors attributed this to the greater surface area and presence
of a large number of biomolecules on the surface of the smaller particles. Additionally,
the spherical-shaped J. regia-mediated showed greater antibacterial activity compared
to chemical-mediated ZnO NPs and J. regia extract. Sharma et al. [94] also studied the
influence of shape on the antibacterial activity of aloe vera-mediated ZnO NPs. The authors
reported that cuboidal-shaped ZnO NPs exhibited relatively better antibacterial efficacy
against S. aureus, B. subtilis, and E. coli bacteria than the spherical and hexagonal-shaped
ones. All these findings demonstrate that plant-mediated ZnO NPs possess outstanding
antibacterial properties and are effective on different types of bacteria.

5. Conclusions and Recommendations

Green synthesis of ZnO NPs using plants is a viable synthesis method that has the
potential to replace chemical and physical synthesis methods as it offers a cheaper and
environmentally friendly option. Biomolecules present in plant extracts can successfully
reduce Zn salt precursors and stabilise ZnO NPs, offering an alternative route to produce
ZnO NPs sustainably. The properties of plant-mediated ZnO NPs are dependent on reaction
parameters such as pH, reaction temperature, annealing temperature, plant concentration,
and Zn salt precursors. Therefore, controlling and optimising these parameters during
synthesis is crucial in producing NPs of diverse applications. However, control of properties
such as the size and shape of plant-mediated ZnO NPs might be difficult due to the need to
optimise several steps of the synthesis process, like pretreatment of the plant, extraction
process, and the synthesis of the plant-mediated ZnO NPs. The mechanism of plant-
mediated synthesis of ZnO NPs is not fully understood presently; therefore, further studies
are required to understand the mechanism as it is crucial in the reproducibility of the
synthesis process as well as tailoring the properties of ZnO NPs. Furthermore, research
Nanomaterials 2024, 14, 1182 30 of 37

efforts should focus on studies on the reproducibility and scalability of the plant-mediated
synthesis processes.
Plant-mediated synthesis has been successfully utilised for the photodegradation
of dyes and antibacterial studies. Generally, plant-mediated ZnO NPs exhibited better
photoactivity against organic dyes and antibacterial activity than chemical-mediated ZnO
NPs. Properties of ZnO NPs such as particle size, optical properties, and morphology can
influence the photodegradation of dyes and the antibacterial activity of plant-mediated
ZnO NPs. Therefore, tailoring these properties during synthesis is crucial for effective
performances in both applications. Moreover, embedding plant-mediated ZnO NPs on
supports such as hydrogels can improve their reusability in photodegradation applications.
Reusability tests of the plant-mediated ZnO NPs have demonstrated their photostability;
however, studies on the immobilisation of the plant-mediated ZnO NPs are needed as
embedding NPs promotes easy separation and recovery of photocatalysts.
The significantly better performance of plant-mediated ZnO NPs compared to chemical-
mediated ZnO NPs shows that plant-mediated ZnO NPs have the potential to contribute
towards fighting antibiotic resistance and applications in industries such as the food and
packaging industry. However, there is a need to standardise the plant-mediated synthesis
of the ZnO NPs for reproducibility. Additionally, research efforts should focus on under-
standing the mechanism of antibacterial activity of plant-mediated ZnO NPs as this will
help in optimising their synthesis for clinical applications. Studies on understanding the
interactions of plant-mediated ZnO NPs with biological systems are also needed to evaluate
the toxicity that may result from the interactions between the NPs and biological systems.

Author Contributions: Conceptualization, D.M.; writing—original draft preparation, D.M.; writing—

review and editing, D.M., visualization, D.M.; supervision, R.T.T. and L.K.; funding acquisition, R.T.T.
and L.K. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by National Research Foundation (NRF), South Africa, grant
number: 138079 and Tertiary Education Support Program (TESP), Eskom Holdings SOC Limited Reg
No. 2002/015527/0.
Data Availability Statement: All of the relevant data are available from the corresponding authors
upon reasonable request. Source data are provided in this paper.
Conflicts of Interest: The authors declare no conflict of interest.

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