Nanoscale

Advances
REVIEW

ZnO nanostructured materials and their potential

Cite this: Nanoscale Adv., 2022, 4,
applications: progress, challenges and perspectives
1868
Sauvik Raha and Md. Ahmaruzzaman *

Extensive research in nanotechnology has been conducted to investigate new behaviours and properties of
materials with nanoscale dimensions. ZnO NPs owing to their distinct physical and chemical properties have
gained considerable importance and are hence investigated to a detailed degree for exploitation of these
properties. This communication, at the outset, elaborates the various chemical methods of preparation
of ZnO NPs, viz., the mechanochemical process, controlled precipitation, sol–gel method, vapour
transport method, solvothermal and hydrothermal methods, and methods using emulsion and micro-
emulsion environments. The paper further describes the green methods employing the use of plant
extracts, in particular, for the synthesis of ZnO NPs. The modifications of ZnO with organic (carboxylic
acid, silanes) and inorganic (metal oxides) compounds and polymer matrices have then been described.
The multitudinous applications of ZnO NPs across a variety of fields such as the rubber industry,
pharmaceutical industry, cosmetics, textile industry, opto-electronics and agriculture have been
Received 22nd December 2021
Accepted 7th March 2022
presented. Elaborative narratives on the photocatalytic and a variety of biomedical applications of ZnO
have also been included. The ecotoxic impacts of ZnO NPs have additionally been briefly highlighted.
DOI: 10.1039/d1na00880c
Finally, efforts have been made to examine the current challenges and future scope of the synthetic
rsc.li/nanoscale-advances modes and applications of ZnO NPs.

by changing the morphology using various synthesis routes and

1. Introduction different materials.
Found in the Earth's crust as the mineral zincite, ZnO appears ZnO has a slew of unique chemical and physical properties,
as a white powder and is nearly insoluble in water. Zinc oxide is viz., high chemical stability, high electrochemical coupling
the second most abundant metal oxide aer iron. It is inex- coefficient, broad range of radiation absorption and high pho-
pensive and safe, and can be prepared easily. The ZnO powder tostability, which make it among all metal oxides a key tech-
has been widely used as an additive in a plethora of materials nological material and confer upon it its wide applications in
and products including ceramics, glass, cement, rubber, lubri- varied elds. ZnO is categorized as a group II–VI semiconductor
cants, paints, ointments, adhesives, plastics, sealants, in materials science because zinc belongs to the 2nd group while
pigments, foods, batteries, ferrites and re retardants. ZnO can oxygen belongs to the 6th group of the periodic table. Its cova-
assume three possible polymorphs, rock salt, wurtzite and zinc lence is on the borderline demarcating ionic and covalent
blende. The rock salt polymorph exists under conditions of high semiconductors. Besides, it has good transparency, high elec-
pressure and is therefore very rare. At ambient pressure and tron mobility, an outsized exciton binding energy (60 meV),
temperature, ZnO has a hexagonal wurtzite crystal structure wide band gap (3.37 eV),1 strong room temperature lumines-
with two lattice parameters, a and c, with values of 0.3296 nm cence, high thermal and mechanical stability at room temper-
and 0.52065 nm, respectively. In hexagonal wurtzite, O2
ions ature, broad range of radiation absorption and high
occupy the hexagonal close packing (hcp) array of lattice sites photostability that make ZnO the most favorite multitasking
while Zn2+ ions place themselves in alternate tetrahedral holes material.2,3,5,6 As a result of its distinctive optical and electrical
in contrast with the zinc blende structure wherein O2
ions properties4 it is considered to be a possible material in elec-
form a cubic close packing (ccp) array with Zn2+ ions occupying tronic applications, optoelectronic applications and laser tech-
tetrahedral voids. ZnO has a wide band gap of 3.37 eV and nology. ZnO among nano-sized metal oxides has also been
a large exciton binding energy of 60 meV. The physical and further extensively exploited to derive possible benets from its
chemical behaviors of zinc oxide nanoparticles are simply tuned antimicrobial and antitumor activities.7 Because of its blocking
and absorbing capabilities ZnO nds inclusion in some
cosmetic lotions.8 ZnO can also be used in human medicine as
an astringent (for wound healing), and to treat hemorrhoids,
Department of Chemistry, National Institute of Technology Silchar, 788010, Assam, eczema and excoriation.9 ZnO nanoparticles have recently
India. E-mail: [email protected]

1868 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

attracted attention owing to their unique features. There are Ao et al.32 carried out a mechanochemical process of
numerous promising applications of ZnO nanoparticles in synthesizing ZnO NPs by exploiting the reaction between ZnCl2
veterinary science due to their wound healing, antibacterial, and Na2CO3 and using NaCl as a diluent.32 The pure nano-
antineoplastic and antigenic properties. Recently, many crystalline ZnO was obtained by removing the by-product NaCl
research studies and experimental analyses have improved the and nally drying in a vacuum. TEM images showed moderately
efficiency of zinc oxide (ZnO) materials by producing nano- aggregated ZnO nanoparticles of size less than 100 nm which
structures where each nano-dimension is reduced to generate were prepared by a 6 h milling followed by a thermal treatment
nanowires, thin lms and other structures for plenty of appli- at 600  C for 2 h. The effect of milling time and annealing was
cations including defense against intracellular pathogens and carefully investigated in the study. A decrease in nanocrystallite
brain tumors.10 One-dimensional structures include nano- size from 25 nm to 21.5 nm was observed as the milling time
rods,11–13 nanoneedles,14 nanohelixes, nanosprings, nanorings,1 increased from 2 to 6 h aer which it attained steadiness. This
nanoribbons,15 nanotubes,16–18 nanobelts,19 nanowires20–22 and phenomenon was chalked up to a critical effect prevailing in the
nanocombs.23 Nanoplates/nanosheets and nanopellets24,25 are course of milling. The crystal size, however, was found to
their two-dimensional forms while owers, dandelions, snow- increase with temperature with the rise being steep aer 600  C.
akes, coniferous urchin-like structures, etc.26–29 count as the The activation energies for nanocrystallite growth in different
three-dimensional morphologies of ZnO nanoparticles. Never- temperature ranges were calculated using the Scott equation.
theless, the challenges in terms of the potential toxic effects of The activation energy was found to be 3.99 for growth in
ZnO nanoparticles do require special attention. between 400 and 600  C while it reached 20.75 kJ mol
1 beyond
600  C. The higher growth rate at higher temperatures was thus
attributed to extensive interfacial reactions driven by greater
2. Chemical methods for synthesis of activation energy.
A reduction in particle size on prolonging the milling time
zinc oxide nanoparticles was reported by Stanković et al.33 in their work of preparing ZnO
A range of precursors and a variety of conditions such as NPs using ZnCl2 and oxalic acid as starting materials. Their
temperature, time, concentration of reactants and so forth can scheme involved milling the powders of starting materials in
be employed for the chemical synthesis of ZnO nanoparticles. a Retsch PM4 planetary ball mill using a ball-to-powder weight
These chemical techniques by virtue of adjustment of the ratio of 10 : 1. Different intervals of time were chosen for
various aforesaid parameters allow better control of milling to investigate the inuence of milling time on particle
morphology in terms of size and geometry. ZnO NPs can be size. Pastes of zinc oxalate thus obtained were then air dried at
chemically synthesized using the following techniques: the 100  C for 1 h and then subjected to thermal decomposition at
mechanochemical process, controlled precipitation, sol–gel 450  C to obtain ZnO NPs.
method, vapour transport method, solvothermal and hydro-
thermal methods, and methods using emulsion and micro- ZnCl2 + H2C2O4$2H2O / ZnC2O4$2H2O + 2HCl
emulsion environments (Fig. 1). The details giving the gist of
ZnC2O4$2H2O + 0.5O2 / ZnO + 2H2O + 2CO2
the various aforementioned strategies are presented in Table 1.
The detailed synthesis conditions, experimental variables, main
mechanisms, properties and applications are highlighted While the XRD analysis substantiated a perfect long-range
(Table 1). The different chemical methods used for the order and a pure wurtzite structure of the synthesized ZnO
synthesis of ZnO NPs are enumerated below. powders regardless of the milling time, Raman spectroscopy
revealed that lattice defects and impurities were introduced into
ZnO powders at the middle-range scale depending on milling
2.1 Mechanochemical process
duration. Extended milling was found to reduce crystal defects
In the mechanochemical process the starting materials are but introduce impurities. The SEM images suggested that the
subjected to a high-energy dry milling which sets off a reaction milling duration of the reactant mixture positively regulated the
by way of ball–powder impacts in a ball mill, at a low temper- morphology of the particles irrespective of the additional
ature. A diluent, oen the by-product of the reaction (salt viz. thermal treatment.
NaCl), accompanies the starting materials during the proce- ZnO NPs were also prepared through a mechanochemical
dure.30,31 The diluent functions as a reaction medium and method by using ZnCl2, NaCl and Na2CO3 as starting mate-
effects separation of the nanoparticles thereby restricting their rials.34 A solid phase reaction triggered by milling the starting
subsequent growth. This in turn prevents serious agglomera- powders led to the isolation of ZnCO3 in the NaCl matrix. The
tion. The starting materials conventionally used in this method ZnCO3 was nally subjected to a thermal treatment at 400  C
are mainly anhydrous ZnCl2, Na2CO3 and NaCl. The following which induced its decomposition to ZnO. The anatomization of
reactions take place during the procedure: TEM results indicated a mean particle size of 26.2 nm. The
mean nanocrystallite size evaluated from the XRD peak width at
ZnCl2 + Na2CO3 / Zn CO3 + 2NaCl 2q ¼ 36 using the Scherrer equation was found to be 28.7 nm.
Meanwhile, the surface area of the ZnO nanopowder evaluated
ZnCO3 / ZnO + CO2

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1869
Nanoscale Advances Review

Fig. 1 Various strategies for the fabrication of ZnO NPs.

from BET analysis was 47.3 m2 g
1 corresponding to a spherical generation coupled with diminished agglomeration of particles
particle size of 27 nm. and pronouncedly homogeneous crystallite morphology and
Another study on the optical properties of ZnO NPs synthe- architecture. The mechanochemical process is particularly
sized through mechanochemical means and using ZnCl2, NaCl desirable for large-scale production of ZnO NPs.
and Na2CO3 as raw materials was conducted by Moballegh
et al.35 The XRD and TEM results revealed that particle size
2.2 Controlled precipitation
increased with calcination temperature. The work proposed
improved optical properties as a result of the decrease in Controlled precipitation is oen resorted to when the idea is to
particle size owing to the enhanced ratio of surface to volume in set off a large-scale generation of nanoparticles in the powder
ZnO NPs. In another study36 a mixture of starting powders form with reproducible properties for their use as industrial
(anhydrous ZnCl2, Na2CO3 and NaCl) was milled at 250 rpm and products. The method involves two stages: (a) precipitation of
then calcined at 450  C for 0.5 h to yield ZnO NPs with a crys- a precursor of ZnO from the solution, and (b) thermal treatment
tallite size of 28.5 nm as estimated from subsequent XRD of this precursor with subsequent milling to induce physical
analysis. The particle size that emerged from TEM and SEM disintegration of the calcined agglomerates and to get rid of
analysis ranged in between 20 and 30 nm. The incongruent impurities. Various methods may be employed for precipitation
particle size estimated from BET analysis was ascribed to an of ZnO by exercising control over a range of limiting factors that
agglomeration of nanoparticles in the course of drying. include reaction temperature, pH conditions, duration of
The foremost shortcoming of the procedure exists in its precipitation and the medium used for washing. Using ZnSO4
fundamental difficulty encountered in the homogeneous and NH4OH, Sadraei37 prepared nano-ZnO akes. Nano-sized
grinding of the powder and controlled minimization of the ZnO akes as conrmed by SEM analysis were eventually ach-
particles to the required size. Note that the particle size reduces ieved. XRD analysis of the akes revealed the hexagonal struc-
with increasing time and intensity of milling. However, if the ture of ZnO akes with high crystallinity and a diameter of
powder is subjected to milling for longer periods of time, the 30 nm.
chances of contamination increase. A highly shrunk size of Kumar et al.38 used zinc acetate (Zn(OAc)2$2H2O) and NaOH
nanoparticles is the prime advantage that can be extracted from as reagents, and the settled white powder was separated fol-
the method apart from the benet of a signicantly low cost of lowed by washing with deionized water thrice and dried over-
night under dust-free conditions at room temperature. XRD

1870 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
 Table 1 Chemical methods of synthesis of ZnO

Chemical methods of
Review

synthesis Precursors Synthesis conditions Experimental variables Main mechanisms Properties and applications Advantages Ref.

Mechanochemical process ZnCl2, Na2CO3 and Calcination, 2 h, 600  C, Milling time and heat- ZnO nanocrystallite Hexagonal structure; Simplicity, relatively low- 32
NaCl milling for 2–6 h treatment temperature growth is particle diameter: 21–25 cost equipment, large-scale
on ZnO nanocrystallite homogeneous, crystal nm production, and
sizes nuclei were formed with applicability for a variety of
decomposition of materials. Operates at
ZnCO3 and grew by room temperature, which
emergence of the increases safety and
secondary formed ZnO. reduces energy utilization.
The driving force of the Induces not only
interfacial reaction morphological and
came from the structural changes of the
activation energy. particles but also modies
Higher activation their optical and electrical
energy above 600  C properties and prevents the
leads to a higher growth agglomeration of the
rate for the ZnO synthesized particles
nanocrystallite
ZnCl2 and oxalic acid Calcination, 1 h, 400  C, Oxalic acid and wet- — Hexagonal structure; 33
milling for 0.5–4 h milling conditions on particle diameter: 1 mm to

© 2022 The Author(s). Published by the Royal Society of Chemistry

the ZnO average particle 50–90 nm
size and morphology
ZnCl2, NaCl and Calcination, 0.5 h, 300– Calcination — Hexagonal structure; 35
Na2CO3 450  C, milling for 9 h temperature on particle particle diameter: 27.7–
size and structural 56.3 nm
properties of ZnO
nanoparticles
Precipitation process ZnSO4 and NH4OH Reaction: 50–60  C; drying: — — Hexagonal structure; The precipitation method 37
60  C, 8 h akes, particle diameter: 30 is an unsophisticated
nm method. High quality of
Zn(OAc)2$2H2O and Reaction: 30 min, 75  C; — On heating the solution Hexagonal structure; ower production typies the 38
NaOH drying: Room temperature, of zincate ions, the shape (length of each petal method. The method
overnight molecules start to did not exceed 800 nm); further has the advantage
rearrange into application: antimicrobial of being monetarily cheap
hexagonal ZnO activity with high production yield
nanorods aer growing
along the h0001i
direction. When the
molecules got
saturated, the ZnO
nuclei grew to give rod
shaped ZnO. Over time,
these freshly formed
nanorods deposited on
the surface of formerly
formed crystalline
nanorods resulting in
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Nanoscale Adv., 2022, 4, 1868–1925 | 1871

a leaf-like structure rst
 Table 1 (Contd. )

Chemical methods of
synthesis Precursors Synthesis conditions Experimental variables Main mechanisms Properties and applications Advantages Ref.

and a number of such

leaves came together in
an ordered array which
appeared as ower
Nanoscale Advances

shaped ZnNSs
Zn(OAc)2$2H2O, Drying: 100  C, 12 h. ZnO Reaction temperature Hexagonal structure; ZnO 39
(NH4)2CO3, and (A): the dried precipitate and time, concentration (A): particle diameter is
polyethylene glycol was ball-milled for 1 h of oleic acid 40 nm. ZnO (B): particle
followed by calcination at diameter is 40 nm.
450  C for 3 h to produce Photocatalytic degradation

1872 | Nanoscale Adv., 2022, 4, 1868–1925

ZnO powder which was of methyl orange dye
further ball-milled for 3 h.
ZnO (B): the precipitate was
ball-milled for an hour and
then a 1 : 10 powder and 1-
butanol mixture was
prepared which was dried
by heterogeneous
azeotropic distillation;
calcination at 450  C for 3 h
ZnCl2, NH4OH, and Aging: 96 h, ambient Particle formation is Zincite structure; particle 41
CTAB temperature, calcination: a very complex process diameter: 54–60 nm, BET ¼
2 h, 500  C and involves 17 m2 g
1
nucleation, growth,
coagulation and
occulation. Addition
of surfactant CTAB
affects the nucleation
during the
crystallization process.
Aer nucleation, the
surfactant can
inuence particle
growth, coagulation
and occulation
Zn(NO3)2, NaOH, SDS, Precipitation: 50–55 min, Addition of sodium Dissolution– Wurtzite structure, rod-like 42
and TEA 101  C dodecyl sulfate (SDS) reprecipitation shape (L: 3.6 mm, D: 400–
(triethanolamine) and triethanolamine mechanism 500 nm), nut-like and rice-
(TEA) like shapes, size: 1.2–1.5
mm
Review

© 2022 The Author(s). Published by the Royal Society of Chemistry

 Table 1 (Contd. )

Chemical methods of
Review

synthesis Precursors Synthesis conditions Experimental variables Main mechanisms Properties and applications Advantages Ref.

Sol–gel Zn(OAc)2$2H2O, Reaction: 60  C; vigorous Wurtzite structure; platelet- Sol–gel shows many 43
polyvinyl pyrrolidone stirring for 1 h. like ZnO with a grain size of advantages over other
(PVP) and NaOH Calcination: 600  C, 1 h 150 nm transformed into techniques such as its
rod-shaped ZnO with simplicity and low
a diameter of 100 nm at 3  equipment cost
10
4 M PVP
Zn(OAc)2$2H2O and Reaction: reuxed at 50  C, Wurtzite structure; 44
oxalic acid 1 h; drying at 80  C for 20 h; uniform, spherically
calcination: 650  C, 4 h shaped ZnO nanoparticles
with a crystallite size of
20 nm; BET surface area of
10 m2 g
1; 69.75%
degradation of phenol and
67.98% degradation of
benzoic acid in 120 min
under UV light
Zinc 2-ethylhexanoate, Reaction: room Weight ratio of 2- Cylinder-shaped 46
2-propanol, and temperature; aging: propanol and crystallites, diameter: 25–
tetramethylammonium 30 min; drying: 60  C tetramethylammonium 30 nm; height: 35–45 nm

© 2022 The Author(s). Published by the Royal Society of Chemistry

(TMAH) (TMAH)
Vapour transport method Zn and water vapour or Heating: 1 h, 800  C, Inuence of the For crystal growth, aer With H2O: nanoowers The vapour transport 48
oxygen pressure: 0.03–0.05 MPa, atmosphere initial nucleation, the constructed by tens of ZnO method has been
cooling rate: 7  C per subsequent growth nanosheets with random emphasised because of the
minute stage strongly governs orientations. With O2: easy control of thicknesses,
the nal morphology of hexagonal nanorod arrays, morphologies and crystal
the crystal. In O2 gas, non-uniform sized structures of ZnO lms and
the growth of ZnO is nanorods nanostructures by varying
simply along the h001i the precursor gas, substrate
direction due to the temperature and substrate
fastest growth kinetics materials
in this direction and
absence of side or
reverse reactions
ZnO powder Heating in a horizontal Due to the small Wurtzite; nanobelts with 49
tube furnace: 1350  C, thickness of the widths of 10–60 nm,
30 min; deposition: 400– nanobelts, spontaneous thickness of 5–20 nm and
500  C under an Ar polarization normal to lengths up to several
pressure of 250 Torr the nanobelt leads to hundreds of micrometers
the growth of helical
nanostructures. The
mechanism for the
helical growth is
attributed to the
consequence of
minimizing the total
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 Table 1 (Contd. )

Chemical methods of
synthesis Precursors Synthesis conditions Experimental variables Main mechanisms Properties and applications Advantages Ref.

energy contributed by
spontaneous
polarization and
elasticity
Nanoscale Advances

Zn powder and O2 Heating in a furnace at Growth temperature The growth mechanism 450  C: ZnO nanorods with 50
450  C, 550  C, and 650  C and growth time of 1D ZnO a diameter and length of
at a rate of 10  C min
1, nanostructures can be 19–27 nm and 2.8 mm,
feeding O2 into the reaction divided into three respectively. 550  C: ZnO
zone at a rate of 5 stages, as follows: rst, nanorods with a diameter
mL min
1 for 30, 45, and the Zn vapor and and length of 85 nm and

1874 | Nanoscale Adv., 2022, 4, 1868–1925

60 min aer reaching catalytic Cu form liquid 3.8 mm, respectively.
a furnace temperature of alloy droplets during 650  C: ZnO nanorods with
450  C the heating process at a diameter and length of
a certain temperature, 190–350 nm and 3.9 mm,
representing the initial respectively, covered with
stage of the nucleation short nanorods with
process. Second, crystal a diameter of 95 nm and
nucleation occurs upon length of 900 nm at the
gaseous species tips. 30 min growth time:
adsorption until ZnO nanorods with
supersaturation is a diameter of 19–27 nm
reached, and the and a length of 2.8 mm.
formed sites serve as 45 min growth time: ZnO
nucleation sites on the nanorods with a diameter
substrate. Finally, the of 65–190 nm and a length
axial growth of the of 3.2 mm. 60 min growth
nanorods begins from time: ZnO nanorods with
these sites a diameter of 80–250 nm
and a length of 3.8 mm
Zn and O2 Heating in a furnace at Gas ow rate, growth The growth mechanism ZnO nanotetrapods: arm 51
750  C, feeding O2 into the temperature, position of zinc oxide tetrapods lengths, 0.5–3.5 mm and
reaction zone at a rate of 50 from the zinc source, is believed to occur by diameters of 120–350 nm
mL min
1 for 15 min and reaction time can growth of four wurtzitic
affect the size, arms from an
morphology, and octahedral zinc-blende
density of the zinc oxide embryo, each at a 109.5
nanostructures angle from the adjacent
one. The tapered ends
of some of the tetrapod
arms indicate
continued growth of
zinc oxide when the
oxygen ow had been
turned off but residual
Review

© 2022 The Author(s). Published by the Royal Society of Chemistry

 Table 1 (Contd. )

Chemical methods of
Review

synthesis Precursors Synthesis conditions Experimental variables Main mechanisms Properties and applications Advantages Ref.

oxygen remains in the

growth chamber
Zn and O2 Heating in a furnace at Different evaporation Wurtzite; ZnO tetrapods 52
700  C, 800  C and 900  C, temperatures with an arm diameter of
50 sccm of oxygen ow for 2 22 nm and length of 90 nm.
h ZnO tetrapods have
excellent supercapacitive
performance. The
maximum capacitance is
160.4 F g
1 at a current
density of 1.0 A g
1.
Excellent capacitance
retention of 94.3% over
1000 cycles
Hydrothermal method ZnCl2 and NaOH pH 5–8 Reaction temperature As temperature was The hydrothermal technique 53
and template agents increased, the ZnO particle is a promising alternative
(organic compounds) morphologies changed synthetic method because of
100  C 10 h Bullet-like; 100–200 nm the low process temperature
160  C 6h Rod-like; 100–200 nm and great ease of controlling

© 2022 The Author(s). Published by the Royal Society of Chemistry

180  C 6h Sheets; 50–200 nm the particle size. The
200  C 6h Polyhedra; 200–400 nm hydrothermal process has
220  C 5h Crushed stone-like; 50–200 several advantages over
nm other growth processes such
Zn(OAc)2$2H2O, NaOH 100–200  C; 6–12 h; 0.2– Concentration of With 0.3 M NaOH and as use of simple equipment, 54
and methanol 0.5 M NaOH precursors (NaOH), employing a growth time of catalyst-free growth, low
reaction temperature 6 h the grain size was found cost, large area uniform
and growth time to increase from 7 nm to production, environment
16 nm with temperature friendliness and less
rise from 100  C to 200  C. hazardous nature. The low
The average grain size of reaction temperatures make
ZnO synthesized at 200  C this method an attractive
for 12 h revealed an one for microelectronics and
increase from 12 nm to plastic electronics. This
24 nm with elevation in method has also been
concentration of NaOH successfully employed to
from 0.2 M to 0.5 M prepare nanoscale ZnO and
other luminescent materials.
The particle properties such
as morphology and size can
be controlled via the
hydrothermal process by
adjusting the reaction
temperature, time and
concentration of precursors
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 Table 1 (Contd. )

Chemical methods of
synthesis Precursors Synthesis conditions Experimental variables Main mechanisms Properties and applications Advantages Ref.

Solvothermal method ZnSO4, NaOH, Na2CO3 Reaction temperature: The ZnO wurtzite phase 56
and stearic acid; using 60  C; water–ethanol was formed. Average grain
the resulting ZnO medium in an autoclave at diameter of 27 nm using
nanoparticles as 180  C for 72–186 h the Scherrer formula
Nanoscale Advances

precursors 180  C: 72 h Precursors and time The process appears to Nanoneedles with
occur via an a diameter of 450–900 nm,
agglomeration/melting length of 8–20 nm and
mechanism and leads aspect ratio of 0.05
to nanoneedles of
relatively large

1876 | Nanoscale Adv., 2022, 4, 1868–1925

dimensions
180  C: 168 h The formation Nanorods with a diameter
mechanism of one- of 40–160 nm, length of 5–
dimensional 8 nm and aspect ratio of
nanostructures does 0.014
appear to be related
more to a rolling-up/
surfactant-segregation
process than with the
characteristic ZnO
crystallite growth
180  C: 168 h Nanowires with a diameter
of 30–50 nm, length of 0.8–
1 nm and aspect ratio of
0.04. Photocatalytic
activities with respect to
the degradation of
methylene blue
Zn powder, Reaction: 24–100 h, 180  C Oxidants and solvents, ZnO rod-like and particle- 57
trimethylamine N-oxide trace amount of water like nanostructures with
and 4-picoline N-oxide in solvent diameters ranging in
in organic solvents between 24 and 185 nm
Emulsion or Zinc oleate in decane Stirring: 2 h, room Morphologies obtained: 58
microemulsion method and NaOH in water or temperature or 90  C, and spherical agglomerates,
ethanol maintaining the decane/ needle shapes, near-
water interface during hexagonal shapes, near-
stirring spherical shapes and
irregular agglomerates.
Diameters obtained: 2–10
mm, 90–600 nm, 100–
230 nm and 150 nm
Review

© 2022 The Author(s). Published by the Royal Society of Chemistry

 Review Nanoscale Advances

revealed the formation of hexagonal ZnO nanostructures. SEM

Ref.

59
and TEM analyses revealed the formation of crystalline ZnO
owers in which a bunch of ZnO nanorods assembled together
to form a leaf-like structure followed by ower-shaped ZnO
nanostructures. The ZnO nanoowers were each formed by the
combination of 8–10 leaf-like petals as shown. The length of
each petal did not exceed 800 nm. The as-synthesized ZnO
Properties and applications Advantages

nanostructures showed good antimicrobial activity towards

Gram-positive bacteria Staphylococcus aureus as well as Gram-
negative bacteria Escherichia coli with a MIC/MBC of
25 mg L
1. Zn(CH3COO)2$2H2O and (NH4)2CO3 were employed
assigned to samples Z1, Z2,
Values of 8 m2 g
1, 10.6 m2
solids (Z1), ellipsoids (Z2),

g
1, 12 m2 g
1 and 23 m2

1110 nm and 615 nm.

g
1 could be respectively

with modal diameters of
rods (Z3) and akes (Z4)

as reagents by Hong et al.39 in their method of synthesizing ZnO

Morphologies such as

NPs. XRD and TEM tests revealed particle sizes of 40 and 30 nm.
396 nm, 396 nm,

Heterogeneous azeotropic distillation thoroughly prevents

agglomeration and reduces the size of ZnO NPs.
Raou et al.40 used the aqueous solutions of Zn(NO3)2 and
Z3, and Z4

(NH4)2CO3 as reagents in their experiments. The precursors

were synthesized by adding Zn(NO3)2 solution in a drop-wise
manner into (NH4)2CO3 solution under stirring. The molar
ratio of Zn(NO3)2 to (NH4)2CO3 was maintained at 1 : 1.5. The
precipitate obtained was ltered. It was further repeatedly
Experimental variables Main mechanisms

washed with deionized water and ethanol. Subsequently, it was

subjected to drying at 100  C for 6 h. The precursor was
annealed at temperatures ranging in between 250 and 550  C
for 4 h to obtain ZnO NPs. XRD analysis demonstrated an
enhancement in crystallinity with a rise in annealing tempera-
NaOH) to Zn(CH3COO)2
Amount of zinc acetate/
Zn(CH3COO)2 solution.

Dosing rate of KOH (or

ture. Using the Scherrer equation, the crystallite size was

Precipitating agent.

however found to increase from 8.34 to 27.58 nm as the

cyclohexane (cm3).
Concentration of

annealing temperature was increased from 250 to 550  C. The

mean crystallite size obtained from BET study also conrmed
(cm3 min
1)

an increase from 8.60 to 42.51 nm upon an increase in

annealing temperature from 250 to 550  C. The conspicuous
incongruence of crystallite size caused agglomeration with
a rise in temperature due to the increased growth rate.
In the precipitation method of synthesizing nanopowders, it
or NaOH. Cyclohexane destabilization: 80  C;
Synthesis conditions

is more or less a ritual these days to use surfactants that would

Zinc acetate and KOH Stirring: 9000 rpm;

enable control over the growth of particles with the simulta-

drying at 120  C

neous prevention of coagulation and occulation of particles

thereby preventing an appreciable reduction in the nal yield.
The surfactants act as chelates encapsulating the metal ions in
an aqueous medium. Wang et al.41 used ZnCl2 and NH4OH and
a cationic surfactant, CTAB (cetyltrimethyl-ammonium
emulsiers in emulsion
polyoxyethylene glycol
ethers as a mixture of

bromide), for the generation of ZnO NPs. The formation of

as an organic phase,

sharply crystalline ZnO NPs with a wurtzite structure and crys-

and nonylphenyl

tallite size of 40.4 nm was conrmed by XRD data, while TEM

examination of the powder bore out the formation of spherical
Precursors

formation

nanoparticles of size 50 nm.

Nano-sized crystals of ZnO possessing a wide variety of
shapes were generated using Zn(NO3)2$6H2O and NaOH by Li
et al.42 with sodium dodecyl sulfate (SDS) and triethanolamine
(TEA) as cationic surfactants. These surfactants were found to
Chemical methods of

exert great inuences on the shape and size of the ZnO NPs.
(Contd. )

Heating a Zn(OH)2 precursor in H2O solvent at 101  C for 4 h

gave rod-like ZnO crystals, with diameters ranging from 400 to
synthesis

500 nm and an average length of about 3.6 mm (aspect ratio

Table 1

8 : 1). When 0.01 M SDS was added into the reaction solution
(keeping the other conditions identical), nut-like ZnO crystals

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1877
Nanoscale Advances Review

with a twin structure were obtained. The diameter of the 2.4 Vapour transport method
hexagonal cross-section ranged from 1.2 to 1.5 mm, and the
In this process, zinc and oxygen or oxygen mixture vapours are
aspect ratio was a little smaller than 1 : 1. A new well-dened
transported and are allowed to react with each other resulting in
rice-like morphology of ZnO appeared when 0.1 M TEA
the formation of ZnO nanoparticles. The vapour transport
replaced 0.01 M SDS in the reaction solution. The diameters of
method has been emphasized because of the easy control of
the particles were similar to those of nut-like ZnO crystals, while
thicknesses, morphologies and crystal structures of ZnO lms
the aspect ratio was slightly larger than 1 : 1. The precipitation
and nanostructures by varying the precursor gas, substrate
method is an unsophisticated method. High quality of temperature and substrate materials.48 Kong and Wang49 re-
production typies the method. The method further has the ported free-standing ZnO nanobelts that grew along the a-axis,
advantage of being monetarily cheap with high production
and their large top and bottom surfaces were the polar (0001)
yield.
facets. The structurally controlled, high-purity and high-yield
ZnO nanobelts were synthesized by a solid–vapor process.
2.3 Sol–gel method SEM and TEM analyses show that the product has a belt shape
with widths of 10–60 nm, thickness of 5–20 nm and lengths up
The synthesis of ZnO NPs by the sol–gel method has recently
to several hundreds of micrometers. The dominant component
gained widespread use. Its ease, effortlessness, soundness, of the as-synthesized sample is nanobelts with a uniform size
repeatability and relatively mild conditions have resulted in its distribution, but a signicant number of nanobelts have a ring
extensive use in the generation of metal-oxide nanoparticles. shape, which has not been found for single crystal nanobelts or
This method facilitates the surface modication of zinc oxide nanowires of any other materials.
with selected organic substances, thereby altering its traits and ZnO nanoparticles were also prepared on Au-coated Si
attributes and expanding its realm of applications. substrates by Wu et al.48 using water vapour and oxygen gas. The
Suwanboon et al.43 using Zn(CH3COO)2$2H2O, polyvinyl
advantage of using a Au catalyst is the fast growth rate of the
pyrrolidone (PVP) and NaOH prepared nano-structured ZnO
oxide material because of the catalytic effect of Au, but the main
crystallites via the sol–gel method. The XRD characterization disadvantage is the remains of the Au catalyst, which may
revealed a wurtzite structure having an average crystallite size of inuence the purity of the ZnO nanostructures. Au covered Si
about 45 nm. The role of PVP at its different concentrations on substrates were prepared by depositing a 200 nm thick layer of
the morphology was checked. There occurred a shi from Au lm on cleaned Si(100) wafers using radio frequency sput-
a platelet-like to a rod shape with an increase in PVP concen- tering (JC500-3/D) from an Au target. The synthesis procedure
tration. TEM images bore out the grain size of platelet-like ZnO included the following steps: (a) owing Ar gas through the
to be 150 nm while the diameter of the rod-shaped ZnO was
quartz tube for 0.5 h to remove the air in it; (b) increasing the
likewise determined to be 100 nm. In another sol–gel method-
furnace temperature to 800  C with the Ar gas ow; (c) main-
based synthesis by Benhebal et al.44 zinc acetate dihydrate and taining the temperature at 800  C for 1 h and replacing the Ar
oxalic acid were used to generate ZnO nanopowder with ethanol ow by a mixture of either Ar/H2O vapour or Ar/O2 gas. The
as a solvent which showed a hexagonal wurtzite structure. The pressure of the quartz tube is maintained at 0.03–0.05 MPa; (d)
crystallite size obtained from the Scherrer equation was found switching off the furnace and cooling down the sample to RT at
to be 20 nm. The SEM micrograph conrmed the formation of a rate of 7  C per minute. The reactions of metallic Zn with H2O
uniform, spherically shaped ZnO nanoparticles. BET analysis vapour and O2 gas can be written, respectively, as follows:
revealed a surface area of 10 m2 g
1. This was characteristic of
a material with low porosity, or a crystallized material. Zn + H2O / ZnO + H2
Sharma45 obtained ZnO NPs with outstanding antibacterial
properties using the sol–gel method. Zinc acetate, oxalic acid 2Zn + O2 / 2ZnO
and water were employed as raw materials in this process. A
white gel precipitate was rst obtained. It was then thermally
treated at 87  C for 5 h, and then at 600  C for 2 h. The ZnO NPs In water vapour, ZnO nanoowers were synthesized. The
exhibited high crystallinity as borne out by XRD data. A diam- nanoowers were constructed from tens of ZnO nanosheets
eter of 2 mm was obtained for the ZnO nano-aggregates from with random orientations. In oxygen gas, ZnO hexagonal
SEM analysis. nanorods were obtained. The size of the nanorods was not
In a study conducted by Ristic et al.46 nano-structured ZnO uniform. It was argued that the size of the Au catalyst under-
crystallites were obtained using the sol–gel route. From XRD neath might have inuenced the size of the ZnO nanorods. Both
examination and using the Scherrer formula, the average value the samples, however, exhibited a hexagonal wurtzite structure.
of the basal diameter of the cylinder-shaped crystallites was Though the samples showed different morphologies and crystal
found to be 25–30 nm, while the height of the crystallites was structures, surprisingly, they had almost the same optical
35–45 nm. The sol–gel method presents a host of advantages in properties. The PL spectra revealed only one UV peak close to
comparison with the previously mentioned methods. Prime 389 nm wavelength for both samples, indicating the high
amongst its merits are the low cost of the apparatus and raw quality of the synthesized ZnO samples.
materials, reproducibility and exibility of generating Novel one-dimensional single-crystalline ZnO nanorod and
nanoparticles.47 nanoneedle arrays on a Cu catalyst layer-coated glass substrate

1878 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

were investigated by Alsultany et al.50 via a simple physical structure. At a growth time of 30 min, ZnO nanorods were ob-
vapour deposition method by thermal evaporation of Zn powder tained with a diameter of 19–27 nm and a length of 2.8 mm.
in the presence of O2 gas. The ZnO nanorods and nanoneedles When the growth time increased to 45 min, nanoneedles were
were synthesized along the c-axis growth direction of the obtained. The needles exhibited mean diameters of 65–190 nm
hexagonal crystal structure. The diameter and growth rate of the and length of 3.2 mm. On the other hand, nanoneedles grown at
high-quality and well oriented one-dimensional ZnO nano- 60 min were approximately 80–250 nm in diameter and 3.8 mm
structures were achieved as a function of varying growth in length.
temperature and growth time. At 450  C, ZnO nanorods were Diep and Armani51 designed a exible light-emitting nano-
uniformly distributed at a high density on the entire substrate composite based on ZnO nanotetrapods (NTPs) which they
surface and quasi-aligned, and small average diameters were prepared using a vapour transport technique. The CVT
obtained. The diameters and lengths of the obtained nanorods synthesis of the ZnO NTPs was self-catalyzed. In the TEM
were in the range of 19–27 nm and 2.8 mm, respectively. When images, the lattice fringes were clearly visible, indicating the
the temperature was increased to 550  C, ZnO nanorods grew single-crystalline nature of the nanostructures. The lattice
perpendicular to the substrate, uniformly throughout their spacing was found to be 2.6 Å, indicating growth in the [0001]
length, and with more consistent shape and dimensions, with direction. X-ray diffraction (XRD) and energy-dispersive X-ray
approximately 85 nm width and 3.8 mm length. The morpho- spectroscopy (EDX) analysis were also performed to conrm
logical change and distribution occurred at a growth tempera- the crystal structure and elemental composition of the NTPs.
ture of 650  C, and ZnO nanorods with a hexagonal shape at the Based on an analysis of the TEM and SEM images, the ZnO NTP
tips of rods of hexagonal hierarchical structures were formed. arm lengths ranged from 0.5 mm to 3.5 mm and the diameters
These rods possessed a typical hierarchical structure with varied from 120 nm to 350 nm.
lengths and diameters of approximately 190–350 nm and 3.9 Luo et al.52 also constructed ZnO tetrapods as potential
mm, respectively, whereas short nanorods with a diameter of electrode materials for low-cost and effective electrochemical
95 nm and length of 900 nm were observed on the tip of each supercapacitors using an oxidative-metal-vapor-transport
rod of hexagonal hierarchical structures. As Cu metal catalysts method. The SEM images of the ZnO tetrapods collected at
were used in the study, the growth mechanism of 1D ZnO different temperatures showed that the products obtained were
nanostructures presented therein followed the VLS method. pure and uniform, and the tetrapods consist of four arms
This method could be divided into three stages, as follows: rst, branching from one center, and the angles between the arms
the Zn vapor and catalytic Cu formed liquid alloy droplets were nearly the same, analogous to the spatial structure of the
during the heating process at a certain temperature, repre- methane molecule. As for the size variation with collected
senting the initial stage of the nucleation process. Second, temperatures, it transpired that smaller size tetrapods were
crystal nucleation occurred upon gaseous species adsorption obtained with lower evaporation temperature. This demon-
until supersaturation was reached, and the formed sites served strated the power of the technique for controlling the size of the
as nucleation sites on the substrate. Finally, the axial growth of tetrapods. ZnO tetrapods with arms as thin as about 170 nm
the nanorods began from these sites. Based on this study of the and shorter than 4000 nm were revealed by SEM analysis. The
mechanism in the presence of Cu metal catalysts at different XRD pattern of the ZnO tetrapods showed that all the diffraction
growth temperatures and according to the nucleation theory of peaks could be indexed to a wurtzite 5 structure with lattice
the VLS growth mechanism, the Cu catalyst nanoclusters constants of a ¼ 0.324 nm and c ¼ 0.519 nm. The TEM and high
formed because of capillarity, which caused beading of the Cu resolution TEM (HRTEM) images of the ZnO tetrapods revealed
layer at high growth temperature. Consequently, the Cu–Zn that the arm diameter and length of the tetrapods are, on
alloy process reached a certain solubility depending on the average, about 22 nm and 90 nm, respectively. The HRTEM
temperature; then, the Zn vapor began to precipitate out at the image of a single arm revealed clear fringes perpendicular to the
interface between the surface and droplet. That in turn deter- arm axis and these fringes were spaced by about 0.25 nm
mined the diameter and size of the nanostructures depending consistent with the interplanar spacing of (0002) suggesting
on the size of the liquid alloy droplets. Notably, large-scale ZnO that the nanowire growth direction was along [0001].
nanorods with a lower diameter were formed at a low growth
temperature of 450  C. The Zn metal powder (melting point of
419  C) vapor pressure at 450  C was sufficiently high to
investigate the growth of ZnO nanorods on the glass substrate 2.5 Hydrothermal method
via the VLS method, and the decrease in Zn vapor as a result of The hydrothermal method is a technique oen used for the easy
the decrease in the growth temperature led to a low lateral generation of nanoparticles. This method of chemical synthesis
growth rate compared with the axial growth rate of the 1D bears an inherently favourable attribute of being harmless to the
nanostructure. In contrast, the higher growth temperature environment. Conventionally, the method involves the use of an
could also lead to the formation of hierarchical nanostructures. autoclave. The substrates in the form of a mixture are placed
In addition, at high growth temperature along with the within the autoclave and then subjected to a gradual heating up
consumption of the Zn vapor during growth, the diameter of the to a temperature of 100–300  C. The heating continues over
nanorods markedly decreased. This condition consequently a specic period of time and cooling then follows. This causes the
caused the production of rods with a typical hierarchical formation of crystal nuclei followed by nuclei growth.

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1879
Nanoscale Advances Review

A 1 : 2 mixture of ZnCl2 and NaOH in an aqueous medium was nanoparticles and stearic acid as precursors and 180  C thermal
employed by Chen et al.53 A white Zn(OH)2 precipitate was formed treatment carried out for 168 h, nanorods having a diameter of
and hydrothermal treatment yielded ZnO NPs. XRD and TEM 40–160 nm, length of 5–8 nm and aspect ratio of 0.014 were
tests were conducted to ascertain the average size and formed. With the ZnO(stearic acid)0.38 nanocomposite as
morphology of the ZnO NPs so formed. Two factors, namely a precursor and 180  C thermal treatment carried out for 168 h,
temperature and reaction time, were found to exert great effects nanowires having a diameter of 30–50 nm, length of 0.8–1 nm
on the size and architecture of ZnO NPs. On increasing the and aspect ratio of 0.04 were formed.
temperature, the particle morphology was found to change from Chen et al.57 also used a solvothermal route to generate ZnO
rod-like to polyhedra. Further in the study, it was also revealed NPs. They eventually prepared nano-structured ZnO crystals that
that different templates cast varying inuences on the size and were devoid of hydroxyl groups. They carried out a reaction of
morphology of the nanostructured particles. Furthermore, zinc powder with trimethylamine N-oxide (Me3N/O) and 4-
a noticeable rise in crystallinity and lengthening of particle size picoline N-oxide (4-pic/NO). The medium for the reaction was
with pH were recorded as a shortcoming of the procedure. a mixture of organic solvents (toluene, ethylenediamine (EDA)
Aneesh et al.54 carried out an experiment in which they used and N,N,N0 ,N0 -tetramethylenediamine (TMEDA)) contained in an
Zn(CH3COO)2$2H2O, NaOH and methanol as reagents. The ZnO autoclave which was kept at 180  C. It was observed that the size
NPs thus formed had a hexagonal wurtzite structure. XRD and morphology of the ZnO nanoparticles/nanowires were
analysis demonstrated an enhancement in average grain size greatly inuenced by the oxidants used and the ligating capac-
with rising temperature and concentration of the substrates. ities of the solvents. The ramications of the presence of water in
The average grain size of ZnO NPs prepared from 0.3 M NaOH the system were additionally investigated. It emerged that the
employing a growth time of 6 h was found to increase from 7 to presence of traces of water catalyzed the zinc/4-picN/O reaction
16 nm with temperature rise from 100 to 200  C. The average and exerted an effect on the size of the nano-structured ZnO
grain size of ZnO synthesized at 200  C for 12 h revealed an crystallites thus obtained. Depending on the reaction conditions,
increase from 12 to 24 nm with elevation in concentration of the ZnO nanostructures had diameters ranging in between 24
NaOH from 0.2 M to 0.5 M. and 185 nm. The solvothermal synthesis method has many
This process has many advantages over other methods. advantages. Foremost among them is the fact that reactions can
Organic solvents do not nd use in this process. This coupled be carried out under determined conditions. As a result, nano-
with the omission of supplementary processes like grinding and structured ZnO with a range of architectures can be generated
calcination within the ambit of the method endows it with the by exercising due control over the reaction conditions.
much sought aer eco-friendly character. Low operating
temperatures, the diversied morphologies and sizes of the 2.7 Method using an emulsion or microemulsion
resulting nano-crystals depending on the composition of the environment
starting mixture and the process temperature and pressure, the Emulsion techniques have recently gained extensive use in
greatly pronounced crystallinity of the nanoparticles and their preparing ZnO nanoparticles. Vorobyova et al.58 employed an
high purity are factors that surely make the process more emulsion to precipitate ZnO by allowing zinc oleate (mixed in
advantageous than others.54,55 decane) to react with sodium hydroxide (mixed in ethanol or
water). The following reaction illustrates the entire process:
2.6 Solvothermal method
Zn(C17H33COO)2 (decane) + 2 NaOH / ZnO (water and
The prime objective of using the solvothermal technique of ethanol) + H2O + 2NaC17H33COO
generating a wide range of nano-structured metal oxides is to
achieve enormous surface area, marked crystallinity and great
thermal stability. Thermal decomposition of an organometallic SEM and XRD analysis showed that the particle size and
compound in an organic medium forms the basis of this proce- phase location were both dependent upon the conditions (ratio
dure. A solvothermal method was adopted by Segovia et al.56 to of two-phase components, substrates and temperature)
fabricate ZnO NPs. The work resulted in the production of ZnO employed for the accomplishment of the process. Depending on
with a range of morphologies – nanoneedles, nanorods and the process conditions, ZnO NPs with different particle
nanowires – obtained under different solvothermal conditions. morphologies were obtained. The morphologies that formed
ZnSO4, NaOH, Na2CO3 and stearic acid were employed as during the process included spherical agglomerates, needle
chemical reagents while ethanol–water mixtures were used as shapes, near-hexagonal shapes, near-spherical shapes and
solvents. Constant agitation of the reaction mixture consisting of irregular agglomerates. These NPs further had a wide range of
ZnSO4, Na2CO3 and NaOH at 60  C yielded the ZnO precursor. diameters. Some had diameters ranging in between 2 and 10
XRD data revealed the formation of the ZnO wurtzite phase. mm, while the diameters of others ranged from 90 to 600 nm,
Estimation of particle size using the Scherrer formula approach some others had diameters in between 100 and 230 nm and yet
indicated an average grain diameter of 27 nm. With ZnO nano- others were characterized by diameters hovering around
particles as precursors and 180  C thermal treatment carried out 150 nm.
for 72 h, nanoneedles having a diameter of 450–900 nm, length of Kołodziejczak-Radzimska et al.59 used zinc acetate and KOH
8–20 nm and aspect ratio of 0.05 were formed. With ZnO or NaOH in an emulsion system. For the generation of an

1880 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

emulsion, cyclohexane was utilized. Cyclohexane was held to was subjected to hydrothermal treatment at 140  C for 15 h in
have furnished a ready organic phase, and also essayed the role a 100 mL Teon-lined autoclave. The autoclave was then le to
of a surfactant that wasn't ionic. In this method for emulsion cool down to room temperature by itself. Collection of precipi-
formation cyclohexane was used as an organic phase, and tates was done by way of their centrifugation at 5000 rpm. This
nonylphenyl polyoxyethylene glycol ethers NP3 and NP6 were was followed by washing and then drying in air at 60  C. XRD
used as a mixture of emulsiers. By tailoring the ZnO precipi- peaks conrmed the hexagonal wurtzite structure of the
tation process by way of altering the precipitating agent, prepared ZnO NPs. The marked crystallinity of the nano-
substrate ingredients and the tempo of substrate dosing, an particles was gured out from the sharpness of the diffraction
amazing variety of ZnO nanostructures were designed. Four peaks. The crystallite size was found to decrease from 40 to
samples were obtained, labelled Z1, Z2, Z3, and Z4, composed of 27 nm with a rise in the concentration of PEG400 additive from
particles of different shapes. Morphologies such as solids (Z1), zero to 50.0% in Zn(NO3)2 aqueous solution exhibiting the
ellipsoids (Z2), rods (Z3) and akes (Z4) with modal diameters regulatory inuence of microemulsions as well as the PEG400
of 396 nm, 396 nm, 1110 nm and 615 nm were obtained. additive on the nucleation and growth of ZnO NPs and their end
They were further characterized by their considerable surface architecture. TEM analysis further revealed that the
areas. Values of 8 m2 g
1, 10.6 m2 g
1, 12 m2 g
1 and 23 m2 g
1 morphology of the ZnO NPs underwent an alteration from
could be respectively assigned to samples Z1, Z2, Z3, and Z4. needle-like to columnar and nally to spherical as the PEG400
If a surfactant possessing balanced hydrophilic and lipo- concentration rose from zero to 50.0%.
philic properties is used in the right proportion, a different oil Yildirim and Durucan63 also synthesized ZnO NPs through
and water system will be produced. The system remains an the use of microemulsions. They made an endeavour to reshape
emulsion, but exhibits some characteristics that are different the microemulsion modus operandi with an eye to generate
from emulsions. These new systems are “microemulsions”. The monodisperse ZnO nanostructures. They subjected the zinc
drop size in a microemulsion is signicantly smaller than in an complex precipitate obtained in the course of the micro-
emulsion, and lies in the range 0.0015–0.15 mm.60,61 In contrast emulsion method to thermal decomposition. Subsequent
to emulsions, microemulsions form spontaneously under calcination was adopted. The use of glycerol as the internal
appropriate conditions. This synthesis method does not require phase of a reverse microemulsion imparted the intended
any complex preparation procedure, sophisticated equipment modication. The synthesized ZnO NPs had spherical shapes.
or rigorous experimental conditions, but still provides possi- They were monodisperse and their diameter measured in
bilities in controlling the size and morphology of the ZnO between 15 and 24 nm.
powders in a size scale approaching nanometers. Even though All the procedures involving chemical synthesis of ZnO NPs
the product yield is low, the narrow size distribution due to well- generate a few toxic chemicals and their adsorption on the
dispersed cage-like small reactors (5–100 nm) formed under surface increases the likelihood of harmful effects being wiel-
uniform nucleation conditions is the superior aspect of the ZnO ded in medical applications. Further, these approaches include
nanoparticles obtained by microemulsion routes. Such low- reactions requiring high temperature and intense pressure for
dimensional uniform ZnO nanostructures offering size and their commencement while some reactions require operations
morphology dependent tunable electrical and optical properties in an inert atmosphere or under inert conditions. Toxic mate-
are of particular technological interest for applications such as rials such as metallic precursors, toxic templates and capping
quantum dots, UV-emission optoelectronic and lasing devices, agents and even H2S nd application in quite a few chemical
and transparent conducting thin lms. routes.64 Very oen toxic substances are employed for the
Li et al.62 prepared ZnO NPs by a facile process based on generation of nano-structured particles and for their stabiliza-
microemulsion. The synthesized ZnO NPs were marked by tion as well. This in turn produces secondary products and
a wide range of morphologies and further exhibited signicant residues that are detrimental to the ecosystem.65,66
optical properties. The microemulsion (ME) was generated by
using a solution of heptane and hexanol in the mole ratio 3 : 1
as the oil phase and polyoxyethylene tert-octylphenyl ether 3. Green methods for the synthesis of
(Triton X-100) as nonionic surfactant. A denite amount of ZnO nanoparticles
Triton X-100 was put in the oil phase, and the mixture was
subjected to stirring for a while up until the mixture became The usual procedures adopting the chemical routes are costly.
transparent. Thus, a microemulsion (ME) consisting of 0.20 M They oen involve the use of chemical substances as reducing
Triton X-100 in the oil phase was prepared. The next step agents and these substances more oen than not turn out to be
entailed the preparation of two microemulsion solutions, toxic.67 Green routes of synthesis of nanoparticles cut down the
namely ME-1 and ME-2, containing different reactants. 3 mL of risk of pollution at the originary level. These procedures lay
a 0.25 M Zn(NO3)2 aqueous solution having various concentra- greater focus on prevention of generation of wastes than their
tions of PEG400 additive was added to 30 mL ME. This micro- treatment or removal aer they are formed. The principle
emulsion solution was named ME-1. Likewise, ME-2 was emphasizes upon the choice of reagents which are eco-friendly.
obtained by adding 3 mL of a 0.5 M NaOH aqueous solution to Thus, eco-friendly chemicals and safe solvents such as water are
30 mL ME. Next, ME-1 was rst added to ME-2 in a slow manner used alongside gentle natural extracts in such procedures.
with constant stirring. This in turn resulted in a mixture that Although chemical methods are quick and easier for the

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1881
Nanoscale Advances Review

generation of nanoparticles the biogenic techniques are supe- morphologies – spherical, triangular, radial, hexagonal, rod-like
rior and eco-friendly.68–70 Biogenic routes involving the use of and rectangle-shaped.
extracts generated from microorganisms and plants have thus One recent experiment used Calotropis procera leaf extract
been preferred over chemical procedures of fabricating ZnO and Zn(NO3)2$6H2O to synthesize ZnO NPs.75 An XRD test
NPs. Besides, ZnO NPs obtained by way of green methods conrmed a hexagonal wurtzite structure of the nanoparticles
demonstrate pronounced biocidal activity against a host of with marked crystallinity. The average crystallite size was
pathogens in comparison with chemically generated ZnO NPs.71 calculated using the Scherrer equation and found to be 24 nm.
Bio-inspired procedures of nanoparticle generation have of late Diffuse Reectance Spectroscopy (DRS) revealed a band gap of
been observed to employ systems including bacteria, yeast and 3.1 eV for the synthesized nanoparticles. In the FT-IR analysis of
other types of fungi.72 Nevertheless, a greatly detailed procedure the synthesized ZnO NPs, a peak attributed to the metal–oxygen
of maintaining cell cultures and intracellular synthesis causes bond of ZnO appeared in between 500 and 700 cm
1. Further,
inevitable complications in the use of microorganisms in the a conspicuous shi and broadening of peaks corresponding to
generation of nanoparticles while numerous purication functional groups like hydroxyl, aldehyde, amine, ketone, and
measures additionally increase the difficulty. Table 2 is a brief carboxylic acid suggests their participation in the stabilization
presentation of the various methods adopted by researchers to of ZnO by the extract. Surface attachment of groups like alde-
fabricate ZnO nanostructures using green routes. The detailed hyde, amine, phenol and terpenoid enhances stabilization
synthesis conditions, experimental variables, surface additionally allowing the extract to function as a bio-template
morphology, mechanisms and applications are discussed thereby preventing aggregation of ZnO NPs. TEM images
(Table 2). revealed an average particle size of 15–25 nm, while SAED and
An extract prepared from Ajwain (Carom-Trachyspermum HR-TEM further conrmed the high crystallinity of the material
ammi) seeds has also been used to synthesize ZnO NPs.70 The prepared.
work boasts of its operation under ambient temperature The effects of Artocarpus heterophyllus leaf extract and
conditions. The ZnO NPs were found to have a wurtzite struc- varying temperatures on the morphology and properties of the
ture. The synthesized ZnO nanostructures were morphologi- ZnO NPs thus prepared were studied by Vidya C. et al.76 XRD
cally characterized by FE-SEM images. The ZnO nanostructure results show an increase in crystallinity and average crystallite
showed uniform hexagonal plates, as well as irregular and size with temperature, the diffraction peaks being increasingly
highly aggregated nanoparticles with a rough surface. The sharper and narrower with temperature. The particles were all
average diameter of the nano-sized ZnO clusters has been spherical and a grain size of 50 nm was obtained from SEM
observed to be 41 nm. XRD results showed an increase in images. SEM analysis also shows similar trends of size and
interplanar spacing with an increase in the extract volume from morphology upon temperature variation. TEM analysis revealed
0.2474 nm to 0.2765 nm with a simultaneous decrease in crys- a particle size of 10–15 nm at 400  C, 15–25 nm at 600  C and
tallite size from 39.51 nm to 28.112 nm. The band gap also fell 25–30 nm at 800  C. This further corroborated the results of
from 3.592 eV to 3.383 eV as the amount of extract increased. XRD and SEM tests. Diffuse Reectance Spectroscopy (DRS)
Phytoconstituents in the extract thus evidently played a key role showed a decrease in the calculated band gaps with increasing
of reductants and furthermore acted as capping agents in the calcination temperatures.
generation and stabilization of ZnO NPs. Archana et al.77 used Moringa oleifera natural extract and
Jamdagni et al.72 used an aqueous ower extract of Nyc- Zn(NO3)2$6H2O for the preparation of ZnO NPs. They took
tanthes arbortristis for making ZnO NPs. The starting materials different volumes of the extract, viz. 2, 6, 10 and 14 mL, to
consisted of zinc acetate dihydrate and sodium hydroxide. XRD prepare ZnO NPs which were accordingly labeled ZnO-2, ZnO-6,
results showed an average crystallite size of 16.58 nm while TEM ZnO-10 and ZnO-14. The PXRD results of all the samples
analysis revealed that the individual particle size ranged within showed great crystallinity. They had a hexagonal wurtzite
12–32 nm and the nanoparticles were obtained in the form of structure. And the average crystallite size was found to be
aggregates. In a very recent study,73 Ulva lactuca seaweed extract 21.6 nm. Field Emission Scanning Electron Microscopy (FE-
was used to prepare ZnO nanoparticles. XRD analysis revealed SEM) analysis showed highly crystalline ZnO-10 and ZnO-14
strong characteristic peaks of ZnO suggesting high crystallinity having a spherical shape and average crystallite size of 20–
of the synthesized material. Further, the average crystallite size 150 nm. HR-TEM micrographs revealed d-spacing of 0.28 and
thus calculated was found to range in between 5 and 15 nm. 0.19 nm for the (001) and (101) planes of wurtzite ZnO. The
TEM micrographs revealed an agglomeration of asymmetrically band gaps calculated using the results from Diffuse Reectance
shaped NPs bearing an average crystallite size of 15 nm. Spectroscopy (DRS) had values of 2.92 eV for ZnO-2, 3.05 eV for
Muraya koenigii seed extract was also recently reported to ZnO-6, 3.12 eV for ZnO-10 and 3.10 eV for ZnO-14. The increase
have been used as a stabilizer as well as a reductant in the in band gap with the amount of fuel was attributed to quantum
preparation of ZnO NPs.74 Sharp diffraction peaks in XRD size effects.
results indicated remarkable crystallinity of the NPs whose In their research work, Rajeswari Rathnasamy et al.78 used
average crystallite size was calculated to be 70–100 nm. Both papaya leaf extract for the synthesis of ZnO NPs. Both FESEM
SEM and TEM micrographs revealed nanoparticles with an and TEM data revealed an average size of 50 nm for the
average size of about 100 nm and bearing a wide range of individual nanoparticles. The extract of Nephelium lappaceum L.
(rambutan) peels (a natural ligation agent) was put into use for

1882 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
 Table 2 Green synthesis of ZnO nanoparticles

Source Synthesis conditions Experimental variables Shape/morphology Mechanism and applications Size Ref.
Review

Carom-Trachyspermum 2 mL of the extract was slowly added — Uniform hexagonal plates, Anti-bacterial activities on 41 nm 70
ammi seed extract dropwise to a 25 mL solution of 0.05 M irregular and highly both Gram-positive
ZnNO3. Magnetic stirring for 2 h at 50  C. aggregated nanoparticles (Staphylococcus aureus) and
Centrifugation and drying at room with a rough surface Gram-negative (Pseudomonas
temperature at 35  C aeruginosa) bacteria
Nyctanthes arbor-tristis 0.01 M solution of zinc acetate and ower Concentration of zinc Aggregate of nanoparticles Nanoparticles were tested for 12–32 nm 72
ower extract extract were added at a pH of 12 and the acetate, pH, and their antifungal potential and
solution was stirred for 2 h. A white temperature were found to be active against
precipitate was obtained and dried at all ve tested phytopathogens
60  C overnight with the lowest MIC value
recorded being 16 mg mL
1
Ulva lactuca seaweed U. lactuca extract was added into 1 mM — Agglomeration of Excellent photocatalytic 15 nm 73
extract zinc acetate and kept under magnetic asymmetrically shaped activity on methylene blue.
stirring at 70  C for 3–4 h. The mixture nanoparticles High antibiolm activity on 4
was centrifuged at 4000 rpm for 10 min species of Gram-positive and
and the solid product was collected and -negative bacteria
heated at 450  C for 4 h
Muraya koenigii seed 20 mL of Murraya koenigii seed extract — Spherical, triangle, radial, ZnO nanoparticles used for 100 nm 74
extract was mixed with 80 mL of zinc nitrate hexagonal, rod and antimicrobial activities using
(ZnNO2) and 2.0 M NaOH solution was rectangle shaped human pathogenic bacterial

© 2022 The Author(s). Published by the Royal Society of Chemistry

added with vigorous stirring for 3–5 h, and fungal species
and incubated overnight at room
temperature. Zinc oxide nanoparticles
(white precipitate) were washed with
distilled water and ethanol and dried at
room temperature
Calotropis procera leaf Leaf extract was added to 50 mL distilled — Spherical When Zn(NO3)2$6H2O is 15–25 nm 75
extract water and heated up to 70  C and 6 g of mixed with C. procera leaf
Zn(NO3)2$6H2O was added and extract, the Zn2+ ions dispense
evaporated. Calcined at 400  C for 3 h consistently and form
a complex with active sites of
hydroxyl groups. Polyphenolic
molecules that interact with
divalent Zn2+ cations forming
a bridge between two hydroxyl
groups from two different
chains come from the
polyphenolic groups in close
contact with Zn2+. The divalent
cations keep the molecules
together and form various
structures of zinc complex.
Photocatalytic degradation of
methyl orange with an
efficiency of 81% within
100 min under UV light
Nanoscale Advances

Nanoscale Adv., 2022, 4, 1868–1925 | 1883

 Table 2 (Contd. )

Source Synthesis conditions Experimental variables Shape/morphology Mechanism and applications Size Ref.

Artocarpus heterophyllus 5 g of zinc nitrate hexahydrate was added Calcination temperature Spherical Photo-degradation of Congo 10–15 nm at 400  C, 15– 76
leaf extract to 150 mL leaf extract and heated at 80  C red dye 25 nm at 600  C and 25–
and calcined in a muffle furnace at 400, 30 at 800  C
600 and 800  C for 1 h
Moringa oleifera 2.97 g of zinc nitrate hexahydrate was Concentration of Moringa Clusters of spherical ZnO nanoparticles with 100–200 nm 77
Nanoscale Advances

dissolved in Moringa oleifera natural oleifera natural extract and nanoparticles smaller size show better H2
extract and heated on a hot plate with time evolution rates up to 360 mmol
a stirrer to form a gel kind of product and h
1 g
1. It is noteworthy that
kept in a muffle furnace maintained at ZnO nanoparticles prepared
400  C via novel green synthesis
exhibit oxygen vacancies and

1884 | Nanoscale Adv., 2022, 4, 1868–1925

register enhanced
photocatalytic activity as well
as good photostability
Carica papaya leaf extract To zinc acetate dihydrate (5 mmol) — Spherical Photocatalyst for methylene 50 nm 78
papaya leaf extract was added and the blue dye degradation
mixture heated at a temperature of 60  C (complete degradation within
for 2 h under stirring at a pH of 8. Finally, 180 min in the presence of UV)
it was washed with a water and ethanol and photo-anode with an
mixture and dried at 80  C for 12 h energy conversion efficiency of
1.6% with a current density of
8.1 mA cm
2 in dye sensitized
solar cells
Nephelium lappaceum L. A volume of 50 mL was prepared and — Multidimensional chain- — 20–50 nm 79
fruit peel extract then 10 mL of rambutan peel extract was like structures in which
added to 0.1 M Zn(NO3)2$6H2O with spherical nanoparticles
heating at a temperature of 80  C for 2 h were intertwined with each
and then incubated at room temperature other
for 1 day to form zinc-ellagate and dried
in an oven at 40  C for 8 h. ZnO
nanoparticles were obtained on direct
decomposition of the zinc-ellagate
complexes in a muffle furnace at 450  C
Moringa oleifera leaf extract 50 mL of Moringa oleifera extract was Concentration of zinc salt Drying at 100  C: Three chemical reactions of 12.27–30.51 nm 80
added to Zn(NO3)2$6H2O at room and calcination agglomerates of spherical the solvated Zn2+ ions are
temperature with a pH of 5 and subjected temperature particles; annealing at considered with the
to heat treatment in air at 500  C for 1 h 500  C: nanorods in phytochemicals of Moringa
addition to the clusters of oleifera, i.e. with a phenolic
spherical nanostructures acid, a avonoid and vitamin
based compounds. An altered
chemical behavior of L-
ascorbic acid and zinc nitrate,
probable oxidation of
biological compound i.e. L-
ascorbic acid to L-
dehydroascorbic acid via free
radicals, followed by
Review

© 2022 The Author(s). Published by the Royal Society of Chemistry

 Table 2 (Contd. )

Source Synthesis conditions Experimental variables Shape/morphology Mechanism and applications Size Ref.
Review

electrostatic attraction
between the free radical and
cation of the precursors.
Electrochemical investigations
by cyclic and square wave
voltammetry
Catharanthus roseus leaf An aqueous leaf extract of C. roseus was — Spherical Antibacterial activity was 23–57 nm 81
extract added to 0.025 M aqueous zinc acetate evaluated. Among the four
and pH adjusted to 12 and the solution bacterial species tested,
was dried in a vacuum Pseudomonas aeruginosa is
more susceptible when
compared with the other three
species and may be used for
the preparation of
antibacterial formulations
against Pseudomonas
aeruginosa
Camellia sinensis leaf ZnO NPs using the aqueous extract of — Agglomerates of irregularly These nano-sized ZnO 853 nm 82
extract green tea leaves. In the prepared extract shaped nanoparticles demonstrated remarkable
zinc acetate was dissolved by way of antimicrobial properties

© 2022 The Author(s). Published by the Royal Society of Chemistry

magnetic stirring. Intense stirring was against Gram-positive and
eventually applied on this solution for 5– Gram-negative bacteria as well
6 h; a temperature of about 150  C was as against a fungal strain
maintained during this time. The solid
mass thus obtained subsequently
underwent a 4500 rpm centrifugation for
15 min; this act was repeated again.
Finally washing and drying at 80  C for 7
to 8 h yielded agglomerates of irregularly
shaped ZnO NPs. UV spectroscopy
analysis showed maximum absorption at
about 330 nm. The size of the particles
was determined using a particles size
analyzer. The average diameter of the
particles was found to be 853 nm
Citrus aurantifolia fruit 50 mL of aqueous Citrus aurantifolia — Near spherical shaped — 9–10 nm 83
extract extract was boiled to 60–80  C.83 It was nanoparticles
followed by the addition of a specic
amount (5 g) of Zn(NO3)2 to the solution
as its temperature rose to 60  C. The
reaction mixture so prepared was then
boiled until a deep yellow coloured paste
was le. This paste was then collected
and heated in a furnace in the presence
of air at 400  C for 2 h to eventually yield
a powder. This powder bearing a faint
white colour was further ground in
Nanoscale Advances

Nanoscale Adv., 2022, 4, 1868–1925 | 1885

 Table 2 (Contd. )

Source Synthesis conditions Experimental variables Shape/morphology Mechanism and applications Size Ref.

a mortar-pestle. The synthesized

nanoparticles were characterized by
moderate stability. They had near
spherical shapes with the most probable
particle-size in the range of 9–10 nm
Nanoscale Advances

Oryza sativa rice extract ZnO NPs were prepared by the — Flake-, ower-, star-, — 200–800 nm, 800– 84
hydrothermal method. The method toothed-edge ake-like, 2000 nm, 200–1000 nm,
involved the use of zinc acetate, sodium rose- and rod-like 250–700 nm, 200–
hydroxide, and uncooked rice our at structures for 0.25 g, 0.50 g, 700 nm, 150–700 nm and
several ratios at 120  C for 18 h. The rice 1.0 g, 2.0 g, 4.0 g and 8.0 g 40–100 nm for 0.25 g,
bio-template was found to exert uncooked rice, respectively 0.50 g, 1.0 g, 2.0 g, 4.0 g and

1886 | Nanoscale Adv., 2022, 4, 1868–1925

considerable inuences upon the size 8.0 g uncooked rice,
and morphology of ZnO NPs respectively
Passiora caerulea. L. leaf The leaf extract was prepared by — Spherical — 30–50 nm 85
extract maintaining a temperature of 70  C for
8 min. 50 mL of aqueous 1 mM zinc
acetate [Zn(O2CCH3)2$(H2O)2] was
prepared and subjected to stirring for
1 h. Subsequently, to this solution,
a 20 mL of NaOH solution was slowly
added. This was followed by a slow
addition of 25 mL of plant extract. As
a consequence, the color of the reaction
mixture was found to change aer
incubation for an hour. This solution was
again subjected to stirring for 3 h. The
subsequent appearance of a yellow color
conrmed the generation of ZnO NPs.
The precipitate so obtained was
centrifuged at 8000 rpm at 60  C for
15 min. Thereaer, the pellets that
resulted were dried in a hot air oven at
a temperature of 80  C for 2 h
Sucrose (as a capping Zinc acetate (Zn(CH3COO)2$2H2O) and — Granular Carbon coated ZnO 10–100 nm 86
agent) sucrose (C12H22O11) served as the nanoparticles are used for
precursor and capping agent, respectively. symmetric supercapacitor
The precursor was prepared by dissolving device fabrication. The
4.3900 g of zinc acetate in 50 mL of double symmetric device yields
distilled water and stirring for 30 min at a specic cell capacitance of 92
60  C. During the process, 3.4229 g of F g
1 at a specic current of
sucrose solution was slowly added. The 2.5 A g
1
resultant solution was stirred for 2 h at the
same temperature. The solution was then
bone dried at 80  C and was calcined in an
atmosphere of air at 400  C for an hour.
The end product was nely ground using
an agate mortar to obtain the required
Review

© 2022 The Author(s). Published by the Royal Society of Chemistry

 Table 2 (Contd. )

Source Synthesis conditions Experimental variables Shape/morphology Mechanism and applications Size Ref.
Review

ZnO/C nanocomposite. Similarly, without

sucrose we synthesized pure ZnO
nanoparticles
Whey (as a chelating agent) Firstly, zinc citrate was obtained by Calcination temperature Spherical — With an increase in 87
mixing Zn(NO3)2$6H2O with citric acid calcination temperature
(CA), previously dissolved in distilled from 400 to 1000  C, the
water (0.1 g mL
1), at a molar ratio of size of nanoparticles
1 : 3. Whey (W) was subsequently added increased from 18.3 to 88.6
to these solutions at a mass ratio of nm
CA : W ¼ 60 : 40 to promote citrate
polymerization. The resultant mixture
was homogenized and maintained under
magnetic stirring for 1 h at 80  C to
complete gelatinization. The obtained
brown colored and transparent stable
resin (xerogel) aspect was heated to
100  C in order to eliminate excess water.
Then, the xerogel was calcined at
temperatures ranging from 200 to
1000  C for one hour to obtain the

© 2022 The Author(s). Published by the Royal Society of Chemistry

resultant ZnO nanoparticles
Citrus sinensis fruit peel An aqueous extract of orange peel was Annealing temperature and Spherical Ligation takes place between 400  C, 700  C and 900  C: 88
extract used as the biological reducing agent for synthesis pH the functional components of 35–60 nm, 70–100 nm and
the synthesis of ZnO NPs from zinc the orange peel and the zinc 200–230 nm, respectively.
acetate dihydrate. The ZnO NPs were precursor. The organic pH values of 6.0 and 8.0:
synthesized by mixing 2 g of zinc nitrate substances (avonoids, 10–20 nm and 400 nm. pH
with 42.5 mL of the extracts. These limonoids, and carotenoids) in value of 10.0: Agglomerates
mixtures were then stirred for 60 minutes orange peel extract act as of blocks with lengths of
and then placed in a water bath at 60  C ligand agents. These hydroxyl 370 nm and widths of
for 60 minutes. Subsequently, the aromatic ring groups, one of 160 nm
mixtures were dried at 150  C and then the extract components, form
heat-treated at 400  C for 1 hour complex ligands with zinc
ions. Through the process of
nucleation and shaping,
nanoparticles are stabilized
and formed. The mixture of
the organic solution is then
decomposed directly upon
calcination at 400  C resulting
in the release of ZnO
nanoparticles. Antibacterial
activities toward E. coli and S.
aureus: without UV light, the
bactericidal rate towards E. coli
was over 99.9%, while the
bactericidal rate towards S.
aureus varied in the relatively
Nanoscale Advances

Nanoscale Adv., 2022, 4, 1868–1925 | 1887

wide range of 89–98%
Nanoscale Advances Review

the preparation of ZnO NPs in another investigation.79 The bio- However, the size of particles seemed to increase when the
mediated ZnO NPs were found to be spherical in shape. They synthesis was done using 0.25 g UR. Different morphologies of
were characterized by diameters between 20 and 50 nm. Some the as-synthesized ZnO were observed with increasing the
of the particles were found in agglomerated form. Aer a day, amount of uncooked rice to 0.5 g. Particles with a very small
multi-dimensional chain-like structures formed. In these ower-like shape could be observed (Fig. 2e and f). A lower
chains spherical nanoparticles were found intertwined to each magnication FESEM image indicated that the mentioned
other. structure showed denticulated petals aggregated and form
An investigation conducted by Matinise et al.80 used Moringa larger owers of particles. Notably the size of the ZnO particles
oleifera extract as a remarkably operative chelating agent to had been obviously decreased for the sample prepared using
prepare ZnO nanoparticles. The ZnO NPs eventually obtained 0.5 g UR. In addition, the tooth-like akes were more dominant
were characterized by a particle size in between 12.27 and for the ZnO sample prepared using 0.5 g UR compared to the
30.51 nm. The sample obtained just aer drying at 100  C one synthesized using 0.25 g UR. Fig. 1g and h indicate the
consisted of agglomerates of spherical particles while that ob- FESEM images of the ZnO sample synthesized using 1 g UR. A
tained aer annealing at 500  C also had nanorods in addition very unique star-like structure could be clearly observed at low
to the clusters of spherical nanostructures. to high magnication. The star-like structure contained small
The biocomponents of leaves of Catharanthus roseus have akes with denticulated edges which attach to other similar
also been utilized to prepare ZnO NPs with zinc acetate and akes in the center. A closer look showed that the lateral ake
sodium hydroxide as reagents.81 SEM micrographs revealed that acted as a substrate for other akes to grow on the surface and
in addition to the individual ZnO-NPs, aggregates were also form a star-like structure. It was therefore argued that the
formed and they were spherical with diameter ranging from 23 branched pattern for so templates of starch revealed that the
to 57 nm. Sharp and clear XRD peaks conrmed high purity and semicrystalline granules of starch were made from concentric
excellent crystallinity. Shah et al.82 generated ZnO NPs using the rings in which the amylose and amylopectin basic components
aqueous extract of green tea (Camellia sinensis) leaves. The size were aligned perpendicularly to the growth rings and to the
of the particles was determined using a particle size analyzer. granule surface. Fig. 2g and h show that the size of the star-like
The average diameter of the particles was found to be 853 nm. ZnO particles decreased in comparison with the previous lower
These nano-sized ZnO particles demonstrated remarkable amount of uncooked rice. In the case of ZnO crystals synthe-
antimicrobial properties against Gram-positive and Gram- sized at 2 g UR, increasing the amount of bio-template resulted
negative bacteria as well as against a fungal strain. in different morphologies of ZnO particles being produced. It
In another experiment, 50 mL of aqueous Citrus aurantifolia formed lots of agglomerated toothed-edge akes which became
extract was boiled to 60–80  C.83 It was followed by the addition a secondary unit for larger particles. The star-like shape of the
of a specic amount (5 g) of Zn(NO3)2 to the solution as its particles could be perceived in some areas but aggregation
temperature rose to 60  C. The synthesized nanoparticles were seemed to be dominant and prevented clearer observation of
characterized by moderate stability. They had near-spherical the particles as they really are. Fig. 2k and l show the FESEM
shapes with the most probable particle size in the range of 9– images of the as-synthesized ZnO particles synthesized using
10 nm. The extract of Oryza sativa rice84 was also used to 4 g UR. The ZnO morphology changed to ower-like structures,
generate ZnO NPs. The extract has been considered a renewable mostly rose-like shapes. A detailed view of the ower-like
bio-resource. Its abundance adds to its list of merits. The extract particles revealed that their akes had the largest diameter
has also been cited as a source of bio-template that typically compared to other samples. In the case of ZnO synthesized
assists the generation of a variety of multifunctional nano- using 8 g UR, a new morphology, different from other and
structured materials. ZnO NPs were prepared using the hydro- control samples, was observed. The ZnO crystals appear mostly
thermal method. The method involved the use of zinc acetate, as rods with around 100 nm size. Moreover, agglomerated
sodium hydroxide, and uncooked rice our at several ratios at without any specic shape, particles coexisted with nanorods in
120  C for 18 h. The rice bio-template was found to exert the structure of ZnO synthesized using 8 g UR. Fig. 3 shows the
considerable inuences upon the size and morphology of ZnO particle size distribution of the ZnO samples synthesized using
NPs. Fig. 2 shows eld emission scanning electron microscopy 0.25, 0.5, 1, 2, 4, and 8 g UR. The particle size distribution of
(FESEM) images of the samples synthesized at different ZnO synthesized without rice is also given for comparison. As
concentrations of uncooked rice (UR). To investigate the effects shown in Fig. 3, the range of particle size for ZnO synthesized
of raw rice on the resulting ZnO morphology, FESEM was con- without UR lies between 200 and 800 nm. When 0.25 g UR was
ducted on ZnO synthesized without UR (Fig. 2a and b). As seen used in the synthesis, the size of particles increased dramati-
in Fig. 2c and d, the ZnO structures were mostly ake-like cally to 800–2000 nm. Notably the size of ZnO synthesized using
structures assembling together. They were much more 0.5 g UR considerably decreased to the 200–1000 nm range. The
ordered in contrast to the one synthesized without UR (as decreasing trend continued for the sample synthesized using
a control) (Fig. 2a and b). The diameter of ZnO akes dramati- 1 g UR and with a size range of 250–700 nm. Although this
cally decreased aer adding 0.25 g UR. This was proposed to distribution was quite similar to that of ZnO synthesized
have occurred due to the inhibition of lateral growth of ZnO without a bio-template, it was slightly narrower. On the basis of
crystals. It was further proposed that the accessibility of the zinc the particle size distribution for the samples synthesized using
ions to the ZnO crystal seeds was controlled by a bio-template. 2 and 4 g UR, it could be clearly observed that the size of

1888 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

Fig. 2 FESEM images of ZnO prepared using different concentrations of uncooked rice (g): 0 (a and b), 0.25 (c and d), 0.5 (e and f), 1 (g and h), 2 (i
and j), 4 (k and l), and 8 (m and n) (reproduced from ref. 84 with permission from Springer).

particles decreased to 200–700 nm and 150–700 nm, respec- 100 nm. As mentioned in the growth mechanism suggested by
tively. In the case of the ZnO sample synthesized using 8 g UR, the study, adding a bio-template, which presumably acts as
the size of particles was within the nano regime, between 40 and a occulant, forces aggregation. Therefore, the surface-active

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1889
Nanoscale Advances Review

continuous cycles) and capacitive characteristics in 1 M Na2SO4

electrolyte.
Zinc oxide (ZnO) nanoparticles were successfully synthesized
using a whey-assisted sol–gel method.87 X-ray diffraction (XRD)
and Raman spectroscopy analysis revealed a wurtzite crystalline
structure for ZnO nanoparticles with no impurities present.
Transmission electron microscopy (TEM), XRD observations,
and UV-vis absorption spectroscopy results showed that with an
increase in calcination temperature from 400 to 1000  C, the
size of the spherical nanoparticles increased from 18.3 to
88.6 nm, while their optical band gap energy decreased to
3.25 eV. The whey-assisted sol–gel method proved to be highly
efficient for the synthesis of crystalline ZnO nanoparticles
whose applications are of great interest in materials science
technology. Eryngium foetidum L. leaf extract was also used for
the nontoxic, cost-effective biosynthesis of ZnO nanoparticles
(NPs) following the hydrothermal route.88 The biosynthesized
ZnO NPs served as an excellent antibacterial agent against
pathogenic bacteria like Escherichia coli, Pseudomonas aerugi-
nosa, Staphylococcus aureus susp. aureus and Streptococcus
pneumoniae. The maximum zone of inhibition in ZnO NPs is
32.23  0.62 and 28.77  1.30 mm for P. aeruginosa and E. coli,
respectively.
Another report presented an efficient, environmentally
friendly, and simple approach for the green synthesis of ZnO
nanoparticles (ZnO NPs) using orange fruit peel extract.89 The
approach aimed to both minimize the use of toxic chemicals in
Fig. 3 Particle size distribution of ZnO samples synthesized using
various concentrations of UR (g); 0, 0.25, 0.5, 1, 2, 4, and 8 (w/w%) nanoparticle fabrication and enhance the antibacterial activity
(reproduced from ref. 84 with permission from Springer). and biomedical applications of ZnO nanoparticles. The sample
obtained without annealing exhibited relatively small spherical
particles (10–20 nm) which were coagulated in large clusters on
sites of the template might inuence the size and state of a matrix of residual organic material from the reducing agents.
aggregation during the particle growth process and ultimately In the samples annealed at 400  C and 700  C, the particle sizes
the resulting ZnO particle size distribution. Another procedure were randomly distributed and ranged from 35 to 60 nm and 70
used the aqueous leaf extract of Passiora caerulea. L. (Passi- to 100 nm, respectively. For an annealing temperature of 900  C,
oraceae).85 The SEM analysis revealed that the ZnO NPs had the particle size increased intensively in the range of 200–
diameters ranging in between 30 and 50 nm. 230 nm. It was thus found that the morphology and size of the
Sucrose was used in a study as the capping agent to ZnO NPs depended on the annealing temperature. Specically,
synthesize a ZnO/C nanocomposite adapting the sol–gel with increasing annealing temperature, the particle size tended
method.86 The presence of carbon in the prepared ZnO/C was to increase and shape larger particles due to crystal growth. For
conrmed through EDAX. SEM images of the ZnO/C samples pH values of 4.0 and 6.0, the particles were sphere-like in shape,
indicate a wide distribution of particles ranging from 10 to and were distorted with distinct grain boundaries and low
100 nm and exhibit only an irregular granular feature. This kind coagulation. At pH ¼ 6, the particle size was in the 10–20 nm
of surface morphology was argued to be more suitable for range and exhibited relative separation. Meanwhile, for a pH of
supercapacitor electrode materials. Electrochemical investiga- 8.0, the particles had a variable shape and were coagulated in
tions of the ZnO/C electrode were carried out using cyclic vol- large clusters around 400 nm in size with indistinct grain
tammetry, galvanostatic charge–discharge, and electrochemical boundaries. For a pH of 10.0, the particles were coagulated into
impedance spectroscopy. The ZnO/C electrode exhibits large blocks with lengths of 370 nm and widths of 160 nm.
a maximum specic capacitance of 820 F g
1 at a constant The ZnO NPs exhibited strong antibacterial activity toward
specic current of 1 A g
1. The symmetric aqueous super- Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus)
capacitor device exhibits a specic cell capacitance of 92 F g
1 at without UV illumination at an NP concentration of 0.025 mg
a specic current of 2.5 A g
1. The aqueous symmetric super- mL
1 aer 8 h of incubation. In particular, the bactericidal
capacitor device achieved an energy density of 32.61 W h kg
1 activity towards S. aureus varied extensively with the synthesis
and a power density of approximately 1 kW kg
1 at a discharge parameters. This study presents an efficient green synthesis
current of 1.0 A g
1. It has been found that the cells have an route for ZnO NPs with a wide range of potential applications,
excellent electrochemical reversibility (92% aer 400 especially in the biomedical eld.

1890 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

4. Modification of zinc oxide form of a thin layer or as nanoparticles depending on the

reaction parameters. ZnO clusters were generated using trie-
nanoparticles thanolamine (TEOH) on a silica surface having silanol (^Si–
The ultimate motive behind surface modication of ZnO OH) and siloxane (^Si–O–Si^) groups via a procedure of
nanoparticles is to harness their high affinity for adhesion and controlled precipitation. TEOH was observed to play a dual role
agglomeration through reduction of surface energy thereby in the synthesis. It rst induced surface modication of silica by
controlling their growth at the nano level. Modication of ZnO getting adsorbed on the silica surface via a mechanism
has been carried out with different classes of modiers, namely involving the splitting of the siloxane and silanol networks and
inorganic compounds, organic compounds and polymer then subsequently reacting with Zn(OAc)2 to form ZnO clusters
whose further growth on the silica surface is sustained via
matrices. Inorganic compounds like SiO2, Al2O3, LiCoO27, metal
ions, etc. when used as modiers brought about a change of ripening and aggregation. The attachment of ZnO on a larger
surface area or particle size, diminished the photocatalytic silica surface was argued to enable rapid collision with other
efficiency of the metal oxide and improved the dispersion ZnO clusters leading to the signicant growth of ZnO on the
degree of ZnO particles. Organic modiers like silanes and silica surface.
carboxylic acids made the following modications: introduction Silica was also used by Hong et al.92 for the modication of
of characteristic groups on the surface of ZnO and alteration of ZnO NPs. In a separate experiment they also used oleic acid as
its physicochemical properties, increase in the compatibility of the capping agent. A reaction between Zn(OAC)2$2H2O and
(NH4)2CO3 produced the precursor that was then subjected to
ZnO with an organic matrix, reduced aggregation of particles
and enhanced long-term stability in an organic matrix and a procedure culminating in calcination to get ZnO. Oleic acid
improved ZnO dispersion in rubber mixtures. Modiers such as was then coated on one sample of ZnO while through a separate
polyethylene glycol, polystyrene, poly(methyl methacrylate), pH controlled procedure silica was coated on another ZnO
chitin, etc. improved the unique electrical, thermal and optical sample using sodium silicate. The oleic acid coated ZnO
properties of ZnO/polymer composites. exhibited remarkable compatibility with the organic matrix.
Cao et al.90 used silica and trimethyl siloxane (TMS) for The FTIR spectra revealed a chemical bond between the –OH
modifying ZnO in order to achieve a two-fold benet: enhancing groups on the ZnO surface and the –COOH groups of the oleic
acid chains. The corresponding reaction is given below:
the compatibility of ZnO and cutting down on its agglomeration
in the organic phase. A chemical precipitation method using
ZnO(OH)x + yOHC(CH2)7CH]CH(CH2)7CH3 /
zinc sulfate heptahydrate (ZnSO4$7H2O), ammonium solution
ZnO(OH)x
y[OOC(CH2)7CH3]y + yH2O
(NH4OH) and ammonium bicarbonate (NH4HCO3) was adopted
to rst obtain the precursor, zinc carbonate hydroxide (ZCH).
The surface of the ZCH was then successively modied by an in The FTIR spectra for the SiO2-modied ZnO revealed inter-
situ method using TEOS and hexamethyldisilazane (HMDS) in phase bonds between ZnO and SiO2. A thin lm coating of SiO2
water. The functionalized ZHC was subjected to calcination, to on the ZnO surface resulted in enhanced dispersion and
yield extremely ne nanoparticles of ZnO. Reduced agglomer- reduced agglomeration of nanoparticles, a fact fairly well
ation was thereby effected through such functionalization of the corroborated by HR-TEM data. The photocatalytic activity of
surfaces of ZnO NPs although a lowered photocatalytic activity SiO2-modied ZnO however suffered a setback in comparison
of the oxide was observed. Nevertheless, a marked increase in with that demonstrated by uncoated ZnO. The work further
the compatibility of ZnO with the organic matrix lent credence demonstrated that the thorough reduction of the crystallinity of
to the method. Further, the greater shielding capacity of UV ZnO achieved through heterogeneous azeotropic distillation of
radiation renders the synthesized nanomaterial an excellent the zinc oxide precursor not only precludes aggregation but also
candidate for use in cosmetics. Below is a schematic represen- brings about a decline in the average particle size.
tation (Fig. 4) of the synthesis of surface-modied ZnO ultrane Yuan et al.93 modied ZnO using Al2O3. A basic carbonate of
particles using an in situ modication method. zinc was obtained from the reaction between zinc sulfate and
Xia and Tang91 also carried out modication of ZnO using ammonium bicarbonate followed by precipitating aluminum
silica. They had a silica surface coated with ZnO either in the hydroxide over it. The resulting compound-precipitate was then

Fig. 4 Schematic representation of the synthesis of surface-modified ZnO ultrafine particles using an in situ modification method (reproduced
from ref. 89 with permission from Elsevier).

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Nanoscale Advances Review

calcined at 400–600  C to obtain ZnO NPs coated with Al2O3. It electron microscopy (SEM) that while pure ZnO NPs suffered
was discovered from TEM analysis that as the Al2O3-coating considerable agglomeration in poly(vinyl chloride) (PVC) lm,
content rose from 3 to 5%, agglomeration decreased signi- the ZnO/polystyrene nanocomposite particles underwent
cantly and correspondingly the particle size decreased from an homogeneous dispersion in the PVC matrix. The scheme
average value of 100 nm to 30–80 nm. The coating thus designed depicted in Fig. 5 explains the mechanism of the mini-emulsion
was 5 nm thick and was highly uniform. The coating-core polymerization method to construct ZnO/polystyrene nano-
interphase possibly had the structure of ZnAl2O4. Zeta poten- composites adopted by Tang and his research group. From SEM
tial data clearly conrm modications on the ZnO surface by micrographs (Fig. 5), it was observed that functionalized ZnO (f-
Al2O3 deposition. The change in pH at the isoelectric point for ZnO) nanoparticles had been well dispersed in the polymer
ZnO NPs upon coating with Al2O3 from around 10 to a value of 6 matrix because the f-ZnO nanoller had outstanding adhesion
might have assisted a greater degree of dispersion of ZnO NPs. and strong interfacial bonding to PEA. As was observed, f-ZnO
In a study by Hu et al.,94 nano-sized ZnO rods doped with nanoparticles were homogeneously dispersed in the polymer
transition metals such as Mn, Ni, Cu, and Co were designed by matrix and their sizes were estimated to be between 20 and
a plasma enhanced chemical vapor deposition method. The 50 nm.
ZnO thus modied had a greater amount of crystal defects Cyclodextrins (CDs) make up a class of cyclic torus-shaped
within its structure. This led to its greater sensitivity towards oligosaccharides. CD has a hydrophilic external surface and
formaldehyde. When the 1.0 mol% Mn doped ZnO nanorods a hydrophobic internal cavity. CDs have been extensively used
were activated by 10 mol% CdO, a maximum sensing of as eco-friendly coupling agents.98,99 Among the derivatives of
25 ppm was obtained and the corresponding response and CDs, monochlorotriazinyl-b-cyclodextrin (MCT-b-CD) with
recovery time were found to be appreciably short. a monochlorotriazinyl group as a reactive anchor was found to
Wysokowski et al.95 developed a b-chitin/ZnO nano- possess the ability to form covalent bonds with substituents of
composite material. The b-chitin used in the synthesis was the nucleophilic type, viz., –OH or –NH2 groups.100–103 Therefore,
derived from Sepia officinalis, a cephalopod mollusk. This MCT-b-CD provides an interesting way of surface modication
nanocomposite was found to exhibit remarkable anti-bacterial for inorganic nanomaterials. Abdolmaleki et al.104 accom-
activity and was touted as an excellent ingredient for the plished surface modication of ZnO NPs by covalently graing
making of wound-dressing materials. MCT-b-CD onto the surfaces of ZnO NPs through a facile and
Ong et al.96 in their work synthesized a heterogeneous pho- single-step procedure. In the next step, f-ZnO nanoparticles
tocatalytic material by loading ZnO on solvent exfoliated gra- were employed for construction of a new series of poly(ester-
phene sheets. For anchoring ZnO onto the graphene sheet, they amide)/ZnO bionanocomposites (PEA/ZnO BNCs) whose TEM
used poly(vinyl pyrrolidone) as an inter-linker which was also image is shown in Fig. 6. MCT-b-CD has monochloro-triazinyl
found to enhance the functionalization of the acid treated groups that react with –OH groups on the surfaces of ZnO
graphene sheets. The thermal stability of the decorated ZnO was NPs through nucleophilic reaction (Fig. 7). Aer the incorpo-
found to be higher than that of the undecorated oxide. The ration of MCT-b-CD on the surfaces of ZnO NPs, polymer/ZnO
modied ZnO proved to be an outstanding photocatalyst being bionanocomposites (BNCs) were designed using a biodegrad-
able to cause 97% degradation of Reactive Black 5 under visible able amino acid containing poly(ester-amide) (PEA). ZnO NPs
light. This improvement was attributed to a host of favourable with b-CD functional groups incorporated on their surfaces
parameters achieved through the modication, namely, an exhibited a near-complete suppression of their tendencies
enhancement of light absorption intensity, widening of the towards agglomeration while simultaneously displaying
light absorption range, suppression of charge carrier recombi- enhanced compatibility with the polymer matrix. Scores of
nation, improvement of surface active sites and rise in the functional groups on the surfaces of ZnO NPs enable possible
chemical stability of the designed photocatalyst. interactions with PEA chains that lead to excellent dispersion
Tang et al.97 demonstrated a way to tackle the agglomeration and compatibility with the polymer matrix. FE-SEM and TEM
tendency of ZnO NPs. They prepared ZnO/polystyrene nano- results bore out a reduction of agglomeration that can be safely
composites via a mini-emulsion polymerization method. For attributed to the steric hindrance induced by the organic chains
this, a silane coupling agent, namely g-glycidoxypropyl trime- of MCT-b-CD between the inorganic nanoparticles. The dis-
thoxysilane (KH-560, AR), was rst allowed to cling to ZnO NPs persibility, surface morphology and particle dimensions of
via reaction between its Si–OCH3 groups and the hydroxyl functionalized ZnO (f-ZnO) with b-CD are shown in Fig. 8.
groups on the surface of the nanoparticles followed by Farzi et al.105 carried out surface modications of ZnO with
anchoring of 4,40 -azobis(4-cyanovaleric acid) (ACVA) onto their oleic acid, trimethoxyvinyl silane and their different mixtures as
surface through reaction of its carboxyl groups with the capping agents. The compatibility of ZnO with different organic
terminal epoxy groups of the aforementioned coupling agent. matrices was found to increase considerably. A greater degree of
Subsequently, polymerization of the styrene monomer was dispersion of the inorganic nanoparticle was simultaneously
initiated using the azo group of ACVA for designing the nal achieved. Modications with trimethoxyvinyl silane were
nanocomposites. The monomer droplet of the mini-emulsion however found to be more effective than those with oleic acid
polymerization system thus obtained contained well dispersed clearly evident from the greater extent of compatibility with the
ZnO/polystyrene nanocomposites with a high graing efficiency organic phase achieved using the former. Thus, different
of 85% as calculated from TGA. It was evident from scanning combinations of these coupling agents were used to get a grip

1892 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

Fig. 5 A schematic diagram showing the synthesis of ZnO/polystyrene nanocomposites by anchoring 4,40 -azobis(4-cyanovaleric acid) (ACVA)
onto the surface of ZnO nanoparticles to initiate styrene polymerization (reproduced from ref. 97 with permission from Elsevier).

on the hydrophobicity and the dispersion capacity of the inor- dispersed more efficiently in the moderately hydrophobic
ganic oxide in solvents that are polar to varied extents. Modi- butylacrylate. Modications attained by a 3 : 1 (by weight)
cations with a 1 : 3 (by weight) mixture of trimethoxyvinyl silane mixture of trimethoxyvinyl silane and oleic acid endowed the
and oleic acid exhibited more efficient dispersion in the highly nanoparticles with greater dispersion in the weakly hydro-
hydrophobic styrene. Meanwhile, ZnO NPs modied with a 1 : 1 phobic methyl methacrylate. The magnitudes of graing yield
(by weight) mixture of trimethoxyvinyl silane and oleic acid

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1893
Nanoscale Advances Review

Fig. 6 FESEM of pure ZnO NPs (a) and grafted ZnO/polystyrene nanocomposite particles (b) dispersed in PVC matrices (reproduced from ref.
104 with permission from Elsevier).

5. Potential applications
Recent years have witnessed a sharp rise in focus on ZnO NPs in
the realm of research courtesy of their unique properties that
have been exploited to achieve a wide range of applications in
transparent electronics, ultraviolet (UV) light emitters, piezo-
electric devices, chemical sensors, opto-electronics, solar cells
and spin electronics.106,107 Being nontoxic, ZnO has of late found
extensive use as an excellent photocatalyst for the degradation
of a great many emerging organic pollutants. ZnO has also
attracted great interest as a raw material in the pharmaceutical
and cosmetic industries, as a pigment in the paint, concrete and
rubber industries, as a UV lter in products, the textile industry,
and medical and biological elds, and so on (Fig. 9). A few of
these applications of ZnO NPs have been presented below.

5.1 Concrete and rubber industries

In the rubber industry, ZnO is extensively used as an additive.
ZnO like a host of other metal oxides and inorganic substances
raises the thermal conductivity of silicone rubber when added
even in low proportions. This it does while retaining the high
electrical resistance of the silicone rubber. However, poor
dispersion of the nanoparticles in the polymer matrix owing to
feeble interactions between the surfaces of nanoparticles and
the polymer is one area that requires improvement and there-
fore has been extensively investigated. Agglomeration of ZnO
NPs bearing high surface energy has been reported.108 This
necessitates surface modication of the ller ZnO NPs in order
to achieve simultaneous reduction in their agglomeration and
an improved degree of dispersion in the polymer matrix.109
Fig. 7 Modification of ZnO nanoparticles with MCT-b-CD (repro- Furthermore, ZnO is widely known to activate sulphur vulca-
duced from ref. 104 with permission from Elsevier).
nization via enhancement of the degree of cross-linking.
Therefore, the mechanical properties of silicone rubber are
found to improve as well when ZnO is incorporated into it as
and graing density of both the coupling agents were also a ller.
found to be within an acceptable range. In their attempt to enhance the interactions between the
nano-sized ZnO particles and the polymer, Yuan et al.110 by
incorporating vinyl silane groups on the surfaces of ZnO NPs
using vinyl triethoxysilane through a procedure premised on
the hydrosilylation reaction during curing carried out their

1894 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

Fig. 8 (A) Photograph of aqueous dispersions of pure ZnO (left) and f-ZnO (right), and (B) FESEM and (C) TEM micrographs of f-ZnO (reproduced
from ref. 104 with permission from Elsevier).

surface modication. The vinyl silane groups on the ZnO ZnO NPs have been widely used as an efficient material for
surface enabled improved cross-linking with the rubber matrix. the enrichment of cross-linking in elastic polymers.111,112 The
In order to solve this problem, surface modication techniques cured polymer produced through incorporation of ZnO NPs
are applied to improve the interaction between the nano- exhibited high ultimate tensile strength, tear strength, tough-
particles prepared by the sol–gel method and the polymer. In ness and hysteresis. The slippage of polymer chains on the
comparison with the nanocomposites of silicone rubber with surfaces of ionic clusters and the renewal of ionic bonds when
ZnO, the nanocomposites of silicone rubber with vinyl trie- the sample gets externally deformed give rise to enhanced
thoxysilane modied ZnO possessing extensive cross-linking capacity of the ionic elastic polymer for stress relaxation which
and a higher degree of dispersion with the rubber matrix in turn results in its upgraded mechanical properties. Further-
exhibited superior mechanical properties and enhanced more, the thermoplastic properties of such polymers enable
thermal conductivity. their processing in a fused state in a manner akin to a thermo-
plastic polymer.113 Nevertheless, carboxylic elastic polymers

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1895
Nanoscale Advances Review

Fig. 9 Applications of ZnO NPs.

with ZnO as a cross-linker suffer from a few drawbacks prom- whiskers, and snowakes) as cross-linkers in a carboxylated
inent among which are their tendency to get scorched, feeble nitrile elastomer. It emerged from their investigation that ZnO
ex properties and high value of compression set. The tendency NPs as cross-linkers imparted improved mechanical properties
to get scorched is gotten rid of by the incorporation of either to vulcanizates than commercially used ZnO micro-particles.
zinc peroxide (ZnO2) or ZnO2/ZnO cross-linkers. ZnO2 serves to The ultimate tensile strength of vulcanizates with ZnO NPs
not only create ionic cross-links but also generate covalent was found to be four times higher than that of ZnO micro-
cross-links as a result of peroxide action. However, prolonged particles containing vulcanizates. As a result, there is a 40%
curing is needed to obtain elastomers with an ultimate strength reduction of the quantity of ZnO that is put to such use. Since
and cross-link density comparable to that of ZnO-cross-linked ZnO is known to have deleterious effects on aquatic life, an
elastomers. The three vital processes that amount to the approach that reduces its usage is highly commendable from
curing of XNBR by ZnO2/ZnO cross-linkers are rapid creation of the point of view of eco-friendliness. However, ZnO cross-linked
ionic crosslinks due to the initial ZnO present, covalent links XNBR undergoes shrinkage on prolonged exposure to heat.
resulting from peroxide cross-links and further ionic cross- Among all the aforesaid morphologies, it was observed that
linking due to the generation of ZnO from the decomposition ZnO snowakes with a surface of approximately 24 m2 g
1 had
of ZnO2. Leaving aside the problem of scorching, ZnO NPs make the highest activity. However, surface area and particle size
good and therefore widely used cross-linkers in carboxylated exerted little inuence on the activity of ZnO cross-linkers. It
nitrile rubbers. was also observed that the ZnO NPs exhibited a minimum
The prime factors affecting the involvement of ZnO in the tendency to agglomerate in the rubber matrix. There gathered
formation of ionic cross-links with the carboxylic groups of the smaller agglomerates with ZnO NPs as cross-linkers upon
elastic polymers are its particle size, surface area and sample deformation as compared to the large agglomerates
morphology. They are also found to govern the dimensions of observed with ZnO microparticles.
the interphase between the cross-linkers and elastomer The usage of ZnO as a cross-linker in rubber has an adverse
chains.114 With a view to ascertain the correlation between the impact on the environment, particularly when it is discharged
characteristics of ZnO NPs and their roles in the curing of into the surroundings upon degradation of rubber.116 Zinc is
elastic polymers, Przybyszewska et al.115 employed a variety of known to cause great harm to aquatic species117 and efforts to
ZnO NPs with different morphological characteristics (spheres, cut down on the content of ZnO in rubber are hence being

1896 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

made.118 Bringing down the ZnO level in rubber, therefore, may ZnO incorporation up to 3% by weight of cement. However,
follow any of the following three fundamental procedures: a slight decline of these parameters was observed for 5% by
(i) substituting the commonly used micro-dimensional ZnO weight of cement incorporation of ZnO. SEM data revealed that
of surface area 4–10 m2 g
1 with nano-structured ZnO with the nanoparticles lled cement pores, promoted the hydration
surface area of up to 40 m2 g; process and given their homogeneous dispersion greatly
(ii) carrying out surface modications of ZnO with carboxylic enhanced the microstructure of the cement mortar.
acids (viz., stearic acid, maleic acid and the like);
(iii) using additional activators.119
In order to get over the eco-toxicity associated with the usage 5.2 Opto-electronic industry
of ZnO in large quantities, Thomas et al.120 designed a few Because of its large exciton binding energy (60 meV), ZnO is
unique accelerators, namely, N-benzylimine amino- considered as a potentially attractive material for light-emitting
thioformamide (BIAT)-capped-stearic acid-coated nano-ZnO devices in the ultraviolet (UV) region. Due to its direct, wide
(ZOBS), BIAT-capped ZnO (ZOB), and stearic acid-coated nano- bandgap of 3.37 eV, ZnO can be used as a light-emitting diode
zinc phosphate (ZPS), to probe their effects on the curing of and photodetector, in sensors, and in solar cells and devices
natural rubber (NR) and thereby its mechanical properties. ZnO emitting a surface acoustic wave.123,124 The optical and electrical
NPs prepared by the sol–gel route were surface-decorated using properties of ZnO have been greatly exploited in recent years to
accelerators such as BIAT and fatty acids such as stearic acid. generate a large photocurrent in ZnO based dye-sensitized solar
The capping agents functioned to reduce the size of agglomer- cells (DSSCs). Since the performance efficiency of solar cells is
ates leading to an improvement of vulcanization and physico- considered to be substantially inuenced by the varying
chemical properties of NR. Capping of ZnO further ensured geometries of ZnO nanostructures, a plethora of investigative
a decline in the time and energy required for dispersion in the studies on the effects of morphology of ZnO have unfolded in
rubber matrix. As a result, there happened a further enhance- recent years. With ZnO nanosheets having inadequate surface
ment of the acceleration of vulcanization and a remarkable area, a conversion efficiency of 1.55% was obtained for
upgrade of the mechanical properties of the emerging vulcani- a DSSC.125 However, the ZnO nanosheets/spheres synthesized
zates. The rubber vulcanized with an optimal dose of BIAT- with oxalic acid as surfactant led to an expansion of the surface
capped-stearic acid-coated zinc oxide (ZOBS) was found to area thereby enhancing the conversion efficiency of the DSSC to
possess superlative curing and mechanical properties in 2.61%.126 An electrodeposited ZnO nanobelt lm was used in
comparison with other countertypes and the reference polymer a DSSC which was found to exhibit 2.6% photovoltaic effi-
containing pristine ZnO NPs. The rigidity of vulcanizates con- ciency.127 DSSCs with lms comprising ZnO tetrapods had
taining ZPS was found to increase as a result of an enhanced conversion efficiencies in the range 1.20–3.27%.128,129 Addi-
cross-link density. The vulcanizates exhibited reduced tendency tionally, it came to the fore that incorporation of ZnO NPs into
to get scorched as a result of incorporation of capped ZnO NPs such lms increased their surface area which in turn boosted
and this was attributed to the delayed release of BIAT from the their efficiency.128 One-dimensional nano-sized structures have
capped ZnO into the rubber matrix for interaction with CBS been known to reduce recombination by increasing the electron
(conventional accelerator). Sabura et al.121 adopted a solid-phase diffusion length via direct electron transport. A number of one-
pyrolytic procedure to synthesize ZnO NPs of particle size in dimensional ZnO nanostructures have thus been put to use in
between 15 and 30 nm and surface area in the range 12–30 m2 DSSCs for enhancement of their efficiency. Notably, a DSSC with
g
1 for use in neoprene rubber as cross-linkers. Two ndings ZnO nanotube lm exhibited a conversion efficiency of 2.3%.130
emerged from this study. One, the optimal content of ZnO Several dopants have also been tested for their effects on
required was found to be low in comparison with commercially photovoltaic efficiency of ZnO based DSSCs. A dye-sensitized
used ZnO. Two, the cure characteristic and mechanical prop- device with ZnO nanoporous nanosheets doped with boron
erties of the rubber showed a marked improvement when was probed131 and a conversion efficiency of 6.75% was ob-
compared with those containing conventional ZnO. tained. A DSSC with uorine-doped ZnO produced a conversion
Since an improvement of the processing time and resistance efficiency of 3.43%.132 With a lithium-doped ZnO photoanode,
of concrete against water can be made by incorporation of ZnO the DSSC generated an efficiency of 6.1%.133
NPs in concrete, ZnO NPs have also been used for The last decade has seen an upsurge in the fabrication of
manufacturing concrete. Nivethitha et al.122 have reported ZnO-based perovskite solar cells (PSCs). Although the conven-
positively about the aforesaid fact in their work. They had the tional choice for an electron transport layer has been TiO2, ZnO
cement partially replaced by ZnO of 0, 1, 3 and 5% by weight of with higher electron mobility is increasingly replacing it as an
cement. They prepared the blended material by using a cement– efficient and low-cost material for electron transport in PSCs.
sand ratio of 1 : 1 and 1 : 2 by weight while the water–binder Additionally, the power conversion efficiency of PSCs at large
ratio was xed at 0.35. The compressive and split tensile has exceeded 20% of late giving the necessary impetus to delve
strength was evaluated aer 7 and 28 days. Studies were also deep into the fabrication of ZnO electron transport layers (ETLs)
carried out on durability parameters that include water for yet more brilliant perovskite solar devices. Bi et al.134 fabri-
absorption, impact strength, sorptivity and microstructure of cated a PSC with ZnO nanorods aligned vertically over the
the mortar. The results show that in general an improvement in substrate. With the length of nanorods, the Jsc (short-circuit
mechanical and impact strength of the mortar was observed for current density), FF (ll factor) and PCE of solar cells were

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1897
Nanoscale Advances Review

found to increase. They however reported a decrease in Voc with Vanalakar et al.142 also prepared ZnO nanorods with preferential
nanorod length. They reasoned that nanorod length has orientation along the (002) direction through the wet chemical
a bearing on the electron transport time and lifetime that in route and studied their gas sensing ability towards NO2 and the
turn inuence the performance of the solar cell. They achieved parameters affecting it, such as the aspect ratio of the rod
a maximum overall cell efficiency of 5%. Son et al.135 substituted lengths, time, operating temperature and gas concentrations.
the single-step method used by Bi et al. by a two-step coating The sample of ZnO nanorods with a (103)/(002) ratio of 0.036
procedure. Such a treatment generated a fully lled perovskite and intermediate spacing between them produced remarkable
lm that covered all ZnO nanorods of varying lengths without sensing performance at a temperature of 175  C for detection of
voids and formed an overlayer on the surface of nanorods. As NO2 at a concentration of 100 ppm with a high sensitivity of
a further consideration, the two-step coating treatment induced 3100%. The mechanism of gas sensing outlined in the work is
optimization of the cuboid size of MAPbI3 and reduced the as follows:
series resistance of the solar cell.136 As a result, a maximum PCE
of 11.13% was obtained. Tang et al. designed ZnO nanowall NO2 (gas) + e
(CB) / NO2
(adsorption)
ETLs.137 The best performance PSC based on ZnO nanowalls
produced a Jsc of 18.9 mA cm
2, Voc of 1.0 V, FF of 72.1%, and NO2 (gas) + O2
(adsorption) + 2e
/ NO2
(adsorption) + 2O

PCE of 13.6%. Meanwhile, the control device shows a Jsc of 18.6 (adsorption)
mA cm
2, Voc of 0.98 V, FF of 62%, and PCE of 11.3%. The
introduction of ZnO nanowalls led to an evident boost in the FF
Zhang et al.143 constructed a Ag loaded ZnO–MoS2 gas
and PCE of the PSCs and this can be ascribed to the greater
sensing lm through a LBL (layer-by-layer) self-assembly route
contact area between ZnO and perovskite offered by the ZnO
and investigated its response upon exposure to a wide range of
nanowalls in comparison with the planar ZnO lm which
gases such as H2, CH4, CO, C2H2, C2H6 and C3H8. It was found
improves not only the electron collection but also trans-
that the nanocomposite lm showed remarkable selectivity
portation efficiency at the interface of the ZnO nanowalls and
towards CO (Fig. 10). Upon contact with CO gas, the Ag NPs of
perovskite. Moreover, the decomposition of ZnO by perovskite
the nanocomposite sensing lm catalyze the oxidation of CO
triggered by the alkaline nature of the ZnO surface leads to the
triggering the release of electrons trapped by anionic oxygen
formation of PbI2 on the perovskite/ZnO interface. The presence
species which in turn causes a sharp fall of sensor resistance to
of PbI2 can suppress the surface recombination and improve
manifest a brilliant sensing response. The Ag–ZnO–MoS2
the FF.138
nanocomposite's gas sensing performance towards CO was
found to be higher than that of Pt–ZnO–MoS2 or ZnO–MoS2 or
5.3 Gas-sensing ZnO lm in terms of response/recovery capability, repeat-
ability, stability and selectivity (Fig. 11). Notably, under the
ZnO nanostructures have exhibited excellent gas sensing
same conditions of the experiment, the Ag–ZnO–MoS2 sensing
properties largely driven by the change in modications in
lm functioned way better than the Pt–ZnO–MoS2 sensor. This
sensor resistance when gas molecules interact with their
was elucidated invoking the Schottky barrier (SB). Fig. 12a and
surface. The overriding feature of ZnO nanostructures when it
b show how a noble metal's SB would tamper with the elec-
comes to gas sensing ability is the large surface-to-volume ratio.
trical properties of the ZnO–MoS2 lm. The equation FSB ¼ F
Under ambient conditions, oxygen molecules get adsorbed on

j allows the calculation of the SB height FSB, where F is the
the surface through a phenomenon termed as ionosorption. In
work function of the noble metal and j is the electron affinity
the course of this phenomenon, they collect electrons from the
conduction band of ZnO and assume various forms (O
, O2

and O2
) depending on the temperature.139,140 This creates
a surface depletion layer that leads to an increase of resistance
in ZnO. Upon approach of reductive gases in the vicinity of the
ZnO surface, the adsorbed negatively charged oxygen species
interact with the gas molecules and the trapped electrons are
released back to the conduction band of ZnO thereby lowering
the sensor resistance. On the other hand, oxidative gases
undergo interaction that raises resistance in the material.
Hydrothermally obtained ZnO nanorods reported in a study
by Cho et al.141 exhibited remarkable sensitivity of NO2 gas in
the presence of CO. The sensor resistance elicited a change by
1.8 times its pristine value upon exposure to 1 ppm NO2 while
an imperceptible change was noticed for a 50 ppm CO. It also
emerged from the study that ZnO nanorods with larger crys-
tallite size turned out to be more sensitive than ones with Fig. 10 Sensing responses of pure ZnO, ZnO–MoS2, Pt–ZnO–MoS2
smaller crystallite diameters. Sensitivity towards NO2 was found and Ag–ZnO–MoS2 film sensors towards 100 ppm CO gas (repro-
to be more pronounced under conditions of low temperature. duced from ref. 143 with permission from Elsevier).

1898 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

Fig. 11 Selectivity of the Ag–ZnO–MoS2 nanocomposite sensor

towards 100 ppm gas species of H2, CH4, CO, C2H2, C2H6 and C3H8
(reproduced from ref. 143 with permission from Elsevier). Fig. 13 Response of the Al-loaded and unloaded ZnO samples
towards 50 ppm CO at different operating temperatures (reproduced
from ref. 144 with permission from Elsevier).

of ZnO–MoS2. Metals with a lowered work function F would

therefore produce a SB of smaller magnitude. Hence, a metal
with a small work function is desirable for a reduced SB and concentrations of CO at 300  C (Fig. 14), the A3ZO sensor
therefore an enhanced sensitivity of the resultant nano- showed the best response. Thus, impregnating ZnO with a low
composite lm. Since Ag has a lower work function (4.26 eV) content of Al in the range of 1–3 wt% resulted in an enhanced
than that of Pt (5.65 eV), the Ag loaded ZnO–MoS2 gas sensing response towards CO sensing. Besides, a signicant response
nanocomposite lm elicited greatly elevated sensing could be observed at a very low CO concentration of 5 ppm.
responses towards CO. Using an improvised sol–gel proce- Also, since exposure of the Al-loaded ZnO samples to CO
dure, Hjiri et al.144 prepared an Al-doped ZnO gas sensor produced a decrease in the resistance of the samples, it was
showing excellent selectivity towards CO. Samples coded concluded that Al-doping sustained the n-type semi-
A0ZO, A1ZO, A3ZO and A5ZO had [Al/Zn] ratios of 0, 0.01, 0.03 conducting properties of the pristine ZnO. Exposure to CO
and 0.05, respectively. The response behaviour of all these caused a great variation in the resistance of the sensing lm
samples towards 50 ppm CO at various operating tempera- (Fig. 15). The signal was further found to go back to its initial
tures was monitored. The response (R0/R) of all samples baseline value aer each pulse indicating that the CO
initially increased with temperature, reached a maximum and adsorption on the surface layer was reversible. The following
then exhibited a decline (Fig. 13). At lower temperatures of 200 mechanism was furnished to explain the decrease of resis-
to 300  C, only A1ZO showed a better response than the other tance of Al-loaded ZnO upon exposure to CO:
samples that responded almost equally. However, in the
CO(gas) + O
(adsorbed) / CO2 + e

temperature range 300–400  C, all Al-loaded samples showed
a greater response than the unloaded ZnO. With different

(a) Schematic diagram of the Ag–ZnO–MoS2 nanocomposite sensor towards CO gas; (b) energy band diagram of the Ag–ZnO–MoS2
Fig. 12
nanocomposite (reproduced from ref. 143 with permission from Elsevier).

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1899
Nanoscale Advances Review

6 s and 94 s, respectively, and the gas sensor displayed repeat-

ability and brilliant stability. Another study146 reported a facile
three-stage synthesis of ZnO–SnO2 composite hollow spheres
for the selective sensing of ethanol by exploiting the synergic
benets of the n–n heterojunction. The basic properties of ZnO
played a pivotal role in the sensing mechanism via dehydroge-
nation of ethanol as elaborated in the work.

C2H5OH (g) / CH3CHO (g) + H2 (g) (basic oxide)

The CH3CHO intermediate is subsequently oxidized to form

CO2 and H2O, as depicted in the following equation:

CH3CHO (ad) + 5O
/ 2CO2 + 2H2O + 5e

Fig. 14 Response of AZO nanoparticles as a function of CO
concentration at a temperature of 300  C (reproduced from ref. 144
with permission from Elsevier). Therefore, the ZnO/SnO2 nanocomposite gas sensor
demonstrated a sharper response to ethanol gas than the pris-
tine SnO2 sensor. Moreover, a possible increase in the effective
barrier height of the n–n heterojunction enabled better
engagement with adsorbed oxygen causing greater depletion of
electrons from the conduction band eventually leading to an
enhanced gas sensing response by the system. Additionally,
remarkable detection at a lower (ppb) limit was shown by the
heterostructured sensor.

5.4 Cosmetic industry

Due to its antibacterial and good antifungal activity, zinc oxide
is widely used in production of various raw materials used in
medicine such as disinfectant agents and for dermatological
applications.147 ZnO NPs absorb UVA and UVB radiations and
can be used in sun protective creams.148
In a study by Reinosa et al.,149 it was brought to light that
a nano/micro-composite comprising nanosized TiO2 dispersed
Fig. 15 Response of the A3ZO sensor as a function of CO concen- on ZnO micro-particles showed a higher sun protection factor
tration at 300  C (reproduced from ref. 144 with permission from
(SPF) than individual TiO2 and ZnO particles. The SPF of the
Elsevier).
synthesized nano-sized TiO2 was found to be higher than that of
its micro-sized counterpart with the former showing maximum
absorption at 319 nm while the latter showed maximum
The electrons injected into the conduction band lower the
absorption at 360 nm. The synthesized micro-sized ZnO had
resistance of the Al-doped ZnO gas sensors. The response and
a higher SPF than its nano equivalent. Both exhibited maximum
recovery times observed for all Al-loaded ZnO samples were 6–
absorption at 368 nm. These data suggested that ZnO has
8 s sand 16–30 s, respectively. The unloaded ZnO sample was
a higher critical wavelength because it covers the entire UV
marked by longer response and recovery times of 30 s and 70 s,
range and has a higher UVA/UVB ratio since the maximum of
respectively. The sensing lms exhibited excellent thermo-
the SPF curve lies in the UVA region (Fig. 16a). Additionally, it
mechanical and electrical stability.
was observed that TiO2, with a lower UVA/UVB ratio owing to the
Chen et al.145 synthesized mesoporous ZnO sensors for
presence of the SPF maximum in the lower wavelength region,
selectively detecting ethanol under UV light at operating
has a lower critical wavelength (Fig. 16b). Therefore, to boost
temperatures lower than 150  C. With the assistance of a low-
the SPF output, a suitable combination of the two oxides was
powered UV LED (2 mW), outstanding response and selec-
thought out. A dry dispersion procedure was adopted to prepare
tivity towards varying concentrations (10 to 1000 ppm) of
the composite consisting of 15 wt% TiO2 NPs and 85 wt% ZnO
ethanol were demonstrated by the sensing layer at 80  C. UV
micro-structured particles. The results obtained from this
illumination induced electron–hole pairs that activated adsor-
composite were compared with those obtained by the standard
bed oxygen leading to their extensive interaction with ethanol
procedure. Raman spectroscopy revealed a superior dispersion
thereby eliciting a remarkable sensing response from the
of the NPs and their anchoring with higher quantum conne-
synthesized ZnO sensors. The response and recovery times were
ment resulting from dry dispersion by using ZnO micro-

1900 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

Fig. 16 SPF curves of COLIPA sunscreen incorporating an inorganic UV filter: nanometric (dashed lines) and micrometric (solid lines) (a) TiO2 and
(b) ZnO particles (reproduced from ref. 149 with permission from Elsevier).

structures as host particles. The SPF output was found to be commercialization of nanotechnological products. Research
higher for the sunscreen with the lter prepared by the dry seeking to manufacture fabrics with water-repellant, self-
dispersion method than the one with the lter synthesized cleaning and UV-blocking properties has, as a result, surfaced
following the standard method (Fig. 17). This observation was in recent years.150–156 The extended surface area and the corre-
chiey attributed by the authors to the correct dispersion of spondingly high surface energy associated with nanostructured
TiO2 NPs over the host ZnO micro-sized particles. materials enhance their affinity for fabrics and induce an
improvement in their textile properties. This, therefore,
warrants their increasingly widespread applications in the
5.5 Textile industry
textile sector.157
Water-repellent and self-cleaning bers come handy in the It has been shown in many research investigations that the
military world where laundering is difficult and inconvenient use of ZnO in the processing of fabrics promotes their anti-
with regard to both time and scope. On the other hand, in the bacterial and self-cleaning properties apart from upgrading
business sectors, water-repellant and self-cleaning fabrics their UV absorption capacity.158 Moreover, in textile applica-
become useful in preventing undesirable stains. Furthermore, tions, coatings of ZnO in the nano-dimensions aside from being
blocking the UV portion of sunlight is another aspect that has bio-compatible are found to exhibit air-permeability and UV-
long concerned researchers. All these facts eventually underline blocking ability far greater than their bulk equivalents.159
the massive potential offered by the textile industry for the Therefore, ZnO nanostructures have become very attractive as
UV-protective textile coatings. Different methods have been re-
ported for the production of UV-protective textiles utilizing ZnO
nanostructures. For instance, hydrothermally grown ZnO
nanoparticles in SiO2-coated cotton fabric showed excellent UV-
blocking properties.160 Synthesis of ZnO nanoparticles else-
where through a homogeneous phase reaction at high temper-
atures followed by their deposition on cotton and wool fabrics
resulted in a signicant improvement in UV-absorbing
activity.161 Similarly, ZnO nanorod arrays that were grown onto
a brous substrate by a low-temperature growth technique
provided excellent UV protection.162
Zinc oxide nanowires were grown on cotton fabric by Ates
et al.163 to impart self-cleaning, superhydrophobicity and ultra-
violet (UV) blocking properties. The ZnO nanowires were grown
by a microwave-assisted hydrothermal method and subse-
quently functionalized with stearic acid to obtain a water
contact angle of 150 , demonstrating their superhydrophobic
nature, which is found to be stable for up to four washings. The
Fig. 17 SPF curves of sunscreens with micro–nanocomposite filters.
UV protection offered by the resulting cotton fabric was also
The solid line represents the SPF curve of the new micro–nano
composite obtained by a nano-dispersion method and the dashed line examined, and a signicant decrease in transmission of radia-
represents the curve obtained by a standard method (reproduced from tion in the UV range was observed. The self-cleaning activity of
ref. 149 with permission from Elsevier).

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1901
Nanoscale Advances Review

the ZnO nanowire-coated cotton fabric was also studied, and cholerae (two biotypes of cholera bacteria (classical and El Tor))
this showed considerable degradation of methylene blue under by Sarwar et al.176 Strong arguments and detailed justications
UV irradiation. These results suggest that ZnO nanowires could of the toxicity mechanism emerged as a result of this rigorous
serve as ideal multifunctional coatings for textiles. investigation. The bacterial membrane bears an overall negative
Research on the use of zinc oxide in polyester bres has also charge that can be ascribed to the acidic phospholipids and
been carried out at Poznan University of Technology and the lipopolysaccharides in it while ZnO NPs possess a positive
Textile Institute in Lodz.164 Zinc oxide was obtained by an charge in water suspension. An initial NP–membrane interac-
emulsion method, with particles measuring approximately tion via electrostatic attraction may result from this charge
350 nm and with a surface area of 8.6 m2 g
1. These results difference following which membrane disruption occurs. As the
indicate the product's favourable dispersive/morphological and membrane plays an essential role by maintaining the vital
adsorption properties. Analysis of the microstructure and function of the cell, such damage induces depolarization of the
properties of unmodied textile products and those modied membrane, increased membrane permeabilization – loss in
with zinc oxide showed that the modied product could be membrane potential and protein leakage and denaturation
classed as providing protection against UV radiation and upon subsequent contact with ZnO NPs. Besides, ZnO NPs also
bacteria. have the ability of interacting with DNA as well as forming
abrasions on it. Signicant oxidative stress was also noticed
inside the bacteria cells. They thus arrived at a conclusion that
5.6 Antibacterial activity binding of ZnO NPs with the bacterial cell surface induces
The remarkable antibacterial activity of ZnO has recently membrane damage followed by internalization of NPs into the
received wide interest and efforts are being continuously made cells, leakage of cytoplasmic content, DNA damage and cell
to tune its size, concentration, morphology and defects to death. Disruption of the membrane by ZnO NPs would addi-
achieve enhanced properties of ZnO with regards to its powerful tionally give easy access of antibiotics into the cell. Their nd-
nanobiological toxicity.165,166 Currently, Gram-negative Escher- ings further corroborated a synergic effect produced by the
ichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. actions of ZnO NPs and antibiotics. They also encountered the
aureus) are largely chosen as prototype bacteria to investigate antibacterial activity of the ZnO NPs in cholera toxin (CT) mouse
the antibacterial activity of ZnO NPs.167,168 Some other Gram- models. It emerged that ZnO NPs could induce the CT
negative bacteria such as Vibrio cholerae (V. cholerae),169 Pseu- secondary structure collapse gradually and interact with CT by
domonas aeruginosa (P. aeruginosa),170,171 Proteus vulgaris (P. interrupting CT binding with the GM1 ganglioside receptor.181
vulgaris),73 and other Gram-positive bacteria such as Bacillus In bacteria treated with NPs of ZnO, it was observed that the
subtilis (B. subtilis)172 and Enterococcus faecalis (E. faecalis)173 are damage to cell membranes was an inevitable phenomenon. The
also subjected to investigations. It has been observed that ZnO pathways of the antibacterial activity of ZnO NPs were investi-
NPs synthesized via green routes responded with greater gated using Escherichia coli (E. coli) as a prototype organism.182
capacities of growth inhibition of Staphylococcus aureus, As was evident from the SEM images of E. coli obtained aer
Escherichia coli and the like than chemically synthesized ZnO treatment with ZnO NPs, a greater number of cell damage sites
NPs and other commonly used antimicrobials. Due to their were noted at higher doses of ZnO NPs. This cell damage has
small size and higher surface area to volume ratio, there is been ascribed to pathways involving both the presence and
a marked increase in the bioactivity of ZnO NPs. Although the absence of ROS. In the absence of ROS, the interaction of ZnO
mechanism by which ZnO NPs exhibit antibacterial activity is NPs with bacterial membranes would lead to damage to the
still being investigated in the world of research, the latest molecular structure of phospholipids culminating in cell
probes into this topic have revealed a few probable pathways: (a) membrane damage.
ZnO NPs are found to directly interact with the cell surfaces Jiang et al.183 studied the potential antibacterial mechanisms
causing a disruption of cell membrane permeability,174–176 (b) of ZnO NPs against E. coli. They reported that ZnO NPs with an
generation of ROS on the surface of the ZnO NPs, and (c) average size of about 30 nm caused cell death by coming into
particle dissolution and subsequent release of free Zn2+ ions in direct contact with the phospholipid bilayer of the membrane
the cytoplasm (and particularly cellular organelles such as and destroying the membrane integrity. The signicant role of
lysosomes which have lower pH values) causing a disruption of ROS production in the antibacterial properties of ZnO NPs
cellular zinc ion homeostasis which in turn leads to an elevation surfaced when it emerged that the addition of radical scaven-
of the ROS level inside cells, thereby destroying the integrity of gers such as mannitol, vitamin E, and glutathione could block
the plasma membrane and mitochondrial functions, and ulti- the bactericidal action of ZnO NPs. However, the antibacterial
mately inducing cell necrosis.177–180 It is also possible that the effect triggered by Zn2+ released from ZnO NP suspensions was
antibacterial effects of ZnO NPs are a cumulative consequence not apparent. Reddy synthesized ZnO NPs with sizes of 13 nm
of the aforesaid pathways. and investigated their antibacterial (E. coli and S. aureus)
Epidemic disease cholera mainly affects populations in activities.168 It was discovered that ZnO NPs effected complete
developing countries.169,180 It is a serious diarrheal disease cessation of the growth of E. coli at concentrations of about
caused by the intestinal infection of Gram-negative bacterium 3.4 mM but induced growth inhibition of S. aureus at much
V. cholerae. The effective antibacterial activity of ZnO NPs and lower concentrations ($1 mM). Besides, Ohira and Yama-
their mechanism of toxicity were explored against Vibrio moto184 also discovered that the antibacterial (E. coli and S.

1902 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

aureus) activity of ZnO NPs with small crystallite sizes was far coli and Staphylococcus aureus) and benecial effects on
more pronounced than for those with large crystallite sizes. microbes, such as Pseudomonas putida, which has bioremedia-
From ICP-AES measurement, it emerged that the amount of tion potential and is a strong root colonizer.193
Zn2+ released from the small ZnO NPs was much higher than Investigations into the antibacterial activities of ZnO micro-
from the large ZnO powder sample and E. coli was more sized particles, ZnO NPs, and ZnO NPs capped with oxalic acid
sensitive to Zn2+ than S. aureus. This is a further conrmation against S. aureus were carried out in the presence and absence
that eluted Zn2+ ions from ZnO NPs also play a key role in of light.194 It was observed that the efficiency of ZnO NPs was
antibacterial action. just 17% in the dark. However, their antibacterial properties
Iswarya et al.,185 having extracted crustacean immune mole- saw a surge up to 80% upon application of light. The antibac-
cule b-1,3-glucan binding protein (Phb-GBP) from the haemo- terial behaviour was greatest for ZnO NPs while it was minimum
lymph of Paratelphusa hydrodromus, successfully designed Phb- for ZnO micro-sized particles, suggesting a higher release of
GBP-coated ZnO NPs. The Phb-GBP-ZnO NPs were spherical Zn2+ ions from ZnO NPs than ZnO micro-sized particles. The
shaped having a particle size of 20–50 nm and halted the growth examination revealed that surface defects of the ZnO NPs
of S. aureus and P. vulgaris. S. aureus was found to be more boosted ROS production in the presence as well as absence of
prone to the bactericidal action of Phb-GBP-ZnO NPs than P. light. Additionally, it was also found that capping lowers the
vulgaris. In addition, Phb-GBP-ZnO NPs could induce drastic amount of superoxide radicals generated because capping
modication in cell membrane permeability and set off outra- blocks the oxygen vacancies that are chiey accountable for the
geous levels of ROS formation both in S. aureus and P. vulgaris. generation of superoxide radicals. In another investigation, the
This work was thus pivotal in bringing to the forefront the inuence of NP size on bacterial growth inhibition by ZnO NPs
immensely great antibacterial hallmark of Phb-GBP-ZnO NPs. and the mechanistic routes of their action were demon-
The mechanism of breaking into bacterial cells by strated.195 ZnO NPs with diameters ranging from 12 nm to
membrane disruption and then inducing oxidative stress in 307 nm were rst generated. Thereaer, they were administered
bacterial cells, thereby stalling cell growth and eventually to Gram-positive and Gram-negative microorganisms (Fig. 18).
causing cell death has been reported in many recent research The results clearly illustrated the greater bactericidal efficacy of
studies.186–191 Important bacterial biomolecules can also adsorb smaller ZnO NPs under dark conditions. The use of UV light
on ZnO NPs. Bacterial toxicity, in the recent past, has been resulted in an enhanced antibacterial behaviour of ZnO NPs
heavily reported to have resulted from structural changes in owing to the enhanced formation of ROS from them. The
proteins and molecular damage to phospholipids.192 The anti- antibacterial properties were rooted in the generation of ROS
bacterial activity of ZnO NPs thus nds its apt application in the and the build-up of ZnO nano-sized particles in the cytoplasm
discipline of food preservation. As a formidable sanitizing and on the external membranes.
agent, it can be used for disinfecting and sterilizing food In another intriguing investigation, the toxicity induced in
industry equipment and containers against attack and antibiotic resistant nosocomial pathogens such as Acinetobacter
contamination by food-borne pathogenic bacteria. ZnO NPs baumannii (A. baumannii) and Klebsiella pneumoniae (K. pneu-
showed both toxicity on pathogenic bacteria (e.g., Escherichia moniae) by photocatalytic ZnO NPs was studied.196 It was seen

Fig. 18 The influence of different sizes of ZnO NPs on the growth of a methicillin sensitive S. aureus strain. (A) Growth analysis curves obtained by
tracking the optical density at 600 nm. (B) Percentage of viable S. aureus recovered after treatment with ZnO NPs of different sizes (reproduced
from ref. 195 with permission from the American Chemical Society).

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1903
Nanoscale Advances Review

that A. baumannii and K. pneumoniae were signicantly utilization of this apparatus additionally enabled real-time
destroyed by 0.1 mg mL
1 of ZnO nano-structures with 10.8 J imaging of gene delivery.
cm
2 of blue light. Further, the mechanistic pathway of the Reports bearing evidence of the applications of ZnO NPs in
antibacterial activity of photocatalytic ZnO NPs against antibi- the delivery of chemotherapeutic agents to treat cancers have
otic deant A. baumannii was investigated. While cytoplasm emerged prolically in the last few years. For instance, a porous
leakage and membrane disruption of A. baumannii were evident ZnO nanorod based DDS (ZnO-FA-DOX), enclosing folic acid
aer treatment with ZnO NPs under blue light exposure, there (FA) as a targeting agent and doxorubicin (DOX) as a chemo-
was no sign of plasmid DNA fragmentation. Therefore, therapeutic drug, was fabricated by Mitra et al.204 The ZnO-FA-
membrane disruption could be associated with the mechanistic DOX nano-apparatus was found to exhibit pH-triggered
route via which the photocatalytic ZnO NPs demonstrated release of DOX and potent cytotoxicity in MDA-MD-231 breast
antibacterial activity. The possibility of the role of DNA damage cancer cells. The biocompatible nature of the ZnO-FA material,
therein was categorically ruled out. as observed from the acute toxicity study in a murine model also
A novel approach comprising a combined application of emerged from the investigation. In another research study by
ultrasonication and light irradiation to ZnO NPs has been Zeng et al.,205 a lymphatic-targeted DDS with lipid-coated ZnO-
developed to boost their antibacterial properties.197 The sono- NPs (L-ZnO-NPs) enclosing 6-mercaptopurine (6-MP) as an
photocatalytic activity of ZnO nanouids against E. coli was anticancer agent was designed. The L-ZnO-NP apparatus
tested. The results revealed a 20% rise in the antibacterial effi- demonstrated pH-susceptive drug release and remarkable
cacy of ZnO nanouids. Further, ROS generation by ZnO cytotoxicity to cancer cells as a result of the generation of
nanouids played a crucial role in bacterial elimination. The intracellular reactive oxygen species (ROS). Liu et al.206 also re-
sono-photocatalysis of ZnO nanouids also enhanced the ported the fabrication of DOX-loaded ZnO-NPs. The researchers
permeability of bacterial membranes, inducing more effica- encountered a pH-susceptive drug release from the DDS and
cious penetration of ZnO NPs into the bacteria. diminished drug efflux with enhanced cytotoxicity in drug
Although ZnO NPs make a promising antibacterial agent deant breast cancer cells (MCF-7R). Likewise, Li et al.207
owing to their wide-ranging activities against Gram-positive as fabricated a novel DDS enclosing hollow silica nanoparticles
well as Gram-negative bacteria, the exact antibacterial pathway (HSNPs) embedded with ZnO quantum dots to co-deliver DOX
of ZnO NPs has not been adequately established. Hence, deep and camptothecin. The nano-apparatus evinced pH-susceptive
investigations into it hold a lot of important theoretical and drug release and cytotoxicity to drug deant cancer cells. A
practical value. In the future, ZnO NPs can be explored as research study used ZnO NPs as caps to cover the pores of
antibacterial agents, such as ointments, lotions, and mouth- mesoporous silica NPs (MSNs), and when the designed drug
washes. Additionally, they can be overlayed on various delivery apparatus came into contact with acids, there took
substrates to prevent bacteria from adhering, spreading, and place a decomposition of ZnO NPs followed by a release of
breeding in medical devices. doxorubicin (DOX) molecules from the MSN nanostructures.208
One major drawback of such an apparatus was that it had
difficulty in degradation thereby resulting in an incomplete
5.7 Drug delivery release of drugs.209,210 Another scheme employed the technique
Nanotechnology has enabled the exploration of better and more of loading drugs onto the ZnO NPs directly.211 Upon contact
efficient avenues concerning drug delivery vehicles. Various with acids, the drug molecules are released following the
research studies suggest the potency of ZnO NPs for drug complete decomposition of ZnO NPs. In another investigation,
delivery in a number of diseases. ZnO NPs encapsulated with a liposome-incorporated ZnO-NP based DDS (ZNPs-liposome-
chitosan, bearing enhanced stability, were found to be effective DNR) enclosing anticancer drug daunorubicin (DNR) was
for importing doxorubicin (DOX) into cancer cells in a recent designed by Tripathy et al.212 The incorporation of ZnO-NPs in
study.195 In various other studies, ZnO NPs were successfully the DDS was observed to prevent the premature release of DNR,
used as vehicles for gene delivery and gene silencing (Fig. 17 which could be prompted only in acidic medium, thereby effi-
and 18).198–200 The use of this apparatus for gene delivery had ciently exerting an anticancer effect on A549 cells. The study of
advantages. For example, the expression of plasmid containing intracellular release in cancer cells with confocal laser scanning
genes on the surface of nanoparticles could ensure safe and microscopy (CLSM) revealed that treatment with ZNPs-
efficient gene targeting to the recipient tissues201,202 enabling the liposome-DNR induced a marked DNR release, causing
nanoparticles to be used as suitable tools for targeting genes to greater cytotoxicity to cancer cells, compared to pure DNR and
various cells such as tumor cells. Nie et al.199 in their study DNR-conjugated liposomes (liposome-DNR), as evidenced by
discovered that synthesized ZnO tetrapod-like nanostructures the green uorescence intensity. For the treatment of lung
could be used as pioneering vehicles for gene delivery. They cancer, Cai et al. accomplished the construction of ZnO
showed that silica-coated amino-modied tetrapod-like ZnO quantum dot-based drug delivery apparatus that was conju-
nanostructures could, via electrostatic interactions, effectively gated with a targeting agent (hyaluronic acid) and an anticancer
bind to DNA which in turn improved the transfection efficiency agent (DOX).213 The nano-apparatus demonstrated CD44
of melanoma cells. In another study conducted by Zhang et al., receptor-specic uptake and pH-driven drug release in lyso-
it was unveiled that polycation-capped ZnO quantum dots had somal compartments of the cancer cells. Kumar et al.214 also
the potential to deliver DNA into COS-7 cells.203 Further, the designed sub-micron sized self-assembled spherical capsules of

1904 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

Fig. 19 Schematic illustration of possible processes of ZnO nanorods encapsulating chemotherapeutic agents for anticancer therapy (repro-
duced from ref. 216 with permission from Elsevier).

ZnO nanorods that successfully effected the delivery of anti- nanorods could raise the drug's targeting efficiency and mini-
cancer agent DOX to K562 cancer cells. Furthermore, Han mize the associated toxicity. Therefore, the DNR–ZnO hybrid
et al.215 also synthesized ZnO NPs conjugated with an aptamer nano-apparatus with UV irradiation was claimed to have the
as a functionalization agent and DOX as an anticancer agent potential of a fruitful scheme for the treatment of cancers
and demonstrated the effect of combined chemo- and radiation (Fig. 20 and 21). In another study, Ye et al.217 using a copoly-
therapy in MCF-7 breast cancer cells employing the nano- merization process also prepared water soluble ZnO–polymer
apparatus. Recently, Zhang et al.216 as a part of their investiga- core–shell quantum dots, and designed a drug delivery appa-
tion devised a new scheme to restrain the proliferation of ratus based on these quantum dots containing Gd3+ ions and
human hepatocarcinoma cells (SMMC-7721) via a combined anticancer drug DOX. The ZnO-Gd-DOX nano-system was found
application of ZnO nanorod based DNR in photodynamic to be biocompatible, pH-responsive and led to a marked release
therapy (PDT), where ROS generation had the possibility to play of DOX into the acidic environment of cancer-afflicted cells and
a key role in the net anticancer behaviour of the hybrid nano- tumors. When administered to human pancreatic cancer (BxPC-
apparatus (Fig. 19). The researchers further discovered that
ZnO NPs were able to transport a larger quantity of DNR via
internalization into SMMC-7721 cells, thereby inducing
outstanding restraint on the multiplication of these cancerous
cells. Besides, UV irradiation on this drug delivery nano-
apparatus further reinforced the arrest of cell proliferation
through photocatalysis of ZnO nanorods. To look into the
signaling pathway of anticancer activity of the DDS in PDT, the
researchers monitored the caspase-3 activity, which is a hall-
mark of apoptosis. The results of immunocytochemistry study
conrmed that upon treatment with a DNR–ZnO nano-
composite under UV irradiation, the cells demonstrated far
Fig. 20 Possible mechanism of ROS production by ZnO nanorods
more pronounced activation of caspase-3 molecules in cancer-
under UV irradiation (reproduced from ref. 216 with permission from
afflicted cells. It was consequently proposed that ZnO Elsevier).

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1905
Nanoscale Advances Review

Fig. 21 Cytotoxicity of DNR or the DNR–ZnO nanocomposite in the absence or presence of UV irradiation against SMMC-7721 cells. The inset
graph shows the IC50 of DNR and the DNR–ZnO nanocomposite in the absence or presence of UV irradiation for SMMC-7721 cells (reproduced
from ref. 216 with permission from Elsevier).

3) tumor containing nude mice, this polymer-modied drug a marked decrease with a rise in ZnO concentration221,222 with
delivery nano-apparatus was found to display higher thera- minimal damage to healthy cells.
peutic efficiency compared to the FDA-approved liposomal DOX The mitochondrial electron transport chain is known to be
formulation DOXIL at 2 mg kg
1 DOX concentration. The closely linked to intracellular ROS generation, and anticancer
histopathology study and ICP-AES analysis of the vital organs agents accessing cancer cells could impair the electron trans-
further conrmed that this ZnO-Gd-DOX nano-apparatus could port chain and release huge amounts of ROS.223,224 However, an
substantially bring about growth-inhibition of tumors without inordinate amount of ROS brings about mitochondrial damage
exerting any toxic effects 36 days post administration. Addi- thereby resulting in the loss of protein activity balance that
tionally, the histopathology study of tumor sections also eventually induces cell apoptosis.225 ZnO NPs introduce certain
demonstrated severe damage to the tumor cells caused by the cytotoxicity in cancer cells chiey by a mechanism that involves
administration of the DDS, compared to the control, DOX and a higher intracellular release of dissolved Zn2+ ions, followed by
DOXIL groups. enhanced ROS induction and induced cancer cell death by way
of the apoptosis signaling pathway. The effects of ZnO NPs on
human liver cancer HepG2 cells and their possible pharmaco-
5.8 Anti-cancer activity
logical mechanism were investigated by Sharma et al.226 They
Cancer, a condition of uncontrolled malignant cell prolifera- observed that ZnO NP-exposed HepG2 cells exhibited higher
tion, has typically been subjected to treatment by chemo- cytotoxicity and genotoxicity, which were related to cell
therapy, radiotherapy, and surgery during the past several apoptosis conciliated by the ROS triggered mitochondrial route.
decades. Although in theory all these therapies appear to be The loss of the mitochondrial membrane potential led to the
exquisitely effective in killing cancer cells, these non-specic opening of outer membrane pores following which some
therapy methods also introduce a lot of serious side effects.218 related apoptotic proteins including cytochrome c were released
Recently, nanomaterial-based nanomedicine possessing high into the cytosol thereby activating the caspase in due course.
biocompatibility, easy surface functionalization, cancer target- Mechanistic studies had proved that the loss of mitochondrial
ing, and drug delivery capacity has displayed the much coveted membrane potential-mediated HepG2 cell apoptosis was
air to rise above these side effects. Substantial research prog- mainly due to the decrease in mitochondrial membrane
ress has been made in biocompatible nanosized zinc oxide potential and Bcl-2/Bax ratios as well as accompanying the
(ZnO) because of its unique physical properties. ZnO nano- activation of caspase-9. Besides, ZnO NPs could noticeably
materials, inspired by the fact that Zn2+ is an essential nutrient activate p38 and JNK and induce and attract p53ser15 phos-
for adults, are considered to be safe in vivo. Considering these phorylation but this was not dependent on JNK and p38 path-
leverages, ZnO NPs can be aptly chosen as biocompatible and ways (Fig. 21). These results afforded valuable insights into the
biodegradable nano-platforms and can also be investigated for mechanism of ZnO NP-induced apoptosis in human liver
cancer treatment.219,220 HepG2 cells. Moghaddam et al.227 took recourse to biogenic
Several studies have thus suggested the cytotoxic effects of synthesis and successfully generated ZnO NPs using a new
ZnO NPs on cancer cells. The cancer cell viability percentage on strain of yeast (Pichia kudriavzevii GY1) and examined their
the MCF7 cell line, A549 cell line, HL60 cell line and VERO cell anticancer activity in breast cancer MCF-7 cells. ZnO NPs have
line has been studied at various concentrations of ZnO. Results been observed to exhibit powerful cytotoxicity against MCF-7
show that the cell viability of the above cell lines exhibits

1906 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

cells. This cytotoxicity is affected more likely via apoptosis than terminate cancerous cells.231–234 An attempt was made to utilize
cell cycle arrest. The apoptosis induced by ZnO NPs was largely the synergic effects of anticancer drugs with ZnO NPs in PDT to
by way of both extrinsic and intrinsic apoptotic pathways. A few induce cell-death in cancer cells.231 The cytotoxic effects of
antiapoptotic genes of Bcl-2, AKT1, and JERK/2 were subjected daunorubicin (DNR), an anti-cancer drug, on drug deant
to downregulation, while upregulation of some proapoptotic leukemia K562/A02 cancer cells were put to the test in combi-
genes of p21, p53, JNK, and Bax was prompted. ZnO NPs have nation with ZnO NPs. The combination of DNR and ZnO NPs
been widely employed in cancer therapy and reported to under UV irradiation could appreciably check the proliferation
promote a selective cytotoxic effect on cancer cell proliferation. of drug-deant cancer cells in a dose-dependent manner.
Chandrasekaran and Pandurangan evaluated the cytotoxicity of Additionally, ZnO NPs were found to induce an enhanced
ZnO nanoparticles against cocultured C2C12 myoblastoma cellular uptake of DNR.
cancer cells and 3T3-L1 adipocytes. The study revealed that ZnO An anticancer treatment using DNR-conjugated ZnO nano-
NPs could be more cytotoxic to C2C12 myoblastoma cancer cells rods in PDT was investigated with human hepatocarcinoma
than 3T3-L1 cells. Compared to 3T3-L1 cells, it emerged that cells (SMMC-7721) (Fig. 19).216 The fabrication of photo-excited
ZnO NPs stalled C2C12 cell proliferation and brought about ZnO nanorods with DNR displayed an outstanding boost in the
a more pronounced apoptosis by way of a ROS-conciliated anticancer properties of the ZnO nanorods (Fig. 20). The ZnO
mitochondrial intrinsic apoptotic route, an upregulation of nanorods raised the intracellular concentration of DNR and
p53, tempered Bax/Bcl-2 ratio, and caspase-3 routes.228 augmented the anticancer efficiency. This is further evidence of
In a study, biogenic zinc oxide nanoparticles (ZnO NPs) were the drug carrying capacity of ZnO nanorods into target cancer
developed from aqueous Pandanus odorifer leaf extract (POLE) cells. UV irradiation additionally reinforced the growth inhibi-
with spherical morphology and approximately 90 nm size.229 tion of cancerous cells via photocatalytic activity of ZnO nano-
The anticancer activity of the ZnO NPs was evaluated by MTT rods. In this study, the promoted mortality of cancer cells
assay and neutral red uptake (NRU) assays in MCF-7, HepG2 indicates that ZnO nanorods under UV irradiation could effi-
and A-549 cells at different doses (1, 2, 5, 10, 25, 50, and 100 mg ciently induce the formation of ROS and further attack the cell
mL
1). Moreover, the morphology of the treated cancer cells membrane (mainly by lipid peroxidation), nucleic acids, and
was examined by phase contrast microscopy. The results proteins (such as enzyme deactivation). The mechanism of ROS
suggest that the synthesized ZnO NPs inhibited the growth of generation of ZnO nanorods under UV irradiation is displayed
the cells when applying a concentration from 50–100 mg mL
1. in Fig. 21. ZnO is a direct band gap semiconductor with a band
Overall, the study demonstrated that POLE derived biogenic gap energy of 3.36 eV at room temperature, high exciton
ZnO NPs could serve as a signicant anticancer agent. Phyto- binding energy of 60 meV and high dielectric constant, which
mediated synthesis of metal oxide nanoparticles have become under UV irradiation will produce a hole (h+) in the valence
a key research area in nanotechnology due to its wide applica- band and an electron (e
) in the conduction band, namely
bility in various biomedical elds. The work by Kanagamani electron/hole pairs. These electron/hole pairs will induce
et al.230 explored the biosynthesis of zinc oxide nanoparticles a series of photochemical reactions in an aqueous suspension
(ZnO-NPs) using Leucaena leucocephala leaf extract. Bio- of colloidal ZnO nanorods, generating ROS. Generally, at the
synthesized ZnO-NPs were found to have a wurtzite hexagonal surface of the excited ZnO nanorods, the valence band holes
structure with particles distributed in the range of 50–200 nm as abstract electrons from water and/or hydroxyl ions, generating
conrmed by TEM studies. The anticancer activity of ZnO-NPs hydroxyl radicals (cOH). Electrons reduce O2 to produce the
against MCF-7 (breast cancer) and PC-3 (human prostate superoxide anion O2
c. ZnO nanorods can be one of the
cancer) cell lines was evaluated using 3-(4,5-dimethylthiazol-2- promising nanomaterials for PDT in cancer.
yl)-2,5-diphenyltetrazolium bromide (MTT) assay. From the The size of ZnO NPs has been reported to have a strong
assay, biosynthesized ZnO-NPs were found to have better cyto- association with their anticancer activities. The UV light-
toxic activity on PC-3 cell lines than MCF-7 cell lines. The in vitro activated anti-cancer effects of various ZnO NPs with different
cytotoxicity studies of biosynthesized ZnO-NPs against Dalton sizes have been examined against human hepatocarcinoma
lymphoma ascites (DLA) cells revealed better antitumor activity cells (SMMC-7721).232 To achieve synergetic cytotoxicity,
with 92% inhibition at a ZnO-NP concentration of 200 mg mL
1, a combination of ZnO NPs and an anticancer agent, DNR, was
and as the concentration increased, the anticancer efficiency subjected to investigation. A schematic illustration of the anti-
also increased. These results suggested that ZnO NPs could cancer effect of DNR-conjugated ZnO NPs under UV irradiation
selectively induce cancer cell apoptosis making them a bright is shown in Fig. 22. The outcome showed higher cytotoxicity of
candidate for cancer therapy. smaller NPs. UV irradiation greatly boosted the cytotoxic effect
Photodynamic therapy requires the administration of on SMMC-7721 cells treated with ZnO NPs via generation of ROS
a photosensitizing agent that is subjected to activation by light and a consequent cell apoptosis. Additionally, when the ZnO
of a specic wavelength thereby generating ROS. The applica- NPs were conjugated with DNR, their cytotoxicity against the
tion of ZnO NPs as effective photosensitizers can be ascribed to cancer cells further increased by leaps and bounds.
their capability to generate ROS in response to visible light or To secure concomitant intracellular drug delivery and PDT
UV light. Recent studies exhibited that photo-triggered toxicity for cancer treatment, poly(ethylene glycol) (PEG)-capped ZnO
of ZnO NPs renders them aptly suitable for targeted PDT in NPs enclosing DOX were fabricated.233 It was found that DOX-
a spatiotemporal manner, providing a surer way to selectively loaded PEG-ZnO NPs on exposure to UV irradiation achieved

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1907
Nanoscale Advances Review

Fig. 22 The schematic image of ZnO nanoparticle cytotoxicity and the PDT process in cooperation with daunorubicin in vitro (reproduced from
ref. 232 with permission from SpringerOpen).

signicantly enhanced cell cytotoxicity through light-driven tetra(o-aminophenyl)porphyrin (MTAP)-conjugated ZnO nano-
ROS production from the NPs. The synergistic anticancer composites were fabricated and examined for synergistic PDT
activity of a combined treatment with PEG-ZnO NPs and DOX against ovarian cancer cells.236 The MTAP-ZnO NPs induced
under UV irradiation came to the fore as a result of this generation of ROS upon UV irradiation, the controlling
investigation. parameters being concentration and light intensity. It emerged
Likewise, poly(vinylpyrrolidone) (PVP)-capped ZnO nanorods that 30 mM MTAP-ZnO NPs wielded high light-induced toxic
(PVP-ZnO nanorods) were designed as a drug carrying nano- effects in cancer-afflicted ovarian cells under UV illumination,
apparatus for the delivery of daunorubicin (DNR), as well as while they remained inactive in the dark. The cytotoxic activity
a photosensitizer for PDT.234 The DNR-loaded PVP-ZnO nano- of MTAP-ZnO NPs under UV illumination was markedly boosted
rods (DNR-PVP-ZnO) encouraged an exceptional upswing in the weighed against that of porphyrin alone.235 This study eluci-
anticancer activity of DNR due to elevated cellular uptake of the dated the targeted and synergistic PDT by nanoparticles of ZnO
DNR delivered by the nanorods. The DNR-PVP-ZnO nanorods loaded with photosensitizing substances. ZnO NPs were
also demonstrated efficient PDT under UV light irradiation. It combined with protoporphyrin IX (PpIX) as a drug delivery
has been demonstrated that NPs can furnish solutions to nano-apparatus for photosensitizers.237 Simple ZnO NPs and
confront the acute demerits of conventional photosensitizers.235 PEG-capped ZnO NPs were synthesized and examined for their
By a dramatic enhancement of the solubility of photosensi- cancer-eliminating effect against human muscle carcinoma
tizers, NPs can facilitate their increased cellular internalization. cells. In the absence of laser light, ZnO NPs at 1 mM concen-
They also upgrade the target-specicity of photosensitizers by tration were found to exert very low cytotoxicity (98% viability).
way of passive targeting to tumor tissues through the enhanced In the presence of 630 nm laser light, PEG-capped ZnO NPs
permeability and retention (EPR) effect. Further, cell-specicity loaded with PpIX exhibited outstanding cytotoxicity owing to
of photosensitizers can be remarkably increased by surface the increased ROS generation. Additionally, a high build-up of
modication of the NPs to bind active targeting components. PpIX in the tumor area was observed when it was delivered by
Complexation of ZnO NPs with other photosensitizers has been ZnO NPs, exhibiting the potency of ZnO NPs as a tumor-
widely researched to increase the efficacy of ZnO NPs in PDT by selective drug delivery system for photosensitizers.
synergistically enhancing the ROS generation.234,235 Meso-

1908 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

5.9 Anti-diabetic activity interleukins, eventually resulting in the development of

cardiovascular diseases. Hussein et al. designed ZnO NPs using
Diabetes mellitus has been deemed to be among the most
hydroxyl ethyl cellulose as a stabilizing agent to alleviate dia-
serious public health scares, and according to the WHO 2014
betic complications.247 The study demonstrated that ZnO NPs
estimation, there are more than 400 million adults with dia-
could signicantly decrease malondialdehyde (MDA), fast blood
betes all over the world.238 It has been known to mankind for
sugar and asymmetric dimethylarginine (ADMA) levels. The
more than 2000 years.239 Diabetes mellitus is a cluster of lifelong
inammatory markers, interleukin-1 (IL-1a) and CRP, were also
progressive metabolic diseases caused by the body's incapacity
to produce insulin or by the ineffective use of the insulin notably lowered aer ZnO NP treatment, concomitant with
produced which in turn induces a high blood glucose level a rise in nitric oxide (NO) and serum antioxidant enzyme (PON-
1) levels in diabetic rats.
(hyperglycemia).240–244 Insulin therapy oen forms a critical part
An investigation was conducted in 2014 into the anti-
of the treatment for people with diabetes. The goal of insulin
diabetic potential of ZnO NPs in streptozotocin-induced dia-
therapy is to maintain the optimum blood glucose level.
betic albino (Sprague-Dawley) rats.243 The researchers inferred
Nevertheless, the use of insulin gives rise to several complica-
that the administration of ZnO NPs in diabetic rats brought
tions, viz., insulin resistance, fatty liver, brain atrophy, etc.247
about a marked lowering of the blood glucose level, boosted the
This has prompted a number of scientic investigations in
recent years to discover new alternative therapeutic schemes for serum insulin level, and elicited the expression of insulin
checking diabetes via a nanomedicine approach. Zinc is a trace receptor and GLUT-2 proteins, suggesting the inherent capacity
of ZnO NPs for diabetic remedy. The anti-diabetic activity of
element and a mineral found in abundance in all human
ZnO NPs in streptozotocin-induced diabetic (types 1 and 2)
tissues and tissue uids. Zinc has a distinct reputation for
Wistar rats was also demonstrated by Umrani et al. in their
maintaining the structural integrity of insulin. It plays a vital
research work.248 The research revealed that ZnO NPs raised the
role in the secretion of insulin from pancreatic cells. It also
levels of parameters like glucose, insulin, and lipid in rats
participates in the synthesis, storage, and secretion of
attesting to the efficient anti-diabetic activity of ZnO NPs. The
insulin.245 The deciency of zinc has further been observed to be
related to the progress of diabetes and associated complica- same research group recently undertook an enquiry into the
tions. All these reasons make zinc-based therapy an attractive mechanistic pathway behind the anti-diabetic properties of ZnO
NPs in vitro.249 They demonstrated that ZnO NPs led to protein
strategy for scientists to combat diabetes. Accordingly, the anti-
kinase B (PKB) activation, enhanced glucose transporter 4
diabetic potential of ZnO has been put under scrutiny by a large
(GLUT-4) translocation and uptake of glucose, reduced glucose
number of researchers of late.
6 phosphatase expression, proliferation of pancreatic beta cells,
A natural extract of red sandalwood (RSW) as an effective
etc., which were critically responsible for the anti-diabetic
anti-diabetic agent in conjugation with ZnO NPs has been
behaviour of ZnO NPs. The antidiabetic effectiveness of ZnO
tested by Kitture et al.246 The anti-diabetic activity was evaluated
with the help of a-amylase and a-glucosidase inhibition assay nanoparticles prepared using U. diocia leaf extract for treating
with murine pancreatic and small intestinal extracts. Results alloxan-caused diabetic rats was evaluated.250 From the char-
acterization of the samples, the envelopment of extract over the
revealed that the ZnO–RSW conjugate effected a moderately
ZnO-extract sample resulted in individual particles with
higher percentage of inhibition (20%) against porcine pancre-
enhanced properties compared to bulk ZnO. The occurrence of
atic a-amylase and proved more effective against the crude
the nettle phytochemicals linked to the ZnO-extract sample was
murine pancreatic glucosidase than either of the two compo-
veried by various techniques, especially using TGA, FT-IR, and
nents alone (RSW and ZnO NPs). The conjugated ZnO–RSW
GC-MS analyses. Among all the employed treatments, the ZnO-
induced 61.93% inhibition in glucosidase while the bare ZnO
NPs and RSW exhibited 21.48 and 5.90% inhibition, extract performed the best for controlling the common
respectively. complications accompanying diabetes. This biologically
produced sample signicantly lowered the levels of Fasting
In an investigation conducted to compare the anti-diabetic
Blood Sugar (FBS), Total Triglycerides (TG), and Total Choles-
activity and oxidative stress of ZnO NPs and ZnSO4 in diabetic
terol (TC) and enhanced the high-density lipoprotein choles-
rats it was observed that ZnO NPs with small dimensions at
terol (HDLC) and insulin levels in the diabetic rats when
higher doses (3 and 10 mg kg
1) had a much greater antidia-
compared to the rest of the remedies. The results conrmed the
betic effect compared to ZnSO4 (30 mg kg
1). The observation
synergistic relationship between ZnO and U. diocia leaf extract
was backed up by a marvelous decline in the blood glucose level,
a steep rise in the insulin level and a renement of the serum where ZnO-extract performed the best compared with the only
zinc status in a time- and dose-dependent manner. However, it extract and ZnO. From the results, the as-prepared ZnO-extract
sample can be introduced as a non-toxic, applicable, and active
was nally inferred in the study that ZnO nanoparticles severely
phyto-nanotherapeutic agent for controlling diabetes
elicited oxidative stress particularly at higher doses corrobo-
complications.
rated by the altered erythrocyte antioxidant enzyme activity,
ZnO nanoparticles were synthesized using a microwave-
enhancement in malondialdehyde (MDA) production, and
assisted method in the presence of Vaccinium arctostaphylos L.
remarkable drop in serum total antioxidant capacity.240 Hyper-
fruit extract.251 A decrease in crystallite size was observed for the
glycemia can squarely trigger off an inammatory state via
activation of C-reactive protein (CRP) and cytokines, such as biologically synthesized ZnO compared to the chemically
synthesized sample. Furthermore, the existence of organic

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1909
Nanoscale Advances Review

moieties over the biologically synthesized ZnO NPs was models. The anti-inammatory activity of ZnO NPs is not just
approved using characterizing methods. Then, the alloxan- restricted to the treatment of atopic dermatitis but has also
induced diabetic rats were divided into an untreated diabetic produced great results in combatting other inammatory
control group and a normal healthy control group, and the diseases. Nagajyothi et al. made ZnO NPs using the root extract
groups received insulin, chemically synthesized ZnO, plant of P. tenuifolia and the anti-inammatory activity was investi-
extract, and biologically synthesized ZnO. Aer treatment, gated in LPS-stimulated RAW 264.7 macrophages.257 ZnO NPs
fasting blood glucose (FBS), high-density lipoprotein (HDL), exhibited outstanding anti-inammatory activity via dose-
total triglyceride (TG), total cholesterol (TC) and insulin were dependently suppressing NO production as well as the related
measured. Analysis showed a signicant decrease in FBS and protein expressions of iNOS, COX-2, IL-1b, IL-6, and TNF-a. The
increase in HDL levels in all groups under treatment. However, ZnO NPs synthesized by Thatoi et al. under photoconditions
the results for cholesterol reduction were only signicant for the using the aqueous extracts of two mangrove plants, Heritiera
group treated with biologically synthesized ZnO. Despite the fomes and Sonneratia apetala, were found to possess a higher
changes in the triglyceride and insulin levels, the results were potential for anti-inammatory activity (79%) compared to
not signicant. For all the studied parameters, bio-mediated silver nanoparticles (69.1%).258 Thus, ZnO NPs also have the
ZnO NPs were found to be the most effective in treating the potential to be employed for anti-inammatory treatment.
alloxan-diabetic rats compared to the other studied treatment
agents. All reports of ZnO NPs for diabetes treatment indicated 5.11 Immunotherapy
that ZnO NPs could be employed as a promising agent in
In the past few decades, immunotherapy, via the delivery of
treating diabetes as well as attenuating its complications.
immune molecules (antigens, adjuvants, and antibodies), has
become a leading-edge strategy to battle against different
5.10 Anti-inammatory activity diseases.259 However, delivery of these molecules in a targeted
manner to achieve therapeutic benets has remained a major
Inammation is a part of the complex biological response of
challenge. In this context, nanotechnology plays a key role in
body tissues to harmful stimuli, viz., pathogens, damaged cells,
the development of schemes for delivering protably different
or irritants.252 It functions to localize and eliminate the inju-
types of immune molecules for vaccination, adjuvant therapy,
rious agent and to remove damaged tissue components so that
and immunotherapy. Recently, ZnO NPs garnered ample
the body can begin to heal. The response consists of changes in
interest in the eld of immunotherapy. For instance, Roy
blood ow, an increase in permeability of blood vessels and the
et al.260 brought the adjuvant effect of ZnO NPs when intraper-
migration of uid proteins and white blood cells (leukocytes)
itoneally administered with ovalbumin (OVA) to the forefront.
from the circulation to the site of tissue damage. Inammation
They illustrated that the serum levels of IgG1 and IgE were
is thus a defense mechanism that evolved in higher organisms
signicantly increased as a result of treatment with ZnO NPs. In
to protect them from infection and injury. In the wake of several
another study,259 researchers fabricated iron oxide–zinc oxide
bio-medical applications of ZnO NPs, the anti-inammatory
core–shell nanoparticles and demonstrated their cell imaging
effects of ZnO NPs have garnered wide interest among
feature and delivery of carcinoembryonic antigen (CEA) to
researchers. Atopic dermatitis (AD) is a chronic inammatory
dendritic cells (DC). The study reported that aer immunizing
skin disease. It is characterized by a signicant disruption of the
the mice with DC loaded with zinc oxide/iron oxide nano-
skin-barrier which is associated with complex interaction
composites impregnated with ZBP (ZnO binding peptide) and
between genetic and environmental factors.253,254 Textiles have
CEA, enhanced tumor regression was observed with an
the longest and most intense contact with the human skin.
improved survival rate, compared to other treatment equiva-
Wiegand investigated the role of ZnO-functionalized textile
lents, including ZBP-CEA, nanoparticle/CEA, CEA, nano-
bers in the control of oxidative stress in AD in vitro and in
particles and only DC (Fig. 23).
vivo.255 It emerged from the study that there was an obvious
improvement in AD pruritus and subjective sleep quality when
AD patients wore the ZnO textiles overnight on 3 consecutive 5.12 Wound healing
days. This is likely owing to the high anti-oxidative and intense Wound healing is a complex and remarkable biological course
antibacterial potential of the ZnO textile. Ilves et al.256 explored of action a body resorts to in order to replace devitalized and
whether ZnO NPs of different sizes would be able to penetrate missing cellular structures and tissue layers. The process
injured skin and injured allergic skin in the mouse AD model. usually consists of four phases: coagulation of blood, inam-
Their experiments clearly offered vivid evidence of the fact that mation, proliferation, and tissue remodeling.261,262 It is widely
only nano-sized ZnO was able to reach into the deep layers of known that the healing process is subjected to a setback under
the allergic skin, while bulk-sized ZnO stayed in the upper layers several pathological circumstances such as major blood loss,
of both damaged and allergic skin. Compared with bulk-sized diabetes, antibacterial infection, etc.,263 which warrants the
ZnO, nano-sized ZnO exerted higher anti-inammatory effects treatment of wounds urgently with utmost care.264 The use of
by drastically cutting down on pro-inammatory cytokines (IL- several wound dressings made of natural (alginate, chitosan,
10, IL-13, IFN-g, and Th2 cytokines) in the mouse model of gelatin, etc.)265 and synthetic (polyvinyl alcohol, polyurethane,
AD. These results conrmed that ZnO NPs with a small size had polylactic acid, etc.)266–268 polymers to heal wounds is quite
remarkable effects on reducing skin inammation in AD common. However, synthetic polymer-based wound dressings

1910 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

Fig. 23 Tumor growth and survival of immunized mice. (A) Tumor volume (left) and survival rate (right) of mice (five mice per group) injected with
MC38/CEA cells. (B) Tumor growth in human CEA-transgenic mice (five mice per group) inoculated with MC38/CEA cells (reproduced from ref.
259 with permission from Nature Publishing Group).

present some disbenets such as toxicity of the degraded NPs oen nd use in wound-healing applications. In an inves-
product and non-hemostatic properties. Notwithstanding that tigation by Diez-Pascual et al.269 castor oil (CO)-based biocom-
natural polymers are biocompatible, non-immunogenic and patible polymeric lms containing CS-decorated ZnO-NPs
biodegradable, wound dressings containing these polymers too (#5 wt%) were developed and their wound-healing capacity in
suffer from some disadvantages. For instance, the ionic Sprague-Dawley rats was put under scrutiny. They demon-
compounds of alginate, especially calcium salts, might induce strated that the hybrid nano-wound-healing-apparatus was able
swelling and degradation while chitosan (CS) is greatly to effect wound-healing in rats at a greater pace than effected by
amenable to degradation by lysozyme.261 In the light of these the administration of only castor oil-based polymer or gauze
complications, researchers seek incorporation of nano- (control experiment), as clearly evident from the snapshots of
materials into wound dressing materials to prevail over these wounds at different points of time (Fig. 24).
drawbacks. Among different metal-based nanomaterials, ZnO

Fig. 24 Photographs of the wounds treated with (1) CO/CS-ZnO (5.0 wt%), (2) CO, and (3) gauze as a control at (A) day 0, (B) day 5, and (C) day 14
(reproduced from ref. 269 with permission from the American Chemical Society).

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1911
Nanoscale Advances Review

The ensuing results revealed that, two weeks aer adminis- electrostatic interaction with the loaded CS hydrogel. The
tration, the synthesized nanocomposite induced a 90% reduc- antibacterial efficacy could reach 98.90% and 99.50% against S.
tion of wound area, while mere 70% wound repair was noted in aureus and E. coli bacteria, respectively, with a low-cost, rapid,
the control experiment thereby bearing evidence of its and effective treatment. ZnO QDs in antibacterial nanoplat-
commanding wound-xing capacity. Augustine et al.270 also forms could immediately produce ROS and Zn2+ under acidic
fabricated ZnO NP decorated polycaprolactone (PCL) scaffolds intracellular conditions. In parallel, when exposed to 808 nm
and demonstrated that their implantation was able to boost laser irradiation, hyperthermia from GO sheets could simulta-
faster wound-xing by elevating the proliferation and migration neously kill bacteria. Thus, the excellent performance of the
of broblasts in an in vivo model (wound-healing model of material stems from the combined effects of hyperthermia
American satin guinea pigs), without showing any marked signs produced under the near-infrared irradiation of GO sheets,
of inammation. Similarly, Bellare et al.271 designed biocom- reactive oxygen species, the release of Zn2+ from ZnO QDs under
patible ZnO NP based scaffolds of gelatin and poly(methyl vinyl an acidic environment, and the antibacterial activity of the
ether)/maleic anhydride (PMVE/MA) with remarkable antibac- hydrogel. This work demonstrated that the synergy of antibac-
terial effects. Their report threw light on the ability of the terial nanoplatforms could be used for wound anti-
scaffolds for endothelial progenitor cell (EPC) adhesion and inammatory activity in vivo indicated by the wound healing
proliferation. Further, the topical application of the scaffolds on results. The hybrid hydrogel caused no evident side effects on
wounds of Swiss/alb mice displayed the potential to expedite major organs in mice during wound healing. Therefore, the
the process of wound-xing. Modern wound care materials biocompatible multimodal therapeutic nanoplatforms were
suffer from several serious shortcomings that include inade- proposed to possess great potential for antibacterial activity and
quate porosity, inferior mechanical strength, lessened exi- wound healing. In a study by Dodero et al.,275 the possibility of
bility, lack of antibacterial properties, etc. Given this backdrop, using for biomedical purposes alginate-based membranes
a CS hydrogel/nanoparticulate ZnO-based bandage which exer- embedding ZnO nanoparticles that were prepared via an elec-
ted antibacterial effects against both Gram-negative (E. coli) and trospinning technique was extensively evaluated. The morpho-
Gram-positive (S. aureus) bacteria was fabricated by Kumar logical investigation showed that the prepared mats were
et al.272 The nanocomposite bandage characterized by biode- characterized by thin and homogeneous nanobers (diameter
gradability, microporosity and biocompatibility produced of 100  30 nm), creating a highly porous structure; moreover,
elevated wound healing in Sprague-Dawley rats and boosted re- EDX spectroscopy proved ZnO-NPs to be well dispersed within
epithelialization and collagen deposition at a remarkable pace. the samples, conrming the efficiency of the electrospinning
Taking into account the crucial factors of biocompatibility, technique to prepare nanocomposite membranes. Mouse
antibacterial effects, and wound-xing capacity, the researchers broblast and human keratinocyte cell lines were used to assess
held that the hybrid nanomaterial-based bandage could be the biological response of the prepared mats; cytotoxicity tests
valuable for the healing of chronic wounds, burn wounds, dia- evidenced the safety of all the samples, which overall showed
betic foot ulcers, etc. Likewise, a porous bandage consisting of very promising outcomes in terms of keratinocyte adhesion and
ZnO NPs conjugated with alginate hydrogel and exhibiting proliferation. In particular, the strontium- and barium-cross-
blood clotting capacity and bactericidal effects against E. coli, S. linked mats were characterized by similar cell viability results
aureus, Candida albicans, and methicillin resistant S. aureus was to those obtained with a commercial porcine collagen
fabricated by Mohandas et al.261 The bandage made from the membrane used as a control; moreover, except for the calcium-
nanocomposite was observed to exhibit biocompatibility at cross-linked sample, the prepared mats exhibited a good
a lower concentration of ZnO-NPs. Further, an ex vivo re- stability over a period of 10 days under physiological conditions.
epithelialization investigation with porcine ear skin demon- Antibacterial assays conrmed the prociency of using ZnO
strated that faster wound-xing was effected by the hybrid nanoparticles against E. coli without compromising the
nanomaterial-based bandage than only alginate control biocompatibility of the membranes. The mechanical properties
bandage. This was ascribed to the release of zinc ions that of the strontium cross-linked mats were similar to those of
would enhance the proliferation and migration of keratinocyte human skin (i.e., Young's modulus and tensile strength in the
cells to the wound area. Nair et al.273 also developed a bandage range 280–470 MPa and 15–21 MPa for the samples with and
consisting of a biocompatible nanocomposite of ZnO NPs without nanoparticles, respectively), as well as the water vapor
conjugated with b-chitin hydrogel. The bandage showed effi- permeability (i.e., 3.8–4.7  10
12 g m
1 Pa
1 s
1), which was
cient antibacterial activity (against S. aureus and E. coli) and had held to be extremely important in order to ensure gas exchange
the ability of blood clotting and activation of platelets. It was and exudate removal; furthermore, due to the low moisture
elucidated that the application of the bandage on wounds of content (i.e., 11%), the prepared mats could be easily and safely
Sprague Dawley rats led to faster healing, with enhanced stored for quite a long period without any negative effect on
collagen deposition and a reduced number of bacterial colonies their properties. Consequently, the achieved results demon-
than in the control experiment, indicating the remarkable strated that the prepared mats could be successfully employed
wound repairing capacity of the hybrid nanomaterial-based for the preparation of surgical patches and wound healing
bandage. A novel, biocompatible ZnO QDs@GO-CS hydrogel products by using alginate as an economic and safer alternative
was constructed by Liang et al.274 through the simple assembly to the commonly employed commercial animal collagen-
of ZnO quantum dots (QDs) with GO sheets and via a simple derived membranes.

1912 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

Ahmed et al.276 fabricated chitosan/PVA/ZnO nanober seems to t the bill.282,283 This resulted in various enthusiastic
membranes by using the electrospinning technique. The investigations that have been carried out in recent years to
samples of chitosan/PVA and chitosan/PVA/ZnO tested for design ZnO NPs that can successfully exploit the Advanced
antibacterial efficacy and antioxidant potential demonstrated Oxidation Process (AOP) mechanism thereby causing enhanced
very encouraging results in diabetic wound healing. The nano- photodegradation of otherwise recalcitrant POPs via very
ber mats displayed outstanding antibacterial properties pronounced generation of hydroxyl (cOH) radicals.
against various strains of bacteria. The samples of chitosan/PVA Ishwarya et al.73 reported the degradation of methylene blue
and chitosan/PVA/ZnO nanober membranes also manifested dye in the presence of ZnO NPs prepared using Ulva lactuca
higher antioxidant properties which made them promising seaweed extract and solar irradiation in their study. With an
candidates for applications in diabetic wounds. In experiments optimum initial dye concentration of 25 ppm and an optimum
involving diabetic rabbits, chitosan/PVA and chitosan/PVA/ZnO catalyst loading of 200 mg, the dye present in 100 mL of water
nanober mats exhibited increased performance of wound got degraded to 90.4% in 120 min.
contractions in a time interval of 12 days. It was thus concluded Gawade et al.75 carried out photocatalytic degradation of
in the study that the chitosan/PVA/ZnO nanobrous methyl rrange dye using green fabricated ZnO NPs. 81% of the
membranes could serve as useful dressing materials for dia- dye (20 ppm) was degraded aer 100 min exposure to UV light.
betic wounds, a major problem for type-2 diabetic patients This they carried out aer the dye solution was stirred with the
worldwide. catalyst for 30 min in the dark for complete equilibrium of the
adsorption–desorption phenomenon when 2% of the dye was
5.13 Agriculture found to be adsorbed. The optimum catalyst dose was observed
to be 1.5 g dm
3 aer the dose had been varied in between 0.1
ZnO NPs have been observed to increase the growth and yield of
and 2.0 g dm
3. The increase in degradation efficiency is
food crops. In peanuts, ZnO induced considerable stimulation
ascribed to two favourable factors: (a) an increase in the number
of seed germination, seedling vigor, and stem and root
of active sites and (b) an increase in the number of photons
growth.277 A colloidal solution of ZnO is used as a nanofertilizer.
absorbed by the catalyst. Beyond the optimal quantity of the
Apart from providing the plants with nutrients, the nano-
catalyst, aggregation of the catalyst results in the active sites on
fertilizer also revives the soil to an organic state without the
the catalyst surface becoming unavailable for light absorption.
harmful impacts resulting from the use of a chemical fertilizer.
The turbidity of the suspension leading to the inhibition of
What gives a nanofertilizer a cutting edge is that it can be used
photon absorption on the catalytic surface of ZnO NPs because
in very low quantities. In a study by Mahajan et al.,278 it was
of the scattering effect was cited as an additional cause for the
observed that there was stimulated growth in the roots and
lowered degradation efficiency aer the optimal catalyst dose.
shoots of mung seedlings till the concentration of ZnO reached
Vidya et al.76 performed the photodegradation of Congo red
20 ppm from 1 ppm and beyond this signicant retardation was
dye using ZnO NPs. With an optimal dose of 60 mg ZnO NPs in
noted. In the same study an optimum ZnO concentration of
250 mL of dye solution in which the concentration had been
1 ppm was found to excite growth in gram seedlings. The
optimized at 30 ppm, they achieved a 90% degradation in an
effective growth at a specic optimum concentration and
hour's time while maintaining an optimum pH of 9. They re-
a retarded growth beyond this concentration were ascribed to
ported that at very low pH, the ZnO NPs display a marked
the accumulation and uptake of ZnO NPs by the roots. The key
tendency to agglomerate and the photon absorption on to the
role played by the concentration of nano-sized ZnO NPs was also
metal oxide surface reduces and in Congo red, the azo linkage
reported by Prasad et al.277 in their work on the benets in the
(–N]N–) is prone to electrophilic attack by the hydroxyl radi-
usage of ZnO NPs in agriculture. An optimum concentration of
cals. At low pH, despite excess H+ concentration, the H+ ion
1000 ppm of ZnO NPs led to an improvement of germination,
interacts with azo linkage decreasing the electron densities at
root growth, shoot growth, dry weight and pod yield of the
the azo groups thereby discouraging the onslaught of hydroxyl
treated peanut seeds. Likewise, at 1.5 ppm concentration of ZnO
radicals via the electrophilic mechanism. At high pH, electro-
NPs, Burman et al.279 noted an improved shoot dry weight and
static repulsion between the negatively charged ZnO catalyst
antioxidant activity in chickpea seedlings. Raliya et al.280 also
and the negatively charged anionic Congo red dye hinders
reported a boost in plant growth and nutrient content in cluster
efficient photocatalysis. Using ZnO NPs synthesized by the sol–
bean seedlings upon treatment with 10 ppm ZnO NPs. In
gel route, Senthilkumaar et al.284 in their brief study, achieved
another study, enhanced plant height and dry weight were
total mineralization of Crystal Violet (CV) dye at pH 10.0 for
observed in maize plants.281
15 min of UV irradiation. The degradation was found to follow
rst order kinetics. The adsorption of the dye onto the ZnO
5.14 Photodegradation surface in the absence of light was found to follow the Langmuir
Studies involving fabrication of metal oxide semiconductors for isotherm. In their study Daniel E. León et al.285 performed
the photocatalytic degradation of Persistent Organic Pollutants photodegradation of an antibiotic cefotaxime under simulated
(POPs) in water have been conducted on a regular basis of late solar irradiation. The ZnO dose was optimized at 1.5 g L
1. An
with an eye to construct a low-cost, non-toxic and highly effi- optimum pH of 7.5 was maintained during the experiment. The
cient photocatalyst. ZnO with its low cost, non-toxicity and high photoreaction showed 60% efficiency and attained equilibrium
absorption efficiency across a large range of the solar spectrum

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1913
Nanoscale Advances Review

aer 60 min. It was found to follow pseudo-rst order kinetics optimized catalyst (1% Ag/ZnO) to treat drinking water con-
and the rate constant was evaluated to be 0.466 min
1. taining phenol with an optimized initial concentration of
Enhanced photocatalytic activity of the Mg doped ZnO/ 50 mg L
1 in 100 mL aqueous solution. Near-complete miner-
reduced graphene oxide nanocomposite has been recently re- alization was accomplished within 180 min of exposure to UV
ported by Nithiyadevi et al.286 They investigated photo- irradiation. Photoreaction was found to t in the pseudo-rst
degradation of cationic dyes Methylene Blue (MB) and order kinetic model. Another investigation289 reported a facile
Malachite Green (MG) under visible light irradiation. They microwave assisted synthesis of two-dimensional ZnO nano-
achieved a 94.41% degradation of MB and a 99.56% degrada- triangles with a band gap of around 3.33 eV. The as-
tion of MG aer exposure to visible light for 75 min in each case. synthesized ZnO nano-triangles were applied for the reduction
Both the photocatalytic degradations showed a marked increase of noxious p-nitroaniline within 50 min. They were further used
in efficiency in comparison with that effected by bare ZnO NPs. for the effective elimination of Rose Bengal dye within 150 min.
They obeyed pseudo-rst order kinetics and the rate constant Likewise, ZnO-nanorods were synthesized290 by adopting
assumed values of 0.0391 and 0.0493 min
1 respectively in the a facile microwave assisted green route of synthesis for the
case of MB and MG. They cited the following reasons for the complete reduction of nitro compounds. Lauric acid was used
enhanced photocatalytic ability of the nanocomposite: (a) the as a complexing and capping agent in the ethanol phase. The
introduction of reduced graphene oxide (RGO) enabled better nanorods had an average diameter of 5.5–10.0 nm with
adsorption of dye molecules through p–p conjugation between a hexagonal crystal structure and further demonstrated unusual
the dye and aromatic compounds of RGO, (b) the ability of RGO luminescence properties wherein high intensity UV and yellow
to facilitate the growth of the ZnO particles on RGO sheets, (c) emission bands were observed along with negligible blue and
the availability of a large reactive surface area, (d) the greater green emission bands. Toxic nitro-compounds p-nitrophenol, p-
interfacial contact between ZnO and RGO, (e) increase in the nitroaniline and 2,4,6-trinitrophenol were completely reduced
lifetime of charge carriers most probably attributed to RGO, (f) into amino derivatives by NaBH4 in the presence of these
narrowing of the energy bands of ZnO due to Mg2+ substitution, nanorods within 120, 45, and 18 min, respectively.
(g) presence of oxygen vacancies and (h) the reduction of Chidambaram et al.291 effectively constructed a ZnO/g-C3N4
particle size. heterojunction using a facile, economically viable pyrolysis
Photodegradation of Methylene Blue (MB) was performed by synthetic route for the photodegradation of methylene blue
Debasmita Sardar et al.287 with an Ag-doped-ZnO nanocatalyst. under visible light illumination. The nanocomposites prepared
On increasing the percentage of loaded Ag the rate of photo- using 0.1, 0.2 and 0.3 molar ratios of zinc nitrate precursor are
catalytic decomposition gradually increased and reached the labeled 0.1ZnO/GCN, 0.2ZnO/GCN and 0.3ZnO/GCN, respec-
maximum for 20% Ag loading on ZnO. The rate constant was tively. The nanocomposites are found to exhibit a fall in charge
found to be 0.0087 min
1 with a fairly high degradation effi- recombination corroborated by their photoluminescence
ciency of 55.87%. However, a sharp fall in the value of rate spectra that showed a fall in the intensity of the concerned
constant was observed for 25% Ag loading which remained emission peak (Fig. 25). A maximum photodegradation of 86%
almost the same on further increasing the Ag content, i.e. for 30 was achieved with 0.2ZnO/GCN in 60 min following a pseudo-
and 35% loading. It was also observed from TEM analysis that rst order kinetic rate constant of 0.032 min
1 while graphitic
too much loading of Ag led to agglomeration and thus covered carbon nitride, 0.1ZnO/GCN and 0.3ZnO/GCN attained 44%,
up the surface of ZnO preventing light absorption. Moreover, 73% and 76% degradation of methylene blue dye in the same
there were large numbers of unattached Ag nanoparticles which time with lower rate constants. The loading of ZnO over g-C3N4
could be oxidized in the presence of reactive oxygen species. sheets created a heterojunction (Fig. 26). The excitation of
Oxidized silver would not initiate any charge separation in the electrons by visible light occurs from the valence band to the
system. It was thus assumed that silver up to this optimum conduction band of g-C3N4. The excited electrons are trans-
amount could act as an electron–hole separation centre. Beyond ferred to the conduction band of ZnO while there occurs
the optimum amount, it could help in charge carrier recombi- a simultaneous movement of holes from the valence band of
nation. In fact, a large number of negatively charged Ag parti- ZnO to the valence band of g-C3N4 via the smooth interface of
cles (which had already accumulated electrons) on ZnO could the heterostructure. This enabled the generation of the super-
capture holes and thus would start acting as a recombination oxide anion radical and hydroxyl radicals that effected
site itself essentially by forming a bridge between an electron improved mineralization of the dye. An excess of Zn was
and a hole. Thus, the efficiency of charge separation and hence deemed to cause recombination of photo-induced charges that
the photocatalytic capability declined to an appreciably large led to decreased photocatalytic efficiency. In a recent investi-
extent. gation by the authors of the current work,292 a destructive
Very recently, Vaianoa et al.288 too tried photo-catalytically photocatalyst made up of ZnO nanorods/Fe3O4 nanoparticles
favourable modication of ZnO by Ag. They too achieved anchored onto g-C3N4 sheets was synthesized using hydro-
similar results with regard to removal of phenol from water. The thermal synthesis and ultrasonication techniques. HRTEM
loading of Ag responded favourably in the range of 0.14– micrographs shed light on the coupling of Fe3O4 nanoparticles
0.88 wt% but backred beyond 1.28 wt%. Similar reasons as with ZnO nanorods and the successful formation of the inten-
mentioned above were cited for the trends observed. A photo- ded ternary heterojunction. The g-C3N4 sheets fostered close
catalytic test was thus performed by using 0.15 g of the contact between ZnO nanorods and Fe3O4 nanoparticles

1914 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

Fig. 25 Photoluminescence spectra of GCN and ZnO/GCN nanocomposites (the inset shows the enlarged PL spectra in the wavelength region
of 350–450 nm) (reproduced from ref. 291 with permission from IOP Publishing).

drug widely known as a recalcitrant organic water pollutant.

This could be attributed to the synergistic interactions between
ZnO, Fe3O4 and g-C3N4. A degradation efficiency of 97.09% was
achieved within 90 min with a remarkable pseudo-rst order
rate constant of 0.0433 min
1. The incorporation of Fe3O4
expectedly facilitated the ready recovery of the catalyst and the
degradation efficiency displayed fair consistency up to 4 cycles.
The work thus offered a cost-efficient strategy for tackling
organic water pollutants.
In another study,293 a facile generation of a quaternary nano-
structured hybrid photocatalyst, g-C3N4/NiO/ZnO/Fe3O4, was

Fig. 26 Schematic depiction of the photocatalytic degradation

mechanism of the ZnO/GCN heterojunction (reproduced from ref. 291
with permission from IOP Publishing).

thereby inducing a mellowed agglomeration of nanostructured

ZnO/Fe3O4 particles. The Tauc plot derived from UV-visible
absorbance data showed that the ZnO/Fe3O4/g-C3N4 nano-
hybrid had a band gap of 2.48 eV. PL studies further
conrmed the successful development of a staggered type II
heterojunction with wide separation between light-induced
charge carriers (Fig. 27). The hybrid catalyst showed remark-
able photocatalytic activity under visible light, as evident from Fig. 27 Schematic depiction of the photocatalytic degradation
the efficient degradation of pantoprazole, a pharmaceutical mechanism of the g-C3N4/ZnO/Fe3O4 heterojunction (reproduced
from ref. 292 with permission from Elsevier).

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1915
Nanoscale Advances Review

proposed for photodegradation of an ecotoxic pharmaceutical occurred under dark conditions. Moreover, outstanding reus-
drug, esomeprazole, in aqueous solution. The photocatalytic ability of Chl-Cu/ZnO, for up to six cycles, was found, with more
annihilation of esomeprazole as a prototypical organic than 80% degradation efficiency.
contaminant was executed under LED irradiation. By itself the In yet another investigation,296 ZnO nanowires (NWs) were
designed ternary heterojunction accomplished a maximum successfully synthesized onto commercially available civil
95.05% photodegradation of esomeprazole and a TOC removal engineering materials using a hydrothermal synthesis method.
of 81.66% and COD reduction up to 70.68% under optimum This easy and low-cost method allowed obtaining an almost
conditions of catalyst dose, esomeprazole concentration and homogeneous repartition of nanostructures on the entirety of
pH within 70 min at a superior pseudo-rst order kinetic rate the surface of the substrates. The measured gap values were
constant of 0.06616 min
1. This actually implied an improve- similar to those of the ZnO NWs grown on typical substrates,
ment of degradation over NiO/ZnO, g-C3N4/NiO and g-C3N4/ZnO i.e., 3.18 eV and 3.20 eV for concrete and tiling, respectively.
up to 74, 57, and 42%, respectively. The specic reaction The excellent photocatalytic efficiency of our samples was
rate also went up remarkably by almost 3.8, 3.18, and 2.85 demonstrated on three commonly used dyes, namely, Methyl
times in comparison with the values obtained for NiO/ZnO, g- Orange (MO), Methylene Blue (MB) and Acid Red 14 (AR 14). All
C3N4/NiO and g-C3N4/ZnO, respectively. The remarkable pho- of the dyes were fully degraded in less than 2 h for MB and AR
tocatalytic potential of the heterostructured photocatalyst in 14, and less than 3 h for the more difficult to degrade MO.
practical applications was evident from its reconcilable perfor- Investigating the durability of the samples so prepared, very
mances under varying initial concentrations of esomeprazole promising results were found, as they showed no loss of effi-
and initial pH of the solution. The effect of the addition of H2O2 ciency aer four experiment cycles. The ability of implementing
was also put under scrutiny and it was found that the photo- ZnO NWs on civil engineering materials, their good photo-
catalytic degradation, TOC removal and COD reduction catalytic properties, and the possibility to re-use samples with
increased to 98.43, 84.72, and 73.86%, respectively, upon minimal efficiency losses, even aer several months, were
addition of an optimum quantity of H2O2 over the same time found very promising for the use of the nanostructures as road
span. The impacts made by inorganic and organic species on surfaces for air or water depollution.
photodegradation and the associated reaction kinetics were
investigated and the results were reported. The inhibiting
inuence of water matrices on esomeprazole degradation was 6. Toxic impacts and mechanisms of
also evaluated for better assessment of the performance of the ZnO NPs
designed photocatalyst in a real aqueous environment.
CdS/ZnO photocatalysts were prepared by two steps via Several toxicological studies have been carried out on zinc oxide
hydrothermal and photochemical methods for the photo- nanoparticles in recent years. These studies revealed the
degradation of rhodamine B (RhB) dye.294 The UV/Vis absorp- potential adverse effects of ZnO NPs on health and the envi-
tion spectra revealed that the absorption performance of the ronment. ZnO NPs have been revealed to be seriously toxic to
heterostructure is extended toward the visible light region. The bacteria, Daphnia magna, freshwater microalgae, mice, and even
photocatalytic activities of both ZnO nanorod and CdS/ZnO human cells.297–301 Although the exact mechanistic pathways of
heterostructures were investigated for the photodegradation the interaction of ZnO NPs with living cells are yet to be known,
of RhB dye. It was found that the CdS/ZnO heterostructure studies have demonstrated their engagement with cell
prepared with 30 min light illumination shows the best pho- membranes, DNA and proteins and the key role they play in
tocatalytic efficiency compared to the one at 15 min and pure producing oxidative stress. Animals in certain regions face
ZnO nanorods. The better and enhanced photocatalytic effi- signicant exposure to ZnO NPs that can have toxic effects on
ciency of the CdS/ZnO heterostructure was ascribed to the high them. Rats on being in contact with ZnO NPs were found to
charge separation efficiency. The maximum photocatalytic demonstrate biochemical abnormalities in blood and patho-
efficiency of 85% was achieved within 8 h with the CdS/ZnO- logical lesions in the stomach, liver and kidney.302 Another
30 min photocatalyst. study on male mice showed drastic physiological changes in
The photocatalytic degradation of rhodamine B (RhB) over them; an increase in the weight of the brain, pancreas and lungs
chlorophyll-Cu co-modied ZnO catalysts (Chl-Cu/ZnO) was accompanied by altered blood enzyme behaviour and mRNA
studied under visible-light irradiation by Worathitanon et al.295 expressions was observed.303 The study conducted on male
It was found that chlorophyll as an electron donor and copper in Sprague Dawley rats by Tang et al.304 reported adverse effects on
Cu2+ form help inhibit the recombination of electron–hole pairs cytokines, enzyme activity, oxidative stress, histological and
and improve the photoactivity of the catalyst. The synergistic hematological parameters of liver and mRNA expression. Renal
effect between chlorophyll and Cu was found to improve the functions were also found to be disrupted by exposure to ZnO
visible-light response of ZnO nanoparticles, resulting in excel- NPs. Tweaked oxidative stress and subdued catalase and
lent performance in photodegradation of RhB. The appropriate superoxidase activity were observed in affected rats.305 Bone
ratio of chlorophyll and Cu loadings over ZnO was 0.5Chl- marrow affected by oxidative stress and liver-DNA degradation
0.10Cu/ZnO. At this ratio, under visible-light irradiation for were also reported in yet another investigation.306 Exposure to
2 h, the degradation efficiency was approximately 99% ZnO NPs also leaves a host of pathological effects on aquatic
(60 mg L
1 of RhB solution), of which 18% of RhB adsorption organisms as has emerged from various investigations carried

1916 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

out on sh as a representative of an aquatic animal. Altered ions. In addition, bacteria could also release the solutes in
gene expression and subdued embryo development have been response to osmotic down-shock in ultrapure water, resulting in
reported in zebrash.307 Similar abnormalities in the growth of damage to the normal physiological functions and the decrease
zebrash embryos were also noted by Du et al.308 Exposure to of tolerance of bacteria to toxicants.323 Therefore, the toxicity of
ZnO NPs could also upset immunity and the serum protein nano-ZnO at 1 mg L
1 in ultrapure water was much higher than
level.309 The toxic effects of ZnO NPs on plants have also been that in 0.85% NaCl solution. To conrm the toxicity mechanism
recorded in several studies. One investigation on Arabidopsis of ZnO-NPs, the ultrastructural characteristics of normal E. coli
noted an 80% reduction in plant growth and 50% decline in cells and those treated with ultrapure water, ZnO-NPs, and Zn2+
chlorophyll.310 Studies have also revealed that ZnO NPs reduced ions were investigated with TEM by Li and his research group.
the number of roots and stunted the length of rice seedlings,311 The morphologies of E. coli cells treated with ZnO-NPs or Zn2+
induced drastic inhibition of chlorophyll-synthesis and reduced ions were signicantly different from those of normal E. coli
the efficiency of photosynthesis in Arabidopsis.312 Yet another cells. The cytoplasmic membranes were deformed, wherein
investigation showed their consequences on germination as some cells swelled and the intracellular substances leaked out
well as shoot-growth of Brassica nigra.313 Toxicological studies of under both Zn stress and osmotic stress. Combined with the
ZnO NPs on ryegrass show that ZnO NPs cause a considerable toxicity results of nano-ZnO, bulk-ZnO, and Zn2+ ions in ultra-
reduction in the biomass of ryegrass and shrinking of the root pure water, Li and co-workers concluded that the toxicity of
tip. Further, in the presence of ZnO NPs, root epidermal as well nano-ZnO to E. coli was mainly attributed to the released Zn2+
as cortical cells of ryegrass became highly vacuolated and ions.
collapsed.314 These days ZnO NPs are regularly used in
sunscreen creams due to their intrinsic ability to block UVA and 7. Challenges and prospects
UVB radiations effectively. However, these nanoparticles can
easily penetrate the skin to reach the viable cells thereby Although a large variety of morphologies, particle sizes and
imposing potential toxicity. structures have been designed for engineered ZnO nano-sized
The toxicity mechanism of ZnO-NPs in zebrash was inves- structures, no accurate mechanisms have been put forward
tigated by Yu et al.315 The toxicity caused by ZnO is primarily elucidating their formation during the reported procedures.
because of the release of Zn2+ ions and through mechanical Although investigations concentrating on the inuence of the
damage in zebrash. ZnO-NPs induced elevation of intracel- conditions of synthesis on the structure and morphology have
lular Zn2+ concentration, leading to over-generation of intra- made inroads, there is still a long way to go until a compre-
cellular reactive oxygen species, leakage of plasma membrane, hensive understanding of the effects of the synthesis parame-
dysfunction of mitochondria, and ultimately cell death.316 ters on structure, particle size and morphology has been
Therefore, it is demonstrated that cell uptake, intracellular achieved.
dissolution and release of Zn2+ are the inherent causes for high With higher electron diffusivity than TiO2, high electron
toxicity of ZnO-NPs. However, there are some disagreements mobility, exceptionally large exciton binding energy, low cost
regarding the role of dissolved Zn2+ in the toxicity mechanisms and considerable stability against photo-corrosion, ZnO has
of ZnO-NPs. Several researchers suggested that dissolved Zn2+ been widely considered a perfect substitute for TiO2 as the
from ZnO-NPs played a minor role in the toxicity of ZnO- electron transport material in DSSCs and PSCs. However, inef-
NPs,317,318 while other investigations indicated that most of the fective surface passivation, interfacial charge recombination
toxicity of ZnO-NPs is due to the dissolved Zn2+.315,316 This and long-term stability have collectively yielded poor electron
discrepancy may be ascribed to the sensitivities of different injection efficiency and thereby low current density and effi-
organisms to dissolved Zn2+, such as single tissue cells, ciency of the ZnO based photovoltaic device. Probable remedies
bacteria, zebrash and so on. In the study of Stella et al.,319 involve incorporation of organic and inorganic dopants for
dissolved Zn2+ from nZnO was considered to play the vital role effective surface passivation and effecting surface modication
in the toxicological mechanisms, which was inferred from the for marked electronic contact. Poor control of the properties of
levels of the biomarkers of metallothionein (MT) and heat individual building blocks and low device-to-device reproduc-
shock protein 70 (HSP70) in the body of O. melastigma larvae, ibility are further areas that require investigative attention. As
but this dissolved Zn2+ was obtained by ltering the ZnO-NP a yet further consideration, adequate studies devoted to the
suspensions with a 0.1 mm sterile syringe lter and it might impact of facet selectivity, structure and morphology of ZnO
include ZnO-NPs whose diameters were smaller than 100 nm. nano-structures on the overall efficiency of solar cells and the
The dissolution of Zn2+ ions from ZnO was also suggested to associated mechanism have to be conducted.
be the main mechanism for the toxicity of ZnO-NPs as claimed ZnO nanostructured particles have revolutionized the eld of
recently.320,321 Li et al.322 also reported the same mechanism for photocatalysis. And their efficacy in water splitting and degra-
the toxicity of ZnO-NPs. They have studied the toxicity of ZnO- dation of recalcitrant organic water pollutants has been widely
NPs with various initial concentrations to E. coli in ultrapure investigated and taken advantage of. However, a few concerning
water, NaCl and PBS solutions. For higher concentrations of aspects about their photocatalytic activity still need to be dealt
ZnO-NPs, although a few ZnO particles may attach to the with through possible corrective measures. First, the photo-
bacterial cells, it was difficult to determine the contribution of degrading ability of a prepared ZnO nano-catalyst needs to be
nano-ZnO itself considering the high toxicity of co-existing Zn2+ checked by taking the pollutant of interest in lieu of

© 2022 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2022, 4, 1868–1925 | 1917
Nanoscale Advances Review

a representative substance which in usual cases is a dye. This is for future biomedical applications of these intriguing nano-
because dye-degradation is relatively plain sailing while materials. Facile conjugation of various biocompatible poly-
removal of pharmaceutical wastes, pesticides, insecticides or mers, imaging labels, and drugs to ZnO nanomaterials can be
other endocrine disruptors offers greater challenges and achieved because of the versatile surface chemistry.
complicacies. Moreover, the archives of scientic literature are Some other issues of ZnO NPs concerning their biomedical
brimming with thorough investigative reports concerning application and their impact on biological systems still need
degradation of dyes. Furthermore, waste water contains a mix of further meticulous inspection. Following are a few such
different contaminants with varying ranges of pH and ionic concerns: (a) lack of comparative analysis of the biological
strength. Few photodegradation studies have been conducted advantages of ZnO NPs to other metal nanoparticles, (b) the
on organic pollutants in such a simulated sample of water while limitations imposed by the toxicity of ZnO NPs toward biolog-
taking into account the effect of the presence of other ical systems continue to remain a hot potato in recent research,
contaminants, varying pH and ionic strength on the degrada- (c) limitations of biocompatible/biodegradable ZnO nanoplat-
tion kinetics. Second, a detailed insight into the mechanistic forms for tumor targeted drug/gene delivery, (d) lack of
routes of the degradation of these compounds and their inter- evidence-based research carrying out as its focal point a thor-
action with ZnO based nano-catalysts is elusive as of now and its ough survey of the therapeutic roles of ZnO NPs in improving
development remains imperative and will unfold approaches to anticancer, antibacterial, anti-inammatory, and anti-diabetic
tackle other emerging contaminants. Third, many improve- activities, and (e) lack of extensive in vivo investigations into
ments in the very architecture of ZnO nanostructures are due the anticancer, antibacterial, anti-inammatory, and anti-
specically in areas such as surface area, particle size, separa- diabetic activities of ZnO. Fresh studies focused on the above-
tion and lifespan of charge carriers and so forth. Fourth, since mentioned issues would bring forth further elucidation and
band positions and band gaps are dependent on particle size, it comprehension of the potential use of ZnO nanoparticles in
becomes difficult to create heterojunctions able enough to biomedical diagnostic and therapeutic elds.
achieve effective charge separation and thereby efficient pho-
tocatalytic activity. Systemic studies with a focus on discovering 8. Conclusion
specic synthesis protocols for the achievement of ZnO based
nanostructures with desired band positions and band gaps have This overview on ZnO is an attempt to conduct a survey of the
to be embarked on. Also, there are a few difficulties associated various strategies that have been adopted to fabricate ZnO
with the operating procedures, such as loss and recovery of nanostructures and their applications across a wide range of
nano-structured photocatalysts in the course of post-synthesis elds. One of the merits of the work lies in putting together the
treatment and photocatalytic activity. Furthermore, more work done in biological and pure materials science elds. The
sweeping research investigations are required to develop and other merit lies in the inclusion of a discussion on studies
verify the mathematical models for photocatalytic operations/ carried out on the toxicity of ZnO nanostructures. Additionally,
systems for water/wastewater treatment in order to predict the a holistic picture of the future prospects of nano-structured ZnO
quantum yield, kinetics and optimum conditions of the vis-à-vis its application in the elds discussed has been pre-
process. sented. This overview demonstrates ZnO as a multitasking
ZnO nanomaterials may be outstanding candidates as material displaying diverse properties, functionality and appli-
biocompatible and biodegradable nanoplatforms for cancer cation in the emerging eld of nanotechnology. The high
targeted imaging and therapy. For in vivo imaging and therapy chemical stability, high photostability, wide range of radiation
applications, the future of nanomedicine lies in multifunctional absorption, biodegradability and biocompatibility enable ZnO
nanoplatforms combining both therapeutic components and NPs to be used in new materials and potential applications in
multimodality imaging. Biocompatibility is also a concern for a wide range of elds of technology. Moreover, the emergence of
the applications of nanomaterials in biomedicine. Surface various eco-friendly bio-mediated syntheses of ZnO particles
modication of nanomaterials plays a vital role in this context. with enhanced properties which can be exploited for their better
Biocompatibility of ZnO nanomaterials might be enhanced by applications in various elds of technology has attracted greater
slowing down the dissolution rate through Fe doping324 or interest in them in the world of research. The opto-electronic
surface capping.325 Therefore, surface coating of ZnO NPs with properties of ZnO NPs are largely exploited in the fabrication
biocompatible macromolecules, such as poly(lactic) acid, PEG, of ZnO based ETLs in DSSCs and PSCs. Modications based on
PEI and chitosan, was attempted to increase their suitability for doping the ZnO ETLs with organic and inorganic substances
further clinical usage. Another idea is the synthesis of ZnO and surface treatment with functionalizing agents for efficient
nanoplatforms using the biodegradable and biocompatible electron transfer will surely lead to noteworthy advancements in
materials already proven clinically. Some biocompatible poly- the eld of photovoltaics. The biomedical applications of ZnO
mers, such as liposomes and dendrimers, have been clinically have drawn great attention from researchers in recent years.
approved for various pharmaceutical applications. Hence, the Efforts are underway in designing more effective applications of
modication or conjugation of already approved therapeutic ZnO NPs in regard to drug delivery systems, antimicrobial
formulations or materials with functional ligands which will activity, anti-cancer activity, anti-inammatory activity, and
improve their diagnostic index could be essential. Much effort anti-diabetic activity as well as bio-imaging activity. Owing to
is needed for long-term in vivo toxicology studies to pave the way their inherent toxicity, ZnO NPs exert profound inhibition

1918 | Nanoscale Adv., 2022, 4, 1868–1925 © 2022 The Author(s). Published by the Royal Society of Chemistry
Review Nanoscale Advances

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The authors declare no competing nancial or non-nancial 25 M. Jose-Yacaman, C. Gutierrez-Wing, M. Miki, D. Q. Yang,
interests. K. N. Piyakis and E. Sacher, J. Phys. Chem. B, 2005,
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The authors deeply appreciate the Director, NIT Silchar and 27 Q. Xie, Z. Dai, J. Liang, L. Xu, W. Yu and Y. Qian, Solid State
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