Advances in Colloid and Interface Science 281 (2020) 102178

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Advances in Colloid and Interface Science

journal homepage: www.elsevier.com/locate/cis

Historical Perspective

Nanostructured metal oxides and its hybrids for photocatalytic

and biomedical applications
Karthik Kannan a, Devi Radhika b,⁎, Kishor Kumar Sadasivuni a,
Kakarla Raghava Reddy c,⁎, Anjanapura V. Raghu b,⁎
a
Center for Advanced Materials, Qatar University, P.O. Box 2713, Doha, Qatar
b
Department of Chemistry, School of Engineering and Technology, Center for Emerging Technology, Jain Deemed-to-be University, Jakkasandra, Ramnagara 562112, Karnataka, India
c
School of Chemical and Biomolecular Engineering, The University of Sydney, Sydney, NSW 2006, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Metal oxide nanoparticles and its hybrids are deemed to be one of the most attractive materials in an
6 May 2020 extensive range of applications due to their impressive optical, electronic, photocatalytic, and biological prop-
Available online 16 May 2020 erties. Metal oxide based nanomaterials with extraordinary characteristics have been proposed, prepared, and
used as main materials in the recent area of photocatalysis and biomedicine, due to their non-toxic nature,
Keywords:
large specific surface area, useful optical bandgap, and high biological activity. Herein, this review reveals
Metal oxide nanoparticles
Nanohybrids
the recent advance development in the area like photocatalytic, anticancer and antibacterial performance of
Photocatalysis metal oxide nanomaterials for multidimensional applications. Consequently, we also focused on the encoun-
Antibacterial activity tered difficulties and prospects for the future application of metal oxide-based composites as promising can-
Anticancer activity didates for the development of highly efficient photocatalytic and biomedical systems. This review article
Biomedical applications also delivers advanced knowledge to the scientific community who intends to design efficient photocatalytic
and biomedical systems.
© 2020 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1. Introduction of nanoparticles and its hybrids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2. Why nanocomposites? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3. Types of nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3.1. Ceramic Matrix Composites (CMC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3.2. Metallic Matrix Composites (MMC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3.3. Polymeric Matrix Composites (PMC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2. Synthesis strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3. Physical properties and applications of metal oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1. Physical properties of CdO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1.1. Importance of CdO nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2. Physical properties and applications of MgO. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.1. Importance of MgO nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.3. Physical properties and applications of NiO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.3.1. Importance of NiO nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.4. Physical properties and applications of ZnO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.4.1. Importance of ZnO nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4. Metal oxide nanoparticles and its hybrids for various applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.1. Water pollution and its remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

⁎ Corresponding authors.
E-mail addresses: [email protected] (D. Radhika), [email protected] (K.R. Reddy), [email protected] (A.V. Raghu).

https://doi.org/10.1016/j.cis.2020.102178
0001-8686/© 2020 Elsevier B.V. All rights reserved.
 K. Kannan et al. / Advances in Colloid and Interface Science 281 (2020) 102178 3

4.2. Semiconductor photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

5. Antibacterial activity of metal oxide nanoparticles/its hybrids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5.1. Microorganism and nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5.2. Antibacterial activity of nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
6. Anticancer activity of metal oxide nanoparticles and its hybrids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
6.1. Cancer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
6.2. Types of cancer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
6.3. Hallmarks of cancer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
6.4. Apoptosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
6.5. Clinical treatment of cancer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
6.6. Nanomedicines for cancer treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
7. Conclusion and future outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

1. Introduction been approved to degrade the organic contaminants included in the

water sources [25].
1.1. Introduction of nanoparticles and its hybrids
1.2. Why nanocomposites?
Several metallic nanomaterials have extensive uses such as sen-
sors, catalysis, fluids, regulated drug delivery, and pigments. With A progressive idea in the present semiconductor technology is
respect to ecological remedial methods, metal oxide nanostructures doping of impurities into the semiconductor lattices that is an effec-
have widespread and become capable material as a result of their tive way for monitoring the electrical conductivity and enhancement
slight bandgap, non-toxicity, low cost, high thermal and chemical of the optical, magnetic, and biological properties. Anticancer and an-
stability [1,2]. Ceria based nanocomposites were propositioned as tibacterial properties have been manipulated by the coupling of metal
possible anodes for IT-SOFCs because they exhibit distinctive oxides such as MgO, NiO, and ZnO which are the best candidates for
mixed ionic-electronic conductivity [3,4]. It was found that mixed biomedical applications [26]. Another ongoing trend in the develop-
metal oxides could display exceptional greater ionic, electronic con- ment of semiconductor nanoparticles and nanocomposites is to
ductive nature and catalytic performance, in turn, which might sus- achieve a widened absorption in the visible region to be used in pho-
tain to accomplish promoted power output [5–7]. Existing literature tocatalytic and solar cell applications [27]. Nanocomposites have drawn
on nanotechnology exposes that numerous nanoparticles counting much scientific attention in current research works because of the en-
CeO2, NiO, ZnO, CGO, CYO have been extensively employed in biolog- hanced features as opposed to pure metal nanoparticles. A nanocom-
ical applications [8–12]. posite is a mixed or matrix material that involves various substances.
Semiconductor nanomaterials have been in the focus of techno- This combination creates novel properties of the materials when the
logical advancements of nanoscience for many years. They have trig- nanocomposite has size varying between 1 and 100 nm [28]. Nanocom-
gered scientific attention because of their extensive use for the posite can be synthesized from different groups of materials which can
lessening of impurities from the water and air. They demonstrate re- be classified into three main building blocks: metals, ceramics, and
markable physical and chemical properties and beneficial perfor- polymers. A nanocomposite can have distinctly various mechanical, cat-
mance when associated with their predictable bulk counterparts. alytic, electrochemical, thermal, optical and electrical characteristics
Continuous absorption bands, narrow and intensive emission spec- from the essential materials behind it. Taking into account the spatial
tra, processability, high chemical stability, and surface functionality structure, nanocomposites can be considered as zero-dimensional (0D)
are the most attentive properties of those materials. The movements such as core-shell, one-dimensional (1D) like nanotubes and nanowires,
of electrons and holes in semiconductors are mainly influenced by two dimensional (2D) such as lamellar, and three-dimensional (3D) like
the widely recognized quantum confinement effect. The transporta- metal matrix composites [29,30]. Based on their properties related to
tion features associated with phonons and photons are highly de- structure, nanocomposites are categorized as nanofilamentary, nano-
pendent on the geometry of the particles and their size. While layered and nano-particulate composites. Nanocomposite materials at-
reducing the size to nanoscale, the surface-to-volume ratio and spe- tract much more attention from researchers, scientists, and engineers.
cific surface area rise extremely. These novel properties of semicon- This had inevitably led to a swift increase in the quantity of research ar-
ductor nanomaterials such as TiO2, NiO, ZnO, ZrO2, WO3, and CuO, ticles examining these materials. Furthest, those nanocomposites have
etc. have been described as noteworthy photocatalysts (organic pol- developed as materials of the 21st century that extend several techno-
lutant degradation) and biocidal agents have applications in evolv- logical and business developments in all segments of life. The focus of
ing technologies like energy conversion [13–16], optoelectronics, this review is on the metal oxide nanocomposites falling under all
sensors [17–19], bio-imaging devices [20], catalysis [21,22], solar three categories: polymer, ceramic, and metal matrix nanocomposites.
cells [18,19], detectors [18,19], biomedicine [23]. These materials have assuring features that make them appropriate
It is mainly utilized for splitting of water molecule (H2 production), for a huge number of functional and structural uses.
odour control, and inactivation of the cell wall of bacteria and cancer
cells. The waste materials liberated directly into the surroundings 1.3. Types of nanocomposites
need to be treated photodegradation to get byproducts into water and
CO2 and no other additional waste formation [24]. It is a renowned real- According to their matrix material, nanocomposites are categorized
ity that water pollution is a huge dispute for current and upcoming into three main types as follow:
years. In context, dyes participate essential roles in the pollution of
water bodies and are highly toxic, which is often utilized in several fac- ☻ Ceramic matrix composite (CMC)
tories. As dyes exhibit a complex structure, it is difficult to degrade nat- ☻ Metallic matrix composite (MMC)
urally. Hence, various semiconductor photocatalysis techniques have ☻ Polymeric matrix composite (PMC)
4 K. Kannan et al. / Advances in Colloid and Interface Science 281 (2020) 102178

1.3.1. Ceramic Matrix Composites (CMC) To overcome all these inadequacies, wet chemical methods like
Ceramic-matrix composites are fabricated of fibres or particles em- chemical-precipitation of metal ions may be assuring substitute. The es-
bedding in a ceramic matrix. The reinforcements in the ceramic matri- sential solid-state reactions ensue more quickly and at lessen tempera-
ces comprise of carbon, glass-ceramics, glasses, non-oxides, and tures. As a result, the preferred product can be found with small particle
oxides. The foremost purpose of the ceramic matrix is to maintain the size and higher reactivity.
reinforcing phase in the preferred orientation or location. The combina- Numerous chemical routes are obtainable for the preparation of
tion of high strength nanofibres into ceramic matrices results in mixed metal oxide nanostructures. Ceria doped nanomaterials have
obtaining nanocomposites with greater toughness. They are non- been stated to be fabricated by different wet chemical methods, such
brittle refractory materials designed for diverse applications in several as chemical-precipitation process [5,13,14,32], ultrasound synthesis [7,
fields. 33-], hydrothermal method [35–37], sol-gel method [38,39],
microwave-assisted- method [4,12,40], salt-assisted aerosol decompo-
1.3.2. Metallic Matrix Composites (MMC) sition process, spray pyrolysis technique [41,42], refluxing synthesis
Metallic matrix nanocomposites are made up of ductile metal or [43]. Further, it has been described that the addition of dopants shows
alloy matrix. Metal matrix nanocomposites comprise of at least two high oxide ion conductivity and co-doping process has been employed
chemically and physically distinct phases. These materials contain in current years and was shown to be successful [5,32,40]. Co-doping
both metal and ceramic characteristics that result in ductility and in- with proper ratio of metal ions can effectively advance the ionic conduc-
creased hardness together with the greater strength and modulus. tivity of rare earth-based metal oxides [1,3,4]. Up to now, there is a lot of
Metal-matrix nanocomposites are suitable for making materials of investigation has been done on the preparation of rare-earth based and
higher strength. transition metal-based ceramic composite powders via co-doping
method. Among the different methods stated, chemical-precipitation
1.3.3. Polymeric Matrix Composites (PMC) process is an effortless and talented process to yield homogeneous
Polymeric matrix composite comprises an organic polymer as ma- and small-sized powders [1,5].
trix and fibres or particles as reinforcement phases. Nanoscale reinforce-
ments lead to the acquisition of special properties such as mechanical 3. Physical properties and applications of metal oxides
[30]. For example, the strength and modulus of fibres are much greater
compared to the matrix material. This causes fibres to be the main 3.1. Physical properties of CdO
load-bearing component in the composite. However, there are matrix
materials with effective adhesion properties that tightly bind the fibres Among various metal oxides, cadmium oxide (CdO) is a transparent
together. In the same condition, the matrix materials homogeneously conducting oxide [20,22]. CdO possesses an elevated transmission coef-
deliver the applied load and transfer it to the fibre. Polymers have ficient in the visible light spectrum. Its optical bandgap varies from 2.2–
been compacted with numerous inorganic compounds any natural or 2.7 eV and the oxide has high exciton binding energy (75 meV) [44].
synthetic to raise their heat or influence resistance, mechanical CdO belongs to the n-type degenerated semiconductors. Its n-type con-
strength, flame retardancy and decrease the electrical conductivity ductivity is ascribed to the non-stoichiometric composition of Cd and
and gas permeability [30]. oxygen because of the negative oxygen vacancies (OV) and cadmium in-
terstitial (Cdi) atoms [20]. CdO has a rock salt (NaCl) crystal structure
2. Synthesis strategies (FCC), a widely dispersed S-like conduction band and a little carrier ef-
fective mass (0.11 m0) [44,45]. CdO does not undergo any phase transi-
There are two approaches available to prepare nanomaterials. Me- tion to pressure as high as 83 GPa [44].
chanical grinding has belonged to top-down approach and the
bottom-up mainly comprises of generation of colloidal dispersion by 3.1.1. Importance of CdO nanomaterials
wet chemical route. It is opted to achieve narrow size distribution of When compared with other toxic semiconductor nanoparticles
nanoparticles and this process concerns a material build-up from the (HgO, PbO), CdO nanomaterials demonstrate the lowest toxicity [45].
bottom-most: cluster-by-cluster, molecule-by-molecule by and atom- Nowadays, most of the multivitamin tablets and dietary supplements
by-atom. About the synthesis of colloidal metallic nanoparticles from comprise cadmium [46]. Furthermore, CdO is present in numerous cos-
their starting materials, numerous chemical reduction methods, com- metics and anti-tan creams [47]. Therefore, CdO can be regarded as a
prising the usage of chemical reductants in aqueous as well as non- chemically well-matched with the body moiety [47]. Furthermore, it is
aqueous solvents, sonochemical method [31] and photochemical a suitable choice for biomedical applications because of its excellent op-
method have been usually considered for various intentions of the ap- tical features like fluorescence and high resolution [45,48].
plication. The wet chemical route to synthesize metal colloids fre- Due to the rare optical, chemical, photoelectrochemical, and electri-
quently depends on the suitable metal salt reduction, using stabilizing cal properties listed in Table 1, CdO nanoparticles are in the focus of
materials. The preparation of metal oxide nanomaterials employing ir- many researchers and scientists. It has been demonstrated that many
radiation is now famous and the mechanism is sensibly comprehended. of the heavy metals including cadmium, can destroy cancer cells at min-
Thermodynamically very much stable due to its Spherical shape and it is imum concentrations [49]. The key mechanism of CdO nanoparticles
more feasible in any wet chemical preparation. Since the optical fea-
tures of metal cluster nanomaterials are delicate to shape, size and ele-
mental proportion, it is of significance to develop a method that Table 1
produces non-spherical nanostructures. Anisotropic metallic nanostruc- Physical characteristics of CdO.
tures have been prepared with the help of the structure-regulating
Stable structure at 300 K Cubic
agent, cetyl trimethyl ammonium bromide (CTAB) [5,32].
The solid-state reaction is the method (diffusion controlled) com- Bandgap 2.2–2.7 eV
Electron carrier mobility 142 cm2 V−1 s−1
monly requires replicated stirring and extended heating at high temper-
Refractive index 2.49
atures to produce a homogeneous and single-phase material [13,14,32]. Density 8.150 g cm−3
The mechanical grinding process will very likely initiate contaminants Melting point 1500 °C
from abrasive materials. Furthermore, lengthy calcination encourages Electron effective mass 0.11 m0⁎
crystallite growth, which is of no use in the construction of dense fine- Exciton binding energy 75 meV

grained ceramics, which certainly possess superior electrical properties. ⁎ m0 - rest mass of the electron.
 K. Kannan et al. / Advances in Colloid and Interface Science 281 (2020) 102178 5

influence on cancer cells is thought to be DNA and protein damage as Table 3

well as the destruction of the cell wall [49]. Along with cadmium, Physical properties of NiO.

some other heavy metals like Cu and Co, also have anti-cancer charac- Stable structure at 300 K Cubic
teristics. The thought-provoking fact about the anticancer features of Bandgap 3.6–4.0 eV
CdO nanostructures is that they are not harmful to human and mamma- Refractive index 2.82
lian cells. Density 6.67 g cm−3
Because of these interesting characteristics, CdO nanoparticles have Melting point 1900 °C
Neel temperature (TN) 523 K
been extensively utilized in different industrial applications. The crea-
Dielectric constant 10.31
tion of CdO nanoparticles is the same as that of other nanomaterials Exciton binding energy 50 meV
but its important activation is via to be the destruction of cell wall
[44,45].

3.3.1. Importance of NiO nanomaterials

3.2. Physical properties and applications of MgO
Bulk NiO shows antiferromagnetic behaviour underneath the Neel
temperature of 523 K. Its magnetic behaviour can be modified with de-
Magnesium oxide (MgO) has a structure with Mg ions engaging oc-
creasing of particle size. The antiferromagnetic behaviour of NiO is
tahedral sites within the anion closed packed structure (FCC). Its ionic
superparamagnetic (300K) when the particles reach a size of around
bonds suggest a comparatively less number of free electrons. Therefore,
100 nm [55]. The nickel oxide nanoparticles are found to cause cytotox-
MgO nanomaterials are required to obtain beneficial properties better
icity and apoptosis in mouse epidermal JB6 cells [55]. They are used for
compared to the bulk counterparts that are shown in Table 2.
studying the cytotoxic effect against human colon adenocarcinoma (HT-
Within the cubic lattice, the point group symmetry of Mg is ideally
28) cells and estimating the antibacterial activity against common
D2d and it has inversion symmetry. MgO nanoparticles have fascinated
foodborne pathogenic bacteria such as E. coli and S. aureus [5,54].
researchers because of their outstanding features like a large definite
surface area, huge pore volume, limited pore-size distribution, broad
bandgap semiconductor activity, thermal and chemical stability [50]. 3.4. Physical properties and applications of ZnO

ZnO, an II-VI group semiconductor, has three crystallographic phases

3.2.1. Importance of MgO nanomaterials
namely hexagonal Wurtzite, cubic zinc blende, and rock salt (NaCl). ZnO
MgO has been applied in countless uses such as photocatalysis, toxic
is a fundamentally n-type semiconductor with the existence of intrinsic
waste removal, adsorbents, refractory, additives in heavy fuel oils, su-
defects such as oxygen vacancies (VO), zinc interstitials (Zni), and zinc
perconductors, reflecting and anti-reflecting coatings, in ferroelectric
vacancies (VZn) that influence its optical and electrical properties. It
thin films as substrates and lithium-ion batteries [51]. MgO-based
has been noticed that higher VO can offer more electron charge carriers
nanostructures like nanorods and nanowires that are grown on various
[56]. ZnO has a broad direct bandgap (3.37 eV) and a huge excitation
substrates are utilized in flat panel displays, UV light emitters, field
binding energy (60 meV) [56]. These properties enable ZnO applications
emission sources and switches [52]. Because of the huge surface-to-
in blue-ultraviolet region optoelectronics including light-emitting di-
volume ratio of these MgO nanoparticles, they can also be used in the
odes, liquid crystal displays, laser diodes, and photodetectors [49,55].
detection of hazardous gas molecules and photocatalytic degradation
Some of the important physical properties of ZnO are registered in
of textile dyes. MgO-based nanostructures are also employed in the
Table 4.
medical field for heartburn relief, bone regeneration and sore stomach
[51,52]. Currently, MgO nanostructures have revealed promising appli-
3.4.1. Importance of ZnO nanomaterials
cations in tumor treatment because of their non-toxic and alkaline na-
ZnO nanomaterials can be used in the detection of hazardous gas
ture. MgO nanoparticles also demonstrate a significant antibacterial
molecules and photocatalytic degradation of textile dyes owing to the
activity [51,52].
larger surface-to-volume ratio. Metal oxide coupled ZnO nanocompos-
ites find promising applications in antibacterial and anticancer due to
3.3. Physical properties and applications of NiO their non-toxic behaviour [3,8,38,56].

Nickel oxide (NiO) is a green and well-described oxide that crystal-

4. Metal oxide nanoparticles and its hybrids for various applications
lizes in a cubic structure and is known to be a p-type wide bandgap
(3.6–4.0 eV) semiconductor [53]. The six coordination numbers both
Metal oxide nanoparticles fascinated numerous young scientists
for nickel and oxygen atoms make NiO crystal lattice looks like that of owing to their noticeable magnetic behaviour, chemical stability, and
NaCl or the so-called rock salt structure [54]. Nickel oxide is a significant biocompatibility [57,58]. The metal oxide nanoparticles are also well-
antiferromagnetic semiconductor with useful catalytic, gas sensing, and known for the application of drug delivery, enzymatic or metabolic deg-
electrochemical properties. Its nanoparticles are extensively employed radation, detection of pathogenic species, tissue repair, hyperthermia
in various fields like as electrochromic films, catalysis, and fuel cell elec- and antigen diagnosis [53,54].
trodes because of their mechanical, magnetic, electronic, and optical
properties [53,54]. Some of them are summarized in Table 3.
Table 4
Physical characteristics of ZnO.
Table 2
Physical characteristics of MgO. Stable structure at 300 K Wurtzite

Bandgap 3.37 eV
Stable structure at 300 K Cubic
Density 5.61 g cm−3
Bandgap 7.8 eV Refractive index 2.01
Refractive index 1.74 Thermal conductivity 0.6–1.2 W cm−1 K−1
Density 3.58 g cm−3 Specific heat capacity (Cp) 40.3 J mol−1 K−1
Melting point 2852 °C Melting point 1975 °C
Thermal conductivity 0.3–0.6 Wcm−1 K−1 Electron effective mass 0.24 m0⁎
Specific heat capacity 37.2 J mol−1 K−1
⁎ m0 - rest mass of the electron.
6 K. Kannan et al. / Advances in Colloid and Interface Science 281 (2020) 102178

4.1. Water pollution and its remediation

Organic dyes from industrial wastewater are huge pollutants which

significantly affect water resources in the industrial surroundings. On a
universal scale, over 0.7 million tons of organic synthetic dyes are mass-
produced annually mostly because of their usage in the textile, indus-
trial painting, leather goods, food, cosmetics, plastics, and consumer
electronics sectors. Approximately 20% of the total global creation of
dyes is lost through the dyeing procedure and is emitted into the envi-
ronment as textile effluent [59]. The release of these dyes in the envi-
ronment is a warning alarm due to the possible carcinogenic features
of these chemicals. Moreover, weathering of these organic dyes through
hydrolysis, oxidation, anaerobic decolouration or other chemical reac-
tions happening in the wastewater, can provide probable carcinogens
that are reported to cause adverse effects on human health as well as
environmental quality [59].
Numerous methods are available for organic matter decomposition
in wastewater which can be categorized into biological, chemical, or
physical oxidation processes. These conventional methods are ineffec-
tive for the effluent treatment since they either fail to accomplish total
dye removal or are useless for pollutants that are not readily adsorbable
or volatile. Additionally, they create disposal problems once again since
Fig. 1. Photocatalytic activity mechanism of nanocomposite.
they transfer the pollutants to other phases. Biological treatment needs
a huge land area and is limited in sensitivity toward diurnal differences
and toxicity of few chemicals. Numerous organic compounds can be de-
graded in this way but some more are uncontrollable because of their purification and photocatalytic hydrogen creation, correspondingly. For
complicated chemical structure and synthetic organic origin. Chemical photocatalytic water/air purification, valence band holes are the key ele-
methods employ large amounts of chemicals and result in a large vol- ments that stimulate the disintegration of environmental contaminants
ume of mud which itself requires treatment. Various physical processes via the oxidation route. The positive hole can oxidize contaminants
like as membrane filtration methods (nanofiltration, electrodialysis, re- straight away but often they react with water to give hydroxyl radical
verse osmosis) and adsorption methods are broadly employed [60]. The (•OH) that is a much powerful oxidant with an oxidation potential of
main drawback of the membrane method is that it has a restricted life- 2.8 V (NHE) [61,62]. •OH quickly hits contaminants at the surface and
time before fouling of membrane happens and the cost of intermittent in solution as well and can mineralize them into water, carbon dioxide
replacement must thus be comprised. Liquid phase adsorption is one etc. MgO, very famous photocatalytic nanostructure due to its compara-
of the important techniques for the ejection of contaminants from im- tively greater performance, available status, chemically stable, minimum
pure water. Activated carbon is extensively employed as an adsorbent production price, and non-toxicity, has been extensively examined and
for wastewater treatment. Nevertheless, the functioning price of acti- developed to have the prospective to entirely oxidize several targeted or-
vated carbon adsorption is high [60]. ganic contaminants [61,62]. There is a lot of research done in the arena of
Nonetheless, with the help of several oxidants such as H2O2, O3, Cl2, metal oxide nanoparticles/ nanocomposites with effective photocata-
and ClO2 chemical oxidation does not practice such a difficulty although lytic performance and they are the photodegradation performance
they could not achieve total mineralization of water impurities. To over- values reported in Table 5.
come these issues, advanced oxidation processes (AOPs) have been in-
troduced to confiscate various toxic compounds that could not be
efficiently eliminated by conservative treatment methods. Semiconduc- 5. Antibacterial activity of metal oxide nanoparticles/its hybrids
tor photocatalysis has been filed in a lot of investigations related to en-
vironmental issues, such as water purification [60]. 5.1. Microorganism and nanoparticles

4.2. Semiconductor photocatalysis Generally, inorganic nanoparticles can interact with microorganisms
acting as a good antibacterial and antifungal agent. Though, before using
Semiconductor photocatalysis has gained much interest throughout microorganisms as a means of transport for bioactive molecules, such as
the past 30 years as an assuring solution for both energy production and nanoparticles or drugs linked to nanoparticles, it is necessary to examine
ecological issues. Subsequently, widespread works have been carried how to incorporate these molecules within microorganisms. It has al-
out to yield hydrogen from splitting of water molecules by applying a ready been demonstrated how gram-negative bacteria can be employed
variety of semiconductor photocatalysts. Currently, scientists and engi- for constructing bacterial ghosts, signifying the latest advances in deliv-
neers gained much attention in heterogeneous photocatalysis that has ery and pointing vehicles appropriate for the distribution of hydrophobic
been also concentrated on ecological uses like as air and water purifica- or water-soluble drugs. Also, in pathogenic fungi like Candida albicans,
tion by eliminating pollutants. Numerous researches focus on numerous components related to the cell wall, have been recognized to
photocatalysis in current literature. In this, electron-hole pairs are intro- participate in a key role in fungal–host interactions [73,74].
duced after the excitation of bandgap. The general mechanism for Danish scientist Hans Christian Gram has developed a technique to
photocatalysis of nanomaterial showed Fig. 1. distinguish two types of bacteria based on the structure of their cell
walls (Fig. 2). The bacteria that contain the crystal violet dye because
þ
Photocatalyst ðhνÞ eCB − þ hVB of a thick layer of peptidoglycan (PG) and do not hold PG (red or pink
color) are called Gram-positive bacteria and Gram-negative bacteria re-
The excited electron-hole pairs can combine again, liberating the spectively. Gram-negative bacteria are more defiant against antibodies
input energy as heat, without any chemical change. The oxidation and re- because of their impenetrable cell wall compared with Gram-positive
duction steps are the essential mechanisms of photocatalytic water/air bacteria. E. coli, Gram-negative pathogenic bacteria, have usually been
 K. Kannan et al. / Advances in Colloid and Interface Science 281 (2020) 102178 7

Table 5
Photocatalytic activity of metal oxide nanoparticles/composites against different dyes.

Photocatalytic materials Synthesis method Model of dye pollutant Irradiation source Performance (%) Ref.

CdO Hydrothermal Methylene Blue Sunlight 78 [63]

CdO Microwave-assisted hydrothermal Congo Red Sunlight 81 [64]
SnO2 Microwave-assisted Congo Red Sunlight 90 [65]
CdO Ultrasound-assisted Alizarin Red S Sunlight 78 [66]
MgO Ultrasound-assisted Alizarin Red S Sunlight 70 [66]
ZrO2 Microwave-assisted Methylene blue UV light 99 [67]
MgO Microwave-assisted Methylene blue Sunlight 88 [68]
MgO Simple hydrothermal Methylene blue Sunlight 92
MgO Microwave-assisted Congo Red Sunlight 82
MgO Simple hydrothermal Congo Red Sunlight 86
NiO Green synthesis Evans blue Sunlight 88.13 [69]
ZnS Reflux method Methylene blue UV light 96.73 [70]
ZnS Methylene orange UV light 94.68
CdO-NiO-ZnO Microwave-assisted Methylene blue Sunlight 89 [71]
CdO-ZnO-MgO Microwave-assisted Methylene blue Sunlight 91 [72]
CdO-ZnO-MgO Microwave-assisted Congo Red Sunlight 81
CdO-MgO Ultrasound-assisted Alizarin Red S Sunlight 82 [66]

chosen for examinations because the virulent strain produces food poi- strains (foodborne pathogens). The strength of nanoparticles is diverse
soning, urinary tract infection and neonatal meningitis [75]. between 50 & 100 μg/mL.
The gram-negative bacterial cell wall is structurally and chemically The antibacterial mechanism of the synthesized nanoparticles based
more complex. The outer membrane of gram-negative bacteria fre- on the subsequent features [81–83],
quently provides confrontation to hydrophobic species comprising de-
I. Creation of reactive oxygen species (ROS)
tergents and holds as an exclusive component, lipopolysaccharide,
II. Heavy metal ions release
that increases the negative charge of cell membranes and is vital for
structural integrity and viability of the bacteria [76–80].
Karthik et al. have stated the photogeneration of ROS on the metal
oxide nanocomposite surface. Usually, the antibacterial performance
5.2. Antibacterial activity of nanoparticles mostly varies upon the specific surface area, ROS and size of particles,
etc. Few nanocomposites are providing ROS via the Fenton reaction
Generally, the antibacterial performance of nanocomposites is ac- directing to DNA damage, lipid peroxidation and protein oxidation can
complished using gram-negative bacteria and gram-positive bacterial destroy bacteria without damaging nonbacterial cells.
There are other possible mechanisms included in the antibacterial
performance. Prepared nanocomposite obstructs the bacterial cell wall
membrane and binds with mesosome. These intracellular functional
modifications are initiated by the oxidative stress influenced by ROS
leading to cell death as shown in Fig. 3.
M2+ is freed from the surface of nanocomposite and communication
with the membrane of cell wall of the microbe. The cell wall (negative
charge) and M2+ (positive charge) are equally enticed and they reason
denaturation of proteins that outcomes in loss of reproduction capabil-
ity of the DNA thus leading the demise of the pathogen.
þ
MO þ hυ⟶e− þ h

þ
h þ H2 O⟶˙OH þ Hþ

Fig. 2. The Gram-positive and Gram-negative bacterial cell wall structure (Source: https://
en.wikipedia.org/wiki/Gram-negative_bacteria). Fig. 3. Antibacterial activity mechanisms of nanohybrids.
8 K. Kannan et al. / Advances in Colloid and Interface Science 281 (2020) 102178

e− þ O2 ⟶˙O2 − The observed antibacterial performance in terms of zone of inhibi-

tion based on current literature displayed in Table 6.
˙O2 − þ Hþ ⟶HO2 ˙
6. Anticancer activity of metal oxide nanoparticles and its hybrids
HO2 ˙ þ Hþ þ e− ⟶H2 O2
6.1. Cancer
The rough surface texture (uneven edges and corners) is account-
able for the mechanical destruction of the membrane of the cell-wall. Over many years, humans have tried to find out the triggering mech-
From the FESEM images, it can be comprehensible that hybrid has anism of sudden cariogenic changes in tissues. Certainly, it was the
rough ridges at the outside of the surface that influences the biocidal Greek physician-scientist Hippocrates (400 BCE), who named cancer
performance. The larger concentrations of all these metal oxide com- “karkinos” or the “the crab”. Along with Paul of Aegina, this name was
posites are injurious to both the host and pathogens, but still nanolevel chosen because the disease “has the veins stretched on all sides as the
concentration is more suitable for the destruction of microbes [81–83]. animal the crab has its feet from which it derives its name”. Shockingly,
The general mechanism of antibacterial activity by nanocomposite is 20 decades later they are still annoying to describe the heterogeneity of
described in Fig. 3. tumors [94].
Antibacterial activity of Mg co-doped ZnO nanocomposites has been Cancer is an irregular, uncontrolled growth of cells triggered by ge-
reported by a few researchers and Ramin et al. have stated the fabrica- netic mutations. It leads to a dis-regulated balance of cell proliferation
tion of PbS-CdO nanocomposite and Mg-Doped ZnO respectively with and can progress as a small population of cells invades tissues and me-
photocatalytic and antibacterial activities [21]. Karthik et al. have ex- tastasize to additional parts of the body causing significant morbidity
plained the luminescence, antibacterial and anticancer features of and death. The probable factors of initiating cancer in personalities con-
microwave-assisted CdO-NiO nanocomposite [84] and Antibacterial ac- tain genetic, lifestyle like tobacco, diet and lack of exercise, few kinds of
tivity (human pathogens) of microwave-assisted CdO-ZnO nanocom- infections, and ecological disclosures to distinctive styles of chemicals
posite [85]. Anitha et al. have prepared NiO-CdO composite by sol-gel and radiations.
method and characterized photocatalytic and biocidal performance
[86]. Jayapriya et al. and Anindita et al. have explained the hybrid phy- 6.2. Types of cancer
tochemical assisted hydrothermal method of ZnO/MgO nanocompos-
ites with biological, optical and catalytic properties [87,88]. Cancer types are characteristically named after the organs or tissues
Solvothermal preparation of CuO-MgO nanocomposite and their cata- where cancer starts. For instance, lung cancer originates in cells of the
lytic uses have been discussed by Alla et al. and P.K. Labhane et al. lung, and brain cancer originates in cells of the brain.
[89,90]. The green route preparation of CdO-ZnO nanocomposite and Breast cancer is a malignant cell growth in the breast. If it doesn't
their thermal and photocatalytic uses explained by Rajaboopathi et al. treated, cancer spreads to other parts of the body. Apart from skin can-
[91]. Graphene-based nanomaterials have been wonderfully investi- cer, breast cancer is a usual type of cancer in women in the US, account-
gated due to their outstanding bactericidal performance on an extensive ing for one of every three cancer diagnoses. The risk factors of breast
range of bacteria. Graphene-based nanomaterials deliver benefits of cancer are unknown, though experimental data reveal that estrogen,
simple preparation, renewable, distinctive catalytic characteristics, and the female hormone created by the ovaries, is engaged.
extraordinary physical properties such as a huge specific surface area Lung cancer is that begins in the lungs and segregated into two im-
and mechanical strength [92]. Numerous metal oxide nanoparticles/ portant kinds: non-small cell lung cancer (NSCLC) and small cell lung
nanocomposite shown outstanding performance against both gram- cancer (SCLC). About 85–90% of lung cancers are NSCLC. This cancer
positive and negative bacteria reported by several researchers as has three types. Among them, there are minor differences but they
shown in Table 6. tend to have a similar outlook (prognosis) and are usually treated the

Table 6
Antibacterial performance of metal oxide nanoparticles and its hybrids against different human pathogens.

Materials Method of synthesis Tested bacteria Concentration (μg/mL) Zone of inhibition (mm) Reference

N-doped graphene quantum dots (GQDs) Hydrothermal synthesis S. aureus 100 16 [92]
CdO Hydrothermal E. coli 20 22 [63]
S. aureus 20 20
MgO Microwave-assisted green route E. coli 100 18 [93]
S. aureus 100 20
NiO Microwave-assisted E. coli 10 18 [85]
NiO S. aureus 10 10
CdO Microwave-assisted hydrothermal E. coli 10 24 [64]
CdO S. aureus 10 22
MgO Microwave-assisted E. coli 10 20 [68]
MgO Simple hydrothermal E. coli 10 24
ZrO2 Microwave-assisted B. subtilis 50 24 [67]
TiO2 Green route E. coli 50 17 [12]
TiO2 S. aureus 50 17
V2O5 Ultrasound-assisted E. coli 100 21 [33]
S. aureus 100 19
CdO-NiO Microwave-assisted E. coli 10 20 [38]
S. aureus 10 20
CdO-ZnO Microwave-assisted E. coli 10 39 [85]
S. aureus 10 40
CdO-MgO Ultrasound-assisted E. coli 10 13 [66]
CdO-NiO-ZnO Microwave-assisted E. coli 100 16 [71]
S. aureus 100 27
CdO-ZnO-MgO Microwave-assisted E. coli 100 23 [72]
 K. Kannan et al. / Advances in Colloid and Interface Science 281 (2020) 102178 9

Table 7
Anticancer activity of metal oxide nanoparticles/composites against MCF-7 breast cancer
cell line.

Sample Method of preparation IC50 (μg/mL) Reference

NiO Simple solution method 11.46 [101]

MgO 15.76 [93]
TiO2 Hydrothermal synthesis 60.00 [102]
ZnO Dry mechano-chemical method 50.8 [103]
CoFe2O4 Combustion method 63.00 [104]
CdO Microwave-assisted route 8.5 [84]
NiO Microwave-assisted route 15.7 [84]
CdO-NiO Microwave-assisted route 9.98 [84]
CuO Green synthesis 16 [105]

infinite replicative potential by telomerase activation.

➢ Inducing angiogenesis: Tumor cells need the process of angiogenesis
Fig. 4. Hallmarks of cancer.
or the construction of new blood vessels for the supply of oxygen and
nutrients to sustain the growing mass, expose their metabolic wastes
same way (Adenocarcinoma, Squamous cell carcinoma, and large cell
and insert the hematogenous metastatic method, as well [95].
carcinoma).

6.3. Hallmarks of cancer 6.4. Apoptosis

Normal cells have a wide range of intrinsic defenses against cancer- Apoptosis is a highly regulated cell death process for the elim-
ous, and there are many changes need to occur before they start to grow ination of damaged cells in which the entire cell is dismantled
uncontrollably to form a tumor mass. Fig. 4 shows the hallmarks of within the cell unity thereby preventing the release of intracellular
cancer. components from the dying cell. Apoptosis is explained by cell
shrinkage, membrane blebbing, chromatin condensation and pre-
➢ Sustaining proliferative signaling: In normal cells, growth- cise DNA fragmentation which contribute to the neat disposal of
promoting signals are subject to a highly controlled process that the cell. Different from apoptosis is necrosis cell death where the
maintains a homeostasis of cell number, tissue architecture, and cell swells, cell membranes leak and cells spill out the contents
functioning by carefully instructing cell growth and division. On into their surroundings causing inflammation to the nearby tis-
the contrary, cancer cells are constantly generating proliferation sig- sue/cell. The reason behind the execution of apoptosis throughout
nals and manage chronic cell growth, characteristically comprising the life of humans or animals is to maintain tissue homeostasis
intracellular tyrosine kinase domains. i.e., the balance among cell proliferation and cell death. Neurode-
➢ Evading growth suppressors: Normal cells have tumor suppressive generative disorders correlate with the case of excessive apoptosis.
protein-coding genes (TP53, PTEN or RB) that are actively involved Conversely, suppression of apoptosis is essential during the devel-
in different modes to suppress cell growth and proliferation. Cells opment of tumors. Till now, there are two chief apoptotic mecha-
will undergo cell cycle to prevent or induce apoptosis with due nisms known namely: the extrinsic or death receptor mechanism,
respect of external or internal stimuli for activation of tumor- and the intrinsic or mitochondrial mechanism [96].
suppressive genes. Therefore, cancer cells must find a method to ar-
rest their expression or activation. Cancer cells can circumvent the 6.5. Clinical treatment of cancer
growth suppression by inactivating the proliferation in genes
through the whole loss of tumor suppressor gene or accumulation Clinical cancer treatments include chemotherapy, surgery, radiation
of mutations. therapy, immunotherapy, gene therapy, and cryotherapy. Surgery is
➢ Resisting cell death: Programmed cell death (apoptosis) is an ordi- mostly employed to physically eliminate the solid tumor mass from
nary barrier for cancer growth and progress. Though, cancer cells the body. Chemotherapy is the method of curing cancer with cytotoxic
can limit the apoptosis by a variety of strategies. The drugs as they are delivered directly to the tumor or circulate via the
defunctionalization of the TP53 tumor suppressor gene is one of blood streaming to any place in the body where cancer may be present.
the most common reasons for preventing proper apoptosis. Chemotherapy can eradicate the swiftly separating cancer cells usually
➢ Enabling replicative immortality: The differentiated normal cells can by troubling the DNA duplication. Radiotherapy is supported on the de-
only separate a limited number of times whereas cancer cells have compose of radionuclides by means of X-rays, γ-rays, electrons, protons,

Fig. 5. Anticancer activity mechanism of nanohybrids.

10 K. Kannan et al. / Advances in Colloid and Interface Science 281 (2020) 102178

Table 8 materials to be used in a diversity of applications. Metal oxide nano-

Anticancer activity of some metal oxide nanomaterials against human A549 lung cancer particles and composites are becoming the heart of research and
cell line.
product growth as monitored from various kinds of researches car-
Sample Method of preparation IC50 Reference ried out on metal oxide nanoparticles and composites in current
(μg/mL) years. As a result, one can predict that in the near future, metal
ZnO Hydrothermal 33.31 [106] oxide nanoparticles composites will be broadly and comprehen-
NiO Combustion method 20.96 [104] sively utilized in the oil, gas, medical, biotechnology, electronics,
ZnO Dry mechano-chemical method 75.5 [103]
and food industries. Metal oxide nanocomposites have also been
CuO Green synthesis 200 [107]
Chitosan-Fe3O4 Reverse micro-emulsion (water-in-oil) 11.37 [108] shown to be feasible choices of synthetic materials for impending
method. replace of conventional materials and technologies in various func-
TiO2 Microwave-irradiation-assisted hybrid 55.7 [109] tional applications in different industries. As metal oxide nanoparti-
chemical approach cles and composites constantly increase the huge attention from
CuO Green synthesis 15 [105]
researchers all over the globe, the direction toward production
and practical applications in advanced technology will quickly en-
large in a way encouraging the shift of novel metal oxide nanocom-
α, γ particles, etc. It damages the local area and kills cancer cells, stops posites from lab to industrial scale.
cancer growth, effectively shrinks tumors and also helps to prevent re-
occurrence by damaging the genetic material in the cancer cells without
harming surrounding tissue. Cryotherapy or cryosurgery includes a Declaration of Competing Interest
practice in which probes are implanted into the tumor to generate tre-
mendous cold by administering liquid nitrogen or argon gas directly The authors report no conflict of interest.
to cancer cells. Conventional clinical treatments have their advantages
and several disadvantages. For example, chemotherapy has been sup- References
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