Journal of Materials Science & Technology 131 (2022) 122–166

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Journal of Materials Science & Technology

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

Review Article

Photocatalysis vs adsorption by metal oxide nanoparticles

Usman Qumar a, Jahan Zeb Hassan a, Rukhsar Ahmad Bhatti b, Ali Raza c,∗, Ghazanfar Nazir d,
Walid Nabgan e,∗, Muhammad Ikram a,∗
a
Solar Cell Applications Research Lab, Department of Physics, Government College University Lahore, 54000 Punjab, Pakistan
b
Department of Physics, University of Lahore (Chenab Campus), Adjacent Chenab Bridge, Gujrat, 50700 Punjab, Pakistan
c
Department of Physics, University of Sialkot (USKT), 1-Km Main Daska Road, Sialkot, 51040 Punjab, Pakistan
d
Department of Nanotechnology and Advanced Materials Engineering, Sejong University, Seoul 05006, Republic of Korea
e
Departament d’Enginyeria Química, Universitat Rovira i Virgili, Av Països Catalans 26, 43007 Tarragona, Spain.

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

Article history: Background: Metal oxide (MO) nanomaterials and related nanocomposites have been extensively studied
Received 7 March 2022 for their potential use in water treatment. Because of their controlled morphologies, texture qualities,
Revised 14 April 2022
variable surface chemistry, distinct crystalline nature, high stability, and tunable band edges, MO nanos-
Accepted 10 May 2022
tructured materials are highly selective towards deleting organic contaminants and heavy metal ions via
Available online 7 June 2022
adsorption and semiconductor photocatalysis. Metal-enhanced photocatalysis has recently received in-
Keywords: creasing interest, mainly due to the ability of the metal to directly or indirectly degrade pollutants. A
Photocatalyst diverse selection of MOs, with titanium dioxide (TiO2 ), zinc oxide (ZnO), iron oxides (IO), and tungsten
Adsorbate (W), as well as graphene-MOs nanocomposites with variable structure, crystalline, and morphological
Metal Oxides properties, offers a powerful platform for the growth of effective catalysts.
Z-scheme Methods: The current work discusses novel advancements and potential for the removal of adsorptive
Surface Modification
and photocatalytic degradation of organic compounds (phenolic, pesticide molecules, dyes, and so on) as
Heterojunction
Semiconductor heterostructures
well as heavy metal ions using semiconductor materials. A photocatalyst based on a MO-scheme het-
Nanoparticles erostructure can manage the appropriate conduction band (CB) and valence band (VB) locations, securing
considerable redox aptitude. This review should be of interest to the broad readership dealing with ap-
plied and fundamental aspects of water treatments and material sciences. Various strategies including
surface modification, plasmonic enhancement, and metal cocatalysts have been introduced to enhance
photocatalytic performance.
Significant findings: The current article discussed the significantly utilized synthesis strategies and mecha-
nism of heterojunction photocatalysts using a Z-scheme. Furthermore, adsorption sections guarantee that
mercury, chromium, cadmium, arsenic, and lead-based ions are successfully removed from polluted water
via the adsorption route. Numerous characteristics, such as concentration, coexisting ions, pH, and kind of
chemical have converged to comprehend the adsorption procedure. The technological challenges and fu-
ture approaches are discussed to maximize the photocatalytic and adsorption efficacy and the reusability
of MO-based nanomaterials for water security.
© 2022 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science &
Technology.

1. Introduction merous waste-generating businesses, such as paper, textiles, chem-

Rapid industrialization, city formation, and expansion along
with excessive reliance on non-sustainable means, and imbalanced
management of natural resources result in unsafe, irreversible, and
catastrophic environmental challenges. The horrific situation for all
living organisms exists beneath lakes, ponds, seas, and rivers. Nu-
∗ total release into aquatic species and terrestrial areas, (b) increased
Corresponding authors.
E-mail addresses: ali.raza.physics@uskt.edu.pk (A. Raza), wnabgan@gmail.com
(W. Nabgan), dr.muhammadikram@gcu.edu.pk (M. Ikram).
icals, pulp, microbes, fertilizers, metal plating, pharmaceuticals, re-
fineries, and food processing, discharge millions of gallons of wa-
ter each day, contaminating our atmosphere, terrestrial land, and
water species. Wastewater contains a variety of pollutants, both
organic and inorganic (e.g., dyes, fertilizers, organohalides, pesti-
cides, medicinal compounds, phenol, and surfactants), as well as
pathogens, nutrients, and agricultural runoff. Organic pollutants
grow more appealing as a result of their (a) widespread use and
persistence, (c) resilient resistance, and finally (d) substantial

https://doi.org/10.1016/j.jmst.2022.05.020
1005-0302/© 2022 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science & Technology.
U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
effects on the environment and human life. Persistent organic pol-
lutants have shown high resistance to dye degradation and detri-
mental effects on all living things [1–4]. Persistent organic pol-
lutants are alleged to induce cancer, immunological dysfunction,
congenital disabilities, multiplicative systems, and endanger in-
fants/growth of children. Organic dyes are challenging to work
with since they impart color to textiles or materials, and some
are also heat resistant and detergents [5–12]. Dyes are a critical
component of industrial applications for large-scale goods. About
>10 0,0 0 0, unlike an assortment of dyes, are industrially accessible
with an annual fabrication ability of over 7 × 105 tons [13,14]. The
amount of organic dyes released into the hydrosphere results in
an undesirable hue and limits sunlight penetration, which is nec-
essary for water species’ photochemical and biological activities.
Numerous dyes are toxic and have been implicated in mutagenic,
carcinogenic, and teratogenic effects [3,15–17]. Contaminated water
can cause significant health problems and harmful effects on vari-
ous human organisms, including the central nervous system, liver,
brain, and kidneys; further, it also causes skin allergies [18,19].
Pesticides are another effective form of organic pollution found in
aquatic bodies. Pesticides are persuaded in water livings mainly for
the following reasons: (a) agricultural forum, where they are pri-
marily used to control pesticides to protect crops from pest dam-
age, (b) pesticide effluent manufacturing industries, and (c) home-
usage. Fungicides, rodenticides, insecticides, plant growth regula-
tors, and herbicides are all instances of pesticides. Pesticide usage
that is out of balance and widespread pollutes water (agricultural
runoff) has a significant impact on humans and water bodies. Ac-
cording to the World Health Organization, the maximum permissi-
ble restriction in freshwater is 0.1 ppm of each pest and 0.5 ppm
of total pests, except for aldrin, dieldrin, heptachlor, and heptachlor
epoxide, which are permissible in the 0.3 ppm range [20,21]. Pesti-
cides used over the specified limit have dermatological, neurolog-
ical, gastrointestinal, carcinogenic, reproductive, and endocrine ef-
fects on humans [22,23]. Rapid industrialization, urbanization, eco-
nomic development, dynamic lifestyle changes, population growth,
and changing attitudes towards water usage have contributed to
elevating water demand [24,25]. Throughout the world, people are
threatened by water shortages and cannot achieve their fundamen-
tal necessities. Water is an essential component of living beings,
so efforts to combat water shortages, improve water quality, rain-
water collection, and water conservation have garnered increased
attention for an extended period [6,25,26]. In the near future, Asia
and Africa will be considered the foremost affected continents that
will run out of freshwater. Nonetheless, much effort has been ex-
pended towards storing water and removing contaminants from
polluted water to make it usable for agricultural and home pur-
poses. Environmental remediation is breeding considerable inter-
est, as it involves the elimination of an assortment of organic con-
taminants using environmentally beneficial procedures. In this per-
spective, interface science among organic compounds in water and
the composites to be employed is becoming increasingly important
for technological implementation [23,27–32].
So, in view of the above context, the review provides a compar-
ative analysis of novel advancements and potential for the adsorp-
tive elimination and organic compounds as well as heavy metal
ions degradation through semiconductor photocatalytic technique.
The unresolved problems are identified and the potential of both
methods is weighed against each other. We think this review
should be of interest to the broad readership dealing with ap-
plied and fundamental aspects of water treatments and material
sciences. The current review is arranged as follows: Section 2 pro-
vides a broad map of MOs photocatalytic systems with the addi-
tion of section 3, which adopt well-known MOs as photocatalysts.
Section 3 highlights Z-scheme photocatalysts and various types of
nanostructures, as well as how they impact photocatalytic perfor-
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Journal of Materials Science & Technology 131 (2022) 122–166
mance, and this section also covers various strategies to improve
the performance of photocatalysts. Absorptive removal has been
delivered in section 4 with the detailed mechanistic view of vari-
ous MOs using their possible opportunities having an extent of one
spot comparison of photocatalysis and adsorption. Finally, this re-
view provides overall performance in both systems with challenges
and possibilities, an overview of the current review is presented in
Fig. 1.
2. Metal oxides-based nanostructures
The MO nanoparticles (NPs) with various morphologies (Fig. 2)
were investigated for wide-ranging applications, i.e., energy-
storage machines, sensors, coatings, lubrication, electrochemistry,
environmental remediation, and so on [33–35]. Transition MO NPs
revealed notable surface belongings, microstructure features, and
large specific surface area, making them attractive candidates for
adsorption procedures [4]. When molecules’ size decreases from
bulk to nanoscale, it causes an exponential increment in surface-
to-volume ratio. By minimizing the size and incorporating active
edges on organic molecules surfaces for interaction, surface en-
ergy or adsorbent composites are improved. However, nanoma-
terials exhibit significant adsorption ability compared to bulkier
counterparts to remove organic contaminants from water. The ac-
tivated carbon is synthesized by employing biomass and innova-
tive forms, e.g., fiber, carbon nanotubes (CNTs), and graphene; oth-
ers have displayed extraordinary adsorption ability towards the
elimination of organic impurities from contaminated water. Fur-
ther, MO NPs, either alone or in nanocomposites, have recently
demonstrated a unique perspective as extremely selective adsor-
bents designed for quickly and efficiently removing organic con-
taminants [36]. Moreover, transition metal oxides (TMOs) and their
nanocomposites have a strong photocatalytic reaction to destroy
organic contaminants. [37]. The MO-based nanocomposites with
accurate structure, crystalline, and surface belongings function as
large bandgap energy (Eg ) semiconductors and exhibit favorable
qualities such as non-toxic and stability in water for organic pol-
lutants degradation. The basic mechanism is generated through
oxygen for photocatalytic degradation of contaminants from the
surface of semiconducting materials. The absorption of semicon-
ducting nanomaterials by photons can boost oxygen vaccines. It
favors environmental remediation by converting organic contami-
nants into low/intermediate toxic yields and ultimately forms com-
pounds like carbon dioxide, water, and inorganic ions [37,38]. Pho-
tocatalytic treatment was once considered the most environmen-
tally acceptable approach to eliminating organic pollutants from
wastewater. Thus, a significant problem of photocatalytic activity
is utilizing a short-range solar spectrum; for instance, ultraviolet
(UV) radiation only comprises 5% of the solar spectrum when MO
semiconductors are used [39]. The shortcoming might be overcome
with Eg engineering of MO nanocomposites through chemical and
structural modifications, the dopant concentration of hetero-atoms,
and fabrication of nanomaterials. Worthy photocatalysts efficiently
absorb solar spectrum in the visible range, delay electron–hole
(e– –h+ ) pair recombination, and perform well as photocatalysts
[40,41]. Several MO nanomaterials (e.g., IOs, Al2 O3 , CuO, CeO2 ,
ZnO, and TiO2 , etc.) have exhibited substantial interest as photo-
catalysts and adsorbents [38,40,42]. The various MO-based com-
posites, viz., porous materials-reinforced MO, magnetic-MO, metal-
MOs, graphene-MOs, etc, were being investigated to boost efficacy
and selectivity [43–45]. These nanocomposites’ surface characteris-
tics, size, and textural govern adsorption events [46,47]. The vari-
ous NPs morphologies offer flexible crystal defects for instance ac-
tive edges on materials’ surfaces for adsorption and photocatalysis
applications. A research group [48] has explained the impacts of
U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 1. Overview of photocatalysis and adsorption by MOs.

ZnO NPs morphology on dye-degradation of methyl orange shown
below.
3. Metal oxide-based photocatalytic systems
3.1. Mechanism
The energy difference between the valence band (VB) and con-
duction band (CB) of a semiconductor is called the “bandgap”.
When photocatalyst semiconductors such as TiO2 , ZnO, ZrO2 , and
CdSe absorb UV energy from solar light or any artificial light
source (fluorescent lamp, LED, etc.), the conduction band electron
(eCB – ) of the photocatalyst gets excited when visible to the acti-
vated light energy. The positively charged holes of the photocata-
lyst in the valence band (hVB + ) split water molecules into hydro-
gen and high-energy hydroxyl radicals. The electron interacts with
oxygen and generates a superoxide anion. This cycle lasts until the
light energy is accessible. The photocatalysis procedure and the re-
lated chemical procedures are described as follows with the aid of
Eqs. (i–ix). The reactive mechanism for ZnO and TiO2 photocata-
lysts was elucidated by Sharma’s group [53,54]. With a semicon-
ductor photocatalyst exposed to light, VB electrons enter the CB,
generating positively charged holes in the VB. If these photocata-
lysts and hVB + took longer to recombine, the photocatalysts would
be more efficient. The eCB – electrons react with oxygen and H+
in the aqueous solution to generate H2 O2 , which further gener-
ates OH ions and OH• radicals. Similarly, hVB + reacts to H2 O to
contribute OH• radicals. The production of these energetic reactive
species helps to reduce the electron–hole pair recombination rate
and provides extra time for processing organic pollutants. Fig. 3(a)
displays the photocatalysis concept graphically.
Mechanisms for the other two cases are (a) the CB of the pho-
tocatalyst is less negative than the O2 /O2 – redox potential and (b)
the VB of the photocatalyst is less positive than the positive redox
potential of H2 O/OH– . To obtain overall wastewater treatment, the
energy requirements show that the bottom of CB should be at a
higher negative potential than the reducing potential of H+ /H2 (0 V
vs normal hydrogen electrode (NHE) at pH 0), while the top of VB
is essentially at a more negative potential than the oxidation po-
tential of H2 O/O2 location of potential correction (1.23 V vs NHE).
Considering this peak value, photocatalysis is only possible when
the photon has energy greater than 1.23 eV [55]. This amount of
energy is equal to the photon-energy (wavelength of ∼1010 nm),
suggesting that visible light holds sufficient energy for wastewater
degradation in an aqueous media.
The photocatalytic oxidation–reduction of organic molecules in
UV light can be described as follows [54]:
Semiconductor photocatalyst + hv → eCB− + hVB+ (1)
h+ + OH− → OH. (2)
e− + O2 → O−
2 (3)
2e− + O2 + 2H+ → H2 O2 (4)
e− + H2 O2 → OH. + OH− (5)
Orgnic pollutant + OH. → degradation products (6)
Organic pollutant + semiconductor photocatalyst (hVB+ )
→ oxidation products (7)
Organic pollutant + semiconductor photocatalyst (eCB− )
→ reduction products (8)
The recombination rate of excited electron–hole pairs gener-
ates enough energy from the excitation of charges, which are re-
leased as heat. Since the recombination method is unwanted and

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Fig. 2. Various morphologies of MO-nanostructures. (a, b) ZnO nanobrushes. Reproduced with permission from Ref. [38]. Copyright 2015 Royal Society of Chemistry. (c)
ZnO@ZIF-8 core-shell microspheres. Reproduced with permission from Ref. [42]. Copyright 2016 Royal Society of Chemistry. (d) ZnO nanospindle. Reproduced with permission
from Ref. [48]. Copyright 2015 Royal Society of Chemistry, (e, f) ZnO nanotubes (NTs). Reproduced with permission from Ref. [49]. Copyright 2018 Royal Society of Chemistry,
(g) KTaO3 . Reproduced with permission from Ref. [50]. Copyright 2008 Springer. (h) ZnO nanorods (NRs). Reproduced with permission from Ref. [48]. Copyright 2015 Royal
Chemical Society. (i) As-prepared nanohusks of iron oxide. Reproduced with permission from Ref. [51]. Copyright 2015 Springer Nature. (j) WO3 nanoflowers. Reproduced
with permission from Ref. [52]. Copyright 2017 Springer Nature.

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 3. (a) Idea of degradation of pollutant by heterogeneous photocatalysis. Here, the redox potentials (E0 ) of some active radicals, such as H+ /H2 , O2 /O2 – , and H2 O/OH– ,
should be noted as 0 V, 0.33 V, and 0.42 V, Reproduced with permission from Ref. [55]. Copyright 2016 Royal Society of Chemistry. (Information is taken from Ref. [59].) (b)
Monitoring of a typical photocatalysis by UV-vis absorption spectrophotometer. Here, a typical aqueous naphthalene solution was mixed with TiO2 -nanofiber, and data was
collected at different time intervals. The inset image shows magnified lmax (monitored at 275 nm wavelength). Reproduced with permission from Ref. [54]. Copyright 2014
American Chemical Society.

points to insufficient photocatalytic ability, the key purpose of pho- this catalysis, the active species • OH is used for different commit-
tocatalysis is to realize the catalytic reaction between the excited ments. The mechanism by which ozone creates hydroxyl radicals
eCB – electrons and the oxidant to harvest the reduced product. It is can appear through the following pathways (Eqs. (9)–(12)) [58].
worth mentioning that the redox reactions take place on the pho-
tocatalyst surface as holes and electrons are generated in this re- O3 + hv → O2 + [O] (9)
action. In the oxidation reaction, the cathode hVB + competes with
the moisture on the catalyst surface to create hydroxyl radicals. Ad-
[O ] + H 2 O → H 2 O 2 (10)
ditionally, if more oxygen is delivered to the photocatalytic reac-
tor from the outside, it will act as an electron acceptor and can
facilitate the degradation of contaminants by further delaying the
H2 O2 + hv → O˙ H + O˙ H (11)
recombination rate [53]. Furthermore, the total time for complete
degradation of pollutants increases with decreasing photocatalyst
loading. Fig. 3(b) illustrates the typical photocatalytic degradation
of naphthalene, e.g., the polycyclic aromatic hydrocarbon contami- [O] + H2 O → O˙ H + O˙ H (12)
nant, in wastewater, where the progressive degradation of contam-
In the same way, the Fenton system yields hydroxyl radicals in
inants is addressed by measuring the uptake of the pollutant over
the following way (Eqs. (13)–(15)):
time.
Fe2+ + H2 O2 → O˙ H + Fe3+ + OH− (13)
3.1.1. Heterogeneous photocatalysis
Heterogeneous photocatalysis is the developed branch of chem-
Fe3+ + H2 O2 → Fe2+ + O˙ OH + H+ (14)
ical catalysis that can be used for water treatment and air cleans-
ing. In the case of heterogeneous catalysis, the catalyst phase is
different from that of the reactants. Heterogeneous photocatalysis
Fe2+ + O˙ H → Fe3+ + OH− (15)
involves various reactions such as dehydrogenation, slight or com-
plete oxidation, hydrogen transfer, hydrolytic poisoning, metal de- In photo-Fenton kind reaction processes, additional sources of
position, deuterium-alkane isotope exchange, gaseous and aqueous O˙ H generate over photocatalysis of hydrogen peroxide and reduc-
contaminants removal, etc. The most general examples of hetero- tion of Fe3+ ions in presence of light energy (Eqs. (16 and 17)):
geneous photocatalysts are TMOs and semiconductors with distinct
properties.
H2 O2 + hv → 2HO˙ (16)

3.1.2. Homogeneous photocatalysis

In homogeneous photocatalysis, the reactants and the photo-
catalyst exist in the same phases. The most widely used homo-
geneous photocatalysts are ozonolysis and photo-Fenton systems.
Fenton shows that hydrogen peroxide and Fe(II) combination in an
acidic medium has very pronounced oxidative properties [55]. But,
the precise mechanism of this reaction, now recognized as the Fen-
ton reaction, remains the subject of some debate [56,57]. It is gen-
erally considered to be the necessary chemical source of hydroxyl
radicals. The classical mechanism can be shown to be a simple re-
dox reaction in which Fe(II) has been oxidized into Fe(III) and H2 O2
and further reduced to hydroxide ions and hydroxyl radicals. In
Fe3+ + H2 O + hv → Fe2+ + H+ + O˙ H (17)
The production of the photon-Fenton classpath is affected by
several operating parameters, i.e., the pH solution, the H2 O2 con-
centration, and the UV light intensity. The main profit of this re-
action is the ability to extend the solar spectrum to 470 nm and
the avoidance of expensive UV and electrical energy. The photon-
Fenton process is considered to be more capable than other pho-
tocatalytic reactions. Nonetheless, the main disadvantage of these
methods is the low operating pH standard required for the reac-
tion, as iron precipitates at higher pH.

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
Fig. 4. Photoinduced response in TiO2 photocatalytic mechanism and parallel time scales. Reproduced with permission from Ref. [61]. Copyright 2014 American Chemical
Society.
3.2. Photocatalytic activity by various metal oxides
3.2.1. Titanium oxides
TiO2 is usually accepted and significant photocatalyst because
of its low-priced photocatalytic stability, plentiful availability, bio-
logical as well as chemical inertness, and lastly, non-hazardous ac-
tions headed for environmental safety [60–63]. Anatase, brookite,
rutile, monoclinic, and orthorhombic are five rutile types. TiO2 has
a high Eg of 3.2 eV for anatase compared to rutile which owns
3.03 eV; also it permits the absorption of the photon in a deep
UV region having a wavelength of ∼387 nm [64]. Under solar light,
TiO2 enables a low-cost and simple photocatalytic degradation pro-
cess. Under solar light irradiation, VB electrons are stimulated and
jump into CB, forming e– –h+ pairs [65] hydroxyl radicals from H2 O
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Journal of Materials Science & Technology 131 (2022) 122–166
molecules and –OH groups in alkaline media. In CB, photogener-
ated electrons reduce molecular oxygen, reacting with H2 O to cre-
ate the strong oxidant H2 O2 . Fig. 4 depicts a complete method of
probable photoexcited events inside and on the TiO2 surface [61].
These powerful oxidizers target organic contaminants near pho-
tocatalysts, eventually converting them into non-toxic sorts (i.e.,
H2 O and CO2 ). Photocatalytic action towards the degradation of
organic pollutants has been displayed in Fig. 5(a), demonstrat-
ing photogenerated e– –h+ pairs [65]. A variety of dyes, for in-
stance, Safranine O’azure II, malachite green, Alizarin green, Indigo
carmine, Amido Black 10B, solvent red 23, Sudan III, Orange G,
Rhodamine 6G, and other organic dyes were degraded in the pres-
ence of TiO2 photocatalyst using UV light illumination [66]. Un-
der near-UV light irradiation, the anatase and rutile natures of TiO2
U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 5. (a) Photodegradation of dye with Ag/TiO2 NPs in the occurrence of effluent organic matter. Reproduced with permission from Ref. [75]. Copyright 2019 Springer
Nature. (b) Representation of (i and ii) adsorption model of cationic RhB dyes on pure TiO2 and F-TiO2 particle surface, and (iii) electron-transferring procedures and
successive excitation of RhB dye on F-TiO2 particle surfaces. (c, d) SEM micrographs of pristine anatase TiO2 and F-TiO2 particles. Reproduced with permission from Ref.
[69]. Copyright 2016 Royal Society of Chemistry. (e) Biogenic synthesized TiO2 NPs degrade industrial reactive yellow 86 dye. Reproduced with permission from Ref. [74].
Copyright 2021 Springer Nature.

demonstrate photocatalytic activity, which is considered only 4% of
the solar spectrum [67]. To make TiO2 -based nanostructures active
photocatalysts under visible light, substantial attempts have been
undertaken to functionalize and dope them. The photocatalytic
acid orange and phenol oxidation favored fluorinated TiO2 (F-TiO2 ),
which has a more promising photocatalytic response than bare
TiO2 [68]. The F-TiO2 particles performed well as a photocatalyst
for photodegrading Rhodamine B (RhB) dye when showing visible
light. The fluorination of TiO2 particles caused the surface elec-
tronegative but did not change the optical properties. Adsorption is
facilitated by electrostatic contact between positively charged RhB
dye and negatively charged F-TiO2 surface; subsequently, adsorbed
RhB dyes’ oxidation continued faster than with naked TiO2 parti-
cles (Fig. 5(b)) morphological analysis can be depicted in Fig. 5(c,
d). The repellent reaction among negatively charged dye methyl or-
ange and F-TiO2 particles obstructs absorption, resulting in methyl
orange photodegradation of only 11% [69]. Compared with pure
TiO2 , the photo-oxidation rate of methylene blue (MB) cationic
dye was much more significant in the 3D hydroxyethyl–TiO2 –
carboxymethylcellulose hydrogel (HEC–TiO2 –CMC) cage that corre-

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
sponds to an appropriate cross-linking network. Further, electro-
static interaction drives the adsorption of MB using cellulose hy-
drogel and adsorbed molecules of dyes above its surface causing
photo-oxidation that stemmed to improve degradation progress for
positively charged dyes [70]. Further, azo dye molecules are widely
utilized, accounting for 60%–70% of all textile pigments. Under sun-
light, several azo dyes have a half-life > 20 0 0 h. As a result, ef-
fective and rapid deterioration is extremely difficult and necessary
for water cleanup. Several azo dyes have been photocatalytically
degraded using TiO2 NPs [71,72]. The photodegradation is accel-
erated by Hombikat UV-100’s high surface area and rapid inter-
facial electron transfer rate [73]. The adsorption process is more
favorable because of increased electrostatic contact between TiO2
and anionic dyes at lower pH. Kaur et al. [74] utilized a narrative
green route to produce TiO2 with piper betle leaves extract. This
prepared material has established its prospective for the degrada-
tion of reactive yellow-86. By retaining a synthesis procedure for
TiO2 NPs according to green chemistry philosophies, the focal point
is implementing a co-precipitation technique, using titanium iso-
propoxide as a titanium source. To sanitize industrially contami-
nated water (Fig. 5(e)), we provide a step-forward procedure for
the growth of economic and environment approachable method-
ologies in the area of material science.
Support heterojunctions are introduced via porous materials
with enormous surface areas to enrich the reactants, therefore re-
sulting in remarkable improvement in photocatalytic experiments.
Further, metal-organic frameworks consisting of varied organic
building blocks and metal-containing nodes, are termed attractive
materials to produce heterogeneous photocatalysts that own ow-
ing significant structural controllability, porosity effects, and higher
stability [76–78]. Xu et al. [79] produced a zeolite-like frame-
work (BIF-20) for the storage and separation efficiency of CO2 ,
as well as integrated BIF-20 with the graphitic carbon nitride (g-
C3 N4 ) nanosheets to produce an elegant composite BIF- 20@g-C3 N4
nanosheet. Improved adsorption efficiency over the sites of reac-
tion was explored via B-H bonding in BIF-20 to trap photoex-
cited electrons and promotion of CO2 activation. This will lead to
suppressing the excitons recombination that stemmed into 10.02-
fold enhancement in CH4 evolution and 9.96-fold higher activity
in CO evolution than g-C3 N4 nanosheet. To solve these problems,
Ma et al. [80] created a TiO2 /UiO-66 heterostructure by glueing
UiO-66 octahedrons to ultrafine TiO2 NPs. The porous TiO2 /UiO-
66 composite has a surface area (452 m2 g–1 ) compared to bare
TiO2 (213 m2 g–1 ), which resulted in a greater CO2 conversion rate
(78.9 cm3 g–1 ) as well as an appropriate active sites towards con-
version (Fig. 6(a)). According to the results of the aforementioned
investigation, the addition of porous support can significantly boost
photocatalytic activity by growing the surface area and providing
high catalytic active edges. Adsorbent-photocatalyst materials for
dye degradation have been prepared using an assortment of adsor-
bent species, for instance, porous carbon, zeolites, metal-organic
frameworks, and polymers. Wrapping MO in mesoporous carbon
is considered a useful method for increasing photocatalysis due
to its enormous surface area, significant light-harvesting capac-
ity, and increased electrical conductivity. Fabrication of N-doped
mesoporous carbon was done by Liu et al. [81] that encapsulated
anatase-rutile phase junction TiO2 via pyrolyzing NH2 -MIL-125, a
typical amine-functionalized Ti-based metal-organic framework. By
employing optimum nanocomposites, mineralization efficiency in-
creased to 51.9% at a styrene degradation of 62.4%, compared to
just 19.7% at a styrene degradation of 31.0% in the same condi-
tions with TiO2 @C-N. A greatly graphitized N-doped mesoporous
carbon wrapped TiO2 surface increases the interfacial connection
between C and TiO2 , which accelerates photogenerated electron
transport (Fig. 6(b)). Liu et al. [82] utilized a sol-gel strategy to
prepare g-C3 N4 - TiO2 by calcining Degussa P25 and urea mixtures,
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Journal of Materials Science & Technology 131 (2022) 122–166
then disseminated the photocatalysts in HCl solution to attach
with waste zeolite. The apparent reaction rate constant (0.0127
min–1 ) for prepared heterostructure towards formaldehyde degra-
dation was 2.3 times superior compared to P25. The visible-light
active g-C3 N4 , quick transferring of photoexcited electrons to TiO2 ,
and greater adsorption of gas-phase formaldehyde with waste ze-
olites might all contribute to enriching photocatalytic efficacy of
g-C3 N4 -TiO2 /waste zeolites. The capacity to absorb CO2 in hetero-
geneous photocatalytic systems is essential for photocatalytic CO2
conversion. However, because of their small surface area and lack
of matching pores, photocatalysts frequently have poor CO2 ad-
sorption. Given this difficulty, introducing a CO2 collection mate-
rial into a photocatalytic system offers promise for increasing CO2
conversion efficiency. Researchers [83] developed a distinct porous
hyper cross-linked polymer-TiO2 -graphene (HCP-TiO2 -FG) compos-
ite structure as a proof of concept. The TiO2 -G (graphene supported
TiO2 ) composite nanostructure was formed by evenly decorating
smooth graphene nanosheets with TiO2 crystals. The graphene sur-
face and TiO2 crystals were wrapped with an ultrathin HCPs layer
with a thickness of 3–8 nm after in situ knittings. The inclusion
of HCPs layers enhanced the surface area and micropore volume
of TiO2 -G to 988 m2 g–1 and 0.306 cm3 g–1 ; taking advantage
of the rich microporous nature and large surface area, resulting
in a 12.87 wt.% increase in CO2 absorption capacity. Because of
the increased CO2 adsorption capability of HCPs and small dif-
fusion length around TiO2 photocatalysts, such distinct HCP-TiO2 -
FG structure exhibits great photocatalytic efficacy, particularly for
fabrication of CH4 (27.62 mol g–1 h–1 ), when exposed by visible
light deprived of sacrificial reagents or valuable metal co-catalysts
use. As a result, covering a porous material layer with a thin
layer of active material can increase active sites, whereas photocat-
alytic progress can rise via reactant adsorption and reduce charge
diffusion distance. Photocatalysis has been thought to be a good
fit for hierarchically porous structured semiconductors. They have
been shown to be useful not just for increasing light absorption
via numerous reflections and refractions but also for reducing the
transit distance of photo-generated charges. For water oxidation,
Liang et al. [84] developed carbon-coated hierarchical TiO2 nan-
otubes (TiO2 /C HNTs) as effective full-spectrum photocatalysts. It
possesses Brunauer–Emmett–Teller (BET) specific surface areas of
∼ 244.4 m2 g–1 , which was much bigger than TiO2 /C NRs (42.6 m2
g–1 ) and TiO2 /C NPs (12.6 m2 g–1 ). Furthermore, a carbon-coated
surface lowers Eg and increases visible and deep-infrared light ab-
sorption ranges, making e– –h+ separation easier (Fig. 6(c)).
3.2.2. Zinc oxides
ZnO NPs have enormous potential as photocatalysts due to
their maximum quantum efficacy, superior stability, low-priced,
and globally acceptable nature [85]. The Eg (3.25 eV) of ZnO is
within an identical range as TiO2 (3–3.25 eV) and is intensively
employed in photocatalysis for the destruction of organic chemi-
cals in water [86]. ZnO’s photocatalytic action is quite analogous
to that of TiO2 , hence ZnO NPs were being proposed as a substi-
tute to TiO2 for water decontamination [87]. For the breakdown of
azo dyes under solar irradiation, the photocatalytic ability of ZnO
was compared to that of other semiconductors, including TiO2 [88].
The capacity of ZnO to absorb a higher proportion of solar spec-
trum was linked to its superior performance as a photocatalyst
compared to other semiconductors examined. The photocatalytic
destruction of numerous organic contaminants was also examined
using fluorescence emission properties of ZnO NPs [89]. The e– –
h+ recombination process is linked to the fluorescence intensity
in ZnO emission spectra. The organic compounds on ZnO’s surface
successfully sifted photoexcited h+ and contributed to the charge-
recombination procedure, which causes fluorescence emission in
ZnO. The photo-reaction of ZnO NPs through organic contami-
U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 6. (a) Representation of preparation of TiO2 /UiO-66 photocatalyst, (i–iii) SEM micrograph. Reproduced with permission from Ref. [80]. Copyright 2020 Elsevier B.V. (b)
Visualization of preparing a scheme of TiO2 @C-N(x) NPs. Reproduced with permission from Ref. [81]. Copyright 2019 Elsevier B.V. (c) Schematic illustration of the evolution
of TiO2 /C HNTs. Reproduced with permission from Ref. [84]. Copyright 2019 Elsevier B.V.

nants reduced the fluorescence intensity of emission spectra. As a
consequence, ZnO NPs in an aqueous solution may efficiently de-
tect and photocatalytically break down organic pollutants [89]. The
photocatalytic activity of ZnO is extremely pH-dependent; strong
acidic conditions (less than pH 4) stimulated photo-corrosion re-
stricts its potential in a less pH medium [87]. Nanocrystalline ZnO’s
superior photocatalytic activity over commercial ZnO has corre-
sponded to (a) small crystalline size improved specific surface area
to photocatalytic response, and (b) the large concentration of iso-
lated ZnO NPs per volume in aqueous increased photon absorption
efficacy for higher performance [90]. The photosensitizer/oxidant
ZnO/Na2 S2 O8 composite was utilized to accelerate the degrada-
tion of a varied spectrum of pests in the escape of water with
natural sunshine. By increasing the oxidative effectiveness of ZnO,
the inclusion of Na2 S2 O8 lowered the time required for photo-
catalytic destruction of pesticides. The photocatalytic efficacy of
ZnO is gradually depleted by photo corrosion, limiting its poten-
tial for long-term photocatalytic applications. Furthermore, ZnO’s
performance efficiency is harmed by the quick recombination of
photoexcited e– –h+ pairs [91]. Several efforts have recently been
devoted to developing ZnO-based nanocomposites that might re-
duce recombination events and boost photo-corrosion resilience.
The electron spin ZnO-SnO2 hetero-nanofibers showed quick and
increased photocatalytic activities for MB degradation, congo red,

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eosin red, methyl orange dyes, as well as high recycling capacity.
The excellent separation of excited e– –h+ pairs and improved ad-
sorption capacity of ZnO-SnO2 hetero-nanofibers were ascribed to
improved photocatalytic activity. ZnO-SnO2 is a significant compos-
ite for water purification due to its facile remembrance of wasted
photocatalyst and good recyclability [91]. The morphological char-
acteristics of ZnO nanocomposites and their photocatalytic reac-
tion were altered by the use of different zinc salts as precursors
[48]. The malachite green and Congo red dyes were successfully
absorbed and decolored by ZnO NPs on Tunisian clay (ZnO-Clay).
When compared to UV irradiation, the photocatalytic response of
ZnO-clay nanocomposite was greater under simulated sunlight. The
neutral range (6.58) of zero point charge of the ZnO-Clay nanocom-
posite makes it an excellent adsorbent and photocatalyst for both
positive and negative charged dyes.
As a consequence, in alkaline (pH N 8) and acidic (pH b 4)
conditions, ZnO-Clay could efficiently adsorb and destroy posi-
tively and negatively charged dyes respectively with photocat-
alytic activity [92]. The major characteristics that control photo-
catalytic activities of MOs are surface area and structural flaws,
notably on the surfaces of nanomaterials. Doping heterostructure-
atoms/molecules, such as MOs, metals, transition metals, and lan-
thanides, can improve surface defects [93]. The dopants can also
change the optical and electrical characteristics of MO nanomate-
rial, shifting absorption sensitivity to the sun’s visible spectrum.
UV and visible light illumination studied the photocatalytic reac-
tion of Mn2+ -doped and pure ZnO NPs for MB degradation. Sur-
face flaws caused by Mn2+ doping in ZnO nanostructures increased
photocatalytic response under visible light [94]. The photocatalytic
capabilities of ZnO microstructures coated with Ag NPs for the
breakdown of MB under UV light exposure were enhanced. The
Ag NPs acted as electron sinks, trap photogenerated electrons and
extend the lifespan of e– –h+ pairs and subsequently increased or-
ganic dye degradation efficiency [95]. By delaying the e– –h+ pair’s
recombination, Cu-doped ZnO NRs removed organophosphorus in-
secticides. It removed 96.97 percent of diazinon and was highly
recyclable [96]. The photocatalytic behavior of Pd-doped ZnO pho-
tocatalysts generated using several techniques, such as microwave
illumination, borohydride-reduction, and photo-reduction differed
significantly for photodegradation of Congo red dye. The significant
photocatalytic behavior of the Pd-doped ZnO photocatalyst fabri-
cated with a borohydride reduction process can be ascribed to a
higher amount of doping and significant Pd dispersibility on ZnO
improved the organic dye degradation efficacy by lowering recom-
bination of photoexcited e– –h+ pairs (Fig. 7(a)), Pd band structures,
and ZnO heterojunction, and Fermi level equilibrium without UV
light illumination illustrated in Fig. 7(b, c) [97]. Er-doped ZnO NPs
with a flexible Er concentration increased photocatalytic activity
in visible light irradiation. The band structure, morphology, Eg , the
half-life of excited e– –h+ pair, and visible light absorption were all
affected by varying dosages of Er dopant in ZnO NPs, resulting in
alterations in their photocatalytic response for the destruction of
Direct Red-31 dye [98]. Recently, Ag-anchored ZnO photocatalysts
were synthesized using a radio frequency (RF) sputtering process
in very little time. The effect on photocatalytic reaction for the
disintegration of RhB and H2 evolution was evaluated depending
upon Ag and ZnO belongings.
Moreover, at the interface, the photocatalyst revealed amaz-
ing physicochemical belongings from Ag/ZnO heterostructure in
situ for charge transfer procedure among the components and in
situ for the electrolyte. The mechanism strategy of Ag-loaded ZnO
nanostructures via UV and visible light illumination is displayed
in Fig. 7(d). The extracted data indicate correlation among ln(C/C0 )
and illumination time is linear representing that the breakdown of
RhB dye follows the first-order law. Xiong and coworkers [99] con-
veyed the fabrication of direct ZnO/CeO2 Z-scheme heterojunction
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Journal of Materials Science & Technology 131 (2022) 122–166
using a wet chemistry route and the product was then applied
to the calcination process. Furthermore, CeO2 NPs were doped (in
situ) with prepared material. Calcination was utilized to obtain in-
timate interface interaction among them. The obtained ZnO/CeO2
nanocomposites show better photocatalytic efficiency over RhB de-
composition compared to bare ZnO and CeO2 ; other composite
shows excellent stability as well. Photocatalytic routes that entirely
meet with the direct Z-scheme process are displayed in Fig. 7(e–g).
3.2.3. Iron oxides
Iron oxide, an n-type semiconductor with photocatalytic activ-
ity for degrading organic contaminants, is widely accessible. Fur-
thermore, the intrinsic magnetic effect forms a viable photocat-
alytic nanomaterial due to its easy recovery from aqueous media.
The Fe2 O3 semiconductor with a low Eg (2.2 eV) was linked to its
visible-light activation [101]. For photodegradation of harmful or-
ganic pollutants in the visible range of the solar spectrum, pho-
tocatalytic degradation properties of Fe3+ oxides in several forms,
i.e., α -Fe2 O3 , γ -Fe2 O3 , α -FeOOH, β -FeOOH, and γ -FeOOH were ex-
amined [102]. When azo dyes were photodegraded with Iron ox-
ide (IO) powder, degraded products replaced benzene and naph-
thalene, which subsequently oxidized and mineralized into carbon
dioxide and water [103]. Congo red was degraded using Fe2 O3 NPs
with varying crystallite sizes (35, 100, 150 nm) and thoroughly de-
graded dyes with and without visible light illumination via Fe2 O3
NPs using the crystallite size of 35 nm. Further, the apparent rate
constant was quicker in light’s presence than in dark [104]. The
Congo red dye degradation in visible light was achieved using hy-
drothermally produced α -Fe2 O3 nanostructures. Within 24 min of
visible light activation, α -Fe2 O3 can successfully destroy 99 per-
cent Congo red. The spent α -Fe2 O3 photocatalyst was also read-
ily removed from aqueous media [105]. However, photogenerated
e– –h+ fast recombination poses a significant barrier to their use
in photocatalytic applications [106,107]. Fabrication of IO-based
nanocomposites and their doping with varying metal or MO mod-
ify charge carrier recombination processes boost photocatalytic ac-
tivity. Under solar light irradiation, Au-Fe2 O3 aerogels with varying
Au loadings were verified as photocatalysts for Disperse Blue 79
dye degradation. By collecting photogenerated electrons and delay-
ing the recombination process, metallic gold improved the photo-
catalytic behavior of Fe2 O3 . Therefore, oxidative species enhanced
by photogenerated charge carriers attacked the adsorbed azo dye
molecules [108]. The microporous and amorphous activated car-
bon (ACs) impregnated Fe2 O3 (ACs-Fe2 O3 ) photocatalyst for pho-
todegradation of organic dyes was discovered to be a less costly
and effective photocatalyst. The MB absorption on ACs-Fe2 O3 pho-
tocatalyst was aided by the large surface area (specific surface area
(SBET) = 900 to 1520 m2 g–1 ) variable through Fe2 O3 concentra-
tion, which could effectively destroy organic dyes in UV light illu-
mination [109].
Zhao and coworkers [110] used a one-step hydrothermal tech-
nique to create and evaluate a photocatalyst made of IOs (FeO)
and carbon spheres (CS). FeO/CS(1:1) absorbed virtually all 200 μg
L–1 of perfluorooctanoic acid (PFOA) after 1 h at a dose of 1.0 g
L–1 . When PFOA-laden FeO/CS(1:1) has been exposed to boost sun-
light radiation at neutral pH, 95.2% of pre-concentrated PFOA had
degraded photo catalytically, and 57.2% defluorinated in 4 h. The
material was also renewed due to efficient degradation, allowing
for numerous usage without the need for chemical regeneration.
FeO/CS’s improved photocatalytic activity was attributed to two
factors: (1) CS facilitated ferrihydrite formation, resulting in PFOA
adsorption through binuclear and bidentate complexation, and (2)
a hybrid ferrihydrite-CS structure that allowed for multi-point and
corporative PFOA adsorption increased direct electron extraction
from PFOA when exposed to sunlight. Furthermore, • OH radicals
had a significant impact on the breakdown of PFOA. Finally, a pho-
U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 7. (a) Visualization of the possible synthesis process of (i) Pd/ZnO-1, (ii) Pd/ZnO-2, (iii) Pd/ZnO-3; (b) Pd band structures, and ZnO heterojunction and Fermi level
equilibrium without UV light illumination; (c) recommended charge separation method and photocatalytic activity of as-prepared Pd/ZnO samples under UV illumination.
Reproduced with permission from Ref. [97]. Copyright 2016 Elsevier B.V. (d) Schematic drawing of charge transfer mechanism in Ag-loaded ZnO nanostructures in UV
and visible light excitation. Photocatalytic response for RhB dye degradation with kinetics plots. Reproduced with permission from Ref. [100]. Copyright 2020 American
Chemical Society. (e) Hierarchical ZnO incorporated into CeO2 NPs as direct Z–scheme heterojunction, (f) photodegradation performance of RhB measured at 554 nm, and (g)
photodegradation rate curves and identical fitted kinetics curves of the blank experiment, CeO2 , ZnO, and ZnO/CeO2 nanocomposites in light illumination. Reproduced with
permission from Ref. [99]. Copyright 2018 American Chemical Society.

todegradation process is presented depending upon experimental
observations and density functional theory (DFT) calculations. Ac-
cording to frontier molecular orbital theory [111], in Fig. 8(a), the
highest occupied molecular orbital (HOMO) energy level for C7 F15 •
mixed with • OH is less than that of C7 F15 • integrated with H2 O,
resulting in a shorter Eg among the highest occupied molecular
orbital–lowest unoccupied molecular orbital (HOMO–LUMO) and
hence a reduced energy need for excitation. Fig. 8(b) depicts the
potential pathway of PFOA degradation in the FeO/CS system, de-
pending on preceding studies and reaction by-products. First, PFOA
is adsorbed on photoactive sites of FeO/CS using both head and tail
attached. Photoexcited charge carriers move from PFOA to Fe(III)
in sunlight illumination, yielding Fe(II) and unstable free radical
(C7 F15 COO• ) experiencing the Kolbe decarboxylation process to

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•
Fig. 8. (a) Iso-surface plots of frontier orbitals of C7 F15 when joined with hydroxyl or water molecules, and matching Gibbs free energy change at 298.15 K and reaction
enthalpy change, (b) purple and blue iso-surfaces shown charge combination and depletion in space, respectively; a proposed pathway of PFOA photodegradation with FeO/CS
under sunlight irradiation, (c) photodegradation by FeO/CS. Reproduced with permission from Ref. [110]. Copyright 2020 Elsevier B.V. (d) Peroxymonosulfate activation
mechanism by Fe-Co-O-g-C3 N4 for light degradation of SMX, (e) degradation rate, (f) first-order kinetics. Reproduced with permission from Ref. [113]. Copyright 2020
American Chemical Society.

generate C7 F15 • [112]. When PFOA-containing nanomaterials are
exposed to sunlight, photocatalytic activities for PFOA are substan-
tially different (Fig. 8(c)). Moreover, g-C3 N4 Co-doping by bimetal-
lic oxides, i.e., iron (Fe), cobalt (Co), and oxygen (O), was studied
in another work [113] to improve its catalytic capacity (Fig. 8(d)).
The findings indicated that Fe, Co, and O codoped g-C3 N4 (Fe-Co-
O-g-C3 N4 ) could completely degrade sulfamethoxazole (SMX, 0.04
mM) in 30 min with 0.085 min–1 reaction rate suggesting Fe-Co-
O-g-C3 N4 ’s better photocatalytic reaction (Fig. 8(e, f)). SMX has a
mineralization efficiency of 22.1%. The activation results in the de-
velopment of peroxymonosulfate radicals as well as singlet oxy-
gen. However, the involvement of singlet oxygen in the degrada-
tion of SMX was not immediately apparent. SMX degradation was
caused by surface-bound reactive species and sulfate radicals, ac-
counting for 46.6% of SMX degradation. The improved photocat-
alytic response was attributed to a significant interaction between
MOs and O-g-C3 N4 , where O-g-C3 N4 could operate as a carrier, ac-
tivator, and electron mediator to enhance the conversion of Fe(III)
to Fe(II) and Co(III) to Co(II) (II). In the presence of Averrhoa caram-
bola leaf extract as a natural surfactant, Padhi et al. [114] proposed
a unique one-step hydrothermal synthesis route that is photo cat-
alytically stable and magnetically separable g-Fe3 O4 /RGO nanos-
tructured for multifunctional water decontamination application.
The Averrhoa carambola leaf extracts significantly impacted Fe3 O4
NP’s structural, optical, and electrical characteristics. At 26 °C, the
g-Fe3 O4 /2RGO nanomaterials reduced Cr (VI) by 97% and phe-

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nol degradation by 76%, respectively. The advanced activity of g-
Fe3 O4 /2RGO was ascribed to in situ RGO loading, and the syner-
gism production among RGO and super magnetic Fe3 O4 NPs re-
sults in higher photogenerated (e– /h+ ) separation, as determined
by photoluminescence and photocurrent measurements.
3.2.4. Conclusive remarks
Photocatalysis is a clean, long-lasting, and ecologically benefi-
cial method for decomposing or degrading organic contaminants.
Because they entirely break down hazardous chemicals or trans-
form them into non-toxic forms, photocatalytic remediation re-
moves organic contaminants from polluted water without leav-
ing harmful products behind. Photocatalytic remediation is a sort
of advanced oxidation that occurs in a photocatalyst that absorbs
photons by energy equal to or more than the Eg between the
photocatalyst’s VB and CB. Charge separation occurs due to pho-
ton absorption, which excites electrons from VB to CB, resulting
in the generation of h+ in VB [60]. In CB, h+ is used to oxi-
dize H2 O to create hydroxyl radicals (OH– ) or pollution, while ex-
cited electrons become the reason to decrease adsorbed oxygen
in photocatalysis. The OH– -free radical assaults the organic pol-
lutant groups through a series of events that transform organic
pollutants into harmless and non-hazardous forms, or disintegrate
into CO2 and H2 O [37]. The photogenerated e– –h+ pairs, which
have a high tendency to recombine, impact photocatalytic effi-
ciency. To enable photocatalytic processes, e– –h+ pair recombina-
tion should be avoided or regulated. The form and nature of photo-
catalysts govern the photodegradation efficacy of organic contam-
inants for wastewater treatment, organic chemicals, temperature,
reaction medium pH, light intensity, the occurrence of solvent, sac-
rificial reagents, and so on [37,65,115]. The photocatalytic reactions
were also regulated by the organic pollutants’ chemical structure
and related functional groups. Mono azo dyes photodegrade faster
than anthraquinone dyes [116]. Various MO/semiconductor-based
compounds (WO3 , CdS, SnO2 , Fe2 O3 , TiO2 , ZrO2 , SnO2 , and ZnO,
etc.) have been discovered for the photodegradation of hazardous
and poisonous organic molecules into non-hazardous and gaseous
molecules [37,40]. This part discusses the latest research on us-
ing MO NPs and nanocomposites for photocatalytic destruction of
pollutants in wastewater treatment applications. The photocataly-
sis reaction is shown in the central region of Fig. 9. Shortly, pho-
tocatalysis is a multipart chemical and physical procedure, which
normally comprises of following four key points: (1) production of
excited e– –h+ pairs; (2) transportation and capture of photoexcited
charge carriers; (3) charge carriers recombination; (4) interfacial-
charge transmission, taking place redox reaction. Photocatalysis is
widely used in green energy and environmental remediation, for
instance, photocatalytic H2 evolution (Fig. 9(a)), CO2 conversion
(Fig. 9(b)), toxin degradation (Fig. 9(c)), and water sterilization
(Fig. 9(d)) [117].
3.3. Metal oxides-based nanostructured photocatalysts
3.3.1. Metal-metal oxide semiconductor photocatalysts
Due to their physiochemical, optical, electronic, magnetic, catal-
ysis, and photocatalysis properties, heterogeneous NPs made up
of two or more distinct functional units are of great interest in
epitaxial conjugation research [76,118–120]. These features can be
generated through the structure’s nanoscopic connection effects.
The material features corresponding to the interface at both ends
of the heterojunction among metal and MO NPs heterostructure
is different from their bulk counterparts. However, the epitaxial
relationship between two different materials plays a significant
role in changing material properties via heterogeneous conjuga-
tion [121,122]. MO nanostructured semiconductor photocatalysts
may generally be divided into two categories. To begin, the ma-
terial must be photons energetic, and excited electrons must be
transmitted to the next share of material during excitation that
can stimulate the catalytic procedure. This category includes plas-
monic nanostructures (Au, Ag, and Pt) with high Eg semiconductors
like TiO2 , where plasmon electrons are taken from gold to TiO2
semiconducting material utilized to initiate catalytic activity dur-
ing photoexcitation [123–125]. These are plasmonic photocatalysts
that are thoroughly characterized and elucidated in the literature.
From Refs. [126–128], a probability of electron elimination from
the gold surface plasmonic state to semiconductor nanomaterials
has shown in Fig. 10(a). The second phase involves photosensitiza-
tion of metal and semiconductor materials, which fascinates solar
light. This is the material class in which gold plasmonic material
is coupled to a semiconductor with a tiny Eg , such as Au-CdS, Au-
CdSe, and Au-PbS [129–131]. It is interesting to note that electron
transport is conceivable from both ends, (i.e., from semiconductor
to metal or vice versa) when Eg is arranged on an excitation basis.
If just metal is stimulated, electron transference may follow a pat-
tern similar to that seen in Fig. 10(a-i), assuming the plasmonic
surface state is above the semiconductor CB. Similarly, selective
semiconductor excitation may ease the passage of electrons from
gold CB to the electronic band, as shown schematically in Fig. 10(a-
ii). However, when both metal and semiconductors are activated
simultaneously, the situation becomes more complicated as shown
in Fig. 10(a-iii). Photoexcited electron coupling is also feasible be-
tween the semiconductor and metal plasmon [131,132]. In contrast,
it has been claimed that when both metal and semiconductor are
excited, the situation becomes more exciting, as they may attract
solar energy and create more excitons than the other two types.
Even though metal-semiconductor heterostructures have been es-
tablished in most situations, metals may also be linked with var-
ious semiconductors and used for efficient photocatalysis. In a
few cases, the platinum plasmon, for example, is even more effi-
cient [133,134]. However, Au metallic is often employed for metal-
semiconductor photocatalysis because it has surface plasmon reso-
nance (SPR) near an intense solar spectrum. Ho’s research group
[135] prepared metal-MO heterojunction catalysts from spatially
confined metal particles to obtain a porous core-shell heterostruc-
ture. The synthesis is easy and can be independently controlled,
with multiple core-shell structural components ranging from shell
thickness to single-core or multi-core composition (Fig. 10(d)).
They described that clustering of gold NPs significantly enhances
the photocatalytic rate and verified the importance of spatially
confined metal nuclei on traditional surface-loaded metal particles
and higher catalytic response, which stems from structural stabil-
ity and improved heterojunction-induced charge transfer proper-
ties. Depending on band position and band bending information, a
band structure was drawn to elucidate this charge trapping effect
of gold NPs (Fig. 10(c)). Fig. 10(e–h) shows morphologies of pre-
pared Au@TiO2 NPs.
Fang et al. [131] mapped photoexcited e– /h+ separation in
metal nanocatalysts at super-resolution. They created CdS semi-
conductor NRs with Au NPs and used millisecond temporal reso-
lution to study real-time redox photocatalysts. Au-CdS hybrid het-
erostructures were chosen as photocatalysts as they absorb light
efficiently and show photocatalytic response in the visible range.
Single-molecule detection by oxidizing non-fluorescent complex
red to highly fluorescent resorufin, high-resolution super-localized
fluorescence imaging was used to analyze photoexcited carriers’
properties and photocatalytic performance redox reactive edges in
Au-CdS hybrid heterojunction structure. Furthermore, utilizing spe-
cially built Au-tipped CdS heterostructures, two unique and inci-
dent energy-dependent charge separation processes were discov-
ered. These Au-CdS heterostructures (Fig. 11(a)) are unique because
they contain relatively slight metal. Excite the 532 nm gold metal

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
Fig. 9. Schematic diagram of semiconductor photocatalysis. Photocatalytic response of (a) hydrogen evolution, (b) conversion of CO2 , (c) dye degradation, and (d) water
sterilization. Reproduced the modified form with permission from Ref. [117]. Copyright 2021 Elsevier B.V.
domain to turn on mechanism A or the 405 nm CdS semiconduc-
tor NR domain to turn on mechanism B, as shown in Fig. 11(b).
Fig. 11(c) exhibits a super-resolution picture of reactive sites cap-
tured at 532 nm over 1 h during the same Amplex Red to resorufin
oxidation cycle. The h+ reaction site (circled blue cross) is located
near gold dots at both ends of the heterostructure, while e– re-
action site (circled red minus) is found along the inner length of
CdS NR, and the distance is only a few tens of nanometers. Con-
sequently, we turned on mechanism A at 532 nm, which is based
on gold metal to CdS semiconductor NRs. Although both the A and
B mechanisms are on when using the 405 and 532 nm lasers, the
ultra-magnified images (Fig. 11(d)) vary from the super-magnifying
image (Fig. 11(c)) when only 532 nm laser is used, showing the
presence of mechanism B: charge transferring from CdS semicon-
ductor NR to gold metal at tip.
3.3.2. Metal oxide-based Z-scheme photocatalysts
Metal oxide-based Z-scheme heterojunction photocatalysts may
be effectively separated e– –h+ and simultaneously confirm that
photocatalysts could maintain suitable CB and VB positions, con-
serving potential redox capacity. This work presented the types
and mechanisms of Z-scheme heterojunction photocatalysts. How-
ever, directed Z-scheme photocatalytic reactions were slowly sub-
stituted via a young S-scheme heterojunction structure mechanism
[117]. TiO2 occupies a significant position in photocatalytic activ-
ity owing to its stable, inexpensive, and non-hazardous character-
istics. Thus, this catalyst has a poor consumption visible light rate
and a limited reduction capacity. However, it has undergone var-
ious revisions. Creating heterojunctions between semiconductors
with the same band potential and TiO2 can effectively separate
photogenerated carriers. At present, it has a strong redox ability
[136]. The synthesized TiO2 -based heterojunction is generally di-
vided into g-C3 N4 /TiO2 heterojunction [137], MO/TiO2 heterojunc-
tion [138], metal-sulfide/TiO2 heterojunction [139], and metal/TiO2
heterojunction [140], etc.
Polydopamine (PDA) is a near-infrared absorbent polymer that
has gotten much press. It has an ecologically safe macromolecule
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Journal of Materials Science & Technology 131 (2022) 122–166
and possesses adhesion capabilities comparable to mussel adhe-
sion proteins (MAPs). Meanwhile, an abundant conjugated p struc-
ture absorbs visible light and carries electrons efficiently. Using
PDA as a bridge, Li et al. [141] built a Z-scheme heterojunction
photocatalyst (ZnAl-layered double hydroxide (LDH) nanosheets
using active phase/g-C3 N4 ), analytically studying photodegradation
efficiency for p-nitrophenol (4-NP) under visible light activation
(Fig. 12(a)). Within 120 min, 4-NP was removed at a rate of 98.95%.
The dazzling degradation effect was caused by active phase disper-
sion in LDH and great conversion efficacy in the multilayer ma-
trix, preventing e– and h+ from recombining. Free radical trapping
studies reveal more about the reaction method of Z-scheme het-
erojunction (Fig. 12(b)), h+ plays a significant influence in several
of them. PDA can also be used as an electron mediator in manufac-
turing a g-C3 N4 @PDA/bismuth oxybromide (BiOBr) heterojunction
in another work [142]. SMX may be nearly destroyed in 60 min
owing to the synergistic impact of enhanced visible light absorp-
tion rate and sufficient charge separation. PDA had greater biocom-
patibility and was more likely to be mixed with other materials
than carbon-based compounds.
Furthermore, because of their superior stability, larger surface
area, and broader absorbance spectrum, g-C3 N4 nanomaterials are
frequently recognized as promising candidates for TiO2 -based het-
erojunction assembly. Some researchers employed a variety of ap-
proaches to create a g-C3 N4 /TiO2 heterojunction with high photo-
catalytic efficiency. In earlier work, Nuraje et al. [120] developed
a straightforward calcination procedure for fabricating g-C3 N4 -TiO2
heterojunctions. The content of g-C3 N4 was shown to have a syn-
ergistic effect on the catalytic efficacy of Z-scheme heterojunctions.
Under UV light exposure, it demonstrated good formaldehyde pu-
rification characteristics. Fig. 13 depicts the charge transfer and
separation mechanism when exposed to UV light. In another inves-
tigation, Jo and colleagues [143] discovered that a TiO2 /g-C3 N4 het-
erojunction could be effectively formed using a wetness impregna-
tion approach, greatly increasing the photodegradation of MB and
atrazine. Furthermore, adding a sufficient quantity of MoS2 and
TiO2 /g-C3 N4 heterojunction could significantly reduce degradation
U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 10. (a) Graphic visualization of charge transferring procedure in a metal-semiconductor heterostructure, (b) representation of charge transfer phenomenon of metal–
MO nanostructures. Reproduced with permission from Ref. [55]. Copyright 2016 Royal Society of Chemistry. (c) Proposed photocatalytic response and energy band diagram
of Au@TiO2 nanospheres in solar light activation, (d) illustration of four different TiO2 nanospheres designs with/without Au NPs, surface-loaded or spatially confined Au
NPs, SEM micrographs of (e) TiO2 nanospheres and (f) Au on TiO2 nanospheres or surface-loaded Au NPs on TiO2 nanospheres. Insets display high magnifying pictures of
respective samples, (g, h) TEM micrographs of Au@TiO2 or spatially confined Au NPs of mono cores and mostly multiple cores. Reproduced with permission from Ref. [135].
Copyright 2014 Royal Society of Chemistry.

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 11. Engineering energy flows on single Au-tipped CdS nanorod heterostructures. (a) TEM image of typical single Au-tipped CdS nanorod heterostructures (top). Enlarged
TEM image (bottom) shows a Au nanoparticle at the tip. (b) Schematic illustrating two distinct photocatalysis mechanisms with the opposite direction of energy flow
(opposite polarity after photoinduced charge-separation). In mechanism A at 532 nm, the photogenerated energetic electrons in the gold metal are injected to the conduction
band (CB) of the semiconductor. In mechanism B at 405 nm, the photogenerated electrons in the CB of the semiconductor are rapidly trapped by the gold metal. (c) Super-
resolution mapping of single reactive sites on a Au-tipped CdS nanorod heterostructure during the oxidation reaction at 532 nm (mechanism A). (d) Super-resolution mapping
of single reactive sites on a Au-tipped CdS nanorod heterostructure during the same oxidation reaction after turning on the 405 nm laser (in addition to the 532 nm laser,
needed to excite the resorufin product) (mechanism B). Reproduced with permission from Ref. [131]. Copyright 2014 American Chemical Society.

time and improve photocatalytic activity. According to previous re-
search, an oxygen vacancy (OV) is a core defect of MO-based semi-
conductors [144]. Controlling the production of OVs is critical for
altering the Eg of TiO2 and promoting light-induced carrier separa-
tion and migration [145,146]. Zhou et al. [147] used a straightfor-
ward solvothermal approach to create g-C3 N4 /r-TiO2 with OV for
the first time. The use of electron paramagnetic resonance (EPR)
spectroscopy revealed that produced composites had stable OVs.
When activated with visible light, all g-C3 N4 /r-TiO2 hybrids ex-
hibited increased catalytic performance for RhB degradation, at-
tributed to the significant impact of OV and high surface area, and
the Z-scheme system. The absorption edge of r-TiO2 migrated to
about 600 nm due to the influence of OV on the control of Eg , in-
dicating increased visible light absorption capability. The Z-scheme
heterojunction was used to model the photocatalytic reaction pro-
cess. It is worth mentioning that external conditions like pressure
and temperature influence defect formation and concentration. Li
and coauthors [125] synthesized g-C3 N4 -TiO2 heterojunction using
a similar calcination process and investigated calcination temper-
ature effect on photocatalytic characteristics. The results revealed
that the annealing temperature significantly impacts the produced
samples’ catalytic efficacy.
After the semiconductor TiO2 was calcined with a specific tem-
perature, oxygen in crystal lattice fled due to oxygen deficiency
in a high-temperature environment, generating OV in crystal. To
maintain electrical neutrality, a portion of Ti4+ was given an elec-
tron and subsequently reduced to Ti3+ . Joining Ti3+ and porous g-
C3 N4 formed by calcination at 600 °C with a Z-scheme heterostruc-
ture facilitated the separation of photogenerated carriers, boosting
propylene degradation and hydrogen production efficiency under
visible light irradiation. The fluorescence test, which used tereph-
thalic acid as a probe molecule, revealed that the g-C3 N4 -TiO2 pho-
tocatalyst was the Z-scheme device, rather than the typical type-
II heterostructure. The Ti3+ defect, according to Kong et al. [148],
was likewise favorable to visible light absorption and success-
fully enhanced transmission and separation of interfacial charge.
When exposed to activated sunlight and visible light, fabricated
g-C3 N4 /Ti3+ -doped TiO2 exhibited excellent stability and photo-
catalytic reaction for hydrogen generation, acetaldehyde, and β -
naphthol degradation. This revealed that in a direct Z-scheme sys-
tem, interface imperfections might operate as interfacial charge
transfer channels, and photocatalytic performance could be in-
creased as a result. All preceding experiments include the de-
velopment of self-defects, e.g., OV and Ti3+ . As a result, stabiliz-
ing OV has an extreme effect on photocatalytic activity. Li et al.
[149] found that doping was important in maintaining OV stabil-
ity. The stabilizing OV was favored by doped N, which cut off the
path of charge transfer from sub-band to VB of TiO2 , facilitating
transferring and separation of photoexcited charge. The clearance
rate of propylene increased when the dosage of g-C3 N4 was in-

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Fig. 12. (a) Visualization of yP-LDH_TCN nanocomposites and structural drawing of PDA synthesis procedures, (b) photograph of two relative photocatalytic methods for
0.5P-LDH_500CN with visible irradiation. A. Z-scheme charges diffusion route. B. direct solid-solid interaction interface heterojunction. Reproduced with permission from Ref.
[141]. Copyright 2020 Elsevier B.V.

creased, indicating a trend of the first ascent and subsequently
decline.
The photocatalytic property of 30% g-C3 N4 -TiO2 was observed
to be excellent, with a propylene elimination rate of up to 56.6%.
The results were consistent with BET surface areas, typical pore di-
ameter, and pore volume. Furthermore, the insertion of impurities
in TiO2 is the most typical way of obtaining TiO2 -based Z-scheme
heterostructured with increased photocatalytic activity. Carbon, as
well as several other metals and non-metals, may be doped to ef-
ficiently minimize the Eg of TiO2 [150]. Li et al. [151] used a hy-
drothermal mixed calcination approach to make g-C3 N4 @CeTiO2
[151]. Carbon has been introduced by degrees by lattice substitu-
tion as carbon content increased, and Eg of TiO2 steadily dropped,
producing the redshift of the absorption edge. The g-C3 N4 @10C-
TiO2 showed the best phenol degradation efficacy. The photocat-
alytic behavior of g-C3 N4 @C-TiO2 Z-scheme photocatalysts might
be increased by the presence of additional non-local impurity lev-
els in semiconductor degradation that expedited the transmission
and separation of light-generated charge carriers. On the other
hand, the successful doping of niobium (Nb) into TiO2 lattice can

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
Fig. 13. Schematic drawing for the charge transfer and separation in g-C3 N4 -TiO2 Z-scheme system illuminated with UV light: (a, b) U100 and (c) U500. (d) TEM and (e)
HRTEM images of sample U100, EDS mapping of (f) Ti element and (g) N element. Reproduced with permission from Ref. [143]. Copyright 2013 Royal Society of Chemistry.
improve its photocatalytic behavior. The photocatalytic response of
produced samples for CO2 conversion was outstanding [152].
TiO2 is a typical n-type semiconductor with a generally good
effect. The increased e– and h+ separation may be obtained by
selecting suitable p-type and n-type semiconductors to form Z-
scheme heterostructure. The Fermi level of a p-type and n-type
semiconductor is near its VB and CB, respectively [153]. A space
charge area forms between the interface of n-type and p-type
semiconductors owing to the passage of e– and h+ , providing a
built-in electric field. The built-in electric field causes e– /h+ to flow
in opposing directions, thus limiting e– –h+ pair recombination.
This is a common feature of p–n heterojunction systems. Cuprous
oxide (Cu2 O) is a p-type semiconductor with a rough Eg of 2–
2.2 eV used to make Z-scheme heterojunctions when combined
with n-type TiO2 . Aguirre et al. [154] used a solvothermal tech-
nique to produce Cu2 O/TiO2 heterojunction and comprehensively
investigated CO2 reduction capability. The carbon monoxide gener-
ation rate reached 2.11 μmol/(g h). The presence of TiO2 , rather
than chemical alterations on Cu2 O particles’ surface, was linked
to the improved performance, as verified with SEM measurements
(Fig. 14(a–d)). The surface of Cu2 O was coated with fine TiO2 NPs,
but the morphology of Cu2 O did not change due to the heat treat-
ment. Cu2 O/TiO2 heterojunction corresponds to the Z-scheme phe-
nomena, according to a strand of characterization data (Fig. 14(e,
f)). Apart from the MO/TiO2 , Z-scheme heterostructure that could
be designed with the p–n junction effect, the heterojunction may
also be built using the energy band theory when the MO is used
as an n-type semiconductor. Currently, n-type semiconductors have
received significantly more attention than p-type semiconductors.
WO3 , SnO2 , indium (III) oxide, ZnO, TiO2 , and other n-type semi-
conductors are common. ZnO is a potential candidate as an n-type
with high catalytic performance, similar to TiO2 [117].
Wang et al. [155] used the standard calcination process to cre-
ate a ZnO/TiO2 heterostructure with a distinct micro/mesoporous
TiO2 framework. The sample has an organized macroporous struc-
ture with similar channels on the grains’ exterior surfaces and
sparsely scattered TiO2 microparticles in the channels. The ZT5
photocatalyst retained a structure comparable to pure TiO2 after
adding ZnO. The specific surface area of ZT5 was increased by em-
bedding a ZnO NPs mass inside the macropores and adhering to
the macropore walls surface. The RhB degradation efficiency of this
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Journal of Materials Science & Technology 131 (2022) 122–166
photocatalyst was higher than that of pure TiO2 and ZnO. After
TiO2 , WO3 is another potential n-type semiconductor with a high
solar absorption rate. Using the hydrolysis hydrothermal prepara-
tion technique, a WO3 -TiO2 vertical heterojunction was effectively
fabricated by creating an internal electric field through the inter-
face, as illustrated in Fig. 15(f) [134]. TEM and EDS images display
the accumulation and spatial separation of e– –h+ pair in Z-scheme
mode (Fig. 15(d, e)). Under irradiation, the internal electric field in-
duces the e– /h+ to analyze the Z-scheme charge transferring reac-
tion, thus attaining effective charge separation (Fig. 15(g–i)), show-
ing significant photocatalytic antimicrobial efficiency.
Generally, Eg for metal sulfide is narrower, and it is significantly
light-responsive when making a heterojunction with TiO2 . Between
them, CdS-TiO2 heterostructure is the utmost analytically investi-
gated photocatalytic technique [157]. The CdS (2.5 eV) is narrow
than the Eg of TiO2 (3.2 eV). The matched band structure makes
the perfect CdS and TiO2 , causing significant charge separation and
boosting the photocatalyst quantum proficiency. It can be observed
from the FESEM micrograph that TiO2 exhibited layered flower
spheres that were conducive to multiple light reflections and scat-
tering, so improving the extent of light harvested (Fig. 16(a–c))
and photocatalyst mechanism is revealed in Fig. 16(d). In addition,
the work function role was also investigated in interfacial trans-
fer. The estimated TiO2 (101) and CdS (110) surface work functions
(Fig. 16(f, h)) are shown at 7.1 and 5.8 eV, respectively, pointing
out that the Fermi level is more positive on the TiO2 (101) surface
than that of CdS (110). Furthermore, the composition of the inter-
nal electric field inhibited the additional electrons’ transformation.
Nickel sulfide (NiS) is a suitable semiconductor using a narrower
Eg , causing extensive attention in photocatalytic applications.
3.3.3. Metal oxide core-shell photocatalysts
In recent times, significant progress was made in engineering
metal core-shell nanostructured photocatalysts [159–164]. To use
these core-shell semiconductor photocatalysts in photoexcitation
processes, i.e., H2 production and H2 O splitting, it is thoughtful
to understand the metal core-shell effect on photocatalytic prop-
erties of outside MO core-shell (display in HRTEM images of an
individual Au-Cu2 O core-metal shell nanocomposite with its SAED
patterns in Fig. 17(a, b), respectively). Both metal-core and semi-
conductor shell nanostructures can do outstanding work as possi-
U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 14. SEM micrographs for (a, b) Cu2 O, (c, d) Cu2 O/TiO2 . Visualization of the proposed method to account for carbon dioxide photoreduction irradiated using UV-vis light
ranging (λ ≥ 305 nm) of (e) octahedral Cu2 O and (f) Cu2 O/TiO2 nanocomposite. Reproduced with permission from Ref. [154]. Copyright 2017 Elsevier B.V.

ble candidates in heterogeneous photocatalysts as a distinct type
of novel metal-core shell photocatalysts. Initially, enclosing metal
NPs’ outer shells inside a MO semiconductor might theoretically
increase their stability compared to agglomeration and promote
free undesired photo-corrosion or suspension in catalytic reaction
processes in real-world applications [165,166]. Second, because it
is a core material, its lower Fermi level may act as a cluster
of photoexcited electrons, extending the lifetime of photoexcited
charge carriers. However, this reaction may improve overall pho-
tocatalytic efficiency [167–173]. These characteristics were defined
by Kamat and his colleagues [174] and maybe realistically modeled
using a semiconductor metal nanostructure system as indicated in
Fig. 17(c). Also, the core-shell nanomaterials design allows for a 3D
tight connection between the semiconductor shell and core metal,
maximizing the metal-support contact. In this method, the inter-
facial charge transferring procedure may be made more accessible.
Finally, the MO core-shell nanocomposite architecture provides a
homogenous photocatalytic process [175,176]. In essence, the out-
standing benefits that MO and core-shell semiconductor nanos-
tructure photocatalysts imply that they might be used as a ground-
breaking strategy for light collection in heterogeneous photocat-
alytic activity.
In this regard, Sang and coworkers [161] used a unique tech-
nique in which electromagnetic induction produced micro-electric
potential that could be used to increase charge separation in a MO-
semiconductor core-shell hybrid structured for high-performance
photocatalysis. The metal-MO core-shell hybrid structure exhibited
a considerable impact of a magnetic field on increasing photocat-
alytic H2 generation. By changing a magnetic field in the photo-
catalytic H2 evolution reactor, a 110% increase in photocatalytic

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Fig. 15. (a) Schematic visualization of charge transferring in WO3 -TiO2 photocatalyst, (b) secondary electron and (c) backscattered electron SEM micrographs of the WO3 -TiO2
photocatalyst using Ag NPs loaded with photodeposition, (d) TEM and (e) EDS mapping micrographs of WO3 -TiO2 after MnOx photodeposition, (f) synthesis procedure of the
WO3 -TiO2 heterostructure, (g) WO3 -TiO2 heterostructure DFT simulated geometries (gray, blue, and red atoms represent Ti, W, and O atoms, severally in the top image) and
electrostatic potentials of (002 )WO3 and (001 )TiO2 facets at the heterogeneous interface (bottom image), (h) indicating WO3 and TiO2 density of states (DOS), the interband
states are underlined with the blue rectangle, (i) schematic view of the internal electric field among TiO2 and WO3 . Reproduced with permission from Ref. [156]. Copyright
2020 Royal Society of Chemistry.

H2 generation was realized using Au-NR-CdS NPs core-shell hy-
brid nanostructure. The amplification is possibly due to the Au-
NR core’s electromagnetic induction-derived micro-electric poten-
tial, which acts as an external electric field forcing photo-excited
charges in the CdS shell in opposing directions. The composite
photocatalyst is presented as a MO core-shell nanostructure by
a micro-electric potential supply within the relative motion in
an applied magnetic field. This hybrid structure offers an effec-
tive method for wirelessly applying an external electric potential
to powder photocatalysts, hence increasing their efficacy. Conse-
quently, due to the impact of an applied magnetic field, several
types of photocatalysts can increase the photocatalytic character-
istics of particular metal-semiconductor core-shell configurations.
The electronic configuration of CdS was considered with and with-
out an electric field, rather than magnetic field impact, to pro-
vide insight into charge transferring in CdS nanocomposite de-
pending upon Au-NR-CdS NP core-shell structure at the magnetic
field. Fig. 18 depicts the hexagonal greenockite CdS’s initial struc-
ture (Fig. 18(a)). The CdS nanocomposite was subjected to the in-
duced electromotive force created on the Au-NR in magnetic field
conditions. The influence of induced electromotive force (emf) on
the electrical structure of CdS was investigated using a 0.05 V m–1

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
Fig. 16. (a–c) FESEM micrographs, (d) TiO2 potential position and CdS band edges, and schematic drawing of direct Z-scheme photocatalytic reaction for TiO2 /CdS photocat-
alyst. Synthesized TiO2 (101) and CdS (220) crystal structure. (e) Red and grey balls stand for O and Ti atoms, respectively; (g) the rose-red and yellow balls represent Cd
and S atoms, respectively. The estimated work function of (f) TiO2 and (h) TiO2 . The blue and red dashed lines presented vacuum and Fermi levels, severally. Reproduced
with permission from Ref. [158]. Copyright 2017 Elsevier B.V.
electric field. At first, there are slits along the c-axis and a-axis,
as seen in Fig. 18(b). This implies that the charge carrier’s trans-
port channel is impeded in some directions. When an electric field
is applied on the a-axis, separated charge density combines at the
a-axis (Fig. 18(c)). The path’s construction permits charge transfer-
ring to occur without regard for direction. The separated charge
density combines using other components at the c-axis when an
electric field is applied on the c-axis (Fig. 18(d)). Within an exter-
nal electric field, the CdS average bond distance is 1.37 Å and 1.35
Å at the a-axis and c-axis, respectively. Fig. 18(e) depicts the influ-
ence of the motional induced emf on the charge carrier separation.
Lorentz force is generated within Au-NR with metal (Au-NR) and
cuts magnetic induction lines across a rotating magnetic field in
Au-NR-CdS NP metal core-shell structures. The charges inside Au-
NR are then polarized in a distribution along the Lorentz force’s di-
rection. The charge concentration at the surface is caused by polar-
ized electron dispersion. As a result of charge concentration on the
surface, there is an electric field in space. This may drive photo-
induced e– and h+ to travel in different directions, resulting in im-
proved charge separation. The charge separation through motional
emf is the most important feature of improving photocatalytic per-
formance, as shown in Fig. 18(f).
The following geometrical configuration of several noble MO
can be seen in Fig. 19(a). The several morphologies frequently
boosted their photocatalytic and photovoltaic belongings and of-
fered appropriate substrates to introduce noble metal NPs. Hence
many nanocomposites with several morphologies may be achieved
with many forms of MOs as templates, for instance, Au-decorated
TiO2 NPs (Fig. 19(c)) [178], Cu2 O/Pd cuboctahedrons nanocompos-
ites (Fig. 19(d)) [179], TiO2 /Ag nanotube heterojunctions (Fig. 19(e))
[180], and hollow toroidal ZnO/Au structures (Fig. 19(f)) [181].
Multi-core noble metal-MO core-shell nanomaterials might be con-
structed via various template approaches (carbon, polystyrene,
and SiO2 spheres) [182,183]. Multi-Pd core/hollow CeO2 core-
shell nanomaterials were fabricated through polyvinylpyrrolidone
(PVP) functionalized carbon nanosphere templates as displayed in
Fig. 19(b). The Ce3+ hydrothermal route and the carbon template
and PVP stabilizer removal may be received in the last calcina-
tion route in the air. This produces Pd/CeO2 core/shell nanostruc-
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Journal of Materials Science & Technology 131 (2022) 122–166
tures construction. Song and coworkers [184] synthesized Au/TiO2
core/shell structures using Au NPs implanted into TiO2 mesoporous
hollow sphere inner wall via sulfonated-polystyrene spheres (SPS)
as a template.
3.3.4. Conclusive remarks
MO nanostructured semiconductor photocatalysts may be clas-
sified into two groups. To begin, the material must be photon-
energetic, and during excitation, excited electrons must be trans-
ported to the following portion of the material, which can drive
the catalytic procedure. This group contains plasmonic nanostruc-
tures (Au, Ag, and Pt) and high Eg semiconductors like TiO2 , in
which plasmon electrons are transferred from gold to TiO2 to com-
mence catalytic activity during photoexcitation. These are plas-
monic photocatalysts with extensive characterization and explana-
tion in the literature. Z-scheme for MO-heterojunction photocata-
lysts can be efficiently separated e– –h+ while also confirming that
the CB and VB locations of the photocatalysts are adequate, pre-
serving potential redox capacity. Directed Z-scheme photocatalytic
processes, on the other hand, were gradually replaced by a new Z-
scheme heterojunction structure mechanism. Because of its stable,
low-cost, and non-hazardous properties, TiO2 plays an important
role in photocatalytic activity. As a result, this catalyst has a low
visible light consumption rate and a restricted reduction capacity.
Photogenerated carriers can be successfully separated by forming
heterojunctions between semiconductors with the same band po-
tential and TiO2 .
Engineering metal core-shell nanostructured photocatalysts
have advanced significantly in recent years. It’s important to under-
stand the metal core-shell impact on photocatalytic characteristics
of outer MO core-shell semiconductor photocatalysts before us-
ing them in photoexcitation processes like H2 generation and H2 O
splitting. As a separate sort of innovative metal-core shell photo-
catalysts, both metal-core and semiconductor shell nanostructures
may accomplish an exceptional job as a feasible candidate in het-
erogeneous photocatalysts. Initially, it was thought that encasing
metal NPs’ outer shells inside a MO semiconductor would boost
their stability compared to agglomeration and encourage free un-
wanted photo-corrosion or suspension in catalytic reaction pro-
U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
Fig. 17. (a) TEM image of a single Au-Cu2 O core-shell NP having a compact MO shell and (b) SAED pattern indicating single-crystal planes. Reproduced with permission
from Ref. [177]. Copyright 2012 American Chemical Society. (c) Pattern of a light-induced charge separation procedure in a typical metal-MO core-shell in photocatalysis.
Reproduced with permission from Ref. [55]. Copyright 2016 Royal Society of Chemistry.
cesses in real-world applications. Second, because it is a core ma-
terial, the lower Fermi level might operate as a cluster of photoex-
cited electrons, increasing the lifespan of photoexcited charge car-
riers. This process, on the other hand, may boost total photocat-
alytic efficiency.
3.4. Strategies to improve performance
3.4.1. Surface modification of metal oxide
Nanostructured MOs, such as TiO2 , ZnO, WO3 , Fe2 O3 , and
BiVO4 , have been broadly investigated for photocatalysis. Surface
modification schemes offer a chance for attaining extremely pro-
ficient conversion procedures by coupling MOs with cocatalysts.
Photocatalytic reactions principally involve three steps: generation
of photoproduced carriers, charge transfer, and surface catalytic re-
actions. Cocatalysts mostly act as redox reaction sites to catalyze
the reduction/oxidation reaction by reducing activation energy and
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Journal of Materials Science & Technology 131 (2022) 122–166
stabilizing the photocatalyst as well as trapping the photogener-
ated e– –h+ to facilitate their separation and transport [187]. De-
pending upon the redox type of the promoted reaction, the co-
catalyst may be categorized as a reduction/oxidation cocatalyst. It
is significant for the cocatalysts to match their energy levels and
electronic structures to those of MO. Therefore, the cocatalyst and
MO must reveal compatible lattices and structures with matching
band levels. In this case, the interfacial charge transport method
can proceed in an ideal direction across the semiconductor and co-
catalysts, which guides to significant charge separation. The ratio-
nal integration of MOs using metal cocatalysts to form heteroge-
neous structures has proved to be an effective technique to pro-
mote the photoexcited e– /h+ pairs separation and maximized light
absorption. Owing to the considerable advancement of electromag-
netic fields and light-scattering qualities, plasmonic metals have
currently received significant attention in photocatalytic fields. Res-
onant optical excitation of surface plasmons generates energetic
hot electrons, thus promoting photocatalytic reactions [188].
U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 18. (a) Demonstration of CdS nanostructure. Electron density difference maps and calculated CdS bond distances before and after applying electric fields in multiple
directions (b) without an external electric field. (c) Application of an applied external electric field (0.05 V m–1 ) in direction of the CdS axis. (d) Application of an applied
external electric field (0.05 V m–1 ) in the direction of the CdS c-axis. (e) Separation of e– –h+ pairs in CdS NPs involves two distinct surfaces of Au-NRs with opposite polarized
charges attributable to electromagnetic induction effects. (f) Illustration of photocatalytic improvement of metal-MO core-shell structures in the magnetic field. Reproduced
with permission from Ref. [161]. Copyright 2020 Elsevier B.V.

3.4.2. Plasmonic enhancement
The plasmonic metal incorporation into MO is a promising
scheme for increasing the photocatalyst’s activity with plasmonic
energy transferring from the metal to the MO [189]. Plasmonic
was proved to be importantly promising in spreading the range of
semiconductors’ light absorption as metal structures act as tuned
light antennas among the full sunlight irradiation [190]. The im-
provement of highly efficient plasmonic metal-MO photocatalysts
fulfills the various practical application requirements [191].
3.4.2.1. Direct electron transfer. The incorporation of plasmonic
metal NPs with MOs through hot carriers is one of the most sig-
nificant procedures in heterogeneous photocatalysis. The results of
the theoretical calculations suggest that the hot-electron injection
rate from NRs is various orders of magnitude higher than that of
the spherical counterparts. Furthermore, the hot carrier’s injection
rate into MOs increases as the NRs aspect ratio increases and then
decreases as the number of NRs increases, thus controlling the as-
pect ratio constant. In this case, the traditional material system is
a gold-decorated TiO2 system, where hot electron injection is the
underlying plasmonic advancement mechanism. For instance, an
Au-TiO2 -Pt nanodumbbell nanohybrid was synthesized for strate-
gic energy transfer modulation in the water reduction reaction. The
TiO2 layer is mainly put on the Au NR tips, while most of the Pt
NPs are collected on the surface side, producing the formation of
the Au-TiO2 -Pt ternary plasmonic nano-dumbbell structure. In the
Au-TiO2 -Pt ternary nanodumbbell, a maximum photocatalytic hy-
drogen evolution rate of 344.6 μmol g–1 h–1 was achieved with an
enhancement factor of about 4.31, attributing to the efficient heat
transfer and injection process. The electrons are from the longitu-
dinal and transverse surface plasmon resonance decay of Au NRs,
respectively. The positive synergistic effect of plasmons and co-
catalysts meaningfully optimizes light utilization and significantly
enhances photocatalytic activity, therefore suggesting a significant
strategy for manipulating the design of proficient artificial photo-
synthesis systems [192].

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 19. (a) Schematics of various structures of noble metal-MO NPs. Reproduced with permission from Ref. [185]. Copyright 2017 Royal Society of Chemistry. (b) Diagram
of the construction of a Pd/CeO2 core/shell nanomaterial: (I) Fabrication of carbon sphere decorated using PVP template; (II) construction of colloidal Pd NPs from tetra-
chloropalladic acid; (III) synthesis of carbon-Pd-Ce(III) nanomaterials by a hydrothermal route; (IV) preparation of Pd/hCeO2 core/shell nanomaterial through hollow inner
space with a calcination method. Reproduced with permission from Ref. [186]. Copyright 2013 American Chemical Society. (c) SEM micrograph of TiO2 /Au NPs. Reproduced
with permission from Ref. [178]. TEM micrographs of (d) Cu2 O/Pd cuboctahedron nanocomposites. Reproduced with permission from Ref. [179]. Copyright 2015 and 2014
respectively John Wiley & Sons. (e) TiO2 /Ag nanotube heterojunctions. Reproduced with permission from Ref. [180]. (f) Hollow doughnut-like ZnO/Au composites. Reproduced
with permission from Ref. [181]. Copyright 2015 and 2012, respectively American Chemical Society.

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
Moreover, the size of plasmonic NPs and the size of metal NPs
also have a major effect on the intensity of hot electron generation
and injection, absorption, and near-field enhancement. Most of the
hot carriers generated in large metal NPs have very low excitation
energies [193]. A series of TiO2 -supported Au, Au@SiO2 , Ag, and
Au@SiO2 NPs were selectively synthesized by Lee et al. [194]. Re-
garding the catalytic response, the optimal sizes of Au and Ag NPs
for Au@SiO2 and Ag@SiO2 NPs measured to be 26 and 25 nm, re-
spectively. The results show that the plasmonic NPs with potential
LSPR effect have better photocatalytic performance, which demon-
strates that the Ag@SiO2 /TiO2 system has superior catalytic activ-
ity than the Au@SiO2 /TiO2 system. In particular, Ag25@SiO2 /TiO2
shows the highest catalytic response in the decomposition of aque-
ous salicylic acid and aniline, which is measured to be 3.8 and 2.5
times higher than that of the bare TiO2 , respectively [194]. Thus,
there is still a limitation that the sole utilization of the hot elec-
tron injection process does not yield sufficient solar energy conver-
sion in plasmonic metal-MO heterojunctions because only a small
fraction of the hot electrons can be collected, although, during the
plasmonic decay process, a large number of plasma hot electrons
will be generated in it.
3.4.2.2. Plasmon-Induced resonance energy transfer. Plasmon-
induced resonance energy transfer (PRT) involves the transition
dipoles coupling and depending upon the distance and spectral
overlap of the energy donor (metal) and energy acceptor (MO).
Though, it may still happen even though there is an insulating
space layer between the plasmonic metal and the MO [195]. A
proficient inorganic photosensitizer was presented by Liu et al.
[196]. Photodynamic therapy achieved by incorporating plasmonic
nanostructures of gold and metal into Cu2 O semiconductors.
By utilizing the PRT process from Au to Cu2 O, Au@SiO2 @Cu2 O
reveals a high singlet oxygen quantum yield of 0.71 under 670
nm laser activation. Particularly, it effectively develops e– /h+
pairs generation in the Cu2 O shell through a distinct PRT charge-
separation behavior as well as photocatalytic activity. Meanwhile,
Cu2 O can absorb O2 and consume photoexcited electrons during
water photocatalysis. Therefore, based on the PRT mechanism,
plasmonic metal positively affects the metal-MO photocatalyst
[196]. Hu et al. [197] first prepared the Au/Ag NRs and fabricated
the uniform Cu2 O shell by a wet-chemical method using CuCl2 . By
comparing the apparent first-order rate constant k of Au/Ag/Cu2 O
nanospheres (0.010 min–1 ) and Au/Ag/Cu2 O NRs (0.026 min–1 ), it is
determined that the photocatalytic efficiency of the latter is about
2.5 higher than that of the former times. This is due to both the
dipole and octopole plasma modes enhancing the e– /h+ separation
in CuO by PRT, as affirmed by transient absorption measurements
[197]. Introducing PRT by incorporating plasmonic metal nanos-
tructures into photocatalyst is an effective strategy to offer MOs
with potential localized electromagnetic fields via nonradiative
dipole-dipole coupling, which is a promising way to suppress
charge recombination and enhance photocatalytic performance.
3.4.3. Other metal cocatalysts
Most metal promoters are plasmonic metals with complex roles
in artificial photosynthesis. Kim and Lee [198] showed that some
other non-plasmonic metals, i.e., Pt, Pd, Ru, and Ni, can absorb
light through interband transitions, generating heat or high-energy
electrons, albeit with weaker absorption compared to LSPR. These
metals were also elucidated to exert light-enhancing effects and
are widely used in heterogeneous photocatalysis [199]. In the next
subsections, the main functions of other non-plasmonic metal pro-
moters to obtain required reactions and conquer competing re-
actions are discussed. Active metal cocatalysts, such as Pt, are
thought to act not only as sinks for captured electrons, thereby de-
laying the recombination of e– /h+ pairs, but also as active sites. For
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Journal of Materials Science & Technology 131 (2022) 122–166
instance, Liu et al. [200] synthesized the ultrathin TiO2 nanosheets
(TiO2 -U) with abundant defects to facilitate the well-dispersed Pt
NPs with low metal loading by the photochemical route. The well-
dispersed Pt NPs supported by TiO2 -U exhibited excellent photo-
catalytic activity to convert CO2 to CH4 and CO with a total elec-
tron yield of 666.6 μmol g–1 h–1 , which is more than four times
that of other catalysts. The CO2 photoreduction was validated using
in-situ Fourier transform infrared spectroscopy to verify the impor-
tant role of sites in the Pt catalyst for CO2 adsorption and activa-
tion. The results show that CO2 can be trapped at the Ti3+ sites,
and the peaks associated with CO2 intermediates are increased,
indicating that the activation and dissociation ability of CO2 on
the photocatalyst is greatly enhanced. As expected, the ultrafine Pt
NPs facilitated the photoproduced electron-hole pairs separation,
producing enhanced light-harvesting capability and quantum effi-
ciency [200]. But, the high cost and limited reserves of platinum
hinder the practical application of platinum. This has led to the
search for highly active, economical, and sufficient metal cocata-
lysts to accelerate photocatalytic reactions. Wang et al. [201] used
nonprecious Mo and Co to decorate TiO2 for the light-induced
semi-hydrogenation reaction of internal and terminal alkynes us-
ing alcohols as H-source. For the semi-hydrogenation reaction, the
catalytic selectivity of MoCo@TiO2 (93%) is higher than that of Pd-
modified TiO2 (68%). Decorating MO surfaces with Mo and Co can
greatly enhance their reactivity, which displays strong efficiency
than Pd-based materials for organic transformations [201]. As pre-
viously mentioned, non-plasmonic metal NPs may facilitate profi-
cient e– /h+ pair separation, providing a surface engineering strat-
egy for the design of efficient photocatalysts. Metal nanocompos-
ites, such as Au–Pt [202], Au–Pd [203], Ag–Pt [204], Ag–Pd [205],
and Ag–Ni [164], have been fabricated and utilized for the surface
reactions. Usually, these bimetallic NPs are composed of plasmonic
and non-plasmonic metals. Plasmonic metals can exert plasmonic
effects, while non-plasmonic metals act as co-catalysts. For exam-
ple, Cai et al. [206] proposed Janus Pd–Au heterojunctions as ad-
vanced cocatalysts for the conversion of CO2 to CH4 , yet attain-
ing an unprecedented average CH4 production rate of 48.2 μmol
gcat −1 h−1 with a higher selectivity of 91.4% and stability over a 20
h period. These asymmetries are much finer than those of other
structures composed of Pd and Au atoms. The Pd–Au interfaces
act as a highly active and selective site for enhanced CO2 to CH4
conversion efficiency [206]. Thus, colloidal heterometallic NPs have
major properties attributable to the synergistic effect induced by
the interaction between the two components. Additionally, proper-
ties including work function can be measured by tuning the metal
species composition ratio.
3.4.4. Conclusive remarks
Finally, it is possible to obtain highly effective energy conver-
sion with the integration of metals using MOs that control the light
absorption and charge separation procedures in semiconductors
through the above-discussed mechanisms (PRT). Plasmonic metals
can play multiple roles, with surface catalysis, surface passivation,
Fermi level equilibrium, and plasmonic growth. It also works as a
light antenna and plasmonic energy transferring to the MO. In con-
trast, metal cocatalysts placed on MOs facilitate the charge carri-
ers’ separation by conquering electron–hole recombination in pho-
tocatalysts. Besides, they behave as reaction sites by reducing the
kinetic barrier to promote photocatalytic response.
3.5. Effect of morphology on photocatalysis
3.5.1. Nanotubes
By changing characteristics, including form, size, and pattern ar-
rangement, researchers are attempting to utilize the unique fea-
tures of these nanoscale photocatalysts. Because of their outstand-
U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
ing physicochemical belongings and anisotropic configurations, 1D
nanostructured morphologies, i.e., NTs, NRs, and nanofibers (NFs),
have been a current study issue in the photocatalysis field [207–
209]. Efforts were being made on several process parameters to
create diversely shaped nanostructures, with tubular and rod-
shaped structures being the most extensively investigated. The
photocatalyst using NTs is structurally stable at several hundred
degrees centigrade. The photocatalytic performance appears to be
influenced by the wall thickness, nano interface, and tube-to-tube
contact locations [210]. Kang and Chen [211] recently produced
TiO2 photocatalyst nanotube nanostructures and exhibited photo-
reduction of MB. They discovered that TiO2 nanotube arrays re-
vealed a binary mix of anatase and brookite crystalline phases
favorable for photolysis within a small temperature range. An
anodic oxidation technique was used to create tapered, conical-
shaped TiO2 NTs [211]. Ratanatawanate et al. [212] produced S-
nitrosocysteine decorated PbS quantum dots/TiO2 NTs for improved
singlet O2 production, where they exploited the morphology as
a nitric oxide discharging vehicle to boost photocatalytic activ-
ity. In recent research, Gupta et al. [213] generated an ultra-dense
ZnO nano-forest (made up of vertically produced better aspect ra-
tio nanotube/NR identical to structures) and showed its potential
as photocatalysts. Interestingly, they showed typical 1D ZnO nan-
otube/NR FESEM micrographs anchored in nanocarpets in Fig. 20.
3.5.2. Nanofibers
Nanofibre photocatalyst is the most advanced skill and is widely
employed because of its enormous specific surface/volume ra-
tio and customizable nanopore shape. It has structural flexibility
and enhanced surface functioning, and the mechanical characteris-
tics of nanofibers, i.e., tensile strength, are astonishing [214,215].
Fig. 21(a) represents the idea of contaminant removal activity
with MO nanofibers via a pictorial illustration. As illustrated in
Fig. 21(b), well-contacted metal-MO nanofibers are beneficial for
creating phase junctions. Commonly, in metal/MO nanofibers, the
metal part may trap the photoexcited carriers and support inter-
facial charge transferring procedures, resulting in fast recombina-
tion and hindering photocatalytic performance. In the past few
years, substantial effort was made toward joining MO nanostruc-
tures using appropriate metallic. Sharma and coworkers [54] par-
tially aligned freestanding mesoporous pure anatase TiO2 nanofiber
(TiO2 -NF) mats which were constructed for photo catalytically re-
sponsive electrospinning with titanium isopropoxide (TTIP) mix-
tures on a rotating drum collector (Fig. 21(d, f)), using a charge car-
rier polymer, PVP in acetic acid and ethanol. Calcination eliminates
PVP and produces mesoporous TiO2 -NF with fiber diameters rang-
ing (25–75 nm) via optimizing the electrospinning components.
UV-vis absorption spectra of TiO2 Eg energy stimulate an increase
in calcination temperature, therefore permitting Eg engineering for
numerous applications. Transformation of electrons to the surface
suggests reacting with the adsorbed molecules producing their ox-
idation via holes or reduction by electrons. Normally, one or more
intermediates like H2 O2 , O2 •– , •OH, or O2 play an important role
in reaction phenomena (schematically shown in Fig. 21(c)). The
naphthalene photoreduction analysis was done spectrophotomet-
rically by evaluating its absorbance at 275 nm using a stable UV
light. The porous TiO2 fibers’ UV-vis spectrum for 50 mL of 25 ppm
naphthalene solution of several time intervals per 15 mg loading
is shown in Fig. 21(e). Researchers discovered that nanofiber pho-
tocatalyst mats are extremely effective kinetically in entire aque-
ous naphthalene photocatalysis, aided by fibrous photocatalysts’
hierarchical porosity and remarkable surface/volume ratio. It is
also worth noting that photocatalyst may be readily customized
by desirable electrospinning metals, carbon, and other nanomate-
rials into fibrous nanostructures [54]. Electrospinning is another
method of the most opportune and scalable technology among
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Journal of Materials Science & Technology 131 (2022) 122–166
the vast range of manufacturing procedures aiming at achieving
1D nanofiber nanostructures [216]. Nanofiber photocatalysts are
now receiving a lot of attention because of their outstanding prop-
erties of 1D nanostructure for photocatalysis [216]. Compared to
alternative nanomorphologies, electro-spin nanofibrous photocata-
lysts were beneficial to the vectorial transit of photoexcited charges
along their grain boundaries, resulting in an enhanced e– –h+ pairs
separation [217]. As a result, the fabrication and architecture of fi-
brous nanostructured photocatalysts that respond to visible light il-
lumination remain a main focus of study. Singh et al. [53] recently
reported a new technique for fabricating free-standing mesoporous
ZnO nanofibrous mats using electrospinning. The morphology of
calcined (Fig. 21(l, m)) ZnO nanofiber and free-standing photocat-
alyst mats (Fig. 21(n)) using porous crystalline (Fig. 21(o)) cre-
ated by electrospinning is shown in FESEM pictures in Fig. 21.
They discovered that nanofiber photocatalysts with a diameter of
60 nm are particularly efficient in polycyclic aromatic hydrocarbon
dye-degradation like anthracene and naphthalene. Sharma’s group
[54] has created electrospun partly aligned free-standing meso-
porous bare anatase TiO2 nanofiber mats in photocatalysis.
Further, a unique TiO2 /ZnO core-sheath NF film designed
with an amazing coaxial electrospinning skill [218]. The ran-
domly oriented PVAc/TTIP/Zn(CH3 COO)2 nanocomposite fibers pos-
sess smooth surface morphology of about 200 nm diameter and
the diameter was decreased by ∼25% to ca. 150 nm after calci-
nation owing to the elimination of dimethylformamide and PVAc
(Fig. 21(j, k)). The heterojunction structures among TiO2 and CuO
yield significant e– –h+ separation. Fig. 21(p, q) represents hybrid
semiconductor (TiO2 /CuO) electrospun NFs with lower and higher
magnification. The reported photocatalytic hydrogen production in
UV light illumination over 4 h is displayed in Fig. 21(r). After a
definite value of CuO doping, the H2 generation rate reaches a
peak, after that the generation rate decreases [219]. A band align-
ment arrangement is shown in Fig. 21(s) for a better understand-
ing of e– –h+ transference. The same authors elucidated that the
TiO2 /CuO nanocomposite fibers have the multifunctional tendency
for photodegradation of organic dyes and effective hydrogen pro-
duction from wastewater [220]. The nanocomposite fibers showed
exceptional significant influence like (a) huge surface area, (b) ab-
sorbance with high wavelength regions, (c) continuous and long
nanofibers for proficient transferring of charges, (d) heterostructure
that can increase e– /h+ separation, and (e) a second MO that can
act as a co-catalyst for hydrogen production. Fig. 21(g, h) displays
the perfect TiO2 /CuO electrospun nanocomposite fibers with lower
and higher magnification. These nanomaterials are also a signif-
icant candidate for environmental remediation as well. Fig. 21(i)
presents the e– /h+ transference path within the nanocomposite
fibers (TiO2 /CuO). When a photon is absorbed on the surface of the
catalyst, electrons are transported from TiO2 CB into CuO CB within
heterojunction due to the potential difference. Subsequently, the
excess of charges which can accumulate in CB of copper oxide orig-
inates a negative shift in its Fermi level, interpreting the high avail-
ability of charge carriers for interfacial charge transferring to H+ in
solution to generate hydrogen. As shown in Fig. 21(t, u), the cross-
sectional SEM micrograph of NP electrode with rice grains and NF-
shaped TiO2 as scattering layer is shown. TiO2 NP electrode aver-
age thickness is ∼10 μm and the average thickness of the scat-
tering layer is ∼2 μm. The performance improved from 6.44% to
7.06% with NFs as a scattering layer, on other hand, Jsc was boosted
in the range of 13.6–14.9 mA cm–2 .
3.5.3. Nanoribbons
The extraordinarily high activity of nanoribbons may be at-
tributed to their ultrathin nanostructures, which give a vast surface
area and nanoscale shape, which facilitates rapid electron mobil-
ity from the interior onto the surface to enhance photocatalysis.
U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 20. FESEM micrograph of ZnO nanoforest, using the regular/angled sample stage of an electron microscope to image at different areas and magnifications. Reproduced
with permission from Ref. [213]. Copyright 2015 Royal Society of Chemistry.

Interestingly, researchers used the hydrothermal method to syn-
thesize micron-thick, ultra-thin Na2 V6 O16 ·H2 O nanoribbons, which
were found to have considerable activity when revealed to visi-
ble light [225]. In a similar vein, Zhang’s group [226] has gen-
erated single-crystalline α -MoO3 nanoribbons for effective pho-
todegradation applications, while Shao and coworkers [227] have
developed widely distributed boron-doped graphene nanoribbons.
Du et al. [228] fabricated anatase TiO2 nanostructured with dis-
tinct morphologies from exfoliated nanoribbons for semiconduc-
tor photocatalysis. In this research, a facile hydrothermal syn-

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 21. (a) Representative of MO Semiconductor, (b) illustration of charge transferring across the metal-MO junction. Reproduced with permission from Ref. [221]. Copy-
right 2017 MDPI. (c) Mechanism of C-doped anatase TiO2 nanofiber mats for dye degradation, (d) FESEM of TiO2 -NF, (e) UV-vis spectra of pollutant elimination, (f) HRTEM
of TiO2 NF. Reproduced with permission from Ref. [54]. Copyright 2014 American Chemical Society. FESEM of TiO2 /CuO nanofibers at (g) lower and (h) higher magnifi-
cations and (i) presentation of excited e– /h+ in TiO2 /CuO. Reproduced with permission from Ref. [220]. Copyright 2013 Elsevier B.V. (j) FESEM and (k) TEM images of
PVAc/TTIP/Zn(CH3 COO)2 . Reproduced with permission from Ref. [222]. Copyright 2012 Elsevier B.V. FESEM of ZnO nanofibers synthesize at (l) 450 °C; (m) 650 °C, (n) ZnO
nanofibers, (o) TEM micrograph and SAED pattern of ZnO nanofibers (inset). The arrows indicated various crystal planes of ZnO. Reproduced with permission from Ref.
[53]. Copyright 2013 Elsevier B.V. (p) TiO2 -CuO FESEM, (q) FESEM micrograph of TiO2 –CuO, (r) photocatalytic proficiency, (s) photocatalytic reaction over TiO2 /CuO het-
erostructures. Reproduced with permission from Ref. [223]. Copyright 2013 Elsevier B.V. Cross-sectional SEM photographs of (t) TiO2 NP–rice grain structure electrode and (u)
TiO2 NP–NF electrode (top side exhibit magnified pictures for scattering layers). Reproduced with permission from Ref. [224]. Copyright 2011 Royal Society of Chemistry.

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
thesis approach was made to prepare anatase nanocrystals with
the nanoribbons colloidal solutions as the precursor. A possible
transformation reaction phenomenon in the hydrothermal route
was proposed from TMA+ -intercalated layered tetratitanate to TiO2
nanostructured, which is demonstrated in Fig. 22(a). By simply
controlling the colloidal solutions’ pH value, rutile TiO2 nanos-
tructures with distinct shapes and exposed {110} and {001} facets
might be controllably obtained. In addition, depending upon the
experimental outcomes, possible reaction formation phenomena
from the conversion of nanoribbons to anatase nanostructures with
several morphologies and visible crystal facets were also exam-
ined. Anatase TiO2 nanospindles at pH 6.0 and 7.0 are shown in
Fig. 22(b–e). Anatase TiO2 nanospindles with tetragonal sides and
truncated pyramid ends are produced during hydrothermal pro-
cessing (Fig. 22(b, c)). Fig. 22(b–e) exhibits TEM and HRTEM mi-
crographs of anatase TiO2 nanospindles achieved at pH 6.0 and pH
7.0. During the hydrothermal reaction, the anatase TiO2 nanospin-
dles using tetragonal sides and somewhat truncated pyramid ends
are generated. Fig. 22(d, e) shows the matching identical HRTEM
micrographs of the dotted circle and rectangle regions as labeled
in Fig. 22(g).
3.5.4. Other morphologies
Much additional nanomorphology has been investigated for
photocatalysis, including nanospheres, thin films, nanocones,
nanoribbons, and so on. Zhang et al. [229] have established a tech-
nique for producing porous TiO2 hollow nanospheres. To deter-
mine photocatalytic processes, the catalysts were exposed to UV
light and measured for photoreduction. Their findings show TiO2
with hollow nanospheres had superior photocatalysis than com-
mercial Degussa P25 in the presence of Cr(VI), attributable to in-
crease surface area. Bi and his colleagues [230] have exhibited
photocatalytic activity toward H2 production using a simple hy-
drothermal technique to produce Bi and Bi-Ag alloy nanospheres.
Mondal et al. [231] used spin coating to manufacture macroporous
TiO2 /polyacrylonitrile and TiO2 /carbon hybrid films in the context
of composite nanostructured photocatalysts. TiO2 NPs having an
average size of 40 nm are photocatalyzed by a porous carbon sheet.
The photocatalytic efficiency of TiO2 /carbon hybrid porous films is
demonstrated by the degradation of aqueous RhB dye. Bi et al.
[230] synthesized with a facile hydrothermal route for the first
time that Bi and Bi-Ag alloy nanospheres show significant pho-
tocatalytic hydrogen generation activities. Interestingly, by incor-
porating Ag to form Bi-Ag alloy NPs, these Bi activities may be
highly stimulated, which can be attributed to significant charge
separation and improved charge carrier concentration (Fig. 22(f)).
The photoelectrochemical property of Bi0.7 Ag0.3 alloy NPs may be
changed by altering the concentration of Ag nanowires. According
to cited literature, the elemental distribution of Bi and Ag NPs,
and Bi-Ag alloy EDS line analysis have been made and are pre-
sented in Fig. 22(g). The red line is passing through a Bi-Ag al-
loy nanosphere at 150 nm. It might be found that the compo-
sition of Bi and Ag is exhibited clearly in the nanosphere area.
HRTEM presents in Fig. 22(h) with calculated d-spacing. In another
research [232], ultra-small ZnO nanosheets are anchored on bis-
muth sodium sulfide nanobelts as a solar-driven photocatalyst to
remove contaminants and photoelectric catalytic water oxidation
(see Fig. 22(i–l)).
3.5.5. Conclusive remarks
The photocatalytic activity method can be affected by pair re-
combination within the photocatalyst. The oxygen molecules that
may be adsorbed on a semiconductor photocatalyst surface be-
have as electron imprisoners and govern the light-induced e– –
h+ pair recombination method. The nanostructured semiconduc-
tor owns greater photocatalytic proficiency than bulk photocata-
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Journal of Materials Science & Technology 131 (2022) 122–166
lysts. The reason behind this could be described through the quan-
tum confinement effect and larger surface area. When the catalyst
particles’ size is less than a definite precarious limit (e.g., size de-
creases to nanoscale), this produces a quantum size effect due to
electron confine movement. Quantum confinement is one of the
highest direct effects that lead to VB and CB of semiconductor cat-
alysts modifying into discretized energy states. This discretization
method relies on material structure size, representing that either
VB potential changes more positively, or the potential of CB be-
comes more negative. Therefore, the redox tendency of e– and h+
is increased, and thus, the oxidation reaction of nanomaterial pho-
tocatalysts is enriched. Another important aspect is the catalysts’
larger surface area. More atoms on the surface of photocatalysts
improve adsorption to carbon-based waste products. Since elec-
trons may quickly go from inside to surface when particles are
nanoscale in size, the redox process is aided by nanoscale cata-
lysts. Lower charge carrier diameter and faster e– –h+ couples dif-
fusing onto a surface from within catalyst as a surface to volume
ratio increases. This may offer a reduced possibility of e– –h+ pair
recombination and more photocatalytic reaction may be attained.
However, nano-regime semiconductors would have greater photo-
catalytic efficiency than bulk. The catalytic activity is impressively
affected by porous nature and photocatalyst porosity distribution.
The ideal porosity distribution in a micro (ranging < 2 nm pore
size) mesoporous (size ∼2–50 nm) catalyst is dynamic for profi-
cient catalysis.
4. Metal oxides as adsorbate
The study of physiochemical contact among adsorbate and ad-
sorbent is called adsorption. Temperature, interaction forces among
the adsorbent and adsorbate, medium pH, foreign elements’ pres-
ence, concentration, and other factors all impact the adsorption
process [233]. Adsorbents must have an enormous surface area, ex-
cellent textural and surface qualities, and mechanical stability to
remove organic compounds from wastewater effectively. Organic
contaminants in wastewater act as adsorbates, slowly adsorbing on
adsorbents’ surface until equilibrium among adsorbents and adsor-
bates is reached (Fig. 23). Several kinds of adsorption isotherms
were being constructed to comprehend the adsorption mechanism.
The adsorption might be chemisorption or physisorption, depend-
ing on contact with the adsorbates. The van der Waals contact,
H2 bonding, dipole-dipole attraction, and other interacting factors
regulate physisorption or physical adsorption. Adsorption of this
sort is more noticeable and reversible. As a result, adsorbents may
be simply regenerated in future batches. The adsorption method
is remarkably adaptable for wastewater treatment because of its
cheap cost and renewable adsorbent resources, minimal mainte-
nance, high effectiveness, fast adsorption, immediate adsorption
of various contaminants, and easy operation. Carbonaceous mate-
rials such as activated carbons derived from biomass, graphene,
CNTs, metal nano-chalcogenides, MO nanomaterials, LDHs, organic-
inorganic nanomaterials, inorganic complexes, metal nanomaterial,
and other carbonaceous nanocomposites have all been extensively
studied as adsorbents organic pollutants eradication [234]. The cur-
rent breakthroughs in several kinds of MO nanomaterials and their
nanocomposites for organic contaminants adsorption from contam-
inated water are highlighted in this section.
4.1. Removal of heavy metallic ions from water
Numerous treatment methods were produced for the deduc-
tion of heavy metals from contaminated water. Conventional pro-
cedures including co-precipitation [236,237] membrane separation
[238], ion exchange [239], electrocoagulation [240], reverse osmo-
sis [241], and filtration/ultrafiltration [242], etc., every aforemen-
U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 22. (a) Transformation reaction mechanism and simulated crystal form of TMA+ intercalated layered tetratitanate to TiO2 nanostructured. TEM micrographs and matching
HRTEM micrographs of anatase TiO2 nanospindles (b, d) pH 6.0-T150, (c, e) pH 7.0-T180 after hydrothermal route for 24 h. Reproduced with permission from Ref. [228].
Copyright 2019 John Wiley & Sons. Bi nanospheres for (f) water splitting, (g) EDS line analysis, (h) HRTEM micrograph, and HRTEM. Reproduced with permission from
Ref. [230]. Copyright 2014 American Chemical Society. ZnO nanosheets for photocatalysis: (i) stability, (j) recycling test, (k) effect of catalyst loading over the NaBiS2 -ZnO
composite, and (l) proposed phenomena for photocatalytic degradation of tetracycline in the presence of NaBiS2 -ZnO composites. Reproduced with permission from Ref.
[232]. Copyright 2021 Elsevier B.V.

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
Fig. 23. Schematic visualization of probable contact ways between As (III) and As (V) and MO nanostructures aimed at arsenic ions elimination. Reproduced with permission
from Ref. [235]. Copyright 2020 Royal Society of Chemistry.
tioned methods have certain particular benefits. For instance, the
chemical precipitation (CP) scheme for eliminating heavy metals
is straightforward to proceed with without further expensive ap-
paratus [243,244]. Ion exchange, electrochemical, and electrodial-
ysis tend to selectively remove pollutants from a mixture. How-
ever, photocatalysis can remove both organic and metal contami-
nants simultaneously. Thus, each apparatus also contains a few in-
herent drawbacks [245]. For instance, CP causes a large quantity
of sludge, producing disposal problems and generating secondary
pollutants. Ion exchange, electrodialysis, membrane filtration, and
electrochemical methods have high maintenance costs and oper-
ations. Photocatalysis can produce additional contaminated degra-
dation substances. Moreover, photocatalytic activity has limited ap-
plications [246,247]. Normally adsorption technique may remove
some of these shortcomings because of its simple handling, regen-
eration tendency, sludge-free process, and cost-effectiveness [248–
251]. Adsorption technology is an established method for heavy
metal removal from wastewater. Specifically, in under-developed
countries where financial means is a major concern, this method
is proved a simple way of eliminating heavy metal ions from
wastewater. The most operative and worldwide used activated car-
bon is expensive, making it unfavorable for large-scale applica-
tion (Fig. 24) [252–254]. So, the quest for young and efficient ad-
sorbent compounds has always been a significant research field.
Commonly, adsorption isotherm models, for instance, Langmuir or
Freundlich models, are used broadly [255]. Generally, adsorption
isotherms elucidate how various adsorbates react with an adsor-
bent and are typical for optimizing adsorption phenomena, the ap-
pearance of surface belongings, adsorbents capabilities, and effi-
cient adsorption systems [256]. Typically, an adsorption isotherm
is a vital curve demonstrating a mechanism governing retention
or substance mobility from aqueous to a solid level with constant
temperature and pH [257].
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Journal of Materials Science & Technology 131 (2022) 122–166
Control proficiency is constantly concerned with an adsorbent’s
effectiveness, affordability, reusability, and application method. For
this reason, adsorption ability and required equilibrium time are
crucial [258]. Adsorption equilibrium is attained when adsorbate
concentration in bulk and dynamic control with an interface. The
kinetics study offers an idea into possible adsorption phenom-
ena using reaction pathways [259]. Other leading factors that can
affect an adsorbate-adsorbent method are pH solution, tempera-
ture, other adsorbate presence, pollutant concentration, and adsor-
bent. A few years ago, various reviews occurred on freshwater or
contaminated water treatment where an adsorption system was
adopted. Wang and Peng [260] reviewed the natural zeolites’ use
and their advanced form for several water contaminants and de-
termined that natural zeolites have been suitable adsorbents for
heavy metal ions and ammonium because of their cation exchange
abilities. Therefore, these zeolites exhibited variable ion selectivity
and good adsorption for a multicomponent scheme. Moreover, a
cationic surfactant can modify the zeolite surface charge forming
them more favorable for anions adsorption and organics. In con-
trast, recently, Lata and Samadder [261] surveyed a review focus-
ing on arsenic removal from wastewater using many adsorbents.
They also concentrated on the optimization process for arsenic re-
moval in terms of several parameters, e.g., pH, the influence of
the synthetic system, medium contact, and competing ions effects.
The authors recommended that mixed MOs and aluminum ox-
ides are best for wastewater and drinking water’s arsenic removal.
Sometimes, nanomaterials exhibit unique and meaningfully differ-
ent physicochemical and biological belongings with nanoscale di-
mensions ranging (1–100 nm). These findings in properties are a
direct way to explore their structure, high surface/volume ratio,
and quantum effect that appears at the nanoscale [262]. Wang
et al. [263] fabricated multi-shelled MOs with an anion-adsorption
phenomenon, as shown in Fig. 25(a, b). Maghemite NPs graphi-
U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
Fig. 24. (a) Schematic diagram of batch adsorption, (b) various mechanisms occurring in the adsorption process. Reproduced with permission from Ref. [254]. Copyright
2020 Royal Society of Chemistry.
tization with sugar solution increased the adsorptive elimination
of Cr+3 ions by 352.1 mg g–1 . Adsorptive reduction involves inter-
acting with protonated functional groups on maghemite NP sur-
faces, then reducing Cr6+ back to Cr3+ by electron-donating groups
like methoxy, carbonyl, hydroxyl, carboxyl, and so on. As shown in
Fig. 25(c), the Cr3+ ions may be adsorbed onto these functional
groups [264].
In this concern, nanotechnology could easily be considered the
most effective tool in wastewater remediation procedures in recent
times. Nanoadsorbents provide significant benefits over traditional
adsorbents owing to their large surface/volume ratio, short intra-
particle, diffusion distance, and tuned pore sizes with novel sur-
face chemistry. Large surface area is the one reason for the greater
adsorption tendency of NPs [265,266]. Moreover, at the nanoscale
large surface, energy size dependency of surface structure can pro-
duce highly active adsorption edges, causing high surface-area nor-
malization adsorption ability. This tendency of fabrication and en-
gineering of nanomaterials with favorable structures and function-
alities through nanoscale building blocks has set a potential ver-
satility to nanotechnology. In addition, most atoms on NPs sur-
faces are unsaturated and bind simply with other atoms; thus, sev-
eral nanomaterials may be functionalized with surface modifica-
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Journal of Materials Science & Technology 131 (2022) 122–166
tion [267]. Normally, inorganic nanocomposites modification using
other material, specific polymer, suggests enhancement in electri-
cal, magnetic, optical, mechanical, rheological, and fire retardancy
characteristics [268]. As surface characteristics assess adsorbate-
adsorbent interaction, solubility, and agglomeration performance,
surface modification may be employed for target-specific pollu-
tants. Nano adsorbents may also be easily incorporated into cur-
rent technologies, i.e., slurry reactors, filters, and absorbers (i.e.,
through coating filter media or transferring into porous granules)
[237,266].
4.2. Adsorptive removal by various metal oxides
4.2.1. Titanium oxides
TiO2 NPs were examined as an adsorbent due to their strong
surface reactivity, precursors availability, balanced structural and
textural properties, and acceptable zero point charge (pH range 6–
6.8) [115]. TiO2 is a photocatalytic material that oxidizes dangerous
organic compounds into harmless ones [269]. Organic pollutants
adsorption assists reaction among the dye-particles and surface-
active sites, e.g., photogenerated h+ , boosts photo-oxidation events
[60,270–273]. Thus, degradation of organic contaminants with TiO2
U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 25. (a) Indicating two synthesis procedures for multi-shelled hollow microspheres of MOs, (b) synthesis parameters affect product morphology. The red arrow specifies
a change in precursor concentration; the yellow arrow shows repeating adsorption phenomena before calcination; the light blue arrow reveals an increase in ethanol ratio;
the green arrows exhibit changing the annealing atmosphere from air to oxygen before calcination. Reproduced with permission from Ref. [263]. Copyright 2016 Nature
publishing group. (c) Adsorption phenomena for Cr6+ ions removal from graphitized maghemite NPs. Reproduced with permission from Ref. [264]. Copyright 2018 Elsevier
B.V.

nanostructure governs through their adsorption efficiency. Funda-
mental revisions regarding first and usually fast photocatalytic pro-
cedures can be induced with photon absorption, the energy of
which exceeds photocatalytic Eg , inside and at semiconductor’s sur-
face, are not attained very often. The understanding of these ap-
proaches is, therefore, of the highest significance for knowledge
of photocatalytic response and hence for a significant construction
of photocatalytic routes. The characteristic surface of TiO2 can be
modified by changing particle size, shape, crystallinity, and phase
configuration, subsequently adsorption, and photodegradation of
organic contaminants. For instance, the hierarchical nanocompos-
ites, TiO2 ’s 1D NRs, 3D-0D, and 3D-1D microspheres synthe-
sized with the hydrothermal technique demonstrated morphologi-
cal characteristics dependent on phenol degradation.
In hierarchical 3D nanocomposite TiO2 , a high surface-active
edge and favorable Eg generated an effective and fast decom-
position of pollutants compared to 1D-nanostructured analogous
[274]. Hierarchical flower-like nanocomposites of sodium titanate
consisting of 1D-nanoribbons indicated outstanding efficiency as
an adsorbent for MB reduction from contaminated water. The
electrostatic contact between a positive charge of MB and neg-
atively charged titanate increase MB adsorption over the surface
of sodium titanate (Fig. 26(a–d)). Titanate flower-like morpholo-
gies (TMF) showed larger adsorption of MB compared with titanate
1D-nanobelt and it has corresponded to high surface active edges
and specific surface area of 3D structural qualities of TMF. The an-
ion methyl orange revealed insignificant adsorption on TMF hierar-
chical nanostructure due to the repulsive behavior of electrostatic
contact [60]. The surface morphological, chemical modifications,
and TiO2 structural properties boosted their absorption efficiency
for organic contaminants. The large specific surface area and filled
active edges of mesoporous TiO2 simplify adsorption events, caus-
ing fast and effective organic dye adsorption [275]. Functionalized
CNTs containing TiO2 nanocomposite revealed high selectivity for
negatively charged dyes and they can adsorb up to (94% and 100%)
of methyl orange in 10 and 30 min, respectively. H2 bonding, hy-
drophobic and π –π interactions among functionalized CNTs with
TiO2 nanocomposites, and dye compounds can increase adsorp-

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 26. (a) SEM and (b) TEM micrographs of sodium titanate (hierarchical flower-like nanocrystals), (c) UV-vis absorption spectra of MB solution (20 mg L–1 , 50 mL) for
prepared material in 20 mg TMF presence, inset revealed digital images of degraded solutions, (d) adsorption MB (20 mg L–1 , 50 mL) by TMF, TiO2 ’s nanobelt, and P25.
Reproduced with permission from Ref. [281]. Copyright 2013 American Chemical Society. (e) Interaction pathways among Orange II dye and surface functionalities of TiO2
aerogel. Reproduced with permission from Ref. [279]. Copyright 2009 Elsevier B.V. (f) Schematic diagram of TiO2 -NPs fixation at external porosity of AC support contaminant
transfer towards photocatalytic centers. Reproduced with permission from Ref. [280]. Copyright 2019 Elsevier B.V.

tion efficacy [276]. The TiO2 NPs functionalization using surfactants
makes them significant adsorbents for negatively charged dyes. The
functionalization of TiO2 NTs using hexadecyltrimethylammonium
chlorine surfactant assists the adsorption rate of negatively charged
dyes (Acid Red 1 and Acid Blue 9) [277]. Introducing metals like Cu
or Zn in TiO2 NPs enhanced methyl orange’s adsorption rate and
boosted photodegradation [278,279]. TiO2 aerogels can be synthe-
sized using supercritical drying of wet gels showing notably high
adsorption ability (402.8 mg g–1 ) for Orange II (azo-dye). The pH
2 exhibited maximum adsorption, and it could correspond to sur-
face charge-driven contact and H2 bonding among titanol groups
of TiO2 aerogel and nitrogen, aromatic rings, and dye molecules
oxygen-functionalities as displayed in Fig. 26(e). The degeneration
of TiO2 aerogel adsorption edges at high pH promises its tendency
as an effective and refillable adsorbing nanomaterial for photocat-
alytic applications [279]. Chekem et al. [280] formalized a new
and simple mathematical modeling of the removal of contaminants
from wastewater, determined by the adsorption/photocatalysis hy-
brid procedure with AC-TiO2 (activated carbon-TiO2 ) nanocompos-
ite. In lab-scale batch experiments, the AC-TiO2 nanomaterials gen-
erated by a straightforward TiO2 coating route of a homemade mi-
croporous AC are checked to eliminate phenol from contaminated
water (Fig. 26(f)).
4.2.2. Zinc oxides
Chitosan modified-ZnO NPs with economical and biocompati-
ble can adsorb Acid Black (26) and Direct Blue (78) dyes effec-
tively [282]. The incorporation of chitosan on ZnO NPs causes the
adsorption rate of permethrin organisms to prompt from (49%
to 99%) [283]. The electrostatic contact between cationic amino
groups of chitosan and anionic of organic contaminants function-
alities, microstructural belongings, ZnO NPs active surface edges,
and the enormous surface area or surface/volume causes to stim-
ulate adsorption progress towards wastewater treatment. The Cr-
doped ZnO NPs with various concentration of Cr+3 was eluci-
dated as a potential adsorbent for anionic dye-molecules elimi-
nation from water. The incorporation of Cr was enriched surface
defects on ZnO NPs making hydroxyl groups for protonation; con-
sequently, a positively charged particle is created on the surface.
Cationic ZnO NPs adsorbed anionic dyes selectively driven with
electrostatic contact [284]. ZnO-ZIF-8 [Zn(MeIM2 )] hollow micro-
sphere composites were described for selective dye adsorption, fur-
ther increased with composite core-shell configuration [42]. Incor-
porating NiFe2 O4 in ZnO NPs minimizes photo-corrosion and fur-
ther increases adsorption progress for Congo red; therefore sug-
gests superior photodegradation. Therefore, before a photocatalytic
performance, the initial step is efficient Congo red adsorption on

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
NiFe2 O4 /ZnO surface which was then facilitated through electro-
static reaction among NiFe2 O4 /ZnO and Congo red elements [44].
High surface area and hierarchical mesoporous microsphere pore
volume of ZnO nanosheets revealed excellent adsorption ability for
Congo red (334 mg g–1 ) as compared to commercially ZnO residue
[285].
Wang et al. [286] offered a method to synthesize econom-
ical cryogel that owns pH and temperature sensitivity through
one-pot polymerization between acrylamide and dimethylamino
ethyl methacrylate (DMAEMA) monomers and flower-like cellulose
nanocrystal/ZnO nanohybrids via an ice-template simple method.
Other than Ag NPs, cellulose nanocrystal/ZnO nanohybrids using
modulated shape, economical rate, and antimicrobial property dis-
play excessive response for bifunctional agents into matrix cryo-
gels [288,289]. Fig. 27(a) reveals the preparation method of cryo-
gels; furthermore, macroporous cryogels-ZnO-1% could eliminate a
greater concentration of MB from a hydrophobic solvent medium
(Fig. 27(b)). Later on, a research group [287] performed an ad-
sorption method to eliminate dye-molecule from polluted water.
To finish that, a newly-built ternary nanostructure devolved by
Ag NPs/ZnO NRs/3DG was fabricated via a mutual hydrothermal-
photodeposition route. In this route, 3DG structure hydrogel used
for ZnO NRs production was characterized by FESEM. Fig. 27(c)
showed the highly 3D porous interconnected graphene network for
3DG preparation. It might be found that ZnO NRs are created with
a hexagonal ‘‘treelike” growth pattern as indicated in the SEM mi-
crographs of ZnO NRs/3DG (Fig. 27(d, e)). The hierarchical ZnO NRs
“treelike” structure is beneficial and promising for reflection and
scattering of light. Fig. 27(f, g) exhibits that the ZnO NRs morphol-
ogy altered and became uneven after Ag photodeposition, which is
evidence for Ag NPs formation on ZnO NRs surfaces. Remarkably,
it was noted that photodeposited Ag NPs might also produce on
the ZnO surface a flake shape as shown in Fig. 27(f), EDS analy-
sis of the prepared nanomaterial has been directed to calculate the
elemental composition (Fig. 27(h)). Also, as depicted in Fig. 27(i),
the qualitative EDS mapping from ternary nanocrystal is a sig-
nificant indication for Ag NPs photodeposition on the surface of
both ZnO NRs and 3DG surfaces. The ln(C0 /C) vs the illuminated
time of the fabricated samples involving 3DG, ZnO NRs/3DG, and
Ag NPs/ZnO NRs/3DG was plotted to determine photodegradation
rate constant under visible and UV light illumination (Fig. 27(j,
k)), Fig. 27(l) shows a micrograph of purified water). Considering
the aforementioned discussions and study, overall photocatalytic
degradation phenomena (for both visible and UV light activation)
are depicted in Fig. 28(a, b) [287].
4.2.3. Iron oxides
The crystalline and structural properties of iron oxide nanopar-
ticles (IONPs) are determined through their oxidation state. The
common IO forms are magnetite (Fe3 O4 ), maghemite (γ -Fe2 O3 ),
and hematite (α -Fe2 O3 ) [4,290]. The broadly used magnetites
IONPs have two kinds of iron with various oxidation states (i.e.,
Fe+2 and Fe+3 ). The high-temperature process (> 400 °C) of
magnetite and spinel structured maghemite yielded hematite of
corundum structure. Nano dimensional IONPs provide a large spe-
cific surface/volume ratio and super-paramagnetism [4]. Further,
they have attained much attraction for different applications ow-
ing to their easy synthesis, surface modification, excess avail-
ability, noteworthy features at nano-scale, magnetic segregation,
and less toxicity [291,292]. The size, textual qualities, structural
and magnetic properties, and IONPs functional groups can be
altered with synthesis methods and reaction precursor’s selec-
tion [293]. IONPs, in their bare, doped, or nanocomposite forms
have widely been used for organic pollutants adsorption. After
the adsorption of organic contaminants, removal of contaminants
from polluted water has become the main concern, and it re-
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Journal of Materials Science & Technology 131 (2022) 122–166
quires a complete energy procedure like centrifugation. There-
fore, in an external magnetic field presence, after organic con-
taminants adsorption, spent iron-oxide-based adsorbents could
be separated easily, focusing on their inherent magnetism [294].
Then, IONPs and their nanocomposites have gained increasing
research interest for wastewater applications. IONPs were being
used for proficient separation of chlorinated pesticides, for in-
stance, 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), dieldrin, 2,4-
dichlorophenoxyacetic acid (2,4-D), hexachlorocyclohexane (α -HCH
and γ -HCH) and lindane (1,2,3,4,5,6-hexachlorocyclohexane), etc.,
from polluted water. The dye-molecules, viz., (Fluorescein, Bro-
mophenol Blue, Bromocresol Green, and Erichrome Black T,) having
hydroxyl ions functional groups have been adsorbed preferably on
magnetite NPs in comparison to non-hydroxylated dyes (i.e., MB
and MO), as shown in Fig. 29(a, b). The hydroxylated adsorption
dyes agreed towards contact with hydroxyl groups decorated above
magnetic NPs surfaces through hydrogen linkages [295]. The Fe3 O4
nanospheres with empty structures contain active edges and enor-
mous surface areas competently revealing superior adsorption and
eliminating Neutral Red dye [296].
The efficiency and selectivity of IONPs might be boosted us-
ing their surface modification with surface-acting agents. In recent
times, potential work was carried out on IONPs surface functional-
ization regarding the assortment of organic species, e.g., glutamic
acid, organosilane polyacrylic acid, etc. The functionalization may
assist organic dye’s adsorption efficiency [297]. The functionalized
IONPs along with the humic acid-enhanced adsorption rate of MB
from polluted water made more reactions by humic acid in com-
parison to pure IONPs [298]. The IONPs can also be functionalized
with other compounds (e.g., chitosan, liquids, ionic, and polymers)
to stimulate adsorption capability. A simple and viable scheme of
spent adsorbent separation needs to be matched using adsorption
properties. Magnetic mesoporous (Fe3 O4 @nSiO2 @mSiO2 ) NPs con-
sist of a super-paramagnetic core of Fe3 O4 , a sandwich between
nonporous nSiO2 , and outer mesoporous silica layer (mSiO2 ) re-
vealed good adsorption efficiency and ability for DDT insecticides
removal [299]. The hierarchical core-level IO@magnesium silicate
(HIO@MgSi) can be synthesized with a hydrothermal route reveal-
ing rapid and effective adsorption rates of cationic dyes.
The HIO@MgSi NRs can adsorb MB ∼99.3% (within 40 min) and
displayed an exceptional adsorption tendency of 2020 mg g–1 [45].
The nanocrystalline MFe2 O4 (M = Ni, Fe, Mn, and Co spinel fer-
rites) has been fabricated with a hydrothermal method to find the
influence of cationic scattering in ferrite structure towards Congo
red absorption. Experimental data showed maximum Congo red
dye adsorption using CoFe2 O4 nanocrystal. The electrostatic reac-
tion among cation structure of MFe2 O4 ferrites and anion Congo
red had been predicted as the main adsorption process. In wastew-
ater, self-assembled Fe3 O4 LDH nano-hybrids revealed perfect ad-
sorption efficiency for organic dyes. The nano-hybrid structure ex-
hibited rapid kinetics of 96% adsorption rate and 505 mg g–1 ad-
sorption capacity within 5 min for Congo red. The sample was sep-
arated easily for a successive batch of dye-adsorption depending
on magnetic effect and charge [301]. The surface modification of
Fe3 O4 @SiO2 NPs through poly (1-vinyl imidazole) was used for the
adsorption of mercury ions from a liquid solution. In this regard,
the interaction between imidazole ring N-atom and Hg2+ ion is an-
ticipated for Hg2+ adsorption through a massive removal capabil-
ity of 346 mg g–1 [302]. The cysteine-modified Fe3 O4 NPs for Hg2+
removal, in this regard –SH group exists in cysteine to assist Hg2+
ions adsorption, while –COOH and –NH2 functionalities reported
increasing biocompatibility and solubility in a solution [303]. The
medium pH governs Hg2+ adsorption. The ZnS shell being a soft
base exhibits better contact through mercury ion (soft acid), es-
pecially in neutral to a weakly alkaline solution, as revealed in
Fig. 29(c) [300]. The alkaline pH greater than nine had enhanced
U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 27. (a) Schematic presentation and smart cryogels-ZnO images and (b) MB (200 mg/L) removal below silicone oil with cryogels-ZnO-1%. Reproduced with permission
from Ref. [286]. Copyright 2017 American Chemical Society. SEM micrographs of freeze-dried (c) 3DG (three-dimensional graphene network), (d, e) ZnO NRs/3DG, (f, g) Ag
NPs/ZnO NRs/3DG composites, (h) EDS spectrum of Ag NPs/ ZnO NRs/3DG composites, (i) only single ZnO NR on the surface of 3DG in Ag NPs/ZnO NRs/3DG sample through
qualitative EDS 2D map analysis of several components in the ternary nanocrystal. Deviation of ln(C0 /C) vs light irradiated time under (j) UV and (k) visible illumination of
prepared materials in comparison to blank, (l) MB decolonization. Reproduced with permission from Ref. [287] Copyright 2019 Elsevier B.V.

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 28. Suggested MB reduction and charge transfer and mechanism on the Ag/ZnO/3DG surface in (a) UV and (b) visible light. Reproduced with permission from Ref. [287].
Copyright 2019 Elsevier B.V.

Fig. 29. (a) Representation of Preferable Adsorption of Different Dyes IONPs and (b) magnetic separation of eriochrome black T and fluorescein adsorbed IONPs by an external
magnetic field. Reproduced with permission from Ref. [295]. Copyright 2011 American Chemical Society. (c) Schematic illustration of contact paths among Hg2+ ions and ZnS
shell coated on IONPx, as a function of pH. Reproduced with permission from Ref. [300]. Copyright 2018 John Wiley & Sons.

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U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
the contact between hydroxyl and mercury ions and prepared solid
base complex Hg(OH)3 ; subsequently, Hg2+ ions adsorption via
ZnS shell reduced to a significant extent [300]. Further, GO in-
creased Fe3 O4 NPs removal efficacy for Hg2+ ions by stimulating
the numerous surface-active oxygen functionalities and greater hy-
brid adsorbent material surface area [304]. The greater volatility
of Hg+2 ions reduced the adsorption efficacy over the GO surface
loaded with IONPs at elevated temperatures [305]. The variation
of Fe3 O4 NPs through defective MoS2 effectually adsorbed (425
mg g–1 ) mercury ions were determined by in-contact with a sul-
fur moiety of damaged MoS2 nanosheets. In addition, MoS2 /Fe3 O4
nano-hybrid exhibits rapid and selective adsorption and easy sep-
aration by using an external magnetic field [306].
4.2.4. Tungsten oxides
Tungsten oxides (WOx ) using flexible configuration, crystalline
and mechanical properties, shape, and size display significant ca-
pability for wastewater remediation. The hierarchical nanostructure
with WOx hollow pattern can be fabricated using the solvothermal
method and has attained significant interest as a reusable adsor-
bent for organic contaminants removal [307–312]. The mesoporous
hexagonal structure of WO3 would be stabilized with Na2 SO4 ex-
hibiting high MB adsorption. The adsorption isotherm outcomes
displayed the Langmuir model leading single layer coverage on
WO3 nanosheets hierarchical nanostructure [313]. WO3 amorphous
nanosheets using micro-porosity exhibit not only exceptional ad-
sorption tendency (600 mg g–1 ) for MB [314]. Eventually, cationic
dyes formed groups on WO3 nanosheets’ surface and displayed
good adsorption ability, while anionic dyes’ interaction through
WO3 nanosheets was insignificant [315]. The anionic monoclinic
WO3 NPs, fabricated through the co-precipitation method, showed
electrostatic contact with the positively charged dye. Consequently,
monoclinic WO3 NPs exhibit superior adsorbents characteristics to
eliminate MB (Fig. 30(a)) [316]. Likewise, WO3 colloidal particles
reveal responsive attraction for xanthene dyes consisting of RhB,
Rh 3B, Rh 19, Rh 6G, Rh 110, and Rh 123, and it has corresponded
to electrostatic contact among WO3 colloidal particles with an-
ion surface charged and dye elements with cationic amino groups
[317]. Later on, Luo et al. [315] utilized the surface of amorphous
tungsten oxide nanosheet (a-WO3 ) for modifiable dye adsorption
treatment. Extracted outcomes show the greater response for a-
WO3 nanosheets towards positively charged dye molecules in wa-
ter. Further, these charged molecules from mixed solutions can be
isolated using selective adsorption property (Fig. 30(e)). Moreover,
the pH-induced desorption possibility of cationic dyes on a-WO3
nanosheets’ surface had also been revealed (Fig. 30(c)). As shown
in Fig. 30(b), produces have a sheet-sharp structure. The dyes des-
orption procedures include the acidic and alkaline behavior, as dis-
played in Fig. 30(d).
4.2.5. Graphene-metal oxide nanocomposites
The thinnest and hardest substance is graphene, a 2D lattice
nanostructure of sp2 hybridized carbon [318,319]. Graphene has
emerged as the most promising nanomaterial in the carbon fam-
ily because of its exceptional electrical, thermal, and mechanical
characteristics. [320]. When it was discovered in 2004, graphene
sparked an enormous interest in everything from basic knowl-
edge to applications [319]. Graphene has been examined for wide-
ranging applications during the last decade, with solar cells, capac-
itors, batteries, sensors, catalysis, and wastewater treatment due
to its π -electron-rich structure and large surface area (2630 m2
g–1 ) [318,321]. Graphene, its oxides GO and RGO, graphene-based
nanocomposites, and chemically functionalized graphene had all
been studied as adsorbents for organic contaminants destruc-
tion in the recent past [321,322]. The electrostatic interface be-
tween cationic centers of dye-molecules and anionic residual oxy-
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Journal of Materials Science & Technology 131 (2022) 122–166
gen functions of RGO was ascribed to RGO’s much better adsorp-
tion ability for cationic dyes in contrast to anionic dyes. Further-
more, cationic dyes are drawn to the π -electron network. Con-
sequently, RGO owns a broad adsorption capacity for malachite
green (Fig. 31(c–e)) [323]. The adsorption of pesticides such as
chlorpyrifos, endosulfan, and malathion has been investigated us-
ing GO and RGO. The water-mediated interface between graphene
and pests was discovered in DFT analysis. Using graphene as an
adsorbent, adsorption capabilities of chlorpyrifos, endosulfan, and
malathion insecticides were reported to gain higher rates as fol-
lows 120 0, 110 0, and 80 0 mg g–1 [324]. Furthermore, Graphene
and GO are selectively utilized as supportive materials for MO
nanocomposites, such as catalysis, energy devices, lubrication, ad-
sorption [325–327], etc. The addition of MO nanocomposites to
graphene surface and GO prevents them from aggregating and en-
hances the surface area of the resulting nanocomposite. Several
kinds of MO graphene nanocomposites with varying compositions,
textural, and surface properties have been synthesized to impart
a significant role as adsorbents for effective organic toxins deduc-
tion from wastewater in the recent past. Incorporating specific MO
and graphene characteristics in the resulting composites enhanced
the adsorption capability for organic contaminants, accelerated the
adsorption efficacy, and made it easier to recover spent nanocom-
posites [327]. By adding an external magnetic force to the spent
adsorbent, the magnetic characteristics of IO-graphene nanocom-
posites make it easier to separate it from water (Fig. 31(a, b)).
The Fe3 O4 -RGO nanocomposite removed dangerous pesticides from
polluted water, including Prometryn, Simazine, Simeton, Ametryn,
and Atrazine. The Fe3 O4 -RGO nanocomposite’s excellent pesticide
adsorption was related to π –π interactions, hydrophobic and elec-
trostatic interface. After pesticide adsorption, the wasted compos-
ite may be readily removed and reused for the next adsorption cy-
cle [328]. Because of their poor stability, Fe3 O4 NPs tend to ox-
idize into Fe2 O3 , α -Fe2 O3 , and γ -Fe2 O3 in continuous flow sys-
tems, which has shown to be a substantial barrier to industrial
use [329]. However, it may be addressed by grafting or incorpo-
rating Fe3 O4 NPs into the graphene matrix, resulting in a consid-
erable increase in the lifespan of Fe3 O4 nanocomposites. He et al.
[330] used tetraethylorthosilicate and (3-aminopropyl) triethoxysi-
lane (APTES) as functional linkers to make Fe3 O4 -GO nanomateri-
als through covalent connections. MB was successfully adsorbable
(190.14 mg g–1 ) by Fe3 O4 -GO nanocomposite.
5. Photocatalysis vs adsorption
Compare to adsorption, photocatalytic degradation is more eco-
logically friendly. While adsorption is a rapid, scalable, and cost-
effective technique for eliminating organic compounds, it has the
major disadvantage of creating secondary waste once the pollu-
tants are absorbed. Similarly, reusing adsorbents for subsequent
batches, pollutant leaching/desorption, and adsorbent disposal are
also environmental issues. On the other hand, the photocatalytic
degradation process results in the transformation of organic toxins
into less hazardous molecules or intermediates, which then pro-
duce mineral-based end products like H2 O and CO2 . Aside from Eg
engineering and light source, the photodegradation process is gov-
erned by the adsorption capability of organic contaminants on the
photocatalyst surface. The photocatalyst increases the adsorption
rate and promotes the degradation process. Adsorption improves
photo-sensitization by forming interfacial contacts between organic
pollutant molecules and photocatalyst [331]. Several studies have
shown that organic pollutant adsorption needs a faster and more
effective photodegradation process. The photodegradation ability of
F-TiO2 for RhB and MO dye-molecules is regulated by their adsorp-
tion to F-TiO2 . According to Liang and coworkers [69], adsorption
U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 30. (a) Adsorption picture of WO3 nano adsorbent for MB adsorption. Reproduced with permission from Ref. [316]. Copyright 2017 Elsevier B.V. (b) SEM micrograph
of WO3 nanosheets separated from substrate, (c) pH-induced MB molecules desorption on WO3 nanosheets surfaces, (d) chart drawing presenting cationic dyes desorption
procedures in acidic and alkaline behavior, respectively, (e) visualization of dye-degradation activity: photographs of (i, ii) MB solution (10 mL) with 15 mg L–1 concentration
and 15 mg L–1 concentration plus mixed solution respectively, (ii) 10 ml MO solution with (iii) before and (iv) and after desorption using 3.5 mg amorphous WO3 nanosheets
in solution, (v–viii) are attributing absorption spectra in (a–d). Small black squares and white circles correspond to the indication of MB and MO molecules’ fundamental
absorption peaks in aqueous solution, respectively. Reproduced with permission from Ref. [315]. Copyright 2015 Royal Society of Chemistry.

160
U. Qumar, J.Z. Hassan, R.A. Bhatti et al. Journal of Materials Science & Technology 131 (2022) 122–166

Fig. 31. (a) Schematic drawing of a likely interaction among pest molecules and Fe3 O4 /RGO nanocomposites, (b) steady diminution in absorbance spectra using time exposed
pest adsorption by Fe3 O4 /RGO adsorbent, which is detached through external magnetism effect. Reproduced with permission from Ref. [328]. Copyright 2017 Elsevier B.V.
(c) Effect of pH on MG dye removal with RGO as an adsorbent, (d) HRTEM images of RGO showing holes (circled in brown) and defects (indicated by white arrows), (e)
schematic illustration of RGO lamella consisting of holes and residual oxygen functionalities. Reproduced with permission from Ref. [323]. Copyright 2017 Elsevier B.V.

of organic chemicals by photocatalyst is essential for their effec-
tive destruction since adsorption or interfacial contact enhances
electron injection. As a result, photocatalytic degradation is a more
beneficial strategy than adsorption in terms of a total breakdown
of organic contaminants. However, to obtain a high photodegrada-
tion rate, effective organic pollutant adsorption is also required.
6. Challenges and future prospective
(3) The application of MO-based NPs in laboratory conditions by
(1) The applicability of nanomaterials containing oxides of metals
at an industrial level with excellent productivity, economically
worthwhile method to their production at a large level, non-
toxic usage and environmentally responsive precursors for their
production, and well-ordered nanomaterials manufacturing to
fabricate them highly effective in sunlight illumination have all
been major challenges.
(2) Heterogeneous photocatalysis is a versatile and potential oxi-
dation process capable of destroying various organic pollutants
present in water and air. Doping TiO2 semiconductors with
metals (i.e., Cr, Fe, Mn, and Zn, etc.) and non-metals (carbon, ni-
trogen, etc.) to reduce the bandgap of TiO2 semiconductors also
greatly contribute to the collection of visible light. Cr-doped
photocatalysts supported on activated carbon have a number of
advantages such as cheap and efficient options for wastewater
treatment and remediation. Because of the high surface area
and the hydroxyl groups’ presence, TiO2 -coated activated car-
bon is considered ideal photocatalyst support.
simulated wastewater as adsorbents has been extensively ex-
plored. Thus, the adsorptive elimination of heavy metal and
metalloid ions must be performed under practical conditions,
such as the use of contaminated natural and industrial wa-
ter, where pH, multiple coexisting cationic and anionic species,
heavy metal ion, and organic pollutant concentrations are
present, controlling the adsorption process. Therefore, many
studies are needed to optimize process parameters to ob-
tain the real-time applicability of MO-based NPs for mitigating
heavy metal pollution on an industrial scale.

161
 U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
(4) The most significant characteristic of MOs and their nanocom-
posites is their flexibility in constructing and tailoring their
shape, size, and surface chemistry, which makes them highly
selective and effective adsorbents for specific needs. Though,
contaminated water encloses various chemicals, viz., Metal ions,
oxides, organic species, etc. Thus, the simultaneous and active
removal of these chemicals needs to be described through the
construction of multifunctional MO-based adsorbents.
(5) Efficient and economical separation of waste MOs and their
composites (sorbents) from wastewater due to their small size,
a good affinity for water, and environmental concerns is a ma-
jor challenge. The separation of MO-based materials from wa-
ter depends on their nature, size, surface properties, and com-
position. Magnetic separation, centrifugation, and filtration are
common methods to separate spent adsorbents from aqueous
media. Fe, Co, and Ni-based NPs are inherently magnetic, and
may easily be separated with an applied magnetic field after
the adsorption.
(6) Particle size, magnetic strength, and magnetic field gradients
control the spent sorbents’ separation from water. Incorporating
magnetism into various nanomaterials, MOs, graphene, biopoly-
mers, etc., by converting them into magnetic composites or hy-
brids, supports magnetically driven separations after adsorption
of contaminants from polluted water.
(7) Centrifugation and membrane filtration are active separation
methods, especially for non-magnetic adsorbents. Pore size, size
of sorbent, electro-kinetic migration, diffusion, vacuum lines,
gravity, etc., control sorbent separation through filtration-based
procedures. Centrifugation is an effective method for separating
different types of spent sorbents, including smaller-sized par-
ticles. High efficiency and scalability make the centrifugation
method promising for the separation of spent sorbents.
(8) Without compromising the adsorption properties of MOs and
their composites, sorbent reusability and recyclability are an-
other research challenge to minimize the use of new batches
of sorbent and resources for industrial-scale implementation
savings. Therefore, to understand the cost-effectiveness of the
adsorption procedure, an inclusive regeneration analysis is re-
quired.
(9) The regeneration processes are divided into chemical, ther-
mal, and electrochemical methods, driven by their chemical
and physical phenomena. Chemical regeneration is the most
common method for recycling MO-based sorbents. It can ab-
sorb adsorbents by treating spent adsorbents with chemicals
such as NaOH, H2 SO4 , HCl, ethanol, acetone, methanol, NaCl,
etc. The pH of the adsorption method effectually controls the
adsorption-desorption procedure of most ionic contaminants.
(10) The higher hydroxyl ions (NaOH) concentration facilitates des-
orption through competition with adsorbed(III)/As(V)-based an-
ions, whereas NaCl stimulated the ionic strength to stimulate
the process. Arsenic and chromium-based oxides adsorbed by
MO-based adsorbents can be desorbed by treatment with NaOH
solution, and the regenerated adsorbents can be used for sub-
sequent batches. HCl is used to remove heavy metal ions (Pb2+ ,
Cu2+ , Cd2+ ) from MO-based adsorbents. Though, HCl dissolved
MO adsorbents; consequently, metals leach into pure water.
(11) Metal ion chelating compounds, e.g., ethylenediaminetetraacetic
acid, can efficiently adsorb metal cations from MOs adsorbents,
without causing adsorption/damage. Mercury cations were ef-
ficiently removed from Fe3 O4 @SiO2 -NH2 sorbents with a mix-
ture of HCl and thiourea, where the strong affinity of thiourea
for mercury supports the desorption process without degrad-
ing MOs compounds [309]. Most regeneration techniques can-
not restore 100% adsorption sites, and their adsorption effi-
cacy slowly decreases with increasing batch numbers. The op-
timal desorption process should restore the ability of the ad-
162
Journal of Materials Science & Technology 131 (2022) 122–166
sorbents and allow them to be reused for numerous adsorption
cycles.
(12) A significant understanding of the desorption process may help
the cyclic adsorption-desorption efficiency. Yet, limited studies
were carried out to know the desorption mechanism, includ-
ing the effects of various parameters viz. This type of active
sites involved in the adsorption-desorption process, the type of
adsorbent-adsorbent (pollutant) interaction, the effect of coex-
isting adsorbent species, the stability of the adsorbent, temper-
ature, ionic strength, etc. MOs and their nanocomposites may
be fabricated from cost-effective minerals and toxic waste, po-
tentially making the process safe and commercially viable. The
disposal of recovered pollutants (secondary pollutants) and de-
pleted NPs is another environmental task that needs to be ex-
plained to mitigate harmful effects. Leaching of MOs during
adsorption-desorption and residual NPs in treated water ad-
versely affects human health and ecosystems. However, con-
sideration would be given to establishing effective methods to
suppress the leaching and release of MO residues in water dur-
ing the adsorption-desorption.
(13) Furthermore, MO-based adsorbents must be biocompatible,
so their exposure can reduce environmental effects. Reac-
tive oxygen produced from MOs during their adsorption-
desorption process has adverse biological effects. However, in-
novative and unique approaches must be explored including
the selection and functionalization of MOs to produce efficient
and recyclable adsorbents while minimizing chemical degrada-
tion/leaching and ecosystem exposure. By properly describing
the above shortcomings, MOs can prove to be ideal adsorbents
for wastewater treatment applications.
7. Summary
Several strategies were being employed for industrial applica-
tions and their maintenance efficacy. Photocatalysis and adsorp-
tion approaches for eliminating organic chemicals from wastew-
ater are reviewed in this article utilizing numerous MOs types
and their compounds as photocatalytic and adsorptive nanomateri-
als. Nanostructured MOs materials with various morphologies, ex-
hibiting texture, chemical nature, and crystalline surface features,
have a high capacity for pollutants, organic in nature, adsorption
via various adsorptive pathways, such as chemisorption, physisorp-
tion, interactions of induced charge, and so on. The utilization of
nanomaterials including MOs and their composites to eradicate or-
ganic chemicals from polluted water, mainly dyes, and pesticides,
is fully addressed. An inclusive variety of MOs, such as IONPs of
iron, copper, zinc, tungsten nanocomposites of MO, and graphene-
MOs composites, are examined in this context, emphasizing cur-
rent developments, trials, and opportunities for remediation of wa-
ter. Adsorption is an authorized approach for eliminating a broad
range of pollutants, including organic compounds, employing var-
ious materials. However, secondary pollutants occur when organic
dye molecules are moved from one stage (water-soluble) to an-
other (spent adsorbents). A wide variety of nanostructured oxides
of metal materials and their composites have lately gained con-
siderable interest as photocatalytic materials for degrading organic
compounds or converting them into non-hazardous products. MOs
and graphene-MOs composites, among others, have been proved
to be effective and recyclable photocatalysts for the breakdown
of organic contaminants when exposed to light. Scientific involve-
ments are essential to produce future sustainable materials for
zero-discharge water treatment. The need of hour is to build smart
nanomaterials that demonstrate substantial specific surface area
and structural features by applying cost-effective and friendly eco-
logical approaches. The regeneration of adsorbents/photocatalysts
is another significant element favoring the process’s economic fea-
U. Qumar, J.Z. Hassan, R.A. Bhatti et al.
sibility, avoiding hazardous disposal, maintaining the balance be-
tween remediation of water and secondary waste management,
and assuring the long-term viability processes. Secondary waste
management is an important issue that has acquired little atten-
tion. Catalysis can be performed on secondary waste (used adsor-
bent). As a result, reducing pollution during MO composite man-
ufacturing and using MO composites for other uses after water
treatment may help develop a greener platform. Developing cost-
efficient, faster, greener, and more effective long-term organic pol-
lutants removal/degradation methods was vital for humans and all
living things.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgment
Authors are grateful to HEC, Pakistan.
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