Journal of Cleaner Production 298 (2021) 126567

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Journal of Cleaner Production

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

Review

Fundamentals and photocatalysis of methylene blue dye using various

nanocatalytic assemblies- a critical review
Muhammad Imran Din a, *, Rida Khalid a, Jawayria Najeeb b, Zaib Hussain a
a
Institute of Chemistry, University of the Punjab, New Campus Lahore, 54590, Pakistan
b
Department of Chemistry, University of Gujrat, Gujrat, 50700, Pakistan

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

Article history: Methylene blue (MB) is a carcinogenic pollutant widely known for its hazardous impacts on humans and
Received 30 July 2020 marine life. Recently, the photocatalysis mediated degradation of MB has been widely reported as an
Received in revised form advanced approach for the removal of this harmful dye from the aqueous mediums. Numerous scientists
23 February 2021
have documented the use of nanomaterials (NMs) based photocatalytic assemblies for the degradation of
Accepted 24 February 2021
Available online 10 March 2021
MB. This study highlights the fundamentals and factors involved in the degradation reaction of MB.
Furthermore, the detailed kinetics and mechanistic description are also presented for providing essential
Handling editorProf. Jiri Jaromir Kleme
s insights into the light mediated reaction of MB. The vast academic literature is organized by classifying
the NMs based photocatalysts based on the utilized stabilization mediums and the advantages/disad-
Keywords: vantages of the peculiar stabilization mediums are also discussed for presenting the comparative analysis
Photocatalysis: review of the reported stabilization mediums for the preparation of photocatalysts. Future prospects are also
Methylene blue discussed for further extending the advancement of scientific research in this field.
Nanomaterials © 2021 Elsevier Ltd. All rights reserved.
Kinetics

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Photocatalytic degradation of MB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Photodegradation mechanism of MB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3. Factors affecting the photocatalytic degradation of MB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3.1. Nature of NMs-PCAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3.2. Effect of NMs-PCAs concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3.3. Effect of MB concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3.4. Effect of pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3.5. Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3.6. Effect of radiation intensity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3.7. Effect of photoreactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3. NMs-PCAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1. Synthetic material based NMS-PCAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2. Natural/non-synthetic material based NMs-PCAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.3. Advanced hybrid NMs-PCAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4. Reusability of the NMs-PCAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
5. Future directions and conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

* Corresponding author. Institute of Chemistry, University of Punjab, Lahore,

54590, Pakistan.
E-mail addresses: imran.chem@pu.edu.pk (M.I. Din), ridakhalid42@gmail.com
(R. Khalid), jiyanajeeb73@gmail.com (J. Najeeb), drzh1972@hotmail.com
(Z. Hussain).

https://doi.org/10.1016/j.jclepro.2021.126567
0959-6526/© 2021 Elsevier Ltd. All rights reserved.
M.I. Din, R. Khalid, J. Najeeb et al. Journal of Cleaner Production 298 (2021) 126567

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

1. Introduction their exceedingly high available surface area because of their very
small size. Furthermore, the interaction between electromagnetic
Synthetic dyes, commonly utilized in various industries, are radiations and photocatalyst is also quantum mechanically more
environmental contaminants and their uncontrollable release into favorable because of comparable size and wavelength (both
the aqueous reservoirs as an industrial effluent owing to the quantities in nanometers) leading to superior surface plasmonic
excessive usage of these dyes is an undesirable and harmful phe- resonance and quantum confinement properties associated with
nomenon (Khan et al., 2020). Food, paper, leather, textile, phar- the NMs (Rahman et al., 2019). These unique features of NMs
maceutical, and paint industries commonly use these dyes as arising due to their small size essentially compliment the process of
coloring agents. According to a documented global estimate, the photocatalysis which is also a surface dependent phenomenon.
approximately 7
105 tons of 1000 different types of dyes and As evident from the name, the process of the photocatalysis
pigments are manufactured annually. These carcinogenic azo dyes fundamentally requires the material capable of acting as a catalyst
when released into the aqueous environment bring forth unfavor- upon irradiation treatment and the irradiation setup. The electro-
able structural changes in the ecosystem. Hypertrophication caused magnetic radiations falling on the surface of NMs activate the
by these dyes reduces oxygenation capacity for marine life and photocatalyst and result in the formation of electron-hole pairs (e/
severely damages the aquatic flora and fauna. As humans utilize hþ). These generated pairs then interact with the species present in
aquatic food, the bioaccumulation and biomagnification of these the reaction medium and carry out the degradation process
toxic dyes in the aquatic environment indirectly affect humans as (Nguyen and Juang, 2019).
well. Methylene blue (MB) is a well-known, extremely carcinogenic For the electromagnetic radiation portion, scientists are focusing
thiazine pollutant that has been manufactured and used in many on the use of the sunlight as the source of the irradiation (Raza
industries for different purposes (for instance: dyeing of cotton, et al., 2020; Saravani et al., 2019). This practice also makes the
wool and fabrics; coloring of paper, as a hair coloring agent and removal of MB dye via NMs-PCA more economical in comparison to
redox reaction indicator in outer space, etc.) (Kumar et al., 2014). other removal strategies. In case of the preparation of the NMs, the
Upon ingestion, MB becomes a serious threat to human health and selection of the stabilization medium is a crucial factor that directly
has been known to cause damages to the nervous system and eyes. affects the photocatalytic efficacy of the NMs. Owing to the small
Other associated ailments include nausea, diarrhea, vomiting, size of the NMs, the stabilization medium is required for inhibiting
breathing difficulties and gastritis infections. Therefore, it is the aggregation tendencies of the NMs. Different types of stabili-
imperative to develop such advanced strategies that can eradicate zation mediums including graphene (Saravani et al., 2019), silica
such hazardous pollutants from the water bodies. (Khanh Nguyen et al., 2020), organic polymers (Duan et al., 2020),
Various removal methodologies that can effectively degrade/ microgels (Javed and Hussain, 2020), dendrimers (Han et al., 2019)
remove such noxious contaminants from the aqueous medium and biomass (Sabouri et al., 2020) etc. have been documented for
have been documented to address this environmental challenge. the effective stabilization of the engineered NMs-PCAs. The orga-
These removal strategies include adsorption (Naseem et al., 2018), nization of the vast literature documented in the recent years
chemical reduction (Begum et al., 2019), membrane filtration regarding the preparation of NMs-PCAs for the photocatalytic
(Pronk et al., 2019), coagulation/flocculation (Ho et al., 2020), removal of MB is the need of these times.
photo-oxidation (Neves et al., 2019), ion-exchange removal (Bashir Several reviews focusing the photocatalytic removal of the
et al., 2019), catalytic ozonation (Hu, 2019), biological (aerobic/ synthetic dyes have been presented in the academic literature
anaerobic) treatments (Saghafi et al., 2019) and photocatalytic (Adnan et al., 2019; Chiam et al., 2020; Din et al., 2018, 2019).
degradation (Din et al., 2020). Although the removal methodologies However, no literature review summarizing the NMs-PCAs specif-
of adsorption and catalytic degradation are also one of the most ically aiming for the photocatalytic removal of MB dye has been
widely reported removal methodologies in the case of dyes, the reported to the best of our knowledge. Instead of concentrating on
photocatalytic removal of the pollutants possess several advantages the whole class of synthetic dyes, this focused review on the single
(including utilization of renewable resource (sunlight), simplistic photocatalytic reaction of the MB will be helpful in providing better
operation scheme, efficient removal and complete mineralization insights for modulating this particular reaction. This review has
of the dye, etc.) over other methodologies. Furthermore, this been structured into four main sections including introduction
removal methodology has become even more significant with the (providing the basic introduction to NMs based photocatalysts),
incorporation of nanotechnology in these removal methodologies. photocatalytic degradation of the MB (discussing the fundamentals
Manipulation of the materials at the atomic and molecular scale and factors influencing the model photocatalytic reaction of MB),
to engineer the functionalized materials having at least one of its NMs-PCAs (organizing, summarizing and analyzing the recent ac-
dimensions in the nanorange (1e100 nm) is termed as nanotech- ademic studies documented in the past three years i.e. 2018-2020
nology. Nanomaterials (NMs) owing to its ubiquitous features have for the light mediated removal of MB) and future prospects
found applications in every field of life including agriculture, (providing the summary of the recent advancements discussed
biotechnology, medicine and wastewater treatment, etc. (Khan alongside the possible new avenues for further improvement of the
et al., 2020). Nanomaterials based photocatalytic assemblies degradation reaction). This study will be helpful in providing
(NMs-PCAs) carrying out light-mediated degradation of the essential insights to the readers regarding light mediated removal
harmful pollutants is one such widely reported application of of MB via use of NMs.
nanotechnology. Various case studies documenting the use of the
NMs-PCAs for the removal of the MB has been reported in the ac- 2. Photocatalytic degradation of MB
ademic literature (Larbi et al., 2019). These assemblies are superior
in comparison to the customarily employed bulk catalysts owing to The utilization of the photocatalytic degradation of the MB as
2
M.I. Din, R. Khalid, J. Najeeb et al.
the model reaction for estimating the photocatalytic capabilities of
the novel and newly engineered NMs-PCAs has become a common
practice in recent times (El-Sheshtawy et al., 2019; Kaur and Jindal,
2019). Some of the considerations that have contributed towards
the excessive usage of this reaction include a) MB is a common
carcinogenic pollutant and its removal from the aqueous medium is
highly desirable; b) MB dye is ultravioletevisible (UVeVis) active
species and exhibit characteristics peaks in the UVeVis spectrum.
Consequently, the qualitative analysis for identifying the MB in any
aqueous medium can be easily performed by using the simple
analytical instrument of UVeVis spectroscopy; c) it is a colored dye
and exhibits the blue color in its oxidized state. Therefore, the
presence of the MB in any medium can also be visually observed; d)
Documenting the progress of the degradation reaction is also quite
facile as the characteristic blue color of the MB disappears owing to
the degradation of MB into smaller molecules in the presence of
radiation mediated activated photocatalytic NMs in the reaction
medium. Furthermore, experimental evidence of the degradation is
also acquired by simply taking the UVeVis spectrum as the char-
acteristic absorption peaks of MB disappear with the degradation of
the MB (Chala et al., 2019); and e) MB dye, after undergoing various
reaction intermediates, is essentially converted into the water
(H2O), carbon dioxide (CO2) and some other species including
ammonium, nitrate or sulfate ions as a result of the photocatalysis.
Therefore, the harmful and noxious MB dye is converted into very
less toxic by-products by utilizing the approach of the photo-
catalysis (Mengting et al., 2019).
2.1. Photodegradation mechanism of MB
The first step of the photocatalysis is the activation of the NMs
by the reconstruction of the NMs surface via electromagnetic ra-
diation illumination as shown by equation (1) (Fig. 1). The elec-
tromagnetic radiations interact with the surface plasmons of the
NMs and excite the electrons into the higher states. Upon the
excitation of the negatively charged electron (e), the positively
charged hole (hþ) is created in its place. These e/hþ pairs are
responsible for the photocatalytic capability of the NMs. The energy
required for this activation is equal to the band gap (the difference
of the energy values between the valence and conduction band) of
the NMs. This required energy is provided by the incident elec-
tromagnetic radiations.
NMs þ hv/NMsðe = hþ Þ
Fig. 1. General Mechanism for photodegradation of MB.
Journal of Cleaner Production 298 (2021) 126567
These generated e/hþ can undergo recombination reactions via
relaxation processes as indicated in equation (2) which would lead
to the deactivation of the photocatalyst. Therefore, avoiding
recombination reactions is essential for achieving the maximum
photocatalytic efficacy of the NMs.
e þ hþ /heat energy þ deactivated NMs (Eq 2)
These dissipation reactions can be avoided owing to the pres-
ence of the oxidizing agents or any other scavenging mediums or
species in case of electrons (Din et al., 2020). The generated e
reacts with the atmospheric oxygen and expedites the formation of
superoxide radicals (,O2 ) as indicated by equation (3). The pres-
ence of the H2O further facilitate the photocatalytic reaction by the
interaction of the hydroxyl ions (OH  ) with the hþ and results in
the formation of the hydroxyl free radicals (,OH) in the reaction
medium as shown by equation (4).
O2 þ e /,O
2 (Eq 3)
OH þ hþ /,OH (Eq 4)
These reactive and non-selective radicals interact with the MB
and the process of demethylation occur leading to the breakage of
the NeCH3 bond. This step is followed by the attack of the radical
species on the aromatic ring. Most of the reaction intermediates
come from the breakage of the aromatic ring of the MB. The frag-
ments of dyes are degraded into further reaction intermediates
including aldehyde, carboxylic species, phenols and amines which
are ultimately converted into the H2O, CO2, ammonium ions and
sulfate ions. Few case studies also document the generation of
hydroperoxyl species (,OOH) achieved by the protonation of ,O 2
which results in the formation of hydrogen peroxide (H2O2) in the
reaction medium (King et al., 2019). The radical species generated
in the reaction medium inhibit the recombination reactions by
carrying out the electron scavenging capabilities. However, similar
to the above mentioned general mechanisms few other mecha-
nisms also has been reported in the literature for photocatalysis
including direct Z-scheme and indirect all solid Z-scheme mecha-
nisms, etc. as given in Figs. 2 and 3. For example, Xu et al. (2015)
reported the Z-scheme mechanism for photocatalysis of MB using
Ag2CrO4-GO nanocomposite. They reported a typical Z-scheme
mechanism with fast separation and transfer of photogenerated e/h
(Eq 1)
Fig. 2. Typical direct Z-scheme photocatalytic mechanism involving fast charge sep-
aration with transfer of the photogenerated electronehole pairs for successful pho-
todegradation of MB.
3
M.I. Din, R. Khalid, J. Najeeb et al. Journal of Cleaner Production 298 (2021) 126567

degradation process carried out in the presence of the catalyst

MgO-NPs (Khan et al., 2020). The negative sign affiliated with the
rate is indicative of the fact that the amount of the MB dye is
decreasing with time as shown in Fig. 4b.

d½MBt
 ¼ Kaap ½MBt (Eq 5)
dt

ðt ðt
d½MBt
 ¼ Kaap dt (Eq 6)
½MBt
0 0

ln½MBt ¼ Kaap t þ constant (Eq 7)

Applying the initial conditions for calculating the value of con-
stant will result in the formation of equation (8).

ln½MBt ¼ Kaap t  ln½MBo (Eq 8)

ln½MB0  ln½MBt ¼ Kaap t (Eq 9)

Fig. 3. Solid-state Z-scheme mechanism [Step I Excitation of nano-heterojunctions
through solar light radiations, Step II Transfer of photogenerated e of CB of PSI to
rGO, Step III Recombination of hþ of VB of PSII with photogenerated e of CB, Step IV
Photodegradation of MB via active radicals  O 
2 (generated via e of CB of PSII) and OH
(generated via hþ of VB of PSI)].
pairs in the presence of Ag2CrO4-GO nanocomposite. Wu et al.
(2017) reported the indirect all solid state Z-scheme mechanism
for photocatalytic degradation of MB using geC3N4erGO-TiO2
nano-heterojunctions as catalyst. They also found that introduction
of rGO into geC3N4eTiO2 nanocomposite would lead to an
improvement in charge separation/transfer along with prompted
electron’s oxygen reduction capacity in g-C3N4 and enhanced
generation of hydroxyl radical due to holes in TiO2 that results in
excellent photocatalytic performance.
2.2. Kinetics
The photocatalytic reaction of MB generally has been docu-
mented to follow the pseudo-first-order kinetics (Tran et al., 2019)
or first-order kinetics. The kinetic study of this reaction is also
carried out by using UVeVis spectroscopy The concentration of MB
ͦ as
in the reaction container at any time’t’, represented as [MB]t, acts
a limiting factor for this reaction. The rate of the degradation re-
d½MB
action written in the case of the MB dye (  dt t ) will depend on
the [MB]t. Fig. 4a provides the UVeVis spectrum of the MB
½MBt
ln ¼  Kaap t (Eq 10)
½MBo
where Kaap represent the rate constant for the reaction and
½MBo shows the concentration of MB at time zero. Table 1 highlights
the kinetic fundamentals of the photocatalytic degradation of MB.
The UVeVis spectroscopy operates on the principle that the
concentration of the UVeVis active species is directly proportional
to the absorbance intensity of that species (Tran et al., 2019).
Therefore, kinetic modeling and reaction progress of this photo-
degradation reaction can be easily monitored by using this tech-
nique. The percentage degradation of the MB dye is another
parameter frequently reported in case of the degradation of MB via
NMs-PCAs (Chen et al., 2019a). It is also calculated via UVeVis
spectroscopy by using the following equation.
½MBo  ½MBt
Percentage ð%Þ Degradation ¼
100 (Eq 11)
½MB0
2.3. Factors affecting the photocatalytic degradation of MB
2.3.1. Nature of NMs-PCAs
The nature of the utilized NMs-PCAs is essentially the most

Fig. 4. a)UVeVis spectral analysis of the degradation of MB using the MgO-NPs and b) rate constant evaluation by linear regression analysis for the degradation of MB under
numerous conditions. Reprinted by permission from Springer Nature [Applied Nanoscience], Khan et al. Copyright (c) 2020, King Adulaziz City for Science and Technology.

4
M.I. Din, R. Khalid, J. Najeeb et al. Journal of Cleaner Production 298 (2021) 126567

Table 1
Kinetic aspects of photocatalytic degradation of MB carried out by using the various NMs-PCA.

Photocatalyst Order of Apparent rate constant Light % Irradiation Time Reference

reaction (min1) source Degradation (min)

Pd-AgNPs/MacroPsi (bimetallic NPs) Pseudo-first 3.3
102 UV light 98.8 e Wali et al. (2019)
order
Graphene-alpha-molybdenum trioxide (a-MoO3) Pseudo-first 5.049
101 UV light 97 240 Mahalingam et al.
nanocomposites order (2017)
2
Fe2O3/graphene/CuO (FGC) e 7.25
10 Visible 94.27 40 Nuengmatcha et al.
light (2019)
Dolichos Lablab L. ZnO NPs Pseudo-first 9.14
103 UV light 80 210 Kahsay et al. (2019)
order
Spirulina platensis AgNPs First order 7
103 Sunlight 100 120 Rojaa et al. (2019)
Fe3O4@C@Ru First order 1.76
102 Visible 92.70 140 Zhang et al. (2019b)
light
Selenium (Se) NPs First-order 3.6
103 UV light 57.63 40 Tripathi et al. (2020)
Pithecellobium dulce peelemediated ZnO NPs Pseudo-first- 8.12
103 UV light 63 120 Madhumitha et al.
order (2019)
Graphene oxide -Fe3O4eNiO hybrid NCs Pseudo-first 8.047
101 Visible 99 15 Mahalingam and Ahn
order light (2018)
Brassica oleracea var. botrytis-AgNPs Pseudo-first 2.308
102 Sunlight 97.57 150 Kadam et al. (2020)
order

Abbreviations: Nanoparticles (NPs), Nanocomposites (NCs), Macro porous silicon (macroPSi), Zinc oxide (ZnO), Silver nanoparticles (AgNPs), Iron oxide (Fe3O4), Ultraviolet
(UV), Palladium (Pd), Copper oxide (CuO), Ruthenium (Ru), Nickel oxide (NiO).

significant factor influencing the degradation rate of the MB. Based
on the nature of the NMs, the NMs possessing more advanced/
complex structural and morphological features have been docu-
mented to exhibit enhanced rates for degradation in comparison to
simple and facile NMs based assemblies. Most of the academic
literature surrounding the photocatalytic degradation of MB re-
ported in the last two years focuses on the bimetallic assemblies
rather than simple monometallic assemblies. Bimetallic NMs-PCAs
reported by Wali et al. (2019), Feng et al. (2019), (Tiwari et al.
(2019), Liu et al. (2019), Zhong et al. (2020) and Lee et al. (2019)
has documented better results for the degradation of the MB in
comparison to their monometallic analogues owing to the syner-
gistic bandgap effects of the metallic nanoparticles (NPs). Reports
of the preparation of monometallic assemblies can also be found in
academic literature but these assemblies are mostly limited to the
biogenic synthesis of the NMs-PCAs (Haseena et al., 2020;
Nilavukkarasi et al., 2020; Pai et al., 2019). Furthermore, the
dimensionality of the prepared NMs also plays a significant role in
determining the efficacy of the NMs-PCAs for the MB degradation.
The NMs having more roughness and surface area such as nano-
flowers or other complex/complicated morphologies exhibit
enhanced photocatalytic results in comparison to unmodified
simple NMs-PCAs (Din et al., 2020). Another factor that signifi-
cantly influences the degradation efficacy of the NMs-PCAs is the
nature of the stabilization medium used for the immobilization of
NMs. Some stabilization mediums perform the dual purpose and
also contribute to electron shutting processes between the dye and
NMs apart from providing the fabrication medium for NMs (Dai
et al., 2014). reported the preparation of a unique 2-dimensional
hybrid assembly of ZnO nanorods (NRs) stabilized via graphene
sheet and utilized it as photocatalyst. The comparison of the pho-
tocatalytic potential of the stabilized ZnO NRs against pristine ZnO
NPs and standard control photocatalyst (P25) revealed the immo-
bilized ZnO NRs assembly to be more effective in terms of the
pollutant degradation. This is attributed to the fact that the two-
dimensional nature and conductivity potential of the graphene
complemented the increased surface area provided by the ZnO
nanorods and this synergy between the two components led to the
enhanced photocatalytic potential of the stabilized NMs assembly.
2.3.2. Effect of NMs-PCAs concentration
The effect of concentration of NMs-PCAs added into the reaction
5
medium on the photocatalytic rate of the dye has been widely re-
ported. A survey of scientific literature indicates the presence of a
generalized trend in case of this reaction variable (Agnihotri et al.,
2018; Boruah et al., 2016; Foura et al., 2017). At the initial stage of
the degradation reaction, the rate of MB degradation was docu-
mented to show an increase in response to the increase in the NMs-
PCAs in the medium. However, the rate starts decreasing after the
attainment of the peculiar concentration termed as the optimum
concentration (Alshehri and Malik, 2019). The initial increase is
accredited to the enhancement in the number of available inter-
active nucleation sites for the MB dye with an increase in the
concentration of NMs-PCAs. The nucleation sites upon irradiation
treatment generate the free radicals in the medium which ulti-
mately increases the degradation procedure of the dye. After
reaching the optimum concentration, any further increase in NMs-
PCAs decreases the working efficacy of the photocatalyst. One of the
main reasons for the decrease in efficacy is the overcrowding of the
NMs-PCAs in the reaction medium. Consequently, NMs undergo
aggregation owing to the constant collisions due to overcrowding
and the working efficiency of NMs-PCAs is reduced (Suresh et al.,
2015). Apart from the increase in the size of NMs owing to aggre-
gation, the solution becomes turbid and light scattering phenom-
enon starts dominating in the reaction medium. This factor also
reduces the efficacy of the NMs-PCAs because the light is now being
scattered rather than being utilized in the activation procedure of
the NMs-PCAs after reaching the optimum concentration.
2.3.3. Effect of MB concentration
The amount of MB utilized in the photocatalytic reaction affects
the value of rate constant in a similar fashion as reported for the
concentration of NMs-PCAs (Agnihotri et al., 2018; Ali et al., 2016).
The increase in substrate concentration after reaching the optimum
value causes a decrease in the photocatalytic rate of MB. The initial
increase in the substrate concentration favors the high quantity of
MB to get absorbed on the catalyst surface. But a further increase in
the MB concentration than the optimum concentration makes the
reaction medium concentrated and the light penetration into the
reaction medium for catalyst activation gets affected owing to the
presence of large number of ions in the medium. Additionally,
higher concentration of MB requires increase generation of
oxidant/free-radical species for effective degradation. High con-
centration of MB also reduces these free-radical generation
M.I. Din, R. Khalid, J. Najeeb et al.
reactions by becoming an interfering species owing to its high
concentration in the reaction medium.
2.3.4. Effect of pH
Unlike the previously described factors, the generalized trend
cannot be defined for the factor of pH and temperature. The reason
is that the nature of the NMs involved in the NMs-PCAs heavily
influences this factor (Agnihotri et al., 2018; Boruah et al., 2016). MB
is a cationic dye and mostly high pH values favor the photocatalytic
degradation of the MB owing to the presence of negatively charged
hydroxyl ions in the medium that can contribute to the generation
of free radicals as indicated in equation (4). However, the isoelectric
point associated with the NMs-PCAs is usually responsible for
determining the optimum pH for the photocatalytic degradation of
MB carried out via NMs-PCAs. Nagarjuna et al. (2015) investigated
the photocatalytic efficacy of TiO2 NPs for the light mediated
degradation of the MB. The effect of pH was investigated for the
range of 5e9 and the optimum pH value was found to be 8.5 for this
particular TiO2 NPs based PCAs. It was proposed that the mecha-
nistic and kinetic approach might be different in acidic and basic
medium. However, mechanistic studies were not carried out in case
of acidic medium. The maximum photocatalytic degradation effi-
cacy was observed in the basic medium. Suresh et al. (2015) also
documented the effect of pH by varying the value of pH from 2 to 12
on the photodegradation of MB. Additionally, the maximum
degradation was observed at optimum pH value of 4. The nature of
the NMs in the utilized NMs-PCAs was accredited for this optimum
pH value.
2.3.5. Effect of temperature
Customarily, the light-mediated degradation reactions in the
case of the MB carried out via NMs-PCAs are recorded under
ambient conditions (i.e. normal room temperature and pressure).
As the kinetics of the degradation reaction is affected by the value
of the temperature, reporting the value of temperature at which the
typical degradation reaction has been studied is considered normal
practice in academic literature (Khan et al., 2020). The optimized
temperature required for the photocatalysis process of MB must not
be so small that the activation energy of few kilojoules cannot be
provided to the system and also must not be extremely high to
disrupt the adsorption-desorption (equilibrium) establishment
process. Therefore, the selection of a suitable temperature is a
requirement for acquiring the maximum efficacy in the case of the
degradation of MB. Apart from the considerations of the photo-
catalytic reaction of MB, the effect of temperature change on the
NMs-PCAs should be considered as well. High-temperature values
can cause structural, degradable/non-biodegradable and configu-
rational changes in the NMs of the NMs-PCAs. Therefore, the factor
of the temperature (similar to the factor of the pH) must be sepa-
rately optimized for every NMs-PCAs used for the degradation of
MB. Lei et al. (2020) investigated the effect of the temperature from
the range of 10 Ce35 C on the rate kinetics of the MB by measuring
the value of rate constants at different temperature. Maximum
degradation was observed at the temperature of 25 C while the
high temperatures values resulted in a decrease for the value of rate
constant indicating that the establishment of equilibrium was
hindered owing to an increase in the kinetic energy of the system.
2.3.6. Effect of radiation intensity
The light intensity is an important factor affecting the rate of
photocatalysis because it is mainly involved in the activation of the
photocatalyst. The more the number of photons interacting with
the NMs in the NMs-PCAs, the more will be the production of
charge carriers and consequently, the degradation rate will be
increased (Osuntokun et al., 2019; Rezaei and Salem, 2016).
6
Journal of Cleaner Production 298 (2021) 126567
Therefore, the light intensity should always be considered when
the photocatalytic process is studied (Alshehri and Malik, 2019;
Suresh et al., 2015).
2.3.7. Effect of photoreactor
The type of photoreactor utilized for the degradation of MB dye
also affects the degradation efficacy of the NMs-PCAs (Table 2). A
variety of photoreactors has been utilized in academic literature for
the photocatalytic treatment of the MB. Generally, these reactors
can be divided into two types based on the fate of the involved NMs
in the NMs-PCAs. These classes include mobilized NMs-PCAs
reactor and immobilized NMs-PCA reactor. In the case of mobi-
lized NMs-PCAs reactors, the catalyst is immobilized on the pecu-
liar substrate for the duration of the photocatalytic experiment.
Such immobilized reactor provides an additional advantage of
removing the separation step from the protocol as the material is
already immobilized on the substrate and other separation pro-
cedures such as centrifugation, filtration, magnetic separation,
mechanical separation, and vacuum filtration, etc. are not required
for the recovery of NMs from the reaction medium. Rokhmat et al.
(2017) engineered one such immobilized NMs-PCAs reactor by
coating the TiO2 NMs on plastic granules and then embedding these
granules in the reactor panel to achieve a flat-panel photoreactor
for the photodegradation of MB. Most of the academic literature
report focusing on the reporting of the novel NMs-PCAs reports the
utilization of the immobilized NMs-PCAs photoreactors where the
NMs are utilized in suspended form for carrying out the hetero-
geneous photocatalysis of the MB dye. Zhang et al. (2018), Adeleke
et al. (2018), and Kurniawan et al. (2020) used such suspension
based photoreactors for carrying out the degradation of MB. Both
photoreactor types discussed above have their advantages and
problems. For the studies that are only documenting the synthesis
of novel NMs-PCAs, simple photocatalytic reactors in the sus-
pended form have been used as the major photoreactor. But for the
case studies that are focusing on the development of point of care
technologies, immobilized NMs-PCAs photoreactors are used to
increase the shelf-life of the NMs-PCAs as well as avoiding the
separation step in the protocol. However, immobilized photo-
reactors exhibit some configurational/structural problems as well
during the photocatalytic experiments which are not observed in
the case of the immobilized photoreactors. For example,
membrane-based immobilized reactors undergo fouling and
degradation problems of the synthesized membrane owing to
irradiation treatment involved in the process of photocatalysis
(Sundar and Kanmani, 2020). Therefore, choosing an appropriate
photoreactor type is also essential for achieving the optimum
photocatalytic efficacy of the NMs-PCAs.
When studying the large scale/industrial level degradation of
MB, mostly immobilized NMs-PCAs reactors are documented to be
utilized. The academic literature points out that on a higher in-
dustrial scale, the debate of the reactor is shifted from the immo-
bilization/suspension of the NMs towards the batch and continuous
flow reactors. The immobilization reactors are the preferred reactor
as the removal of the separation step presents a clear advantage
when dealing with the large-scale degradation of the MB dye.
However, the challenge is to decide whether the batch technique or
continuous flow photometry is better for the degradation of
organic dyes or MB. Jo and Tayade (2016) developed the immobi-
lized NMs-PCA reactor (batch reactor) having TiO2 NMs immobi-
lized on the mosquito net which was then immersed in the reactor
containing 125 mL MB solution and UV based light-emitting diode
(LED) as the irradiation treatment set up (operating at
power ¼ 8 mWcm2, wavelength ¼ 350 nm and combination of
30LEDs for the batch process). The 95% degradation was achieved
for 125 mL of MB dye in 4 h. Repo et al. (2013) also documented the
M.I. Din, R. Khalid, J. Najeeb et al. Journal of Cleaner Production 298 (2021) 126567

Table 2
Description and types of photoreactor used for photocatalysis of MB dye.

Photoreactor Description Reactor Type/Light Catalyst % Reference

source Degradation

Micro-channel Reactor consist of cylindrical porous disks of ceramics with TiO2 capped on it, Immobilized/250 W TiO2 supported on 64 Teekateerawej
Reactor where the dimensions of disk is diameter 5 mm
0.2 mm and 1250 holes of 360 nm Hg lamp porous ceramic et al. (2006)
diameter 50 mm disks
UV LED Reactor consist of three number TiO2-QT each having 120 mm length, Suspended/390 TiO2-QT 61 Natarajan et al.
Photocatalytic diameter 5 mm with 15 UVA-LEDs which is mounted on cylindrical on TiO2-QT e410 nm 10 (2011)
Reactor e12 mW UVA LEDs
Continuous fixed Continuous fixed bed reactor comprises of feed tank and two stainless steel Immobilized TiO2 immobilized on 75 Vaiano et al.
bed reactor tubes of about 1 cm diameter surrounded with two pyrex windows pyrex (2015)
(2.5 cm ¼ thickness), packed bed N doped TiO2 onto pyrex spheres and five UV
lamps
Flat plate solar Flat plate solar photocatalytic reactor consist of TiO2 is coated onto plastic Immobilized/Solar Coated TiO2 on 99 Rokhmat et al.
photocatalytic granules with dimensions of about 70 cm
68 cm x 1 cm irradiation plastic granules (2017)
reactor
Translucent Translucent packed bed reactor comprises of TiO2 coated borosilicate beads Immobilized/192 TiO2 P25 coated 99 Claes et al.
packed bed (3 mm ¼ diameter) and 192 LEDs are used in array structure to irradiate the LED array board borosilicate beads (2019)
reactor photocatalytic reaction zone of 5 cm
15 cm
Packed bed The main component includes cylindrical tube made of Pyrex glass (40 cm Immobilized/81.6 W NeTiO2 100 Sacco et al.
photoreactor length, 5 cm diameter) and N doped TiO2 on polystyrene spheres as 400e700 nm Visible immobilized on (2019)
photocatalyst bed. Visible LEDs strip was wrapped on the walls of polystyrene LED
photoreactor Strip

Abbreviations: Centimeter (cm), Nanometer (nm), Watt (W), Millimeter (mm), Micrometer (mm), Titanium dioxide (TiO2), Mercury (Hg), Ultraviolet light emitting diode (UV-
LED), Microwatt (mW), TiO2 coated quartz tube (TiO2-QT), Nitrogen doped Titanium dioxide (N doped TiO2).

batch process for the degradation of a 200 mL MB solution via an discussed down below.
LED photoreactor. 100% degradation efficacy was achieved under
the irradiation period of 3 h. Another approach that competes
3.1. Synthetic material based NMS-PCAs
alongside batch processing is the continuous flow approach. Many
scientists are reporting the advantages of flow photochemistry over
The synthetic material can be further divided into organic and
the conventionally used batch approach these days. As the dyes
inorganic assemblies used for the fabrication of NMs in NMs-PCAs.
present in the industrial effluent are released in the form of a
Table 3 summarizes the different case studies associated with
stream, the development of such photoreactors that can effectively
synthetic material based NMs-PCAs documented for the photo-
degrade the dyes in that particular moving stream is highly desir-
catalytic degradation of the MB dye.
able. But continuous flow photochemistry requires the develop-
Inorganic synthetic materials include rigid, non-biodegradable
ment of complicated setups which serves as a disadvantage
and complex NMs based assemblies such as graphene, carbon
economically in comparison to rather simplified batch reactors.
nanotubes (CNTs), graphene oxide (GO), reduced graphene oxide
However, the usage of batch reactors for photocatalytic degradation
(rGO), silica, zeolite, etc. The preparative methods utilized for
process is theoretically hindered via constrained imposed through
achieving the stabilization via inorganic assemblies are multi-
Beer-Lambert law (larger path lengths, larger reaction times, etc.)
stepped and are mostly carried out under harsh reaction condi-
(Elliott et al., 2014). However, the batch process is the most widely
tions. However, the inorganic synthetic material based NMs-PCAs is
reported in the case of the photocatalytic degradation of MB. Few
quite effective in the fabrication of the complex and multi-
case studies reporting the usage of continuous flow processes are
dimensional NMs. Graphene and its different forms (rGO and GO)
also documented in the case of MB. For instance, Natarajan et al.
are the most widely used (Chen et al., 2019b; Jung and Kim, 2014;
(2011) developed a continuous flow reactor for the degradation of
Shehzad and Xu, 2020). Banerjee et al. (2018) utilized graphene as
MB having three impregnated pipes containing TiO2 NMs coated on
supporting material for the fabrication of Fe3O4eTiO2 PCAs. The
quartz. The MB was effectively degraded with 100% efficacy within
advantages of using graphene included large surface area (owing to
100 min under alkaline conditions. Further work is required in the
its dimensional features), excellent stability and high conductivity
domain of photoreactors for investigating the efficacy of both the
potentials. Graphene also facilitated the process of photocatalysis
batch and continuous processes as the comparative studies car-
by providing electrically conductive channels for the transduction
rying out the degradation reactions under similar conditions are yet
of electrons into the conduction band. These features make these
to be reported in the academic literature for the case of MB
inorganic materials even more attractive for the preparation of
degradation.
NMs-PCAs as these mediums also synergistically boost the process
of photocatalysis alongside the NMs. Furthermore, the presence of
3. NMs-PCAs functional groups such as epoxide, carbonyl and carboxyl func-
tional groups in 2-dimensional carbon sheets of graphene increases
Photocatalytic assemblies containing the NMs have been the fabrication potential of the graphene as well. NMs are immo-
extensively reported in the scientific literature for carrying out the bilized by developing interactions with these functional groups.
degradation process of various dyes particularly MB. The produc- Fan et al. (2016) fabricated 3D- CeVO4/graphene nanocomposites
tion of the charge carriers in the NMs helps in overcoming the ki- (NCs) by utilizing the strong interactive forces between the sup-
netic barrier required for carrying out the degradation process. porting medium and the NMs. The MB dye adsorption was also
Based on the stabilization system utilized for the fabrication of the increased due to the interactive forces between the NCs and the MB
NMs, the NMs-PCAs are broadly classified into two major categories molecules owing to these functional groups.
including synthetic material stabilized NMs-PCAs and natural ma- In recent years, many scientists have focused on the utilization
terial stabilized NMs-PCAs. These classes are categorically of non-polymeric porous supporting matrices like zeolites, clay,
7
 Table 3

M.I. Din, R. Khalid, J. Najeeb et al.

NMs-PCAs utilizing the synthetic stabilization mediums for the fabrication of NMs used for the photocatalytic degradation of MB.

Nature of PCAs NMs Type of Supporting medium (a) Average diameter Dark Light source Method of preparation Ref
stabilization assembly Degradation (nm) reaction Irradiation
medium (%) (min)
(b)
Degradation
time
(min)
(c) Initial
concentration
of MB
(mg/L)

Inorganic ZnO/Au/rGO ternary ZnO/Au Nanocomposite Reduced graphene oxide (a)95 ZnO ¼ 11.46 30 Sunlight Two-step process (i) Pulsed laser Naik et al.
nanocomposites (b)120 ZnO/Au ¼ 12.11 synthesis (ii) Wet chemical (2020)
(c)10 ZnO/Au/rGO ¼ 15.10 process.
rGO-Ag/ZnO Ag/ZnO Nanocomposite Reduced graphene (a)99 e 60 UV light Facile synthesis route by grafting Belachew et al.
Oxide (b)120 Ag/ZnO with rGO (2020)
(c)10
MoS2e(rGO) composites MoS2 Nanocomposite Reduced graphene oxide (a) 99 e 30 Visible light Microwave-assisted reduction Li et al. (2014)
(b) 60
(c) 60
BaTiO3/graphene BaTiO3 Nanocomposite Reduced graphene oxide (a) 69.5 e 60 Visible light Hydrothermal approach Wang et al.
(b) 30 (2015)
(c) 480
TiO2/rGO nanocomposite TiO2 Nanocomposite Reduced graphene oxide (a)92 e 60 Sunlight Hummer’s method (Kocijan et al.)
(b)120
(c)10
TiO2/graphene porous TiO2 Nanocomposite Reduced graphene oxide (a) 96 Polystyrene 30 Visible light Hummers’ method Yang et al.
Microsphere ¼ 580
8

composites (b) 150 (2016)

(c)10
CuONPs@GO CuO Nanocomposite Reduced graphene oxide (a) 93 GO ¼ 93.6 120 Visible light Green laser ablation route Ahmed et al.
(b) 40 CuO ¼ 59.0 (2020)
(c) 5
Cu/rGO nanocomposite Cu Nanocomposite Reduced graphene oxide (a) 94 Cu ¼ 12.21 30 Visible light Hummer’s method Aragaw and
(b) 50 Dagnaw (2019)
(c) 40
Graphene/CuO CuO Nanocomposite Graphene nanosheets (a) 76 Graphene/CuO ¼ 15.8 30 Visible light e Udayabhaskar
nanostructures (b) 90 et al. (2019)
(c) 10
rGO/TiO2/Co3O4 TiO2/Co3O4 Nanocomposite Reduced graphene oxide (a)100 Decrease form 45- 15 Visible light Co-precipitation Ranjith et al.
nanocomposite (b)120 18 nm on addition of (2019)
(c)10 rGO
rGO/Fe3O4 NCs Fe3O4 Nanocomposite Reduced graphene oxide (a)74 rGO/Fe3O4 NCs ¼ 19.2 30 UV light Solvothermal synthesis Vinodhkumar

Journal of Cleaner Production 298 (2021) 126567

(b)60 et al. (2020)
(c)12.5
WO3eZnO@rGO ternary WO3eZnO Nanocomposite Reduced graphene oxide (a)94 ZnO Nanorods ¼ 118 90 Visible light Ultrasound assisted fabrication Chaudhary
nanocomposites (b)90 et al. (2020)
(c)5
GO/Fe3O4/BiOI nanoflower Fe3O4 Nanoflower Reduced graphene oxide (a)91.4 e 120 Visible light Self-assemble of rGO with Fe3O4/ Xia et al. (2020)
(b)170 BiOI
(c)10
NiSeIn2O3/GO In2O3 Nanocomposites Reduced graphene oxide (a) 98.25 NiSeIn2O3/GO ¼ 66.0 30 UV light Ultrasonic/hydrothermal method Ashraf et al.
nanocomposites (b) 40 In2O3 ¼ 56.0 (2020)
(c) 10
TiO2/CDs/rGO TiO2 Nanocomposites Reduced graphene oxide (a)99.93 TiO2 ¼ 50 30 UV light e Mohamed and
Carbon quantum dots (b)60 Alsanea (2020)
(c)20
TiO2 Nanocomposite Graphene oxide 60 UV light Sol-gel
 M.I. Din, R. Khalid, J. Najeeb et al.
GO/TiO2 (a)92 GO ¼ 13.45 Velasco-
Nanocomposite (b)300 GO-TiO2 ¼ 50 Herna ndez
(C) N/A et al. (2020)
BiFeO3/graphene oxide BiFeO3 Nanocomposite Reduced graphene oxide (a)70 BiFeO3 ¼ 36.03 20 Sunlight e Noori and
nanocomposites (b)80 BiFeO3/rGO ¼ 33.23 Gholizadeh
(c)10 (2020)
Hybrid kaolin/TiO2 TiO2 Nanocomposite Kaolinite (a)90 TiO2 ¼ 14e20 30 Visible light Wet precipitation method Wongso et al.
composite (b)270 (2019)
(c)50
Zeolite/TiO2 composite TiO2 Nanocomposite Zeolite (a)93.6 TiO2(P-25) ¼ 25 60 UV light In situ synthesis Liao et al.
(b)60 (2019)
(c)50
Bi2MoO6/ZIF-8 Composite Bi2MoO6 Nanocomposite Zeolite (a)66 Pure ZIF-8 ¼ 50 30 Visible light Self-assembly process Xia et al. (2019)
(b)100
(c)20
TiO2-zeolites hybrid TiO2 e Zeolite (a)90 e 60 UV light e Kim et al.
(b)60 (2019)
(c)20
TiO2-zeolites hybrid TiO2 Nanocomposite Zeolite (a)100 e 20 UV light Hydrothermal method Alberti et al.
(b)60 (2019)
(c)50
TiO2-zeolites TiO2 e Zeolites (a)96 Z@TiO2 ¼ 76.6 e Compact Liquid impregnation (LI) method Saqib et al.
(b)180 TiO2 ¼ 51.1 fluorescent (2019)
(c)150 light
Pd-AgNPs/Psi Pd-AgNPs Nanoparticles Porous Silicon (a)98.8 PdNPs ¼ 5 e UV light e Wali et al.
(b)150 AgNPs ¼ 30 (2019)
(c)10 Pd-AgNPs ¼ 30
Silica-supported titanium TiO2 Nanocomposite Silica (a)99 e 15 UV light Solegel mechanism Fatimah et al.
oxide (b)40 (2019)
(c)20
9

Organic TiO2-hydrogel TiO2 Nanocomposite Hydrogel (a)N/A TiO2 ¼ 21 e UV light Thermal-polymerization of acrylic Pardo et al.
nanocomposite (b)N/A acid monomer (2018)
(c)10
PMMA/ZnO ZnO Nanocomposite Polymer (a)99 e 180 Sunlight Green synthetic route Rani and
Nanocomposite (b)180 Shanker (2018)
(c)10
Fe2O3-Porolas composites Fe2O3 Nanocomposite Porolas (a)98 Amorphous 720 UV light Impregnation method Hojamberdiev
nanoparticles Polymer (b)N/A Hematite ¼ 4 et al. (2019)
(c)N/A Ferrihydrite ¼ 5-6
Ag-doped Ag-doped Nanocomposite Microgel (a)100 PAA microgel ¼ 15-20 30 Visible light Free radical solution Iqbal et al.
CuO NPs/PAA microgel CuO NPs (b)N/A Nanocomposite ¼ 40 polymerization (2020)
(c)N/A
Ni Ni Nanorods Microgel (a)95 e e Tungsten Inverse phase polymerization Javed and
Doped ZnO/PAA microgel Doped ZnO (b)60 lamp of method Hussain (2020)
(c)N/A 500 W

Journal of Cleaner Production 298 (2021) 126567

TiO2/PNIPAM TiO2 Nanocomposites Microgel (a)86.3 TiO2 ¼ 20 30 Hg One-step in-suit method Duan et al.
(b)210 Lamp (2020)
(c) 5
N-doped TiO2 PNIPAM-co- N-doped Nanocomposites Microgel (a) 95 e 60 Visible light Sol-gel method Galata et al.
PAA microgels TiO2 (b)150 (2019)
(c) 2
Organic- PVA/TiO2/Graphene- TiO2 Nanocomposites Organic ¼ PVA (a)70 MWCNT ¼ 30e50 e UV light Solvothermal Jung and Kim
inorganic MWCNT Nanocomposites Inorganic ¼ Graphene- (b)180 (2014)
Composite MWCNT (c) N/A
TiO2/rGO/PMMA TiO2 Nanocomposites Organic ¼ Poly methyl (a)90 e 10 UV light e Momen et al.
Nanocomposite methacrylate (PMMA) (b) N/A (2020)
Inorganic ¼ Reduced (c)10
graphene
Oxide
(continued on next page)
 Table 3 (continued )

M.I. Din, R. Khalid, J. Najeeb et al.

Nature of PCAs NMs Type of Supporting medium (a) Average diameter Dark Light source Method of preparation Ref
stabilization assembly Degradation (nm) reaction Irradiation
medium (%) (min)
(b)
Degradation
time
(min)
(c) Initial
concentration
of MB
(mg/L)

GO/PANI/TiO2 TiO2 Nanocomposites Organic ¼ Polyaniline (a)98 TiO2 ¼ 15.91 e UV light In situ oxidative polymerization Baruah et al.
Nanocomposite (PANI) (b)60 (2020)
Inorganic ¼ Graphene (c)8
Oxide
PVDF/GO/ZnO composite ZnO NPs Nanocomposites Organic ¼ PVDF (a)86 e 20 Sunlight Immersion-precipitation phase Zhang et al.
Inorganic ¼ Graphene (b)180 transformation (2019a)
oxide (c)10
Ag3PO4/graphene oxide- Ag3PO4 Nanocomposite Inorganic ¼ (a)99 Graphene oxide- 60 Visible light Hydrothermal process Deng and
aerogel composites Reduced graphene oxide (b)60 aerogel ¼ 23.1 Huang (2020)
Organic ¼ Aerogel (c)2 Ag3PO4 ¼ 79.6
TiO2/Diazonium/Graphene TiO2 Nanocomposites Organic ¼ Diazonium (a)100 TiO2 ¼ 11.7 120 UV light e Hoan et al.
Oxide Composites Inorganic ¼ Reduced (b)120 (2020)
graphene oxide (c)10
P25/graphene/ TiO2 Nanocomposite Organic ¼ Polyacrylamide (a)100 PGP gel ¼ 14.01 30 Sunlight Facile synthesis route by Moztahida and
polyacrylamide hydrogels hydrogel (b)90 combining PAM with rGO and P25 Lee (2020)
Inorganic ¼ Reduced (c)N/A
graphene oxide
10

Graphene oxide/poly (vinyl TiO2 Microspheres Organic ¼ PVA (a)95 30 Sunlight One-pot synthesis Wang et al.
alcohol)/TiO2 microspheres Inorganic ¼ Graphene (b)120 (2017)
oxide (c)20
PVA-assisted Bi2WO6eCdS CdS Nanocomposite Organic ¼ PVA (a)92 e 60 Visible light Hydrothermal method Rajendran et al.
nanocomposite Inorganic ¼ Bi2WO6 (b)100 (2018)
(c)20
PVAeZnOeAl2O3 ZnO NPs Nanocomposite Organic ¼ PVA (a)100 e 30 Sunlight Solvent casting method Rahman Khan
Nanocomposite Inorganic ¼ Al2O3 (b)30 et al. (2018)
(c)5

Abbreviation: Reduced graphene oxide (rGO), Graphene oxide (GO), Titanium dioxide (TiO2), Titanium dioxide reduced graphene oxide (TrGO), Ferric oxide (Fe3O4), Copper oxide (CuO), Barium titanate (BaTiO3), Cadmium
selenide (CdSe), Molybdenum oxide (MoO3), Nickel oxide (NiO), Nickel ferrite (NiFe2O4), Porous silicon (Psi), Poly(vinyl alcohol) (PVA), Multiwalled carbon nanotubes (MWCNTs), Aluminium oxide (Al2O3), Bismuth tungstate
(Bi2WO6), Bismuth molybdate (Bi2MoO6), Cadmium sulfide (CdS), nanoparticles (NPs), NiS (nickel sulfide)eIn2O3 (Indium oxide), Molybdenum disulfide (MoS2), Nanocomposite (NCs), Gold (Au), Silver (Ag), Copper (Cu), Cobalt
tetra-oxide (Co3O4), Tungsten (VI) oxide (WO3), Bismuth oxyiodide (BiOI), Nickel Sulfide(NiS), In2 O3(indium oxide), Carbon Dots (CDs), Bismuth ferrite (BiFeO3), Nickel (Ni), Poly (acrylic acid) microgel (PAA microgel), Poly(N-
isopropylacrylamide) (PNIPAM), Poly methyl methacrylate (PMMA), Polyaniline (PANI), Poly vinylidene fluoride (PVDF), Silver phosphate (Ag3PO4), Polyacrylamide (PAA), Zeolitic imidazolate framework-8 (ZIF-8), Cadmium

Journal of Cleaner Production 298 (2021) 126567

sulphide (CdS), Zinc oxide (ZnO).
M.I. Din, R. Khalid, J. Najeeb et al. Journal of Cleaner Production 298 (2021) 126567

silica and alumina etc. for the stabilization of NMs. Zeolite has been et al. (2018) stabilized TiO2 on hydrogel through thermal poly-
wide as an efficient capping agent owing to its peculiar features merization of acrylic acid and utilized this for the degradation of
including porous morphology, excellent adsorption capabilities, MB. Other examples of organic assemblies are discussed in Table 3.
remarkable stability, high crystallinity, exceptional ion-exchange Another advanced class known as organic-inorganic hybrid class
capabilities and large surface area. The structural framework of has also been utilized recently. These hybrid assemblies are sig-
the zeolites due to the presence of various cavities not only en- nificant as they combine the different fundamental properties of
hances the interaction between NMs and zeolite but also facilitates both organic and inorganic assemblies into one system. Zhang et al.
the photocatalytic process by reducing the chances of the electron- (2019a) engineered an inorganic-organic hybrid assembly with
hole recombination. Moreover, zeolites are transparent materials Polyvinylidene fluoride acting as the organic polymeric component
that make the penetration of radiation and activation of the NMs in and GO as the inorganic component. This hybrid stabilization sys-
NMS-PCAs quite easy resulting in a high photocatalytic perfor- tem was utilized to effectively fabricate ZnO nanomaterials. Apart
mance for the degradation of MB. Zeolite supported on TiO2 has from carrying out the degradation of MB, the properties of both the
been widely reported in literature used for the photocatalysis of materials i.e. aids in the photocatalysis by the synergistic effects of
MB. Various synthetic zeolites such as Zeolite-Y (Wang et al., 2014) GO (inorganic material), imparting of the better dispersing prop-
and HZSM-11 (Foura et al., 2017), etc. have been reported in the erties to the soft organic material (owing to the addition of GO or
literature for stabilization of NMs. However, these synthetic zeo- inorganic material) and better recovery properties (owing to the
lites suffer from the disadvantage of non-biodegradability. In this presence of organic material), etc. were observed for this complex
regard, natural zeolite is considered more advantageous than system. Other reports documenting such assemblies are also pre-
synthetic zeolites. These zeolites are cost-effective, non-hazardous sented in Table 3.
and readily available resources. Liao et al. (2019) reported the
synthesis of TiO2 NMs stabilized on the natural zeolite via the sol- 3.2. Natural/non-synthetic material based NMs-PCAs
gel method and studied the photocatalysis of MB under UV-light
irradiation. Apart from the advantages of using the natural Non-synthetic material or natural materials involve the utili-
zeolite, it should also be considered that the synthetic methodology zation of biomass in the form of biological extracts of various fruits,
used for the fabrication of NMs by the natural zeolite still suffers vegetables, seeds, bacteria, and plants as reductant and capping or
from the drawbacks of the lengthy procedure and involvement of stabilizing agents for the production and stabilization of NMs
hazardous solvents. present in NMs-PCAs (Fig. 5). In recent years, the green synthesis of
The use of clay and silica as the stabilization mediums for the NMs is getting huge interest because of its eco-friendlier and cost-
NMs has also been documented for the degradation of the MB. Clay effective nature. Vinay et al. (2019) synthesized nanocomposite
contains minerals that impart porous nature to it. Barbosa et al. using Rauvolfia tetraphylla (devil pepper) plant extract as a reduc-
(2015) reported that the presence of natural kaolinite mineral in tant and fabrication medium. The engineered nanocomposite
the clay is responsible for the incapacitation potential of clay for showed enhanced photocatalytic performance for the degradation
TiO2 NPs. The Kaolinite stabilized TiO2 dispersion was documented of MB pollutants. They also performed a phytochemical analysis
to have the excellent photocatalytic potential for the degradation of which proved that bioactive components of the extract are profi-
the MB in comparison to its unmodified counterpart. Silica has also cient enough for reducing precursor salt. Similarly, Pai et al. (2019)
gained huge interest in recent years owing to its characteristic prepared ZnO based PCAs by utilizing plant extract of peltophorum
properties including low density, enhanced surface area, and high pterocarpum leaves as a reductant or stabilizing agent and found it
stability. Silica acts as a micro-reactor that aids in the stabilization to be an excellent catalyst for photocatalysis of MB. Although
of NMs. Fatimah et al. (2019) stabilized TiO2 photocatalyst on silica
surface and found that the synthesized PCAs exhibits excellent
photocatalytic performance for the degradation of MB. Addition-
ally, mesoporous silica (ZnO/SBA-15) also showed successful pho-
todegradation of MB dye as reported by (Khanh Nguyen et al.,
2020).
Apart from the inorganic material, organic materials such as
polymers, hydrogels, dendrimer and surfactants, etc. are also used
for the stabilization and fabrication of nanomaterials that effec-
tively carryout photocatalytic degradation of MB. Their biode-
gradable and environment-friendly nature is the main advantages
these organic materials have over the inorganic material. Assem-
blies fabricated by using the organic materials are generally soft
and flexible and the fabrication of NMs is although quite effective
but is not as effective as compared to that of the rigid inorganic
materials (Rani and Shanker, 2018). This difference is particularly
evident in case of the organic hydrogels which are utilized as the
stabilizing and fabricating medium for NMs. The hydrogels are the
two-phase heterogeneous system comprising of the crosslinked
organic polymer network as the main dispersion medium with
water/solvent molecules dispersed in the dispersion medium as the
dispersed phase. If the dispersed phase in the gel system is water,
the term of hydrogels is used. These hydrogels are smart polymeric
assemblies that efficiently act as a nanoreactor for the stabilization
of nanomaterials. Furthermore, the rate of photocatalysis can be
varied by utilizing the responsive nature of the hydrogels towards
the stimuli including pH, temperature and ionic strength, etc. Pardo Fig. 5. Non-synthetic stabilizing mediums for photocatalysis of MB.

11
M.I. Din, R. Khalid, J. Najeeb et al. Journal of Cleaner Production 298 (2021) 126567

Table 4
NMs-PCAs utilizing biogenic stabilization mediums for the fabrication of NMs used for the photocatalytic degradation of MB.

Non- Nanoparticles Type of assembly Supporting Percentage Initial Degradation Average Dark Light Reference
synthetic medium degradation concentration of time (min) diameter reaction source
medium (%) MB dye (mg/L) (nm) (min) Irradiation

Plant Fe2O3 NPs Nanoparticles Caralluma 100 e 30 25 e Sunlight Haseena et al.

Fimbriata (2020)
ZnO NPs Nanoparticles Capparis zeylanica e e 105 38 30 Visible Nilavukkarasi
light et al. (2020)
CuO NPs Nanoparticles Verbascum thapsus 94.6 15 120 15 40 Sunlight Weldegebrieal
(2020)
ZnO NPs Cylindrical Prunus 98 5 60 60e80 e Sunlight Singhal et al.
Nanoparticles (2020)
AgNPs Nanoparticles Morinda citrifolia 100 5 140 35 30 Visible Rajivgandhi et al.
light (2020)
ZnO NPs Nanoparticles Solanum nigrum 98 50 49 10 Sunlight Muthuvel et al.
(2020)
ZnO NPs Nanoparticles Quince seeds 80 120 25 e UV light Moghaddas et al.
(2020)
Ag NPs Spherical and Areca 100 10 360 12 e Sunlight Vinay and
irregular shaped Catechu Chandrasekhar
NPS (2019)
MnO2/BC Nanocomposite Nigella sativa 85 10 120 59.11 e Sunlight Siddiqui et al.
(2019)
Ag NPs Spherical-shaped Theobroma cacao 98.3 10 180 6e18 60 Sunlight Thatikayala et al.
Nanoparticles (2019)
Ag NPs Spherical-shaped Trichodesma 82 210 33 e Sunlight Kathiravan (2018)
Nanoparticles indicum
Ag NPs Nanoparticles Prosopis farcta 70.2 10 30 30 30 Visible Miri et al. (2018)
light
Ag NPs Nanoparticles l-Histidine (His) 98 20 40 7e20 30 Visible Suganthi et al.
light (2019)
Ag NPs Nanoparticles Ananas comosus 98.04 e 173 14e20 180 Sunlight Agnihotri et al.
(2018)
Ag NPs Nanoparticles Salvia leriifolia 100 15 60 ~12.8 30 UV light Yazdi et al. (2019)
Benth
Ag NPs Nanoparticles Rauvolfa tetraphylla 81 e 300 40 30 Visible Vinay et al. (2019)
light
Ag NPs Nanoparticles Tinospora 70 e 120 19.05 15 Visible Parvathiraja et al.
cordifolia light (2019)
Ag NPs Nanoparticles Anbarnesa 80 35 70 35 e Sunlight Kakhki et al.
(2019)
ZnO NPs Flower like Kalopanax 97.5 e 30 500 30 UV light Lu et al. (2019)
Nanoparticles septemlobus
ZnO NPs Flower like Stevia Rebaudiana 70 e 30 500e1000 30 UV light Hoon Seo et al.
Nanoparticles (2019)
ZnO NPs Flower like Trigonella foenum- 88.37 e 90 70e90 30 UV light Alshehri and
Nanoparticles graecum Malik (2019)
(Fenugreek)
MgO NPs Nanoparticles Brassica oleracea L. 74 e 180 14 e UV light Osuntokun et al.
var. italic (2019)
ZnO NPs Nanoparticles Peltophorum 95 e 120 10.77 30 Sunlight Pai et al. (2019)
pterocarpum
FeO NPs Nanoparticles Psidium guavaja- 99 e 60 40e90 30 Sunlight Madubuonu et al.
Moringa oleifera (2019)
Cu2O NPs Nanoparticles Zea mays L. Dry 91 e e 30e90 e Visible Nwanya et al.
husk light (2019)
ZnO NPs Nanoparticles Suaeda japonica 54 e 60 10e15 30 UV light Shim et al. (2019)
Algae CuO NPs Nanoparticles Cystoseira trinodis 89 5 e 9 30 UV light Gu et al. (2018)
Ag NPs Nanoparticles Spirulina platensis 75 e 120 10 e Sunlight Rojaa et al. (2019)
Ag NPs Nanoparticles Sargassum muticum 94.6 e 60 20 30 UV light Harinee et al.
(2019)
ZnO NPs Nanoparticles Ulva lactuca 90.4 5 120 15 15 Visible Ishwarya et al.
light (2018)
Fungi Ag NPs Nanoparticles Aspergillus terreus 95.5 e 4320 >10 30 Sunlight Krishnaveni and
sps, Ragunathan
(2015)
ZnS NPs Quantum dots Penicillium sp. 100 10 240 11 30 Sunlight Jacob et al. (2019)
ZnO NPs Nanoparticles Cordyceps militaris 97 10 180 10.1 30 UV light Adnan et al.
(2019)
Ag NPs Nanoparticles Saccharomyces 100 10 360 10 e Sunlight Roy et al. (2015)
cerevisiae
Bacteria Ag NPs Nanoparticles Bacillus subtilis SJ 76.5 10 900 10e30 900 Sunlight Roshmi et al.
15 (2017)
Cu2-xSe NCs Nanospheres Pantoea 93.4 26 300 80 60 Sunlight Qi et al. (2019)
agglomerans
Ag NPs Nanoparticles Cyanobacteria 18 20 240 140 e UV light

12
M.I. Din, R. Khalid, J. Najeeb et al. Journal of Cleaner Production 298 (2021) 126567

Table 4 (continued )

Non- Nanoparticles Type of assembly Supporting Percentage Initial Degradation Average Dark Light Reference
synthetic medium degradation concentration of time (min) diameter reaction source
medium (%) MB dye (mg/L) (nm) (min) Irradiation

Keskin et al.
(2016)
Protein ZnWO4 NPs Nanocomposite Bovine serum alum 100 e 60 50 e Sunlight Singh et al. (2013)

Abbreviation: Zinc tungstate oxide nanoparticles (ZnWO4 NPs), Cubic berzelianite nanocrystals (Cu2-xSe NCs), Silver Nanoparticles (Ag NPs), Zinc oxide nanoparticles (ZnO
NPs), Zinc sulfide nanoparticles (ZnS NPs), Copper oxide nanoparticles (CuO NPs), Cuprous oxide nanoparticles (Cu2O NPs), Iron oxide nanoparticles (Fe2O3 NPs), Bamboo
charcoal doped manganese dioxide nanocomposite (MnO2/BC NCs), Magnesium oxide nanoparticles (MgO NPs), Iron oxide nanoparticles (FeO NPs), Cuprous oxide Nano-
particles (Cu2O NPs), Milligram per liter (mg/L), Minutes (min), Nanometer (nm).

Fig. 7. Recyclability of Fe2O3/graphene/CuO nanocomposites (FGC) catalyst used for

photodegradation of methylene blue (Nuengmatcha et al., 2019).

biogenic assemblies found to be an efficient catalyst for photo-

catalytic degradation of MB, it is also reported in various studies
Fig. 6. Metal organic framework-Graphene oxide (MOF/GO) hybrid composite for that it has the poor capability to act as an efficient stabilizing me-
photocatalysis of MB. dium in terms of long time storage. This fact can be easily confirmed

Table 5
Advanced hybrid NMs-PCAs used for the photocatalytic degradation of MB.

Advanced materials Material Average Degradation % Initial concentration of Dark Light source Time Ref
diameter MB dye (mg/L) reaction irradiation
(nm) (min)

MOF Fe based MOFs Oil bath e 76.16 for e e Visible light 180 Zhao et al.
MIL-53Fe methodology NH2-MIL- (2019)
MIL-88B 53Fe
NH2-MIL-53Fe 10 mg/L
NH2-MIL-88B
Zn based MOF [Zn (2- Slow 1.4 82.3 e 60 UV light 120 Jing et al.
methylimidazole)2.2H2O] ¼ ZIF- evaporation (2014)
8
Fe based MOF e 24.7 100 10 30 Visible light 20 Xu et al.
MIL-88A (2014)
Zn2 (odpt) (bpy) (H2O) (bpy)0.5 Hydrothermal e 90.9 10 120 UV light 120 Wang et al.
method (2016)
Ti based MOF e e 100 e e Visible light 20 Gao et al.
NTU-9 (2014)
MOF@stabilization Zr based MOF immobilized on Solvothermal e 100 e 60 Visible light 240 Zhang et al.
mediums graphitic Carbon Nitride method (2018)
UiO-66@g-C3N4
Al based MOF immobilized on e 60.71 59 30 e Visible light 210 Yang et al.
reduced GO (2017)
NH2-MIL-53(Al)@rGO
Fe based MOF immobilized on e e 100 e e Visible light 20 Wu et al.
GO (2014)
MIL-88(Fe)@GO
Cu based MOF immobilized on e e 98 e 50 UV light 60 Samuel
Chitosan/GO et al. (2020)

Abbreviation: Metal Organic frameworks (MOFs), Materials from Material of Institute Lavoisier series (MIL; trivalent metal centers with 1,4-benzenedicarboxylate (H2BDC)
ligand or trimesic acid (H3BDC) ligands), Iron (Fe), Zinc (Zn), Zirconium (Zr), 4,40 -oxidiphthalic acid (odpt), 4,40 -bipydine (bpy), Graphene oxide (GO), Cu (Copper), Aluminum
(Al), Graphitic carbon 25 nitride (g-C3N4), Titanium (IV)-based porous metaleorganic framework (Ti based MOF NTU-9), Amine (NH2).

13
M.I. Din, R. Khalid, J. Najeeb et al.
Table 6
Reuse-ability of photocatalyst.
Catalytic system Pollutant No.of cycles
TiO2 supported zeolite-4A MB Photocatalyst could be recycled 5 times
Zeolite supported TiO2 MB Photocatalytic performance decrease up to 10% after every cycle of regeneration.
nanoparticles
ZnO-PMMA MB Photocatalyts could be reused up to 10 consecutive cycles with 96% MB photodegradation
performance.
TiO2/NiFe2O4/rGO MB Photocatalytic performance slightly decreased up to 71-59%
Biogenic ZnO NPs MB Catalyst could be used up to 4th cycle with minor change in performance
ZnSegraphene aerogels (ZnS MB, Cr After four photocatalytic cycles 93.84% photodegradation of MB maintained.
eGas)
Abbreviations; Methylene blue (MB), Congo red (Cr), Zinc oxide (ZnO), Zinc sulfide (ZnS), Poly (methyl methacrylate) (PMMA), Nickel ferrite (NiFe2O4), Titanium dioxide (TiO2),
Reduced graphene oxide (rGO).
by the micrographs acquired Scanning electron microscopy (SEM)
of these assemblies. Documentation of the aggregates owing to the
aggregation of the NMs is considered a common occurrence for
such green routes (Vanaja et al., 2013). Therefore, more research is
required for further improving the photocatalytic and stabilization
potential of such green assemblies. Case studies documenting the
NMs-PCAs utilizing the biogenic supporting mediums for the
immobilization of NMs are given in Table 4.
3.3. Advanced hybrid NMs-PCAs
Advanced NMs based PCAs where the combination of the
different class of materials including synthetic/natural or organic/
inorganic materials has also been documented to be utilized for the
production of the PCAs responsible for carrying out the degradation
of the MB dye. Zhao et al. (2019) engineered a fascinating class of
the advanced porous crystalline NMs-PCAs having the inorganic
metal atoms (NMs) surrounded by the polyfunctional organic li-
gands for the photocatalytic degradation of the MB. These metal
organic frameworks (MOFs) having the Iron (Fe) as the central atom
in the assembly were synthesized by using oil bath methodology.
The SEM of the synthesized series of the Fe based MOFs indicated
that the addition of the peculiar moieties in the ligand structure
directly affects the morphology of the synthesized NMs. For
instance, the functionalization of MOF by the NH2- group modified
the morphology of the Fe based MOF from octahedral to spindle-
shaped NMs. In the case of the photocatalytic degradation of MB,
pseudo-first-order kinetics was followed. The values of rate con-
stants further suggested that the functionalization of MOF with
ammonia (NH3) enhanced the photocatalytic potential by
increasing the light absorption potential, lowering the bandgap
values, and facilitating the absorption of dyes onto the surface of
the NMs present in the NMs-PCAs. Apart from simple MOFs, the
combination of numerous stabilization mediums with the MOFs
has also been reported in the academic literature for the photo-
catalytic degradation of MB. Metal organic framework-Graphene
oxide (MOF/GO) hybrid composite has been shown in Fig. 6.
Samuel et al. (2020) synthesized the Cu-based MOF [Cu3(btc)2;
where btc represented the ligand of benzene-1,3,5-tricarboxylic
acid] and immobilized it covalently on the organic/inorganic
combination material of Chitosan/GO. Enhanced photocatalytic
results were observed in the case of such hybrid assemblies as the
peculiar properties of different substances were merged into one
system for acquiring a functionalized hybrid system. Photocatalytic
degradation of 98% was acquired within the 60 min when the NMs-
PCAs were subjected to the irradiation treatment with UV light.
Several case studies documenting the use of such advanced mate-
rial are summarized in Table 5.
14
Journal of Cleaner Production 298 (2021) 126567
References
Nagarjuna et al. (2015)
Foura et al. (2017)
Rani and Shanker (2018)
Saravani et al. (2019)
Alshehri and Malik
(2019)
Reddy et al. (2015)
4. Reusability of the NMs-PCAs
Estimating the reusability potential of the NM-PCAs is one of the
major requirements for investigating the applicability potential of
any newly designed NMs-PCAs (Fig. 7). Recently, documentation of
the reusability potential of the photocatalyst is no considered a
convention these days. However, most of the previous studies lack
these studies. The exceptional reusability results are observed in
case of inorganic and hybrid assemblies. Results observed for the
natural material based NMs-PCAs are not that encouraging. ZnO
nanorods stabilized by GO sheets showed 87% photodegradation in
case of MB even after 5 cycles of usage (Dai et al., 2014). Yu et al.
(2011)compared the photocatalytic performance of TiO2/PANI fi-
ber film with TiO2 fiber film and observed that TiO2 fiber film
showed exceptional photocatalytic performance even after four
usage runs. Nuengmatcha et al. (2019) checked the stability of the
FGC catalyst and observed slight polymer degradation during the
photocatalysis of MB from first to the fifth usage of the catalyst as
shown in Fig. 7. Hence, organic polymers are far behind the inor-
ganic assemblies in terms of imparting long term stability and re-
usage capabilities. Further literature related to the reuse of photo-
catalyst has been summarized in Table 6.
5. Future directions and conclusion
Usage of NMs-PCAs as the photocatalysts for the degradation of
MB is being hailed as an excellent solution for addressing the
problem of the presence of harmful dyes (i.e. MB) in aqueous
environment. The fundamentals including factors, mechanism and
kinetic aspects are discussed in detail in this review for presenting
an overview of this light-mediated degradation reaction. The recent
case studies are organized by utilizing the nature of the stabiliza-
tion medium utilized for fabricating NMs in NMs-PCAs as the basis
of classification. Although numerous types of materials have been
utilized for this purpose, the inorganic assemblies and hybrid as-
semblies were found to be most effective for the immobilization of
the NMs. These two assemblies also exhibited enhanced photo-
catalytic potentials owing to the synergistic effects provided by the
stabilizing medium as well alongside the NMs that aided the pro-
cess of photocatalytic degradation of MB (in the case of the
graphene-based assemblies). The natural material possessed the
advantage of the eco-friendlier nature over other assemblies.
However, improvements are still required for the effective immo-
bilization of the NMs in such assemblies.
Academic literature survey indicates that the attempts to utilize
the natural biomass as the organic substitute in hybrid assemblies
(instead of the synthetic polymers) have not been exploited as of
now. This domain can be explored further. Moreover, the NMs
utilized are mostly monometallic oxide assemblies involving TiO2
M.I. Din, R. Khalid, J. Najeeb et al.
and ZnO based NMs. Other NMs including doped assemblies, pe-
rovskites, quantum dots, florescent NMs, etc. that are known to be
involved in studying other light-based phenomena can be utilized
for the photocatalytic studies as well. Bimetallic and trimetallic
assemblies can be prepared for improving the photocatalytic po-
tential of the NMs-PCAs. Organic material such as hydrogels can
also be utilized in conjunction with inorganic materials to prepare
hybrid assemblies to get the assemblies that can provide assemblies
with variable degradation rates. The aspect of hydrogels can further
be explored for improvements as well.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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