Solar Energy 255 (2023) 99–125

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Solar Energy
journal homepage: www.elsevier.com/locate/solener

Solid-supported photocatalysts for wastewater treatment: Supports

contribution in the photocatalysis process
Hassanin M. Ali a, Farzaneh Arabpour Roghabadi a, b, *, Vahid Ahmadi b
a
Department of Process Engineering, Faculty of Chemical Engineering, Tarbiat Modares University, Tehran, Iran
b
Optoelectronics and Nanophotonics Research Group, Faculty of Electrical and Computer Engineering, Tarbiat Modares University, Tehran, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: Recalcitrant and dangerous organic contaminants can be degraded using photocatalysis, a green and environ­
Photocatalysis process mentally friendly method. Photocatalytic wastewater treatment by employing UV or solar-active photocatalyst
Organic and inorganic solid substrates (PC) particles immobilized on/in solid supports provides new avenues for energy-efficient purification processes
Organic pollutants
compared to using slurry. Fortunately, PC immobilization on/in solid supports can avoid the costly and ineffi­
Immobilization techniques
Wastewater treatment
cient post-treatment recovery of wasted photocatalysts on a wide scale. Encouraged by the advantages of this
type of photocatalyst, this review focuses on the usage of various supporting mediums to immobilize photo­
catalysts (PCs) for the degradation of wastewater pollutants. Since photocatalysis is a complex process where
optical, electronic, and chemical phenomena occur together to degrade the pollutants, it is shown how the PCs
and their supports are chosen to provide the requirements. This work searches the contribution of the utilized
organic and inorganic solid supports in the optical, electronic, and chemical steps of photocatalysis, emphasizing
the issues. It shows that as the results of a lot of studies regarding solid supports, more stability, reusability, and
lowering cost have been achieved while they still suffer from the lack of efficient participation in the optical,
electronic, and chemical steps of photocatalysis. From a perspective, opto and electro-active solid supports would
be promising candidates for the future development of solid-supported PCs.

1. Introduction increase have led to a decrease in the availability of safe drinking water.
The textile industry has emerged as a major source of water pollution
Despite the fact that water is one of the most abundant resources on because effluents containing dyes are discharged into natural water
the planet, only about 3% of all water sources are drinkable. As the bodies (Kabra et al., 2012; Sarkar et al., 2020). The organic contami­
population grows, the need for freshwater grows as well. Accordingly, nants found in wastewater effluents from both industrial and domestic
discovering a feasible solution to make freshwater is essential. Thus far, sources should be eliminated or destroyed before they are discharged
several strategies have been employed for removing pollutants from the into the environment (Shan et al., 2010). Numerous researches have
water such as sedimentation, chemical precipitation, ion exchange, recently been carried out to study the usage of new methodologies in
evaporation, etc. (Arif et al., 2019; Karami et al., 2021b, 2021a). Even if order to address the shortcomings of previous strategies. In the recent
a contaminant is present in low amounts, these traditional treatment decade, certain novel sophisticated approaches focused on the usage of
methods are not cost-effective and may not be able to effectively remove heterogeneous compounds to remove organics as well as ions (Huang
it (Arif et al., 2019; Reza and Afarani, 2008). These technologies, have et al., 2018, 2017; Kabra et al., 2012; Omri et al., 2014; Zeng et al.,
several drawbacks that prevent them from meeting strict water quality 2016). The advanced oxidation process (AOP) is one of the strategies
regulations (Arif et al., 2019). It is a widespread concern around the that effectively remove harmful contaminants from the environment
world to deal with water that has been contaminated with harmful (Shan et al., 2010). The photocatalytic process is one of the AOPs that
substances. To satisfy the requirements stated, new treatment methods can be classified into three methods including the photo-Fenton process,
are needed that address both local and worldwide concerns in terms of photo -Fenton like process, and the semiconductor-based process (Ola­
associated research and development of treatment technologies tunde and Onwudiwe, 2020). The photo-Fenton process is a homoge­
(Mukherjee, 1999). Industrialization, urbanization, and population neous photocatalysis process that utilizes inorganic oxidizing agents like

* Corresponding author at: Department of Process Engineering, Faculty of Chemical Engineering, Tarbiat Modares University, Tehran, Iran.
E-mail address: [email protected] (F. Arabpour Roghabadi).

https://doi.org/10.1016/j.solener.2023.03.032
Received 16 January 2023; Received in revised form 3 March 2023; Accepted 16 March 2023
Available online 27 March 2023
0038-092X/© 2023 International Solar Energy Society. Published by Elsevier Ltd. All rights reserved.
H.M. Ali et al. Solar Energy 255 (2023) 99–125

H2O2 along with Fe+2 as a catalyst under exposure to light (Ortiz et al., photocatalytic operation over a wide pH range to minimize the use of
2019). There have been investigations into a further photo-Fenton-like oxidant additives; (iv) using new coupling or incorporated system for
method using Fe+3 and another oxidizing agent such as S2O2- 8 under improving photo-decontamination or photo-mineralization kinetics; (v)
light irradiation (Koltsakidou et al., 2017). Semiconductor photo­ designing a parabolic solar collector or an efficient photocatalytic
catalytic methods can be more cost-effective than other methods reactor system to maximize solar energy usage and hence reduce power
because of their low-cost preparation methods, longer usage, inexpen­ costs (Faruque Hossain, 2019), (vi) managing charge separation and
sive and simple technology (operation apparatus), no sludge (secondary transport, and (vii) controlling the morphology of the PCs (Lakhera and
pollution) at the end of treatment, no need for adding chemical auxil­ Neppolian, 2021).
iaries, using clean energy sources (sunlight or low energy-consumption One of the main parameters of PC is the bandgap value that defines
lamps), and achieving high efficiency using only a small amount of the energy of photons needed to start the degradation process. More­
semiconductor. It is possible to synthesize photocatalysts (PCs) from a over, since the absorption depth of each photon in materials is different,
variety of elements, including non-metals and metalloids based on their the dimension of the PC such as its thickness or diameter plays a key role
chemical and physical characteristics (Akerdi and Bahrami, 2019). in the light absorption as the first step. Moreover, the reflectance of the
Since the 1970s, when PCs were first discovered to remove con­ PC surface affects the light absorption efficiency. After the successful
taminants from water, the field of water treatment has seen an uptick in absorption of the incident photons, the electron in the valence band (VB)
interest (Li et al., 2020b). When it comes to degrade organic pollutants is activated by absorbing the energy of the incident photon, leading to
(Akerdi and Bahrami, 2019; Iervolino et al., 2020; Li et al., 2020b), the generation of an exciton or electron-hole pair, as shown in Fig. 1a.
convert energy (Iervolino et al., 2020), and synthesis chemicals, pho­ Activated oxygen and hydroxyl radicals, which can oxidize contami­
tocatalysis has emerged as an eco-friendly alternative process. Alongside nants, are created as a result of this process (Sosnin et al., 2021).
wastewater treatment, carbon dioxide reduction (Fakourian, 2019), Reactive oxygen species (ROS) can be formed on the PC surface by
water splitting for H2 production (Fakourian, 2019; Liu et al., 2021; electrons reducing O2 and H2O, which is illustrated in Fig. 1b. In the
Tayyab et al., 2023, 2022b, 2022a), air treatment, electrical energy presence of enough oxygen, the process continues to produce hydrox­
generation (Fakourian, 2019), production of H2 and CO (Muhammad ylated products and finally full mineralization of the pollutants to CO2
Irfan et al., n.d.), and antibacterial applications have all been considered and H2O. PC holes interact with donor species simultaneously, resulting
prospective applications of photocatalysis (Goutham et al., 2019; Singh in the decomposition of organic contaminants (Long et al., 2020). In
et al., 2013). During the COVID-19 pandemic, the importance of the general, pre-adsorption of the activated species on the semiconductor
photocatalytic process also has emerged, as it is an environmentally surface improves the efficiency of electron transfer processes. Oxygen is
friendly process. In addition to wastewater treatment, it attracts the the most prevalent electron acceptor in environmental cleaning appli­
attention of many researchers in the field of air treatment. For example, cations. Photogenerated electrons can be used to convert molecular
an always-on photocatalytic anti-bacterial facemask was created by oxygen to O2.- in this process. HO•, hydrogen peroxide (H2O2), hydro­
Uyen Nhat Trieu Nguyen et al. It consisted of a separate layer of UV- peroxyl radical (HO•2), and hydroperoxyl anion HO–2 are all examples of
LEDs to provide UV light when needed and a reusable filtering layer ROSs. Generally, ROS, free electrons, and holes interact with different
of polypropylene covered with a photocatalytic lamination ZnO/TiO2 types of contaminants such as bacteria, viruses, organic, and inorganic
bilayer. Regardless of solar irradiation, this facemask might be used
regularly and sustainably anywhere and at any time. The ZnO/TiO2
bilayer prevented electron (e-) and hole (h+) recombination as well as
made the filter surface super hydrophilic, providing strong photo­
catalytic antibacterial activity (Nguyen et al., 2022).
In this work, after introducing the optical, electronic, and chemical
fundamentals of the photocatalytic treatment of water, the preparation
and uses of wastewater treatment PCs immobilized on/in solid sub­
strates are focused on. The solid substrates are categorized into two
organic and inorganic groups, the fundamentals, advantages, and ob­
stacles are discussed. The contribution of the solid supports in the
photocatalysis steps is emphasized, defining the issues. Lastly, a sum­
mary of the review and the perspective on these technologies is
presented.

2. Photocatalytic process

Photocatalysis has demonstrated significant potential to be

employed as a low-cost and environmentally acceptable process for
water treatment. For widespread application, PCs should be optimized
to achieve high quantum yield and light absorption, and reaction
selectivity. Besides, the photocatalytic reactor should be designed effi­
ciently and suitable catalyst recovery/immobilization techniques should
be focused on (Faruque Hossain, 2019). Moreover, to ensure the safe
application of photocatalysis and other advanced oxidation processes
(AOPs) for water treatment, the toxicity of catalysts should be properly
studied (Lin et al., 2020).
For the advancement of photocatalytic water treatment technology,
a number of critical technological aspects should be considered, ranging
from PC development to process optimization and reactor design such
as; (i) Tuning of the PC bandgap to harvest broader solar spectrum; (ii)
enhancement of the catalyst immobilization policy to provide profitable Fig. 1. (a) Photocatalytic mechanism (Opoku et al., 2017), (b) Formation of
separation of the solid and liquid phases; (iii) providing the ROS (Nosaka and Nosaka, 2017).

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compounds that adsorb on the surface of PCs and breakdown them. This photochemical principles behind heterojunction photocatalysis have
type of reaction encourages the full photo-mineralization of organic been documented in several studies. During photocatalysis, a suitable
molecules into mineral acids, H2O, and CO2 (Karthikeyan et al., 2020). heterojunction interface could effectively prevent photoinduced e- & h+
As is generally known, a band gap is a crucial physical property of recombination, hence increasing the total photoactivity of catalysts (He
materials that influences their electronic behavior (Kamarulzaman et al., 2021). For instance, Kundan Kumar Das and coworkers’ synthe­
et al., 2015). In fact, bandgap designing is an essential prerequisite for sized S-scheme heterojunction PC using a ternary composite from
maximizing PC capacity for solar light harvesting. In several efforts, ZnFe2O4@WO3 and supported by polypyrrole which acted as a substrate
metal or nonmetal elements were added to the PC to tune its bandgap. and the bipolaron and polaron species of polypyrrole worked as e- and
However, a significant problem impacting the photocatalytic effective­ h+ acceptors, respectively. As a result of this engineering, the separation
ness is the presence of dopants since they act as charge carrier recom­ and transmission of charge carriers in the PC were improved (Kumar Das
bination centers. Commonly, the bandgap of the PCs is tuned via one of et al., 2021). Also, the developed heterojunction PCs can be used as an
the following methods: doping by metal or nonmetal elements, coupling alternative to herbicides in the treatment of water hyacinth since they
with another material, forming a heterojunction with another semi­ effectively produce ROS under visible light (Jawed et al., 2022). Thus
conductor or metal, and dye sensitization (Friehs et al., 2016). far, different photocatalysis processes and mechanisms for the dissoci­
As summarized in Fig. 2, in a photocatalysis process, optical, elec­ ation of photoexcited carriers have been found in heterojunction
tronic, and chemical phenomena occur simultaneously where different structures such as p-n type, Schottky type, Z-scheme, step-scheme, type
parameters are responsible for the final performance. Though the PCs I, and type II that are depicted in Fig. 3 (He et al., 2021; Qi et al., 2017a,
play key roles in the aforementioned phenomena, the support should be 2017b).
consistent with the process steps. The photocatalytic technique has numerous benefits over conven­
The photocatalytic capabilities of semiconductor materials are tional catalytic methods. Using sunlight (Li et al., 2020b; Zhiyong et al.,
strongly dependent on their physical properties and the reaction starts 2008) as the source of energy, occurring at room temperature, and at­
after the photons are absorbed by the semiconductor (Sosnin et al., mospheric pressure are all readily advantages of photocatalytic tech­
2021). nology. Secondly, according to the low-carbon environmental
The free electrons and holes generated after the successful dissocia­ protection standards, photocatalytic decomposition methods and their
tion of the exciton run the reduction and oxidation reactions where this products are pollution-free. Other factors encouraging their growth are
dissociation depends on the exciton binding energy, transferring, and the nontoxic, stable, low-cost, and recyclable features. There are
lifetime. Free charges mobility and their lifetime are other key param­ different types of materials that can be used as PCs in photocatalytic
eters in the electronic step of this process. Free photogenerated charges technology (Li et al., 2020b).
can be trapped in the structural defects, leading to their loss. Managing In photocatalytic reactors, the employed light source has progressed
the charge’s transport and reducing their recombination have encour­ from sunlight to conventional lamps to light-emitting diodes (LEDs).
aged researchers to study the heterojunction structures. The hetero­ Conventional lamps, such as incandescent and gas discharge lamps,
junction is indeed a contacting interface that forms when two have a low efficiency at the wall plug (the ratio between optical power
semiconductors/metals with differing band and electrical structures output to electric power input). Conventional lights contain poisonous
hybridize (Kumar et al., 2020). The fundamental photophysical and mercury and have a shorter life expectancy than LEDs, despite their

Fig. 2. Photocatalytic process and key parameters.

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Fig. 3. Different types of heterojunction structures.

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lower cost. As a result, photocatalysis research has shifted to the use of 6. To avoid charge dispersion, which would otherwise inhibit pho­
LEDs which are more energy-efficient, longer-lasting, and non-toxic. tocatalysis, its dielectric constant should be high (2.2–3.5).
Additionally, the LEDs might be orientated in numerous directions 7. To avoid PC separation during exploitation, a good adhesive
within a photocatalytic reactor, giving them a greater degree of flexi­ between the support and PC particles is required.
bility. In 2005, the first LED photocatalytic reactor was built for pho­ 8. It should be transparent, in order to eliminate the appearance of
tocatalysis. LED reactors outperformed traditional reactors twice as well shadows and to make full use of the support on two sides.
as consuming five times less energy and costing a quarter of the price 9. It should be flexible, which allows the support to be installed on
(Sundar and Kanmani, 2020). LEDs have a number of advantages, curved surfaces (Abdolhosseinzadeh et al., 2019), and to be used
including selective wavelength, greater robustness, and longevity in a variety of reactors (Hofstadler et al., 1994).
(approximately 100 times that of traditional (Hg and Xe) lamps (10.000 10. To compensate its immobility, the support should have a high
h of life), low heat output, and stable linearity for irradiation-current, as surface area (Long et al., 2020; Singh et al., 2013).
well as the ability to operate with pulsed illumination (Devia-Orjuela
et al., 2019). So, as summarized in Fig. 4, the requirements for ideal support can
In addition to the type of light source, the irradiation source location be categorized into two groups. In the first group, stability, reusability,
is critical for any photocatalytic reactor in order to maximize incident environmental aspects, and the cost of the preparation are considered
light intensity on the reactor surface and thus ensure effective catalyst while the second group includes the features attributed to the photo-
illumination. However, when light intensity increases, the photo­ electro-chemical reaction. Providing better light harvesting, prevent­
catalytic reaction grows linearly up to a point at which the reaction rate ing charge losses, and making more contact between the pollutant’s
becomes proportional to the square root of the illuminating radiation molecules and the photogenerated ROSs are focused. Though both
intensity (Adams et al., 2013). The intensity of the light is employed as a groups work simultaneously to have an efficient process, the first group
parameter to control the reactor reactivity. Increased light intensity is more achievable. It means that in the current statutes of the solid-
results in an increase in the concentration of electron-hole pairs, causing supported photocatalysts, the supports contribute more in providing
an enhancement of the recombination rate (Claes et al., 2021). The the requirements listed in the first group.
degradation rate is influenced by factors such as the distance between a Physical surface forces or chemical connections hold the catalyst to
light source and reaction media. In the reaction media, the length of the the support (de Lasa et al., 2005). The immobilization of PCs on support
light path should be kept to a minimum value (20 to 50 mm) in order to substrates eliminates the use of ultrafiltration separation and reduces
maintain a uniform intensity throughout the medium and prevent the shear stress upon catalyst particles. Nevertheless, opaque catalyst sur­
formation of dark spots that could potentially reverse reactions (Sundar face area, reduced luminous catalyst surface area, and greater rates of
and Kanmani, 2020). photon scattering can all reduce the efficiency of anchored systems
Recently, pulsed light (PL) has been used as a source of energy for (Loeb et al., 2019). There are some limitations to use immobilized PCs.
photochemical AOP development. The main advantage of PL xenon over For instance, the design of a reactor is inherently more complicated, and
other UV light sources such as LED, XeBr, and KrCl is that high energy is it is ultimately a balance between increasing the luminous catalyst-
created for the photolysis of oxidants in a relatively short period, which covered surface area and reactor capacity while reducing the waste­
reduces the time needed for the process (Olatunde and Onwudiwe, water route length above the covered surface from the source of light.
2020). Moreover, immobilization procedures for PCs can be complicated and
expensive (Iervolino et al., 2020).
3. Immobilization system The continuous photocatalytic processes can benefit from the use of
this type of catalyst, which reduces the need for separation operations
It has been widely accepted since 1993 that an immobilized PC on an and lowers operating costs. In comparison between supported PC and
inert substrate can remove the costly phase separation processes (Grčić powder, the support only coats one face of the PCs, and the number of
et al., 2021; Shan et al., 2010). PCs are often offered in powder form and affected spots is decreased compared to powder. Using more powder to
can be employed either as a suspension or as an immobilized structure coat the substrate is one way to maintain the supported catalyst highly
(Loddo et al., 2011; Singh et al., 2013). In suspended mode, PCs are effective (Gomes et al., 2019). While keeping the cost (weight) fixed,
more in contact with the solution and light (Dijkstra et al., 2001; Singh lowering the size of nanoparticles (NPs) boosts their catalytic perfor­
et al., 2013) though PC extraction and recovery might be a challenge. It mance, but their application becomes more difficult (Abdolhosseinza­
is considerably simpler to separate the PCs once they are immobilized on deh et al., 2019). Increased surface area, faster charge transfer, and more
a support. Ideally, the PC and support should have a high affinity and the exposed active sites all contribute to nano PCs enhanced photocatalytic
PC should be stable on the support surface even when it is exposed to activity (Long et al., 2020). In contrast, aggregation of NPs (typically less
strong oxidizing agents. Additionally, the coating process should not than 10 nm) reduces their catalytic activity; however, immobilization on
impair PC activity (Singh et al., 2013). appropriate substrates can largely alleviate this issue (Alhaji et al., 2017;
Support (carrier) material for water purification must meet certain Arif et al., 2019; Li et al., 2020b).
requirements, which are as follows (Hofstadler et al., 1994; Sosnin et al.,
2021): 3.1. Immobilization techniques

1. To prevent the support from degradation under the impact of the Thus far, different types of immobilization methods have been
PC and contaminants, chemical stability is required. employed such as sol–gel technique, hydrothermal treatment method,
2. Support must be low in toxicity to prevent inserting further dip-coating method, solvent casting method, chemical vapor deposition
contamination in the water which is being purified. (CVD), electrophoretic deposition (EPD), and photo-etching. However,
3. Support should possess low water solubility to extend the com­ due to their complicated procedures, pricey apparatus, and high calci­
posite operational time and avoid the PC from reaching into the nation temperature requirements, the majority of these techniques are
water. not frequently used (Srikanth et al., 2017). The selection of the most
4. It should be able to be separated easily from a liquid medium appropriate immobilization techniques largely depends on the kind of
(Hofstadler et al., 1994). contaminants, the medium (air or liquid) through which degradation
5. It should have hydrophobic features to attract organic contami­ occurs, and the kind of support (Alhaji et al., 2017). Here we summa­
nants from water, increasing photocatalysis efficiency. rized some of the famous immobilization techniques used by
researchers.

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Fig. 4. Summary of the requirements for a solid support of wastewater treatment PC.

3.1.1. Sol-gel technique the activity shouldn’t be impacted by temperature unless the immobi­
Sol-gel methods are one of the most used immobilization techniques lized PC benefits from it by changing the bulk or/and surface Physico-
due to the comparatively inexpensive processing cost, the low temper­ chemical features (Robert et al., 2013).
ature needed for the process (Goutham et al., 2019; Robert et al., 2013),
high uniformity and purity achieved for the deposited material (Srikanth 3.1.3. Chemical vapor deposition (CVD)
et al., 2017), and customizable application onto a wide variety of sub­ In order to create high-quality and high-purity solid materials, a
strates in terms of form, size, and chemical makeup, sol–gel methods are chemical procedure called CVD is used. Numerous CVD procedures are
one of the most used immobilization techniques (Goutham et al., 2019; employed widely and frequently cited in the literature. The types of
Robert et al., 2013). The sol–gel procedure is a widely used, straight­ precursors employed, the supports used, the required level of thin film
forward approach for producing metal oxides by utilizing metal salt homogeneity, as well as the process conditions, vary among these pro­
solution as a precursor. These precursors have a significant impact on cedures (Li Puma et al., 2008). As shown in Fig. 6a, a typical CVD
the surface shape of the deposited PCs. These precursors may result in technique involves exposing substrates to a gassy flow of a mono or
the formation of a densely packed (gel-like) lattice of separate particles multicomponent volatility precursor in a lazy atmosphere at controlled
or polymers (Goutham et al., 2019). Colloidal particles are dispersed in a temperature and pressure. The volatile precursors decompose at the
fluid matrix during this process while moving in a Brownian motion. support surface, resulting in the production of thin films (Li Puma et al.,
Afterward, through the sol–gel process, the colloidal suspense of parti­ 2008; Nolan et al., 2006). The kind of precursors employed, the kind of
cles can change first into viscous gels, then into solid materials (Fig. 5a) substrates, the operating circumstances, and the intended level of purity,
(Aboualigaledari and Rahmani, 2021; Shan et al., 2010). crystalline nature, or thin film homogeneity can all affect how CVD
procedures are carried out (Dunnill et al., 2009; Nolan et al., 2006). One
3.1.2. Hydrothermal treatment technique can specifically mention plasma-enhanced CVD, which uses plasma to
The hydrothermal treatment approach is a popular and appropriate speed up the precursor rate of a reaction (Nizard et al., 2008), metal­
technique for manipulating the PC physical properties to advance the –organic chemical vapor deposition (MOCVD), and hybrid phys­
activity of the PC. As opposed to the CVD and sol–gel processes, which ical–chemical vapor deposition (HPCVD) (Shan et al., 2010), in addition
need precursors to produce PC, a hydrothermal technique was becoming to the traditional atmospheric pressure chemical vapor deposition
favorable for the immobilization of PC because PC powder is used (APCVD) (Dunnill et al., 2009; Nolan et al., 2006). The MOCVD is an
directly (Fig. 5b) (Chauhan and Mohanty, 2014; Shan et al., 2010). By intriguing option that makes use of the employment of organometallic
impregnating the PC suspensions at an optimal concentration, the PC is precursors for drastically lowering the depositing temperature if the
primarily first deposited on the substrate. It is important to keep in mind CVD doesn’t satisfy the strict constraints set by the chemical nature of
two important factors which also are the method’s limitations. First, the support. In order to execute the deposition methods over non-planar
regarding the support’s thermal and chemical stability, the treatment substrates or even substrates with complicated geometry, as required in
temperature needs to be appropriate. This eliminates or restricts the use the area of supported photocatalysis, the various CVD processes should
of brittle supports like polymers that have a low-temperature upper generally benefit from studies in engineering chemical reactions (Shan
bound of resistance or carbon materials that, although they can with­ et al., 2010). Decreasing the deposition temperature, achieving unifor­
stand greater temperatures, often oxidize in air at 500–600 ◦ C. Second, mity and huge-area growth on diverse substrates, and creating safe

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Fig. 5. (a) Different sol- gel methods (Aboualigaledari and Rahmani, 2021), (b) Hydrothermal method (Chauhan and Mohanty, 2014).

precursors for MOCVD growing of a variety of transition metal dichal­ 3.1.5. Electrospinning technique
cogenide (TMD) materials are the main issues that need to be resolved in Electrospinning has been considered as one of the attractive tech­
CVD of 2D materials mentioned by L. Sun et al. (Sun et al., 2021). niques for preparing solid-supported PCs. Different nanofibers
including, inorganic, organic/inorganic composites, and organic ones,
3.1.4. Dip-coting technique have been produced using the electrospinning technique. Simple fabri­
Fig. 6b presents a schematic of the dip-coting technique that is one of cation apparatus, a regulated process, lower spinning costs, and a large
the widely used methods for PC immobilization on support. In this range of spinnable materials are all benefits of this technique. According
process, the ejection rate, which defines the thickness of a layer coated to Fig. 7a, the main components of an electrospinning apparatus are a
over the support, is controlled by an adjustable motor utilized to fiber-collecting device, a nozzle, liquid feeding tool, and a high-voltage
perform the dip-coating process. The procedure is started by dipping the power source (Zhang et al., 2019). Electro-spun mixed membrane ma­
support into a suitable solvent with known viscosity and composition, trix comprising PC and polymer mixture was successfully fabricated by
then slowly and steadily removing the support sheet from the dip. This electrospinning. As reported, the electrospinning process resulted in a
method might be used to produce a thick-film coating of nanoparticles membrane with a huge surface area and high porosity (Gao et al., 2020).
above the substrate (Sonawane et al., 2002), as well as a thin film (1–2 Also, it was claimed that electrospinning can give the manufactured
μm) (Alhaji et al., 2017). Before deposition, degreased the supports by photocatalytic membrane greater mechanical characteristics (Zakria
cleaning and after that drying the sample. To increase the anchoring et al., 2021). Fig. 7b, illustrates the membrane fabrication using the
medium’s sticky tendency toward the catalyst, it is typically sonicated at electrospinning method and its application in a photocatalytic applica­
extremely high frequencies for roughly an hour. However, with a few tion (Gao et al., 2020).
exceptions, it is prevented to avoid particle aggregation on the surface of
the catalyst. After being dipped the support in the appropriate precursor 3.1.6. Phase inversion technique (PI)
solution, it is drawn out at a fixed speed of up to 1 mm s− 1 (Sonawane Phase inversion (PI) as a demixing process is another technique
et al., 2002). employed for PC immobilization. In this technique, a coagulation bath is

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4. Types of solid substrates

Since photocatalytic materials are immobilized, they have inherent

drawbacks, such as low exposed surface area-to-volume ratios, mass
transfer limitations, complexity in harvesting the incident photons,
charge transport within the PCs, increased pressure drops within the
catalytic reactor, and possible catalyst washout or fouling. Supported
(a) materials are designed considering the overcoming or at least mini­
mizing of these inherent drawbacks. A few of the issues may be partic­
ularly pronounced in certain reactor setups and supported
photocatalytic material designs. There are several ways to mitigate or
even eliminate these negatives, depending on the specific situation
(Robert et al., 2013). Activated carbon and glass have been the most
used substrates for heterogeneous photocatalysis for many years. Their
unique properties, such as resistance to corrosion in glass and huge
surface area, as in activated carbon, make them ideal for usage in these
applications (Alhaji et al., 2017). Thus far, different kinds of supports
such as glass plates, porous glasses, glass beads, glass tubes, glass fiber,
quartz (Friehs et al., 2016), silica (Barroso-Martín et al., 2018; Ekka
et al., 2019; Friehs et al., 2016), activated carbon (Ao and Lee, 2003;
(b) Boumad et al., 2021; Carpio et al., 2005; Friehs et al., 2016), aluminum
(Choi et al., 2007; Friehs et al., 2016), pumice stone, perlite granules,
stainless steel (Friehs et al., 2016), fabric, plastic, polymers (Srikanth
et al., 2017), clays (Mogyorósi et al., 2003; Srikanth et al., 2017), zeolite
(Hisanaga and Tanaka, 2002), ceramic membranes (Srikanth et al.,
2017), teflon tubes (Long et al., 2020), plant fibers, metals, reactor
walls, fly ash, vycor glass, optical fibers, raschig rings, etc. have been
used as PC substrates (Srikanth et al., 2017). Herein, the substrates are
Fig. 6. (a) Chemical vapour deposition (CVD) (Sun et al., 2021), and (b) Dip- classified into organic and inorganic substrates and reviewed.
coating methods (Taşdemir et al., 2021).
4.1. Organic substrates (Polymers)
used to submerge a homogeneous solution of polymer, transferring it
into two phases (Zare and Kargari, 2018). It is the most popular tech­ Environmental stability and high durability (Sosnin et al., 2021;
nique for creating polymeric porous membranes with complex struc­ Srikanth et al., 2017), chemical inertness and resistance to ultraviolet
tures. The choice of polymer, as well as the selection of casting solution radiations, mechanical stability (Raja and Mattoso, 2020; Sökmen et al.,
additives, affect the membrane structure, chemical interactions, and 2011; Sosnin et al., 2021), nontoxicity, processability (Srikanth et al.,
properties during PI membrane formation (Purkait et al., 2018). The 2017), low prices (Raja and Mattoso, 2020; Sosnin et al., 2021; Srikanth
conversion is done using several methods such as immersion precipita­ et al., 2017), high corrosion resistance (Colmenares et al., 2016), ease of
tion, thermally induced phase separation (TIPS), evaporation-induced availability (Sosnin et al., 2021), flexibility, controllable surface chem­
phase separation (EIPS), and vapor-induced phase separation (VIPS) istry, and desired transparency (Raja and Mattoso, 2020) are all reasons
(Gohil and Choudhury, 2019; Zare and Kargari, 2018). Adriana Popa for choosing organic polymer substrates for the immobilization of active
et al., prepared a polyvinylidene fluoride (PVDF) membrane via the PI catalyst particles. Using polymer nanocomposites as PCs also allows the
technique (Fig. 8). ZnO particles were deposited on the surface of PVDF easy separation and reusing of the materials, thereby avoiding post-
membranes using a simple and inexpensive process, and then the per­ treatment separation steps and indirectly reducing the procedure costs
formance of the membrane was checked by photodegradation of (Farshchi et al., 2019; Melinte et al., 2019; Singh et al., 2013; Xie and
rhodamine B (RhB) dye under UV light. It was found that 85% of RhB Hung, 2018). It is significantly easier to make PC/polymer composites
dye was degraded after 240 min (Popa et al., 2021). Adlan Mohd Hir than metal-matrix or ceramic composites. The breakdown of polymer
et al. employed the PI method to generate a number of polyethersulfone- substrates by active oxygen species is limited in the case of the polymeric
TiO2 (PES/TiO2) PCs film, which were then used for the elimination of substrate (Matsuzawa et al., 2008). In the application of polymeric
the methyl orange (MO) dye. As found, the film photoactivity increased substrates, the recyclability of the polymer and the selection of an
as the TiO2 level rose to 13 wt% (PT-13). The decolorization of MO acceptable solvent are two critical considerations. Chemical interaction
exhibited pseudo-first-order kinetics, and in acidic circumstances, 98% can be used to promote the recyclability of catalysts and polymer
of MO (10 ppm) elimination was practically attained at 540 min under composites in extended processes due to their stable bonding (Akerdi
UV light by using two PT-13 films at pH 2. Because of its excellent and Bahrami, 2019). The following criteria should be met by good
degradation efficacy even after cycles, the PT-13 film PC was introduced polymer support: (I) PC to-support affinity is critical for stable anchoring
as a stable PC. By increasing TiO2 loading, the produced film of the catalyst; the chosen attachment technique must not influence
morphology altered to porous structures with finger- and tear-shaped catalytic activity. Furthermore, it must give a large specific surface area
pores (Hir et al., 2017). and, have a significant affinity for the adsorption of pollutants. (II) A
In addition, other methods that are mostly solution based have been variety of reaction conditions should be avoided to prevent the PC from
employed for attaching or adding PCs on or in the solid supports like in- being leached from the support surface. Because it is exposed to high
situ synthesis (Jiang et al., 2021; Xue et al., 2020), impregnation method levels of oxidative radicals during the photocatalytic reaction, the
(Zendehzaban et al., 2020), melt phase separation method (Ni et al., composite of PC and substrate must be stable over the long term (Col­
2019). Thus, the immobilization technique is selected by considering the menares and Kuna, 2017; Shan et al., 2010).
type of pollutant, PC, reactor, and support alongside economic and Furthermore, the supporting process is an extra step with associated
environmental aspects. expenses. The application should choose the supporting method and
material. For example, most polymers that could be utilized to support

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Fig. 7. Diagrammatic representation of the (a) electrospinning device and nanofibers application (Shahriar et al., 2019), (b) rGO/TiF membrane fabrication process
and the photocatalytic filtering system by using this membrane (Gao et al., 2020).

N–TiO2 have not functioned with photocatalytic ozonation. Ozone can and synthetic polymers.
degrade the polymer, causing the catalyst to decompose and contami­
nate the water. As a result, during the selection of support, keep catalytic 4.1.1. Natural polymers substrates
application technology in mind (Gomes et al., 2019). According to Natural polymers are those made from renewable resources or
source, functions, structure, thermal behavior, and polymerization agricultural wastes. Because of the presence of numerous functional
mechanism or preparation procedures, polymers are a diverse class of groups (such as COOH, –OH, and –NH2) and important characteristics
materials (Olatunji, 2016). Besides serving as fillers in polymer matrices, such as environment-friendly, excellent sustainability, nontoxicity,
functionalized polymers, and their nanocomposites serve as hosts or biodegradability, and also more availability, a natural polymer can
supporting materials for inorganic metals and semiconductors as well represent favorable support for semiconductor materials in photo­
(TiO2, ZnO, Fe2O3, and so on). With their low cost, environmental catalysis, like synthetic polymers (Iervolino et al., 2020; Mafra et al.,
friendliness, and ability to replace petroleum-derived products, func­ 2021; Srikanth et al., 2017; Zhang et al., 2016). On the other hand, in
tionalized polymeric composites generated from either natural or syn­ comparison with synthetic polymers, various natural polymers can only
thetic polymers are attracting a lot of attention from governments, be processed into a limited number of shapes due to the needed high
industry, and academia (Raja and Mattoso, 2020). Polymer supports temperatures that damage their structure (Colmenares and Kuna, 2017).
have many advantages over slurry systems in terms of preventing the Thus far, polysaccharides-based biopolymers including starch, cel­
aggregation and release of nanoparticles, making it easier to recover the lulose, alginate (Chkirida et al., 2021), chitosan, and gum (Araujo et al.,
catalytic materials, and in most cases, maintaining or even improving 2020) have been considered promising supports for PCs since they can
the photocatalytic efficiency (Melinte et al., 2019). Generally, polymers adsorb the pollutants and be modified by nanoparticles (Sohouli et al.,
utilized as PCs can be classified into two categories, natural polymers, 2022). Chitosan, a natural biopolymer, was employed by Balakrishnan

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Fig. 8. Membranes preparation steps via the PI method and the photocatalytic testing apparatus (Popa et al., 2021).

Table 1
A summary of the performance of the PCs with natural polymer supports.
Year Photocatalyst Substrate Immobilization Light Main results Ref.
technique

2019 TiO2/ZrO2 Carboxymethyl chitosan Microwave UV Decolorization of 90.5% of RhB. (Tian et al.,
hydrothermal 2019)
method
2020 WO3 Sodium alginate/PVP Solution method Visible light Removal of 98% of MB for nanorods and (Elsayed et al.,
91% for nanospheres in 90 min 2020)
2020 TiO2 Cellulose nanofibrils derived One-pot hydrothermal Visible light Removal of 100% of both RhB and Cr (VI) (Li et al., 2020a)
carbon/ bacterial cellulose method
2020 Au-TiO2 Cellulose membranes Tape casting Visible light Decolorization of 90% of RhB (Yu et al., 2020)
2020 TiO2 Chitosan Phase inversion method UV Degradation of 92% of 2,4- (Balakrishnan
dicholorophenoxyacetic acid et al., 2020)
2020 TiO2/ carbon dots Chitosan- grafted polyvinyl In situ deposition under Sunlight Removal of 95% of 2,4-dicholorophenol, (Midya et al.,
imidazole microwave irradiation 95.8% of reactive blue 4, and 98.2% of 2020)
reactive red 15.
2020 ZnO Natural Arabic and Karaya gums Solution method Visible light Removal of 77 % of MB by KGZnO and 19 (Araujo et al.,
(polysaccharides) % by AGZnO in 120 min 2020)
2020 CdS Carboxyl methyl starch (CMS) In situ formation method Visible light Removal of 86.72% MB, 81% CV, and no- (Xue et al.,
effect RhB 2020)
2020 ZnFe2O4 Methyl cellulose Microwave-assisted UV Photodegradation of 92.65% of (Tamaddon
coprecipitation method Metronidazole (for synthetic wastewater) et al., 2020)
and 71.12% (for real wastewater)
2020 TiO2 Trimethylchlorosilane-polyvinyl Impregnation method UV to visible 63% removal of ammonia under UV and (Zendehzaban
alcohol-sodium alginate (MPVA- range 57% under visible light et al., 2020)
Alg)
2020 Reduced graphene Sodium alginate Simple hydrothermal UV-A 78% removal of ibuprofen and 90% (Nawaz et al.,
oxide-TiO2 treatment removal of sulfamethoxazole. 2020)
2021 Silver quantum dots Chitosan − polyethylene oxide In situ self-assembly Simulated Removing 91.1% of p-nitrophenol (Alshorifi et al.,
facile casting method sunlight 2021)
2021 Ag/Bi2WO6 Magnetic chitosan Hydrothermal method Solar light Adsorption of 68.68 mg/g of Cu (II) (Yang et al.,
simulator 2021)
2021 CdS sensitized nano- Chitosan In-situ synthesis via an Sunlight Removal of 94.34% of Congo red in 30 min (Jiang et al.,
ZnO aqueous route at room 2021)
temperature
2021 g-C3N4 Calcium alginate Solution method Sun light Removal of 80.94% of MB in 42 h (Hao et al.,
2021)
2021 graphitic carbon Beads of calcium alginate Solution method Visible Removal of 99% of RhB dye in 30 min. (Fu et al., 2021)
nitride nanosheet
2021 Polyamide (nylon- Cellulose paper Dip- coating Sunlight & Under LED irradiation: removal of 65% (Mafra et al.,
6)-TiO2 LED estrone, 62% 17β-estradiol, and 52% 2021)
nanocomposite estriol.
Under sunlight irradiation: removal of
99.5% of estrone, and 17β-estradiol, and
98.5% for estriol.
2021 TiO2 NPs lignocellulose nanofibers Colloidal processing / Solar light/ Decolorization of 100% of MO (Gonzalez et al.,
Dip coating Xe-arc lamp 2021)

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et al. to immobilize TiO2. 2,4-Dichlorophenoxyacetic acid degradation was tested by Ata et al. utilizing a solvent-cast technique at ambient
was investigated using TiO2/chitosan beads. The phase inversion temperature. They developed an easy and low-cost production approach
approach was used to create spherical-shaped TiO2/chitosan beads. for immobilized PCs for large-scale commercial wastewater treatment
When exposed to UV light, TiO2/chitosan beads demonstrated 92 % under direct sunlight. The new PCs effectiveness was then assessed in the
degradation of 2,4-dichlorophenoxyacetic acid. This research was deactivation of an antibiotic-resistant (AR) Escherichia coli (E. coli)
extended to the continuous photocatalytic degradation mode and strain that was chosen from the biological process effluent of an urban
compared to findings obtained with bare TiO2 (Balakrishnan et al., wastewater treatment facility. Photocatalytic studies using MB water
2020). Xue et al. used an in-situ production process to create a complex solutions demonstrated that after 180 min of irradiation, 83–100% of
film of CdS and carboxyl methyl starch (CMS). There were numerous MB can be destroyed. The system also degraded phenol photocatalyti­
analyses performed on this film’s shape, content, and optical properties. cally. The photocatalytic technique also reduced the AR E. coli strain by
The CdS was evenly dispersed throughout the starch matrix, as well as 97% after 30 min of treatment (Ata et al., 2017). Wang et al. synthesized
the absorbance spectrum of this film remained in the visible region. boron-doped zinc oxide (BZO) sheet-spheres on polyethylene
Organic dyes such as methylene blue (MB), crystal violet (CV), and RhB terephthalate-tin-doped indium oxide (PET–ITO) flexible substrates
were removed from aqueous solutions using this starch-based complex hydrothermally for 5 h at 90 ◦ C which is illustrated in Fig. 9a. Three
film. 120 min of exposure of the wastewater to 0.1 g of CdS/CMS film carrier transport models were investigated: hot carrier tunneling theory,
resulted in the removal of approximately 86.72% MB and 81% CV. tunneling recombination, and series resistance. The BZO/PET–ITO
Remarkably, CdS/CMS film showed selective photocatalysis degrada­ nanostructures degraded reactive yellow 15 (RY 15, a non-ferrous azo
tion of MB and CV in the MB/RhB and CV/RhB binary systems and had dye) better than pure ZnO, with a degradation rate of 41.45%.
almost no effect on RhB (Xue et al., 2020). Under sunlight, a polyamide- Increasing the number of electron carriers involved in redox reactions
TiO2 nanocomposite dip-coated onto cellulose paper by Mafra et al. was and raising the built-in electric field separated the photo-induced elec­
assessed for its efficiency in degrading estrogens. In a miniature exper­ tron-hole pair, causing an increase in holes, O2, and OH as powerful
imental setting, the photocatalytic performance was examined in both oxidants which were considered as the main reasons for this improve­
artificial and natural light (batch of six reactors). In the 420 min of light ment. As revealed, ZnO/PET–ITO with B-doped and pure ZnO/PET–ITO
exposure, the LED source removed 65% of estrone, 62% of 17β-estradiol, had different photocurrent densities (Wang et al., 2017). Poly­
and 52 % of estriol. After 180 min of irradiation under sunlight, dimethylsiloxane (PDMS) is one of the suitable candidates for optical
increased the removal efficiency of estrone, 17β-estradiol increased to applications since it is transparent, highly chemically, and mechanically
99.5%, and estriol enhanced to 98.5% (Mafra et al., 2021). CaAlg gel stable. Moreover, it can be easily shaped in different shapes like mi­
beads with interconnecting macropores immobilized on graphitic car­ croparticles (Ahdieh Amjadi et al., 2020; Amjadi et al., 2020). According
bon nitride nanosheets for efficient pollutant removal in water via to Bertram and Nee’s work, a low-density microbubble of PDMS beads
visible photocatalysis were created by Guo-Bao Fu et al. The impacts of with integrated TiO2 produces a buoyant PC. Even though the PC was
pre-gel solution formulations on the structures and photocatalytic per­ only present at the solution surface, it degrades MB faster than other
formances of gel beads were studied in detail. When used to remove buoyant TiO2-based PCs. The TiO2/PDMS beads were also reusable, with
pollutants like RhB, CNNS-immobilized CaAlg gel beads with inter­ no loss of photocatalytic activity after five degradation tests. Under
connecting macropores showed outstanding photocatalytic perfor­ UV–visible light irradiation, 100% of the aqueous MB solution was
mance. By using the prepared gel beads, it effectively removed 99% of degraded (Bertram and Nee, 2018).
RhB from water in 30 min under visible light. They were easily recy­ As shown in Fig. 9b, an easy melt phase separation method was used
clable and had stable photocatalytic properties. To make PC- by Ni et al. to immobilize TiO2 NPs in a poly (vinyl alcohol-co-ethylene)
immobilized gel beads with interconnected macropores, a new tech­ nanofibrous scaffold. MB was used as the model pollutant for the hybrid
nique was developed (Fu et al., 2021). A summary of the performance of film. The hybrid film with incorporated TiO2 NPs removed 97.3 % of MB
some of the PCs with natural polymer supports is presented in Table 1, under UV irradiation in 150 min, and this efficiency might be improved
confirming that this category is a suitable candidate for removing the by linking with a dye-enriched filtration procedure. As a result, the
pollutants from the wastewater. hybrid film would be an attractive choice for efficient organic dye
removal from wastewater due to its promising filtering capabilities,
4.1.2. Synthetic polymer substrates strong photocatalytic breakdown activity, and well-repetitive usage
Synthetic polymers are commonly referred to as man-made poly­ performance (Ni et al., 2019). Olga Sacco et al. created a packed bed
mers. Thermosets, thermoplastics, and elastomers are the three main photoreactor employing a visible light PC. The packed bed reactor was
types of synthetic polymers. Variations in the main chain as well as the illuminated with LEDs to assess photocatalytic performance in removing
side chains are further subclassified, leading to the formation of poly­ various water contaminants. Using a flexible LED strip as the external
mers with different characteristics. Carbon-carbon (C–C) bonds form the light source allowed for a simple cylindrical photoreactor shape,
backbones of most synthetic polymers, although heterochain polymers improving contact between the PC and the treated water. Particles of N-
have additional elements (such as O, S, and N) along the backbone as doped TiO2 supported on PS spheres were used as a visible light active
well (Raja and Mattoso, 2020). Due to their physicochemical features, structured PC, and after 120 min of irradiation, practically all MB was
synthetic and semisynthetic polymers derived from crude oil have had a removed. After 180 min of visible light irradiation, the designed packed
major impact on modern science and technology. It is important to select bed photoreactor effectively removed ceftriaxone, paracetamol, and
a polymer that is resistant to chemical, physical, and biological stresses caffeine, virtually completely degrading the pollutants and removing
when determining its functional properties (Colmenares and Kuna, over 80% of total organic carbon (Sacco et al., 2019). Suman Das and
2017). Hari Mahalingam produced reduced graphene oxide (rGO) and graphitic
Salcedo et al. immobilized Ag/ZnO in cross-linked poly (acrylic acid) carbon nitride (g-C3N4) catalysts, which were immobilized in a PS film
–PAA-. The morphology, chemical structure, thermal characteristics, using the simple solvent casting approach. The photocatalytic degra­
and crystallinity of the composites were evaluated. The silanized parti­ dation of remazol turquoise blue dye synthetic wastewater was tested in
cles were found to be chemically attached to PAA and evenly distributed an internal loop airlift reactor with a 1.2 L working volume. The dye
throughout the matrix. For continuous operations, immobilized Ag/ZnO decolorization with O3 or H2O2 was complete and faster. The immobi­
demonstrated equivalent photodegradation performance compared to lized catalyst was utilized 4 times (Das and Mahalingam, 2020). Moz­
the pure Ag/ZnO in the process of UV-assisted photocatalysis of tahida and Lee created an eco-friendly hydrogel by immobilizing
bisphenol-A aqueous solutions (Jasso-Salcedo et al., 2016). The photo­ Degussa P25 on a reduced graphene oxide-polyacrylamide matrix
catalytic activity of N-doped TiO2 particles on polystyrene (PS) surface (PAM). Since the amount of PAM in the P25-rGO-PAM (PGP) hydrogel

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Fig. 9. (a)The schematic of the preparation of BZO sheet-spheres on PET–ITO flexible substrates (Wang et al., 2017), (b) Illustrating the filtration method and
synthesis steps of PVA-co-PE/TiO2 film (Ni et al., 2019), (c) Schematic of PCH20 synthesis steps (Myint et al., 2020).

affected the adsorption and photocatalytic degradation of MB, the op­ strengthen hydrogel. PAM, like cheese on a pizza, densely covered and
timum value reported for PAM was 10% (w/v). rGO also boosted the immobilized GCN into the interpenetrating network, Fig. 9c illustrates
photodegradation efficiency of the hydrogel by separating electron-hole the preparation steps of this PC which was named PCH20. On average,
pairs. The synthesized PGP was stable and had a high MB degrading PCH20 was reused 5 times compared to 3 times for GCN/PAA, with a
efficiency of up to five UV cycles. The optimal conditions were pH 9.4, a 95% photodegradation efficiency. GCN also acted as an initiator in PAM
temperature of 31.2 ◦ C, and a starting MB concentration of 5.2 mg/L polymerization and PCH20 was made without employing any photo-
(Moztahida and Lee, 2020). In another work, a graphitic carbon nitride initiators or crosslinking agents except GCN. The photodegradation ef­
(GCN) PC was immobilized in a network of polyacrylic acid (PAA) ficiency of PCH20 over RhB solution (10 mg L-1) was above 95% within 2
hydrogel where PAM was added to further immobilize GCN and h under visible light (100 mW cm− 2). The swelling of PCH20 provided a

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huge surface area for GCN to harvest light (Myint et al., 2020). Sosnin maximal photocatalytic degradation efficiency was 91.1% for the 12 wt
et al. studied the photocatalytic characteristics of a PDMS carrier sub­ % Ag QDs/CTSPEO PC. In general, Ag QDs mounted on CTSPEO mix
strate covered with ZnO microparticles. PDMS-ZnO composite was made composites considerably enhanced the SPR and synergistic effects and
by mechanically depositing ZnO particles onto PDMS. Using an ultra­ narrowed the bandgap, resulting in strong photocatalytic activity
sonic bath for 10 min eliminated excess ZnO. The resultant PC was very (Alshorifi et al., 2021).
active at 410 nm (visible light) in the breakdown of phenol in water, According to the summary presented in Table 2, highly efficient
whereas ZnO was inefficient below the UV domain. In a similar setup, photocatalytic degradation of the wastewater pollutants can be achieved
the photocatalytic activity of the ZnO/PDMS composite was compared using PCs immobilized on/in the different types and shapes of polymers
to ZnO powder suspension. They found that the same performance is like thin films, spheres, beads, and scaffolds. In addition to the advan­
realized by three orders of size smaller quantities of ZnO in their com­ tages, they possess regarding the material aspects like stability, cost, and
posite contrasted to the suspension of powder. Due to the limited flexibility, they contribute to the optical step by transferring and scat­
amount of connected ZnO, the photocatalytic material retained PDMS tering the incident light to provide better light absorption in PC though
transparency (about 0.1 percent by mass). As a result of the material they do not participate in the light absorption and exciton generation.
transparency, multilayer or manifold fluid treatment devices can be They do not participate in exciton transferring, exciton dissociation,
easily constructed (Sosnin et al., 2020). Using the mixture of synthetic recombination, and charge transferring since almost all of the utilized
and natural polymers as the PC support is another strategy that was natural and synthetic polymers are electrical insulators. However, in
considered by Alshorifi Fares T. et al. They used an in situ self-assembly some cases, the insulating feature causes the movement of the charges
easy casting method to create silver quantum dots (Ag QDs) anchored on and excitons just in the PC media, considered as a favored limitation.
polymeric chitosan polyethylene oxide (CTSPEO) blend sheets. The Regarding the chemical step, some of them contribute to the kinetic of
CTSPEO mix polymer functioned as a reducing and stabilizing agent for the reaction by adsorbing the pollutants molecules on their surfaces.
Ag QDs while emitting no chemical pollutants into the environment. The Fig. 10 illustrates the polymer supports situation. Boosting the efficiency
results revealed that the Ag QDs/CTSPEO composites were successfully of the photocatalytic treatment of wastewater would be provided by
synthesized via the interactions and complexation of Ag QDs and employing the semiconducting polymeric supports that can participate
CTSPEO blend sheets. The photocatalytic effectiveness of the produced in both light absorption and charge transport.
composites was determined by the photodegradation of p-nitrophenol
(PNP) in the presence of simulated sunlight. Within three hours, the

Table 2
A summary of the performance of the PCs with synthetic polymer supports.
Year Photocatalyst Substrate Immobilization technique Light source Main results Ref.

2016 Ag/ZnO PAA – UV 47% photodegradation of bisphenol- A (Jasso-Salcedo

et al., 2016)
2017 N-doped TiO2 PS Solvent-cast Visible light 83–100% decolorization of MB, and 97% (Ata et al., 2017)
inactivation of AR E. coli strain.
2017 Boron-doped zinc PET–ITO Hydrothermal method UV Degrade 41.45% of RY 15. (Wang et al.,
oxide sheet-spheres 2017)
2018 TiO2 PDMS beads – UV–visible 100% degradation of MB solution. (Bertram and
light Nee, 2018)
2019 TiO2 NPs Polyvinyl alcohol co- Melt phase separation UV Photodegradation of 97.3% of MB (Ni et al., 2019)
ethylene nanofibrous
scaffold.
2019 N-doped TiO2 PS spheres – Visible light 100% decolorization of MB and 100% removal (Sacco et al.,
of ceftriaxone, paracetamol, and caffeine. 2019)
2019 ZnS NPs Polyvinyl alcohol (PVA) Solvent casting procedure Sunlight Complete decolorization of MB in 660 min (Rahman Khan
et al., 2019)
2020 N-doped TiO2 PS spheres Solvent casting method Sunlight Removal 5% of trimethoprim (TMP) in 300 (Kowalska et al.,
min, 100% of diclofenac (DCF) in 270 min, 2020)
and 32% of carbamazepine (CBZ) in 270 min
2020 rGO/ g-C3N4/TiO2 PS film solvent casting method UV 100% degradation of Remazol turquoise blue (Das and
dye. Mahalingam,
2020)
2020 Degussa P25TiO2 rGO- PAM matrix – UV 100% degradation of MB (Moztahida and
Lee, 2020)
2020 Graphitic carbon PAA – Visible and Photodegradation of 95% of RhB. (Myint et al.,
nitride (GCN) solar light 2020)
2020 ZnO microparticles PDMS Depositing ZnO particles UV visible Removal of ~ 95% of phenol at ~ 30 h (Sosnin et al.,
onto the PDMS sample Removal of ~ 95% of phenol at ~ 48 h 2020)
mechanically
2020 TiO2 Hydrophobic PVDF and Electrospinning method Visible Decolorization of 80 % RhB by PVA/TiO2 and (Lou et al., 2020)
hydrophilic PVA 100 % by PVDF/TiO2 at 49 days
2020 TiO2 Poly methyl New method inspired from UV Photodegradation of 60% of MB in 250 min (Ounas et al.,
methacrylate inverted phase method 2020)
2020 Ag2CO3@UiO-66-NH2 GO/Polyvinylidene Vacuum filtration self- Visible light 100% removing of MR, MB, RhB, and Cr (VI) (Zeng et al.,
fluoride membrane assembly method (xenon) in 200 min 2020)
2021 Au /Pt/TiO2 NPs PS Self-assembly method UV Photodegradation of ~ 85% of MO and 4- (Li et al., 2021)
chlorophenol
2021 Ag QDs CTSPEO In situ self-assembly facile Simulated Removing of 91.1% of p-nitrophenol (Alshorifi et al.,
casting method sunlight 2021)
2021 ZnFe2O4@WO3− X Polypyrrole Polymerization method Visible light Degradation 95% of Gemifloxacin in 60 min (Kumar Das
and generation 657 µmol/h of H2 et al., 2021)
2022 TiO2 Polyamide 3D-structure Impregnation method UV Decolorization of 94.1% MB in 180 min. (Grandcolas and
Lind, 2022)

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Fig. 10. Summary of the current situation of polymeric supports.

4.2. Inorganic substrates wt%, resulting in 86.2% decolorization efficiency within 30 min irra­
diation. After five cycles, the decolorization efficiency was 81.9% of the
The fundamental rationale for picking inorganic supports is their starting decolorization efficiency (Huang et al., 2008). Saqib et al. used
high porosity, which can accommodate catalyst particles (Huang et al., crystalline zeolite immobilized TiO2 nanoparticles to decompose MB, a
2008) though this is crucial because increasing the calcination temper­ basic cationic dye. The new method of physically altering (impreg­
ature can significantly reduce the specific surface area of the catalyst. nating) with zeolite was discovered to be effective in overcoming the
Huang et al. (Huang et al., 2008) found that adding TiO2 over natural need for UV light for a photocatalytic reaction including TiO2. The
zeolite reduced the specific surface area and thus the decolorization rate. biphasic nature (anatase = 85% and rutile/brookite = 15%) and the
Because these solids contain metals and metal oxides, they can be prone presence of zeolite support increased the photocatalytic degradation of
to leaching (Gomes et al., 2018; Huang et al., 2008). Generally, the MB up to 4 times compared to pure anatase TiO2. The maximum pho­
various inorganic materials employed as the support for PCs can be tocatalytic elimination efficiency for MB was 155 mg l− 1 (qm = 62 mg
divided into five categories that are introduced in the following sections. g− 1) (Saqib et al., 2019). A modified zeolite/TiO2 composite (MZTC)
was produced in situ by Liao et al. The microscopic characterization
4.2.1. Zeolites revealed that TiO2 was homogeneously diffused in the zeolite structure
Zeolites are aluminosilicate minerals with exceptional adsorption at the nanoscale, forming a strong chemical interaction with zeolite. The
characteristics that Na+, K+, Ca2+, Mg2+, and Al3+ are found in them degradation rate of MB dye in an aqueous solution was investigated to
(Srikanth et al., 2017). Zeolite structures are particularly interesting assess MZTC photocatalytic performance. The degradation experiment
supports with considerable benefits for specific immobilization ap­ revealed that MZTC-2.5 had the highest MB degradation rate (93.6%),
proaches as well as for recycling and reuse operations due to their high 2.4 times higher than hydrolysis TiO2 powder (HTOP) containing the
porosity, mechanical (Diban et al., 2021; Angela et al., 2022), and same quantity of pure TiO2. MZTC-2.5 showed an 86.5% MB degrada­
photo-chemical stability, homogeneous pore distribution in both the tion efficiency after five tests, indicating good recyclability (Liao et al.,
channel and cages and activity under UV visible irradiation over 240 nm 2019). Albouyeh et al., employed the agricultural waste material rice
wavelength (Adnan et al., 2018). husk silica (RHS) as a source of silica for the MFI zeolite produce. Solid-
Huang et al. produced Pt-TiO2/zeolites using the sol–gel method and state reactions were used to generate magnesium oxide (MgO) NPs in
photoreduction deposition. Their photocatalytic activities were tested zeolite substrates. The BET results showed MgO/RHS-MFI NC had a
by decolorizing MO solution under UV light irradiation. Pt doping smaller specific surface area than RHS-MFI zeolite. MgO NPs can be
increased photocatalytic decolorization and optimal Pt doping was 1.5 encapsulated in RHS-MFI zeolite holes. The assessment of the

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photocatalytic process performance of MgO/RHS-MFI zeolite hetero­ re-excite TiO2, improving photon usage and thus photocatalytic effi­
geneous capability across MB dye was the main goal of this study. Under ciency for organic dye degradation (Sun et al., 2019). The three-
UV light at pH 9, MB breakdown reached 80%. RHS-MFI enhanced the dimensional network of open-celled Al2O3 ceramic supports was
photocatalytic activity of MgO by decreasing the electron-hole recom­ created by Tuba Yildiz et al. The PC ceramic powder was applied layer
bination rate. A reasonable oxidation mechanism was also suggested by layer by repeatedly immersing the rigid Al2O3 supports in a TiO2
(Albouyeh et al., 2020). Rodríguez et al. studied the photocatalytic powder slurry. To avoid phase change, the dipped TiO2 was sintered at
performance of TiO2/zeolite, WO3/zeolite, WO3/TiO2/zeolite, and 700 ◦ C. The photocatalytic destruction of reactive orange 16 (RO16) azo
WO3/TiO2 composites. The semiconductor/zeolite composites were dye molecules dissolved in water was used to assess the efficacy of the
produced via a simple physical mixing and calcination process. The sample. Color removal was nearly complete in 75 min with UVC (Yildiz
material photocatalytic activity was assessed by degrading MO in near- et al., 2020).
UV light (365 nm). Results from several characterization techniques
showed that Zeolite Y, TiO2, and WO3 all maintained their crystallinity 4.2.3. Carbon-based materials
after the preparation process. When WO3 and TiO2 particles were spread Due to their chemical inertness and lack of reactivity, carbon-based
on the zeolite surface, no substantial variations in photocatalyst band materials are used as PC support materials. Furthermore, the majority of
gap energies were identified. Added TiO2 and WO3 decreased the surface carbon materials exhibit excellent surface characteristics and a potent
area of zeolite FAU. No synergistic impact between semiconductor ma­ affinity for the adsorption of both organic and inorganic molecules
terials and zeolite FAU was discovered, although TiO2 P25 and WO3/ (Adnan et al., 2018). As a result of this variety of carbon material
TiO2 heterojunction showed the highest MO breakdown under near-UV qualities, the intermediates generated during a photocatalysis process
light. Finally, UV–vis spectroscopy revealed that the TiO2/zeolite com­ are reduced or eliminated, and the mass transfer rates and process ef­
posite PC had the maximum density of positive holes (González Rodrí­ ficiency are increased (Trisha Ghosh and Won-Chun Oh, 2012). Acti­
guez et al., 2020). vated carbon (AC) also known as activated charcoal is cheap, porous,
has a huge surface area, and is readily available (Alhaji et al., 2017; Li
4.2.2. Clay and ceramics Puma et al., 2008; Liu et al., 2018; Omri et al., 2014; Ouzzine et al.,
Due to their good permeability, huge surface area, lower density, and 2014). Many studies have been done on AC photochemical character­
high given strength, ceramic-supported PCs with open-pore architec­ istics (Shan et al., 2010). The use of ultrasonic sound waves in
tures are of significant and prospective interest (Adnan et al., 2018). Due conjunction with UV radiation improved the performance of AC as a PC
to their vast surface areas and chemical stability, clays, ceramics, and substrate, solving issues with support’s opaqueness and porosity. AC has
other siliceous materials are often utilized as PC immobilizing agents also been suggested as a potential photocatalytic support because it
(Guan et al., 2015; Xuzhuang et al., 2009). These compounds make it promotes interface charge transfer and decreases hole and electron
easier and more eco-friendly to separate the catalyst from the reaction recombination (Alhaji et al., 2017).
mixture and the treated effluents (Srikanth et al., 2017). For instance, Dong et al. immobilized Er3+: YAlO3/TiO2 on the surface of spherical
Montmorillonite makes up the majority of bentonite. The surface of this activated carbon (SAC) using a sol–gel technique. The PCs activity was
kind of clay is oily and soapy. The substitution of Mg2+ and Zn2+ and measured by photodegrading MO using an LED lamp (λ greater than
Al3+ and Si4+, in the octagonal and tetrahedral layers of montmoril­ 400 nm). The Er3+: YAlO3 upconversion lighting agent transforms
lonite’s chemical structure, respectively, results in a net negative charge visible light into ultraviolet light. The maximum photocatalytic activity
on the soil’s surface. Internal cations, primarily Na+ and Ca2+, balance of Er3+: YAlO3/TiO2 was seen at 700 ◦ C calcination. Photocatalytic
and compensate for the electric charge’s imbalance. As a result, mont­ oxidation degraded MO by breaking the N-N and C-N bonds (Dong et al.,
morillonite exhibits physical–chemical characteristics like high contact 2012). Reactive Brilliant Blue KN-R decolorization was accomplished by
areas, high structural stability, exceptional absorption power, and Zhang and Lu using a sol–gel method to synthesize titanium dioxide
potent ability to induce suspensions at low concentrations (Dinari and (TiO2) supported on coconut shell biochar (BC) (calcined at 450 ◦ C). UV
Mahmoudi, 2022). M. Abdel Salam et al. removed Cr (VI) ions and high pressure Xenon lamp (300 W) photocatalysis tests showed that the
malachite green dye (MG.D) by using a green composite made of highest decolorization efficiency occurred under strong acid and alkali
organically modulated bentonite substrate by Co3O4 NPs (OB/Co). This conditions (pH = 1 and 11) within 60 min. As a result, the TiO2/BC
composite was successfully created and is now being studied as a PC, composites showed photocatalytic and adsorption capacity for KN-R
possibly eco-friendly, and inexpensive adsorbent. Under visible light, decolonization, and they were also very durable in the recycling cycle
the composite had strong photocatalytic activity, which led to 100% and could be widely applied in anthraquinones dyeing wastewater
elimination of 100 mg/L of Cr (VI) and MG.D after 240 and 180 min, treatment (Zhang and Lu, 2018). Thanh et al. used a sol–gel approach to
respectively (Abdel Salam et al., 2020). create a carbon and iron co-doped titanium dioxide catalyst coated on
Linjing Du et al., created porous alumina ceramics with well-ordered AC (Fe-C-TiO2/AC). The catalyst’s phase composition, particle size, and
capillaries using an ionotropic gelation technique. The porosity of structure remained constant. Degradation of RhB occurred in solutions
alumina ceramics was regulated by altering the initial solid loading due to the huge surface area of AC. The Fe-C-TiO2/AC catalyst out­
(10–30 wt%) and pore size (180–315 µm). Porous ceramics were used as performed pristine TiO2 and Fe-C-TiO2 in photocatalytic RhB degrada­
PC supports for TiO2 catalysts whose photocatalytic activity was tion. The best catalyst load for RhB breakdown was found to be 1.6 g/L.
measured by decomposing MB under UV irradiation. Sol-gel TiO2 Toxic chemical compounds can be degraded by Fe-C-TiO2 on AC samples
coatings showed outstanding adherence to surfaces (Du et al., 2014). when exposed to visible light (Le Thi Thanh et al., 2019). Luo and co­
Hui et al. created montmorillonite-supported nano TiO2 photocatalytic workers reported assembling well-aligned single-crystalline wurtzite
composites using a solid diffusion technique. The results revealed that ZnO nanorod arrays (ZnO NRAs) on activated carbon fibers (ACFs)
the montmorillonite matrix inhibited nano-TiO2 aggregation and utilizing a sequential sol–gel and hydrothermal synthesis process. With a
increased UV–vis absorption, enhancing photocatalytic activity. The defect level (shown by a very acute blue emission, strong green and
photocatalytic activity was determined by the cyclic breakdown of MB. yellow emissions), aspect ratio (ca. 20:1, rod length/rod diameter), and
The material was UV irradiated 5 times in fresh MB solution (Liang et al., high rod surface area (up to 20 m2/g), ZnO NRAs grow nearly perpen­
2017). H. Sun et al. placed TiO2 over a UV emitting support synthetic dicularly on the ACF surface. Customizing ZnO NRA/ACF structural and
from Ca2MgSi2O7:Ce3+ phosphors to improve photon usage and prevent optical properties requires fine-tuning the sol–gel and hydrothermal
suspension forming. The TiO2 powder was uniformly distributed over procedures. They have superior photocatalytic destruction of MB and
the substrate, allowing it to absorb photons flowing through it and are more recyclable than individual ZnO NPs (powder, NRs, and NRAs)
produce a 380 nm secondary emission. This secondary emission could (Luo et al., 2020). Prasenjit Kar et al. described how iron (III) oxide

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(Fe2O3) NPs were applied on bismuth carbonate (BC) sheets and Abdelazeem S. Eltaweil et al. produced an Ag@biochar nanostructure
immobilized on ACF using a two-step simple solution way to create a through a novel and entirely green process, in which Chenopodium
(Fe2O3@BC/ACF) heterojunction. According to a fluorescence investi­ ambrosioides biomass (C. ambrosioides) was utilized as a green and
gation, excellent electron-hole separation and transportation at the natural source of biochar and its extracts were employed as a reducing
interface brought an improvement in photocatalytic activity. Under agent for silver ions, preventing the usage of chemicals throughout the
reactor operation, the created PC displayed visible light photocatalytic entire process (Fig. 11a). Due to its excellent electron transfer rate,
action toward the degradation of 95% of pharmaceutical contaminants Ag@biochar showed an elimination efficacy of up to 88.4% for MB (25
(antipyrine) at 20 h (Kar et al., 2021). Pratyush Jain et al. successfully ppm) at 75 min under visible light irradiation. Additionally, it dropped
immobilized (31 mg/g) TiO2 in ACF pores via impregnation/hydro­ to 70.65% after 6 recycling rounds, indicating a high level of regener­
thermal technique. The efficiency of the PC was proven by removing ation effectiveness. Moreover, Ag@biochar demonstrated powerful
99% of the MB dye in 180 min (Jain et al., 2019). Siara Silvestri et al. antibacterial effectiveness by the total inhibition of E. coli growth as
produced composites, utilizing Salvinia molesta biochar as a carbon well as the prevention of C. albicans, B. subtilis, P. aeruginosa, and K.
source support for TiO2. For TiO2 precursors, TiOSO4 and TTiP were pneumoniae growth. It was shown that C. ambrosioides played a dual
evaluated. The composites made from TTiP had greater crystallinity, a role in the creation of biochar from easily obtainable biomass and in the
smaller band gap, and a bigger pore size. They discovered that Salvinia reduction of silver ions to AgNPs and their support on biochar.
biochar contains quinone-like structures, which act as the main electron Ag@biochar 1.9 eV band gap energy validated its potential for usage as a
acceptors that reduce electron/hole recombination. The photocatalytic PC. AgNPs had a surface area of 47.61 m2/g and were mainly spherical
efficacy of TiO2/biochar in the decolonization of the acid organic 7 dye in shape, with a diameter ranging from 25 to 35 nm. Moreover,
(AC7) was 90% at 180 min under UV radiation (Silvestri et al., 2019). Ag@biochar was determined to be stable at a zeta potential of − 5.87 mV

Fig. 11. (a) Schematic illustration of the fabrication steps of green Ag@Biochar (Eltaweil et al., 2022), (b) Schematic of the BiOCl nano/micro structures deposition
on the AAO supports (Wu et al., 2011). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

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(Eltaweil et al., 2022). BWS (Direct Red), Direct Brown N/B, and Direct Copper Blue 2B128
(Direct Blue)) photodegradation efficiency after 4 h. The degrading ef­
4.2.4. Metals and metal oxides ficiency of the reused catalyst did not vary considerably in the second
Metals are chosen in industrial applications because of their me­ cycle, proving its reusability. The optimal ratio of anatase to rutile
chanical qualities and light-weight. Due to their widespread use in in­ phases (3.5:1) was reported in TiO2 immobilized on glass and iron beads
dustrial catalytic reactors with organized structures, aluminum, and calcined at 700 ◦ C. G700 and I700 also had substantial photocatalytic
stainless steel are the most popular metal supports. If metallic supports activity under UV-A. The results show that increasing the calcination
are employed, PC like TiO2 may also be covered on the reactor’s walls temperature reduced the amount of the anatase phase while increased
(Giornelli et al., 2006). Among the many supports, iron beads have the rutile phase. Furthermore, immobilized TiO2 on glass and iron beads can
advantage of being magnetically attracted, making it simple to recover be employed to effectively cure textile dyeing effluent (Chairungsri
and reuse them throughout the magnetic separation process (Chair­ et al., 2022). Lenzi et al., synthesized Ag/ZnO/CoFe2O4 magnetic PCs
ungsri et al., 2022). It should be noted that metal oxides can be also utilizing the Pechini technique. The behavior of Ag/ZnO/CoFe2O4
considered in the category of ceramics. comprising various concentrations of CoFe2O4 (5, 10, and 15% wt), as
Wu et al. produced BiOCl nano/micro structures on anodic well as pure Ag/ZnO (5% Ag) was assessed in the photodegradation of
aluminum oxide (AAO) templates which are illustrated in Fig. 11b, by ibuprofen (IBP). After 120 min, 100% of IBP was removed under UV
using sol–gel and vacuum air extraction. BiOCl materials on AAO tem­ irradiation and it was shown that the PC was stable during the degra­
plates have morphologies that are strongly influenced by the sol con­ dation cycle. The ferrite load had a direct effect on the photocatalytic
centration. Specifically, 0.3 M sol concentration produces nanowire activity. It has been found that the behavior of IBP degradation
arrays, while 0.5 M sol concentration produces vertically oriented flakes decreased with increasing ferrite load. The IBP degradation was not
on the surface. The photocatalytic degradation of RhB dye using BiOCl significantly affected by the outcomes of the photolysis and adsorption
nano/micro structures was studied. Compared to the horizontally ori­ experiments. Their study on PC reuse showed that it could be recovered
ented BiOCl flake-like film on a glass substrate, the vertically aligned and utilized at least three more times without suffering a significant
flake and nanowire arrays on AAO templates showed better photo­ reduction in catalytic activity. A magnet was used to easily remove the
catalytic efficiency (Wu et al., 2011). cobalt ferrite from the aqueous media due to its high magnetic proper­
According to Tian et al., Oriented Cu-Cr layered double hydroxide ties (Lenzi et al., 2021). A novel ZnO/NiFe2O4/Co3O4 magnetic het­
(LDH) films were created on copper substrates using the electrophoretic erogeneous PC driven by solar light was created by Mohammadreza
deposition method (EPD), and they can be employed as PCs to degrade Doosti and his colleagues. The ZnO/NiFe2O4/Co3O4 exhibited super­
organic pollutants when exposed to visible light. The voltage or time of paramagnetic behavior, with a saturation magnetization of 32.38 emu/
EPD influenced the LDH film thickness. The 16.5 µm film possessed good g. The PC had an enhanced and robust light response, according to the
photocatalytic activity for 2,4,6-trichlorophenol (2,4,6-TCP), sulfo­ UV–Vis test. With a bandgap value of around 2.65 eV, ZnO/NiFe2O4/
rhodamine B (SRB), and Congo red degradation. Because of its high Co3O4 demonstrated high potential for the efficient destruction of
efficiency, low cost, ease of manipulation, and recyclability, this film tetracycline (TC) under natural solar radiation. They believed that the
may be employed as a PC in water treatment (Tian et al., 2012). increased photocatalytic effectiveness of this PC under the ideal cir­
Zargazia and Entezari used an anodic electrophoretic deposition cumstances (PC dosage = 0.02 g/ L, radiation time = 20 min, TC con­
technique to create an active visible light PC. The separation of photo­ centration = 30 ppm, pH = 9, and TC degradation efficacy = 98%)
generated electron-holes was evaluated using electrochemical imped­ resulted from synergistic optical influences between ZnO, Co3O4, and
ance spectroscopy (EIS). The photocatalytic activity of thin films was NiFe2O4 species (Doosti et al., 2022). Islam Ibrahim et al. used a hy­
examined by degrading RhB in a photocatalytic reactor. The conductive drothermal procedure to create TiO2/CoFe2O4 magnetic composites
substrate (stainless steel mesh) allowed for improved separation of (5–15 w/w%). Six organic dye contaminants were chosen to assess the
photogenerated electrons and holes. Moreover, high surface roughness photodegradation performance of the prepared nanocomposites,
films improve light absorption capability and thus photocatalytic reac­ including CV, rhodamine 6G (Rh-6G), MB, MO, RhB, and acridine or­
tion rate. The thin layer entirely removed the dye from the aqueous ange (AO). TC, a pharmaceutical model contaminant, was also photo­
solution and the COD was near nil (Zargazi and Entezari, 2018). The degraded under visible light and UV. Without the addition of any
auto-clave approach was used by Ahmed et al. using porous nickel to oxidants, all dyes showed substantial degradation efficiency: AO (more
anchor maghemite PC NPs. The photocatalytic behavior of 3DMNP than 91%), CV (more than 83%), MB (more than 95%), RhB (58%), Rh-
(three-dimensional maghemite-Ni PC) was investigated by degrading 6G (56%), and MO (45%) at 180 min and under UV light. The photo­
MO in both UV and natural sunshine. The produced 3DMNP showed degradation of TC demonstrated that the CoFe2O4/TiO2 (5 w/w%)
good photocatalytic activity in both UV and sunlight and was easily composite had higher photodegradation ability than pure CoFe2O4 or
recycled for at least three cycles. The addition of nickel improved pho­ TiO2, with a decomposition efficiency of 75.31% under UV and 50.4%
tocatalytic activity by separating charge carriers (Ahmed et al., 2019). under visible light at 180 min. Because of the composites inherent
Ebrahimi et al. employed a plasma electrolytic oxidation (PEO) way to magnetic properties, they could be easily separated from the solution
immobilize the rGO/ZnO hybrid on a zinc substrate. The average surface using a simple magnet (Ibrahim et al., 2022).
roughness and porosity of the hybrid coatings were found to be lower
than the ZnO coatings, resulting in a superior hydrophobic behavior. 4.2.5. Glass
The optical characteristics of the coatings demonstrated a decrease in Silica has good optical characteristics, allowing photons to disperse
band gap energy with increasing rGO concentration. Under UV irradi­ to the catalyst surface in a reactor. Commercially available amorphous
ation, the photocatalytic activity of PC was evaluated in the decolor­ silica SiO2 and artificially generated SBA-15 mesoporous materials with
ization of 55.3% of MB at 16 h (Ebrahimi et al., 2020). Chairungsri a defined pore size are both known for their efficiency as catalyst sup­
Woottikrai et al. investigated TiO2 immobilization on glass and iron ports (Alhaji et al., 2017). In aqueous environments, silica supports such
beads. The composite materials were made by spraying liquid dispersion as silica gels and mixed oxides of silica-titania have been used to facil­
onto the substrates and then calcining them at 600–750 ◦ C. SEM and itate PC separation (Shan et al., 2010). The surface area and pore
EDS examinations demonstrated that the TiO2 particles were equally structure of silica substrates should be increased by carefully selecting
dispersed on the substrates at 700 ◦ C calcination temperature. The the required percentage weight of silica to be impregnated with semi­
formed TiO2 particles were mixed-phase anatase and rutile structures, conductor (like TiO2) particles. Moreover, silica is abundant and cheap.
both advantageous to photocatalysis. The composite materials calcined So it works economically (Alhaji et al., 2017).
at 700 ◦ C achieved a 64% direct dye (consisting of T/S Direct Fast Red Estévez et al. used a dip-coating process to apply TiO2 coatings to the

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inner tube of a glass tubular reactor. To increase the adhesion and which was used as a model pollutant in the breakdown of commercial
photoactivity of the coatings to degrade phenol, diclofenac, and iso­ diazo textile dye Congo red (CR). The photocatalytic efficiency of sol–gel
proturon in the presence of UV light, aggregate size was reduced. By TiO2 films prepared from the sol with the addition of PEG was found to
grinding the TiO2 suspension, the coatings became more homogenous be superior to that of films prepared from the sol without PEG. The
and free of surface particles. The coating adherence following abrasive photocatalytic capabilities of sol–gel TiO2 films are influenced by the
blasting was also examined. The redesigned support had slightly less surface shape and roughness, as well as the ratio of two crystalline
adhesion to the substrate. Using phenol as a model molecule, the pho­ phases, anatase (the primary phase) and rutile (the secondary phase)
toactivity results showed that coatings made by wet milling catalyst for (Šegota et al., 2011).
30 min and then chemical disaggregation were more efficient in A summary of some of the used inorganic supports for providing the
degradation and mineralization. After five consecutive uses of the TiO2 heterogeneous photocatalytic reaction is presented in Table 3. Similar to
coatings, a promising photocatalytic performance was demonstrated polymeric supports, as reviewed almost all utilized inorganic supports
with a very low decay rate (Espino-Estévez et al., 2015). Saidani et al. are electrical insulators and have no contribution to electronic man­
developed undoped and copper-doped ZnO thin films on glass substrates agement which can be focused on as a future study. Since most of them
using a sol–gel dip coating technique. The degradation of orange II (OII) are porous, light scattering for harvesting more photons, and a large
in an aqueous solution under UV and visible light at ambient tempera­ surface area is provided for pollutant adsorption however they do not
ture was studied. The results showed that adding Cu reduces crystallite absorb the photons. So, using engineered supports for reducing incident
size. The AFM study found that increasing Cu concentration reduces photons losses can make photocatalysis a more reliable strategy for
surface roughness, from 20.2 nm for undoped ZnO to 12.16 nm for wastewater treatment, especially on a commercial scale.
doped ZnO 5 wt% Cu. It was found that all deposited films exhibit
acceptable optical transmittance (77–92%) in the visible region and that 4.3. Hybrid and other’s substrates
the optical gap rises with Cu content. Copper from 1% to 5% in ZnO thin
films slows the photocatalytic activity (Saidani et al., 2015). The photocatalytic degradation of wastewater has been carried out
Plasmonic nanostructures are another category of light absorber that on a variety of other supports, in addition to those already mentioned.
has been extensively considered by researchers for harvesting photons Other materials such as optical fibers (Lin et al., 2016; Zhang and Lu,
more efficiently, especially for water treatment (Aliakbari et al., 2022; 2018), eggshell (Dzinun et al., 2022), and other materials were also tried
Kohnehpoushi et al., 2016). Thinh et al. produced plasmonic Au- and as support materials.
Ag-decorated ZnO films on a glass substrate using plasma electrolyte Fe-doped TiO2 (Fe–TiO2) nanocomposite thin films deposited on
oxidation and high-voltage discharge, and then adorned them with Au SOFs (side-glowing optical fibers) for organic pollutant degradation
nanoparticles. As the Ag precursor concentration increased, Ag-ZnO were described and assessed for photocatalytic effectiveness by Lin et al.
films thickness reduced and the bandgap width increased, and this SOFs were successfully generated with the PAHD (polymer-assisted
resulted in an improvement in near band-edge UV light, accompanied by hydrothermal deposition) approach for the first time, yielding Fe–TiO2
a considerable increase in the photocatalytic efficacy for the decolor­ thin films with mixed anatase and rutile phases. Optical fibers were
ization of RhB during solar simulator exposure, and the inhibition of a utilized to minimize the incident photons losses in the photoreactor. The
visible emission in the luminescence spectra (Thinh et al., 2020). degradation of RhB served as a typical organic contaminant for testing
Rouabah et al. studied the production of CdS nanoparticles embedded in the photocatalytic efficiency of the catalysts coated on SOFs. Under UV
a polyvinylchloride (PVC) matrix. Sol–gel produced PVC/CdS nano­ and visible light irradiation, the results showed that 5% Fe–TiO2 thin
composite films were spin-coated on glass substrates. XRD and Raman’ films (Fe: TiO2 molar ratio) mixed with anatase and rutile phases had the
results support the production of hexagonal CdS nanoparticles in the maximum photocatalytic activity (Lin et al., 2015). Lin et al. produced
PVC matrix, with average crystallite sizes between 17 and 69 nm. The and coated TiO2-rGO on side-glowing optical fibers (SOFs) using the
visual transmission is between 80 and 95%, while the direct energy PAHD method, and analyzed by crystallographic and spectroscopic
bandgap was between 4.07 and 3.85 eV. The surface modification of methods. The photocatalytic performance of the synthesized nano­
PVC also has a big impact on the particle optical performance as well as composites was determined by the degradation of three medications,
the particle size distribution in the PVC matrix. According to the pho­ carbamazepine, ibuprofen, and sulfamethoxazole when exposed to UV
tocatalytic investigation, PVC/CdS nanocomposite films can degrade and visible light. TiO2-rGO nanocomposites demonstrated considerably
MB when exposed to UV light (Rouabah et al., 2020). Komaraiah et al. greater photocatalytic activity as compared to pure TiO2, which its
coated Ag+ doped TiO2 thin films on glass substrates using a sol–gel spin performance is strongly dependent on the rGO concentration. The
coating process and then annealed them at 550 ◦ C. This is owing to the photocatalysis with 2.7% rGO degraded 54% of carbamazepine, 81% of
narrow band gap energy (3.17–2.75 eV), high surface area (85–231 m2/ ibuprofen, and 92% of sulfamethoxazole after 180 min UV irradiation.
g), and diminished luminescence of Ag-doped TiO2 thin films. The 5% of Moreover, the mineralization rates of the pharmaceuticals were similar
Ag–TiO2 film had the highest photocatalytic activity, as measured by the between 52% and 59% (Lin et al., 2016). Low-cost leftover mutton bone
visible light decolorization of MB and MO (Komaraiah et al., 2020). was used by Narendra Singh et al. to produce hydroxyapatite (HAp) that
Muñoz et al. revealed the structure of certain recently discovered silica- was employed as a PC substrate for TiO2 NPs. The photocatalytic effi­
supported TiO2 PCs and evaluated the porous structure of the support in ciency of (MBHAp-T) NPs was evaluated using the model pollutant MB
the observed photocatalytic activity. Unlike the amorphous silica sup­ dye. Under UV illumination, prepared PC NPs showed an effective
port, the mesostructured silica SBA-15 provided an ordered structure breakdown of an MB dye (~93% at 4 h). It was shown that when sub­
with TiO2 crystals of equal sizes distributed throughout the support’s jected to 10 decolorization cycles, the efficiency of (MBHAp-T) NPs
mesoporous channels. The photocatalytic treatment of numerous barely dropped by 8.4%, and also the structure and morphology of the
cyanide-containing compounds was studied and described in terms of PC were unaffected too (Singh et al., 2018). Photocatalytic paint based
each catalyst’s structure. The TiO2/SBA-15 materials unique structure on TiO2 NPs and acrylate-based photopolymer resin was developed by
allowed them to attain up to eight times the activity of Degussa P25 TiO2 Islam et al. Substrates like plastic Petri dishes and glass jars were painted
(López-Muñoz et al., 2005). In order to degrade the diazo reactive dye, with TiO2@polymer, which was then polymerized/solidified by
Šegota et al. used immobilized TiO2 as a PC and applied heterogeneous exposing them to ultraviolet light. The photocatalytic degradation of
photocatalysis as an AOP. The sol–gel dip-coating process was used to model organic pollutants such as MO, MB, and indole in deionized
form thin films of TiO2 on a borosilicate glass substrate, with and water, simulated fresh drinking water, and tap water matrices was
without the inclusion of polyethylene glycol (PEG). The photocatalytic carried out using the painted petri dish and glass jars. During the pho­
activity of TiO2 films was evaluated using UV/vis spectrophotometry, tocatalytic degradation studies, UV-B light was utilized. Solar-powered

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Table 3
A summary of PCs immobilized in the inorganic substrates and its applications.
Year Photocatalyst Substrate Immobilization Light source Main results Ref.
technique

2005 Degussa P25 TiO2 Mesostructured silica Sol-gel / hydrothermal UV-A Photocatalytic treatment of several cyanide- (López-Muñoz et al.,
SBA-15 containing compounds. 2005)
2008 Pt modified TiO2 Natural zeolite Sol-gel technique UV Decolorization 86.2% of MO. (Huang et al., 2008)
2011 BiOCl nano/ AAO & glass Sol-gel combined with UV & Visible Photocatalytic decomposition of RhB dye. (Wu et al., 2011)
microstructures the vacuum air
extraction method
2011 TiO2 & TiO2/PEG Borosilicate glass Sol-gel dip coating UV Degradation of the commercial diazo textile (Šegota et al., 2011)
CR dye
3+
2012 Er : YAlO3/TiO2 SAC Sol- gel method Visible Photodegradation of MO. (Dong et al., 2012)
2012 Cu–Cr layered Copper Electrophoretic Visible Degradation of 2,4,6-trichlorophenol (2,4,6- (Tian et al., 2012)
double hydroxide deposition method TCP), SRB and CR.
2014 TiO2 Alumina ceramics Sol-gel method UV Degrading MB dye (Du et al., 2014)
2015 TiO2 Wall tube, a glass Dip-coating UV Degradation and mineralization when using (Espino-Estévez
tubular reactor phenol and also removal of diclofenac and et al., 2015)
isoproturon
2015 ZnO & Cu/ZnO Glass Sol-gel dip coating UV and visible light Degradation of OII in aqueous solution (Saidani et al.,
2015)
2017 Nano TiO2 Montmorillonite Operated solid diffusion UV Decomposition of MB. (Liang et al., 2017)
process
2018 Bismuth ferrite Stainless steel mesh Anodic electrophoretic Visible (solar) Degradation of ~ 100% of RhB. (Zargazi and
deposition Entezari, 2018)
2018 TiO2 Coconut shell biochar Sol-gel method UV Decolorization of ~ 90% of Reactive Brilliant (Zhang and Lu,
Blue KN-R at 60 min 2018)
2019 TiO2 NPs Zeolite conventional liquid Household compact Degradation of MB. (Saqib et al., 2019)
impregnation fluorescent
2019 TiO2 Zeolite method of saturated UV Degradation of 93.6% of MB. (Liao et al., 2019)
infiltration and
synthesis in situ
2019 TiO2 Ca2MgSi2O7:Ce3+ – UV Decolorization of organic dyes (Sun et al., 2019)
phosphors
2019 Fe-C-TiO2 AC Sol-gel method Visible Decomposition of RhB dye. (Le Thi Thanh et al.,
2019)
2019 Maghemite NPs Porous nickel Auto- clave method UV & natural sunlight Degradation of MO. (Ahmed et al.,
2019)
2019 TiO2 NPs ACF Impregnation- UV Decolorization of 99 % of MB at 180 min (Jain et al., 2019)
hydrothermal method
2019 TiO2 Biochar from Salvinia Sol-gel method and UV Photodegradation of 90% of AO7 at 180 min (Silvestri et al.,
molesta mechanical mixing 2019)
2020 MgO NPs RHS/MFI zeolite Solid-state reaction UV Degradation of 80% of MB. (Albouyeh et al.,
2020)
2020 Co3O4 NPs Bentonite Impregnation method Visible light Removing 100% of 100 mg/L of MGD and Cr (Abdel Salam et al.,
(VI) after 180 and 240 min respectively. 2020)
2020 TiO2 NPs Porous ceramic Dip-coating method UV light Decolorization 83% of RhB in 120 min (De Araujo
Scharnberg et al.,
2020)
2020 TiO2 Sepiolite clay Sol-gel method UV light Degradation 72% of eosin (EA) dye in 150 (De Oliveira et al.,
min 2020)
2020 WO3/TiO2 Zeolite fujasite (FAU) Straight forward UV Degradation of MO. (González
physical mixture and Rodríguez et al.,
calcination treatment 2020)
2020 ZnO nanorod ACFs Sol-gel and UV Photocatalytic degradation of MB. (Luo et al., 2020)
arrays hydrothermal method
2020 TiO2 Al2O3 ceramic Layer by layer through UV Degradation of ~ 100% of RO16 azo dye. (Yildiz et al., 2020)
dipping
2020 rGO/ZnO Zinc Plasma electrolytic UV Photodegradation 55.3% of MB dye at 16 h. (Ebrahimi et al.,
oxidation (PEO) process 2020)
2020 Au NPs-Ag-ZnO Glass Plasma electrolyte Solar simulator Photodegradation of RhB (Thinh et al., 2020)
films oxidation method irradiation
2020 PVC/CdS Glass Sol–gel / spin-coating UV Degradation of MB. (Rouabah et al.,
nanocomposite 2020)
films
2020 (Ag-TiO2) thin Glass Sol–gel / spin-coating Visible Decolorization of MB and MO. (Komaraiah et al.,
films 2020)
2021 ZnO Natural zeolite Ion-exchange and UV Photodegradation 74% and 87% of 2,4- (Iazdani and
(Clinoptilolite tuff) calcination method Dichloroaniline in 180 and 300 min Nezamzadeh-
respectively Ejhieh, 2021)
2021 TiO2 NPs SiO2 microspheres Wet impregnation Solar simulator Degradation of ~ 30% of MO in 375 min and (Marques et al.,
method 65% of paracetamol in 14 h 2021)
2021 TiO2 AC Chemical activation UV 90% decolorization of MB. (Boumad et al.,
method 2021)
2021 TiO2/Ag Bentonite Sol-gel method UV 100% removal of MB and 77% of direct red 80 (Javanbakht and
Mohammadian,
2021)
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Table 3 (continued )
Year Photocatalyst Substrate Immobilization Light source Main results Ref.
technique

2021 TiO2 nanotube TiO2 foils Electrochemical UV 100% degradation of caffeine in ~ 3hr (Marinko et al.,
method 2021)
2021 Fe2O3 NPs @BC ACF Two-step simple Visible light Degradation ~ 95% of antipyrine at 20 hr (Kar et al., 2021)
solution way
2021 Ag/ZnO CoFe2O4 Pechini method UV Removal 100% of IBP at 120 min (Lenzi et al., 2021)
2022 ZnO NiFe2O4/Co3O4 – Natural sunlight Removal 98% of TC at 20 min (Doosti et al., 2022)
2022 TiO2 CoFe2O4 Hydrothermal method All dyes degradation Degradation efficiency of AO (more than (Ibrahim et al.,
under UV and TC 91%), CV (more than 83%), MB (more than 2022)
removal under UV 95%), RhB (58%), Rh-6G (56%), MO (45%),
and visible and TC (75.31%) under UV and (50.4%)
under visible light, all occur at 180 min.
2022 TiO2 Glass and iron beads Spraying liquid UV-A Breakdown 64% of Direct Brown N/B, T/S (Chairungsri et al.,
Direct Fast Red BWS, and Direct Copper Blue 2022)
2B128 at 4 h.
2022 Polypyrrole/nano- GO/membrane – Visible light 100% degradation of MB in 2 hr (Yu et al., 2022)
TiO2
2022 Fe-TiO2 Beta (BEA) zeolite Sol-gel method Visible light (blue 100% TC removal in 90 min (Jalloul et al., 2022)
LED)
2022 Mo-HRTiO2 α-Al2O3 ceramic Dip-coating method UV Removal of IBU, 98% in 80 min (without (Anucha et al.,
ceramic), and 93% in 360 min (with ceramic 2022)
and 3rd cycle)
2022 Ag NPs Biochar extracted Green synthesis method Visible light Elimination efficacy of MB (25 ppm) of up to (Eltaweil et al.,
from C. ambrosioides (impregnation 88.4% at 75 min, and total inhibition of E. coli 2022)
biomass procedure) growth as well as the prevention of C.
albicans, B. subtilis, P. aeruginosa, and K.
pneumoniae with suppression zones of 16, 22,
19, and 18 mm, respectively

Fig. 12. (a) The process for making the altered MOF-5/BiCoO3 composite (Sarwar et al., 2022), (b) Schematic of the structure and Z-scheme mechanism of SnS2COF
PC (Liu et al., 2023).

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photocatalytic degradation of MO and MB was more efficient than UV-B- a suspension system. In comparison to the other two ratios, the one of
powered photocatalytic degradation. There was an 80% degradation TiO2/eggshell (1:9) produced the highest levels of adsorption and
rate in 120 min of UV-B light-irradiated MB solution (6 ppm). In 56.41% photodegradation of MB solution within 130 min. Additionally,
contrast, sunlight-irradiated MB solution degraded 90% in 60 min (Islam pure eggshells showed a significant level of adsorption but no trace of
et al., 2020). The colloidal processing of a heterostructure consisting of photocatalytic destruction. It demonstrated that the eggshell had
TiO2 NPs and lignocellulose nanofibers (LCNFs) produced from biomass exceptionally high adsorption capacity despite merely supporting the
leftovers were reported by Zoilo Gonzalez et al. Adding 4% biotemplate TiO2 for a TiO2/eggshell hybrid PC. It was determined that eggshell
to the formulation boosted the degradation rate and decreased operation offers excellent promise as a catalyst and as a support for PCs (Dzinun
time to eliminate 100% MO from a liquid solution. A regulated thickness et al., 2022). Table 4 presents a summary of the various advanced and
and mass range of 3 to 12 µm and 0.9 to 5.6 mg were obtained by hybrid supports used for photocatalysis.
optimizing the deposition and sintering steps, respectively. The micro­
structures were varied by altering the amount of LCNF in the formulated 5. Conclusion and prospects
suspensions. The suggested method adaptability allows it to be applied
to photocatalytic reactors internal surfaces or as a photocatalytic layer In summary, photocatalysis, a green and environmentally friendly
on their membranes. The processing method could also be used to method, can be potentially employed for the degradation of recalcitrant
immobilize other semiconductors with stronger intrinsic photocatalytic and dangerous organic contaminants. As an advantage, different pho­
characteristics (Gonzalez et al., 2021). Hojamberdiev et al., produced tocatalysts that are active in both UV and visible wavelength ranges
multiphase PCs by simply calcining waste products from the have been developed where the visible range is preferred since it is safer
manufacturing of ammonium molybdate (WU PCs) and combining them and the free and abundant solar energy can be used as the light source.
with WO3 (WW PCs). These PCs were used to eliminate antiviral med­ Among the different photocatalysts, the ones immobilized on solid
icine SARS-CoV-2 (ritonavir and lopinavir) in real and model waste­ supports are preferred economically because they can be separated from
water. Within 15 min of being exposed to visible light, the formed the reaction media more easily compared to the homogenous ones,
multiphase PCs demonstrated 95% efficiency in the photocatalytic though in most cases a lower performance is achieved. Especially,
degradation of ritonavir. In comparison, photocatalytic elimination of developing different categories of supports such as polymers, ceramics,
lopinavir required 60 min of irradiation by visible light to reach 95% glasses, and carbons that can be prepared from both natural and syn­
efficiency. According to the XRD data, the MgFeAlO4, Fe2O3, Fe3O4, thetic sources, has encouraged the researchers to focus more on photo­
MgMoO4, and FeMoO4 crystal phases dominated in the WU PCs, while catalysts for pollutant removal from wastewater. However, this
the MgWO4, Fe2O3, Fe2Mo3O12, and FeWO4 crystal phases predomi­ technology has some drawbacks that need to be overcome to get ready
nated in the WW PCs. Due to the existence of crystalline phases that are for industrialization. For instance, though recyclability is one of the
visible-light active, the WW and WU PCs would capture visible light up advantages of the photocatalysts on solid supports, the immobilization
to 620 nm (Hojamberdiev et al., 2022). As shown in Fig. 12a, a one-pot on/in the supports makes the preparation process more complex and
hydrothermal procedure was used by Bazla Sarwar et al., to create the costly. As presented, different kinds of technology such as castings,
metal–organic framework-5 (MOF-5) based on BiCoO3 (MOF-5/BiCoO3) coatings, CVD, hydrothermal, electrospinning, phase inversion, and
complex. The MOF-5/BiCoO3 composite showed superior photocatalytic electrodeposition are used for immobilization. Especially, the photo­
efficiency of 99.6% for the breakdown of Congo-red (CR) dye at 90 min catalytic activity of the catalyst is strongly influenced by the preparation
under visible light irradiation, when contrasted with pure MOF-5. method and substrate type. The type of support employed, the type and
Because, MOF-5 and BiCoO3 formed a heterostructure that improved concentration of pollutants to be degraded, and the design of the pho­
charge carrier separation. Regarding the MOF-5/BiCoO3 composite, the toreactor should all be taken into account when selecting a deposition
addition of BiCoO3 altered the surface shape, raising the surface area of method. Furthermore, they should be recycled across multiple runs
CR to adsorb and enhancing photocatalytic activity. The hydroxyl and without significant loss in photocatalytic activity. From another point of
superoxide radicals were the main species in the CR breakdown process, view, the responsibilities of the solid supports can be divided into two
according to investigations with radical trapping. The process was more groups, physical like providing the stability and reusability and lowering
cost-effective because the reusability studies showed that the MOF-5/ the cost, and opto-electro-chemical like light absorption, exciton, and
BiCoO3 complex may be utilized successfully for up to 5 cycles (Sarwar free charges generation and transfer. Addition to the type of the support,
et al., 2022). In another work, covalent organic frameworks (COF) and using advanced porous structures like MOFs and COFs that their porosity
SnS2 were combined by Xin Liu et al. to form a Z-scheme van-der-Waals and physical properties can be adjusted easily, the performance of the
heterojunction PC (SnS2COF) for decreasing U (VI) in rare earth refuse photocatalysis would be improved.
wastewater. The van-der-Waals heterojunction synthesis process was Special issues arise when the catalyst is immobilized on support like
straightforward and addressed the issue of no hanging bind in composite the interaction of the support and photocatalysts, the chemical and
materials. In this heterojunction, huge van der Waals contact regions mechanical stability of the support, the optical losses, the active sites for
formed rise-speed electron transport routes. The path of electron running the reactions, and the compatibility of the support with the
transport was reversed during photoexcitation, which aided in the sep­ reactor. As reviewed, improving the stability, lowering the cost, facili­
aration of the photogenerated hole-electron under the influence of the tating the separation, and recyclability are the main advantages of
created electric field, preserved the excellent reducibility of the CB, and immobilizing the photocatalysts on supports that have been focused on
prevented SnS2 from being photo-corrosion. SnS2COF offers a larger in previous researches. While, they suffer from the lack of full contri­
light absorption spectrum, higher e--h+ isolation and transfer efficacy, bution in the photocatalytic process like absorbing the light and
and extra active sites than inorganic-inorganic heterojunction. Thus, it generating the electron-hole pairs, successfully separating the charges
had a greater U (VI) lowering removal rate, exceeding that of its SnS2 and reducing the recombination, transferring the photogenerated
and COF counterparts under UV/visible light by up to 1123.3 mg/g. And charges, and generation of the ROSs that help the degradation of the
in rare earth waste effluent, the U (VI) elimination rate was 98.5%. pollutants. As reviewed, almost all utilized organic and inorganic sup­
Fig. 12b illustrates the structure and Z-scheme mechanism of PC (Liu ports are electrical insulators and have no effect on the electronic pro­
et al., 2023). cess that occurs through photocatalysis. Furthermore, regarding light
Hazlini Dzinun et al. employed a solid-state dispersion technique to absorption, most of the support contributions are related to their
generate PC TiO2/eggshells composite with various ratios. As control transparency and light scattering that provide better photon harvesting
specimens, TiO2 and eggshell PCs were also employed. They used MB while they do not act as the media for the photogeneration of electron-
solution as the targeting pollutant to assess the effectiveness of the PC in hole pairs and free charges. Thus, using photo and electro-active

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Table 4
A summary of PCs immobilization in the others substrates and its applications.
Year Photocatalyst Substrate Immobilization Light source Main results Ref.
technique

2015 (Fe–TiO2) Side-glowing optical PAHD method UV and Degradation of RhB (Lin et al., 2015)
nanocomposite thin fibers (SOFs) visible light
films
2016 TiO2-rGO Side-glowing optical PAHD method UV and Degradation of three pharmaceuticals, including (Lin et al., 2016)
nanocomposites fibers (SOFs) visible light carbamazepine, ibuprofen, and sulfamethoxazole.
2018 TiO2 NPs MBHAp Sol-gel method UV Photodegradation of an MB ~ 93% at 4 hr (Singh et al.,
2018)
2020 TiO2 NPs and acrylate- Plastic Petri dish and Polymerized/solidified Sunlight In deionized water, simulated fresh drinking (Islam et al.,
based photopolymer glass jar by ultraviolet light and UV-B water, and tap water, photocatalytic degradation 2020)
resin irradiation light of model organic contaminants such as MO, MB,
and indole was studied.
2021 TiO2 NPs LCNFs created from Colloidal method UV Decolorization of 100% of MO (Gonzalez et al.,
leftovers 2021)
2022 WO3 Waste products from the Simple calcination Visible light 95% removal of ritonavir at 15 min. and 95% of (Hojamberdiev
manufacturing of method lopinavir at 60 min. et al., 2022)
ammonium molybdate
2022 BiCoO3 MOF-5 One-pot hydrothermal Visible light 99.6% Breakdown of CR at 90 min (Sarwar et al.,
procedure 2022)
2022 TiO2 Eggshells Solid-state dispersion UV Elimination of 56.41% of MB at 130 min (Dzinun et al.,
way 2022)
2023 SnS2 COF Van-der-Waals UV/visible Elimination of 98.5% of U (VI) in rare earth waste (Liu et al., 2023)
heterojunction method light effluent

supports that can participate in all steps of the photocatalysis process – Using advanced light sources with high illumination efficiency,
can be taken into account as a perspective for this field to make them controllable temperature during the operation, and efficient design
more efficient. Though these kinds of supports should be selected to prevent the photon losses, the PCs use in commercial scale would
considering the fabrication methods, the stability, and the cost. Using be accelerated which needs more study.
low-cost semiconductor supports with tuned energy levels such as
semiconductor polymers can be the proper option to overcome this Declaration of Competing Interest
challenge. This review showed that the performance of the solid-
supported photocatalysts would be boosted if the gap between the The authors declare that they have no known competing financial
partial contribution and full contribution of the supports in the process interests or personal relationships that could have appeared to influence
would be covered and new advanced photo and electro-active supports the work reported in this paper.
would be employed.
Regarding the employed light sources, this review showed that Acknowledgements
visible light has focused more recently which is consistent with the
benefit of the free solar light and the required safety. However, for light The authors would like to acknowledge the research department of
sources utilized for lab-scale tests, the electrical power consumption, the Tarbiat Modares University (Research group of phase change materials,
heat generated during the illumination, their design, and cost have been Grant No. IG-39710).
considered. Using advanced light sources like pulsed light (PL) xenon,
the process would be more controllable. References
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