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Photocatalysis: an effective tool for photodegradation of dyes—a review
Article in Environmental Science and Pollution Research · January 2022

DOI: 10.1007/s11356-021-16389-7
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Environmental Science and Pollution Research (2022) 29:293–311
https://doi.org/10.1007/s11356-021-16389-7
REVIEW ARTICLE
Photocatalysis: an effective tool for photodegradation

of dyes—a review
Muhammad Saeed 1 & Majid Muneer 1 & Atta ul Haq 1 & Nadia Akram 1
Received: 11 May 2021 / Accepted: 3 September 2021 / Published online: 14 September 2021
# The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2021
Abstract
The disposal of dye-contaminated wastewater is a major concern around the world for which a variety of techniques are used for
its treatment. The photocatalytic treatment of dye-contaminated wastewater is one of the treatment methods. Semiconductor-
assisted photocatalytic treatment of dye-contaminated wastewater has gained pronounced attention recently. This review outlines
the recent advancements in the photocatalytic treatment of dye-contaminated wastewater. The photocatalytic degradation of dyes
follows three types of mechanisms: (1) dye sensitization through charge injection, (2) indirect dye degradation through oxidation/
reduction, and (3) direct photolysis of dye. Several experimental parameters like initial concentration of dyes, pH, and catalyst
dosage significantly affect the photocatalytic degradation of dyes. The photocatalytic materials can be categorized into three
generations. The single-component (e.g., ZnO, TiO2) and multiple component semiconductor metal oxides (e.g., ZnO–TiO2,
Bi2O3–ZnO) are categorized as first-generation and second-generation photocatalysts, respectively. The photocatalysts dispersed
on an inert solid substrate (e.g., Ag–Al2O3, ZnO–C) are classified as third-generation photocatalysts. Finally, we reviewed the
challenges that affect the photocatalytic degradation of dyes.
Keywords Dyes . Wastewater . Photocatalysts . Photodegradation
Introduction color of the aqueous body imparted by dyes inhibits the

access of sunlight to the interior of the aqueous body
The concern about water pollution has gained much attention (Shen et al. 2021; Di Mauro et al. 2021; Cheng et al.
recently. The water pollution due to dye-contaminated waste- 2021). Dyes have complex structures and are classified into
water is a major part of aqueous pollution. Several industries, different classes based on their molecular structures as di-
e.g., textile dyeing, paper making, food processing, paints, rect dyes, basic dyes, solvent dyes, reactive dyes, and vat
and cosmetics, release their dye-contaminated effluents to dyes (Anwer et al. 2019) as given in Table 1.
the environment resulting in dye-contaminated wastewater These dyes are used in many industries like textile, plastic,
(Zeghioud et al. 2021; Saeed et al. 2020a; Muneer et al. and paper. The textile industry is the largest user of dyes. The
2015). It is estimated that about one million tons of dyes are effluents of industries using dyes, particularly, the textile in-
produced annually around the world. More than 15% of these dustry, contain a high concentration of dyes. The disposal of
dyes are released as pollutants in industrial effluents to the textile industrial effluents to the water stream results in ad-
environment (Atta-Ul-Haq et al. 2019). The dyes released verse aqueous pollution. The color associated with dye-
in wastewater are highly toxic, carcinogenic, and xenobiot- contaminated wastewater is quite noticeable which prevents
ic towards living organisms. The dyes present in wastewa- the penetration of sun rays into the interior of the aqueous
ter badly affect the aqueous ecosystem because the intense system. The azo dyes which are commonly used in the textile
industry are the most harmful. These azo dyes are easily
Responsible Editor: Sami Rtimi water-soluble and difficult to remove or degrade due to their
high solubility, stability, and composition ratio of the aromatic
* Muhammad Saeed rings in their molecular structure. Most of the azo dyes are
[email protected] known to be largely non-biodegradable in aerobic conditions
and they are also photochemically active (Nenavathu et al.
1
Department of Chemistry, Government College University, 2018; Zhang et al. 2012; Xiang et al. 2012; Baranowska
Faisalabad, Pakistan et al. 2002).
294 Environ Sci Pollut Res (2022) 29:293–311
Table 1 Classification of dyes

Dyes
Direct dyes Basic dyes Solvent dyes Reactive dyes Vat dyes
Polyazo compounds Hemicyanine Azo compounds Metallic azo Anthraquinone

Stilbenes Triarylmethane Anthraquinone Triphendioxazine Ingold
Phthalocyanines Cyanine Phthalocyanine Phthalocyanine
Oxazines Thiazine Triarylmethane Formazan
Oxazine Anthraquinone
Acidine
Accordingly, several techniques including biological 3. The AOPs do not produce secondary pollutants as H2O,
and physicochemical techniques have been applied for the CO2, and small inorganic ions are produced as final
treatment of dye-contaminated wastewater. The biological products.
treatment methods including both aerobic and anaerobic
methods are popular techniques because these techniques With the abovementioned merits, the AOPs have attracted
offer the possibility of energy recovery and are practical significant attention from both scientific research and indus-
and comparatively less costly. However, these biological trial processing (Comninellis et al. 2008). The AOPs include
techniques have certain limitations; for example, these heterogeneous and homogeneous chemical and photochemi-
techniques required lengthy time for operation, and are very cal processes; electrochemical oxidations; Fenton processes;
sensitive to experimental conditions (accumulation of am- photolysis under irradiation of gamma rays; photolysis under
monia, concentration of pollutants). As a result, the biolog- ultraviolet rays in combination with H2O2, O3, or catalyst; and
ical treatment techniques fail for the treatment of wastewa- various combinations thereof (Lucas et al. 2009; Lin and
ter containing a high concentration of dyes (Garcia et al. Mehrvar 2018). Table 2 lists some advantages and disadvan-
2020; Lin and Mehrvar 2018). Similarly, the physicochem- tages of some common AOPs.
ical techniques like adsorption, precipitation, reverse osmo- Among all these techniques, heterogeneous
sis, flocculation, anaerobic oxidation, and coagulation are photocatalysis had gained many concerns in recent years,
also not effective because these techniques produce second- since Honda and Fujishima (Honda and Fujishima 1972)
ary pollution due to use of chemicals. Furthermore, these carried out the first photo-catalyzed AOP based on
techniques are costly due to infrastructure and engineering titanium-oxide (TiO2) in 1972. The photocatalysis with
expertise (Jain et al. 2021). Alternately, the advanced oxi- semiconductor metal oxides can also be used for harvesting
dation processes (AOPs) are considered potential and solar energy and the production of hydrogen fuel. It can
promising techniques for the treatment of dye- also be used for the degradation of pollutants other than
contaminated wastewater. The AOPs are more effective dyes like paints, phenols, antibiotics, and pesticides (Ni
for the removal of organic pollutants in comparison to other et al. 2007; Pirilä et al. 2015; Opoku et al. 2017; Rtimi
chemical techniques. It has been reported that AOPs can et al. 2015). Up until now, a rich dictionary of photocata-
remove up to 90% of COD compared to 60% COD removal lytic treatment using semiconductor metal oxides as cata-
efficiency of chemical methods. Similarly, AOPs can re- lysts has been designed. In this technique, the dye-
move up to 96% of colored compounds in comparison to contaminated wastewater is treated with semiconductor
49% removal of colored compounds by conventional fer- metal oxides catalysts under irradiation of light.
rous sulfate treatment (Deng and Zhao 2015; Tomar et al. Several studies have been reported for photocatalytic deg-
2020; Ibrahim et al. 2019). radation of dyes. Figure 2 shows the available literature related
The AOPs have many advantages over other techniques as to photocatalytic degradation of dyes. The percentages given
follows. in Figure 1 show that thiazine dyes are mostly studied dyes.
Methylene blue is an example of thiazine dyes. The Xanthanes
1. The pollutant molecules are mineralized in inorganic sim- dyes are at second position among the studied dyes.
ple and non-toxic molecules rather than transforming Rhodamine B dye is a representative of xanthan dyes.
them to another phase. However, azo dyes are widely used in industries. It has been
2. Due to non-selective nature, the AOPs can be used for the reported that more than 50% of the dyes used in industries are
treatment of wide range of pollutants including organic azo dyes (Ammar et al. 2001; Rauf et al. 2010; Trandafilović
molecules, inorganic molecules, and pathogens. et al. 2017; Huang et al. 2008; Li et al. 2006; Li et al. 2013b;
Environ Sci Pollut Res (2022) 29:293–311 295
Table 2 Main advanced oxidation processes (AOPs)
No. AOP Oxidant Merits Demerits

hierarchy
1 Photocatalyst UV Low energy requirement than other AOPs. Requirement of pre-treatment.

·
O2− No formation of bromate. Loss of catalytic activity with time.
·
OH Use of solar irradiation. Sensitivity to pH.
·
HO2 No off-gas treatment.
2 Fenton’s ·
O2− No formation of bromate. Maintenance costs.
·
reaction OH No off-gas treatment. Works in low pH only.
Less energy-intensive than ozone and UV alone. Requirement of Iron extraction system.
3 O3 O3 The established technique for the treatment of Requirement ozone off-gas treatment.
·
OH wastewater.
Supplementary disinfectant.
4 H2O2/O3 UV Higher generation of OH. Requirement of high cost and energy.
O3 More effective than O3 or UV alone. Formation of bromate.
·
O2− Supplementary disinfectant. Inhibition to penetration of UV light due to
·
OH turbidity.
Contamination due to failure of the UV lamp.
·
5 Cavitation H Less energy consumption. Not scalable for practical application.
·
OH No formation of bromate. Efficiency is low.
Low maintenance cost.
No off-gas treatment.
6 Electron beam eaq No formation of bromate. Requirement of skilled professionals.
H2O2 Minimal effect of turbidity. Not scalable for practical application.
·OH No off-gas treatment. Energy and cost intensive.
·H Can help in disinfection.
7 H2O2/UV H2O2 No formation of bromate. Inhibition to penetration of UV light due to
UV No off-gas treatment is required. turbidity.
·
O2− Can oxidize more MTBE compared to H2O2 or UV Contamination due to failure of the UV lamp.
·OH alone. Absorption of UV by interfering compounds.
8 O3/UV O3 Higher production of OH than H2O2/UV. Inhibition to penetration of UV light due to
UV More effective than UV or O3 alone. turbidity.
·
O2− Contamination due to failure of UV lamp.
·OH Formation of bromate.
Comparatively costly.
He et al. 2013; Liang et al. 2017; Du et al. 2017; Rochkind greater than the material’s bandgap resulting in the excitation
et al. 2015). of an electron from the valence band to the conduction band of
semiconductor metal oxide which leads to the formation of
pair of electron and positive hole. The photoinduced positive
General mechanism of photocatalytic hole and electron interact with dye molecules and produce
degradation of dyes exciting dye, Dye*. Then, the unstable excited dye, Dye*,
converts to anionic (Dye −) or cationic (Dye+) radicals.
Dyes have been extensively used as model pollutants for the Finally, these anionic and cationic radicals spontaneously de-
evaluation of the photocatalytic activity of the metal oxide compose to degradation products. Figure 2 explains the
catalysts. photodegradation of dyes through the sensitization
The mechanism of photocatalytic degradation of dyes has mechanism.
been classified into three types (Isac et al. 2019; Pingmuang The indirect mechanism is well known and consists of ab-
et al. 2017; Pavithra et al. 2019): sorption of photons with energy equal to or greater than the
material’s resulting in the excitation of an electron from the
I. Dye sensitization through charge injection valence band to the conduction band of semiconductor metal
II. Indirect dye degradation through oxidation/reduction oxide which leads to the formation of pair of electron and
III. Direct photolysis of dye positive hole. These photoinduced positive holes and elec-
trons undergo a series of reactions and finally produce hydrox-
According to the dye sensitization mechanism, the first step yl (OH) radicals. The hydroxyl radicals are the strong non-
consists of the absorption of photons with energy equal to or selective oxidizing agent that degrades the organic pollutants
Figure 3 Mechanism of photocatalytic treatment of pollutants
Figure 1 The number of reports on photocatalytic degradation of dyes visible light as well. Ordinary sunlight consists of about 45%
visible light, and 10% ultraviolet light in addition to other
and leads to complete mineralization (Ng et al. 2019; Al- types of radiation (Adeel et al. 2021).
Mamun et al. 2019; Chun et al. 2013). This mechanism can A wide range of materials like metal oxides, magnetic
be summarized in the form of redox reactions as below and in cored dendrimer, metal-organic frameworks (MOFs), quan-
the form of Figure 3. tum dots, carbon-based nanostructures, and other materials
The direct photolysis of dye molecules is a slow process have been extensively used as photocatalysts for the degrada-
and is independent of the catalyst. tion of dyes in wastewater (Zhang et al. 2014; Bhattacharyya
et al. 2004; Jaiswal et al. 2015; Zou et al. 2016; Liu et al. 2018;
Metal oxide þ Light→hþ −
Metal oxide þ eMetal oxide Jung et al. 2016; Mosleh et al. 2016).
hþ
Metal oxide þ H2 O→OH
e−Metal oxide þ O2 →O−2

Kinetics of photocatalytic degradation
O−2 þ H2 O→OH
Dye molecules þ OH→Degradation products As the photocatalytic degradation of organic pollutants is
based on degradation of the pollutants by reaction of highly
An efficient photocatalyst for the treatment of wastewater reactive OH radicals. These OH radicals are produced by re-
can be used in the presence of not only ultraviolet light but action of positive holes and electrons that are induced in va-
lence band and conduction band of the photocatalyst by irra-
diations. Hence, the rate of reaction can be expressed as (P:
pollutant; I: irradiation; kr: rate constant)
Rate of reaction∝Pad O2 ðadÞ I
OR
Rate of reaction∝Paq O2 ðadÞ I
Under constant irradiation and partial pressure of oxygen,

the rate equations change as
Rate of reaction ¼ k r Pad
OR
Figure 2 Mechanism of photodegradation of dyes by sensitization of Rate of reaction ¼ k r Paq
dyes
These two rate equations describe the Langmuir- Adeel et al. have reported a decrease in performance of Co–
Hinshelwood and Eley-Rideal mechanism respectively ZnO catalyzed photodegradation of methyl orange with an
(Saeed and Ilyas 2013, 2016a, b, 2017c; Wu et al. 2010; increase in initial concentration of methyl orange (Adeel
Haghseresht and Lu 1998; Jiao et al. 2015). The concentration et al. 2021). It was found that photodegradation decreased
of adsorbed dye can be expressed in the form of adsorption from 77 to 42% with an increase in initial concentration from
isotherm. Various adsorption isotherms including Langmuir, 100 to 400 mg/L. Similarly, 72, 85, and 93%
Temkin, and Freundlich can be used for this purpose. On the photodegradation of methylene blue have been reported with
other hand, the rate equation with aqueous concentration of 0.0063, 0.015, and 0.0188M as initial concentration of meth-
dye can be given by following equations for 1st order and 2nd ylene blue with Ag–Fe3O4 as catalyst respectively (Saeed
order respectively (Zeghioud et al. 2019b; Shahid et al. 2020a; et al. 2020b). Saeed et al. have reported 80, 44, 29, and 19%
Iqbal et al. 2020; Shahid et al. 2020b; Naseem et al. 2019; photodegradation of methyl orange using 50, 100, 150, and
Begum et al. 2020). 200 mg/L as initial concentration of methyl orange in the
presence of ZnO as catalyst respectively (Saeed et al.
½Po
ln ¼ k1t 2017a). The photocatalytic performance of Pt/Al2O3 towards
½P t photodegradation of rhodamine significantly depended on the
1 1 initial concentration of rhodamine B dye. It was found that
¼ k 2t þ
½Pt ½P 0 about 39, 45, and 65% photodegradation of rhodamine B
achieved using 300, 200, and 100 mg/L as initial concentra-
tions of rhodamine B dye respectively (Saeed et al. 2015). The
increased concentration of dye prevents the access of photon
to the surface of catalysts resulting in decreased catalytic per-
Factors affecting the degradation of dyes formance. The decrease in the rate constant of ZnO–TiO2
catalyzed photodegradation of methyl orange with an increase
Several factors like concentration of dyes, pH of the solution, in initial concentration of methyl orange (0.0149, 0.010, and
catalyst dosage, intensity of light, and intermediate species 0.0072 per minute with 100, 200, and 300 mg/L, respectively)
affect the performance of photocatalytic degradation of dyes. shows the effect of the initial concentration of dye on photo-
The effects of these factors on the dye degradation perfor- catalytic performance for photodegradation (Saeed et al.
mance will be discussed in the following subsections. 2021b). The dependence of photodegradation of acid red
dye on the initial concentration of dye was also investigated
(Bhandari et al. 2006). The increase in the concentration of
Effect of dye concentration acid red from 20 to 40 mg/L decreases the rate of degradation.
A higher concentration of dye imparts an intense color to the
The concentration of dyes greatly affects the performance of solution which prevents the photons from reaching the cata-
photocatalytic degradation of dyes. The dyes molecules have lyst surface and ultimately stops the production of ROSs. It
various functional groups. The abundance and nature of the has been shown that the formation of ROSs in lower concen-
functional groups present in a dye affect the interaction be- trations is the main reason for the decrease in the rate of deg-
tween dye and photocatalyst substrate. As different dyes have radation with an increase in the initial concentration of dyes.
different types of functional groups, therefore the optimal con- Furthermore, the photocatalytic performance is also affected
centration of dye depends on the nature of the dye. Generally, by the presence of inorganic metal ions in the solution. The
the rate of a reaction increases with an increase in the concen- increase or decrease in photocatalytic performance due to met-
tration of reactants but the performance of photocatalytic deg- al ions depends on the nature of dye molecules. Generally, the
radation of dyes decreases with an increase in the initial con- surface of the photocatalyst becomes a slightly positive charge
centration of dyes due to the following reasons (Zhang et al. due to the adsorption of metal ions on the catalyst. As a result,
2016a): the anionic dyes interact easily with catalyst leading to en-
hancement in degradation performance. On the other hand,
1. As the concentration of dye is increased, the ratio of the the degradation performance of cationic dyes decreases due
active sites of the photocatalyst to the dye molecules to repulsion between dye and positively charged catalyst
decreases. surface.
2. As the concentration of dye is increased, the ratio of OH
radicals to dye molecules decreases. Effect of pH
3. The increased concentration of dye results in absorption
of light rather than its penetration to the surface of the The pH of the dye solution is also an important factor that
catalyst. affects the photodegradation performance. The pH of dye
solution significantly affects the electrostatic interactions be- (Saeed et al., 2018). Prabakaran and Pillay have reported pH 9
tween catalyst, dye molecules, and ROSs in the degradation as optimum pH for N-doped-ZnO catalyzed photodegradation
process (Zangeneh et al. 2015; Shukla and Srivastava 2016). of methylene blue dye as given in Figure 4 d (Prabakaran and
Umar and Halim studied the pH dependence of the photocat- Pillay 2019).
alytic activity of TiO2 (Umar and Halim 2007). They reported
the highest catalytic oxidation performance of TiO2 at pH 2. Effect of catalyst dose
The effects of pH on Ag–TiO2 catalyzed photodegradation of
rhodamine B and methylene blue have also been investigated The mass of photocatalyst also significantly affects the perfor-
(Saeed et al. 2019c). It was found that the photodegradation of mance of photocatalytic degradation of pollutants. Generally, the
both dyes was higher at pH 10. Siddique and his co-workers performance of photocatalytic degradation of pollutants increases
have reported the highest photodegradation of rhodamine B with an increase in catalyst dose up to a certain limit, and then
dye over bismuth ferrite catalyst at neutral pH (Siddique et al. further increase in catalyst dose decreases the rate of reaction. As
2019). Nisar et al. have also reported neutral pH as optimum the amount of catalyst is increased, more electron-pairs are
pH for ZnO–rGO catalyzed photodegradation of methylene formed which leads to an increase in the rate of reaction.
blue dye (Nisar et al. 2021). However, further increase in catalyst dose increases the turbidity
Adeel et al. have investigated the effect of pH on Co–ZnO of the reaction mixture thereby decreasing the penetration of light
catalyzed photodegradation of methyl orange as given in to the surface of the catalyst. It results in a decrease in the rate of
Figure 4 a. The highest catalytic performance was observed reaction with a higher catalyst dose (Zangeneh et al. 2015). Lu
at pH 4 (Adeel et al. 2021). In another study as given in et al. reported the effect of the amount of CdS/graphene catalyst
Figure 4 b, the highest photodegradation of rhodamine B on photodegradation of rhodamine B dye (Lü et al. 2014). They
dye has been achieved at pH 10 in the presence of Ag– observed that photodegradation capacity increased from 49 to
Co3O4 as catalyst (Saeed et al. 2018). Figure 4 c shows that 86% with increasing the catalyst dose from 200 to 1800 mg/L
the photocatalytic performance of Ag–MnO towards and then further increase in catalyst dose decreased the
photodegradation of rhodamine B dye was highest at pH 12 photodegradation. Recently, the photodegradation of methylene
Figure 4 Effect of pH on photocatalytic degradation of dyes a methyl orange/CoZnO, b rhodamine B/Ag–Co3O4, c rhodamine B/Ag/MnO, d methylene
blue/N-doped-ZnO
blue has been reported with 0.05, 0.1, 0.15, and 0.2 g of ZnO– photocatalysts (Tan et al. 2015; Xie et al. 2014). The intensity
rGO photocatalyst. The optimum catalyst dose was found as 0.1g of radiation plays an important role in photocatalytic perfor-
(Nisar et al. 2021). Adeel et al. have reported the effect of Co– mance. Muruganandham et al. (Muruganandham and
ZnO dosage on photodegradation of methylene blue dye (Adeel Swaminathan 2006) have investigated the effect of intensity
et al. 2021). They have reported 0.011, 0.0152, 0.0074, and of light on photodegradation of reactive yellow dye. They
0.0054 per minute as rate constant under identical conditions have reported that increase intensity of light from 16 to 62W
with 0.01, 0.05, 0.1, and 0.15 g Co–ZnO respectively. They caused 33% more degradation of dye under similar experi-
reported that the rate of reaction first increased with catalyst dose mental conditions. The increase in intensity of light enhances
and then decreased with further increase in catalyst dose. the penetration and access to the surface of catalyst which
Similarly, the degradation of para-nitrophenol (PNP) has been ultimately increases the production of charge carriers.
reported with 0.05, 0.15, 0.25, 0.35, and 0.45 g/L of rGO/ZrO2/ Similarly, Bhati and co-workers (Bhati et al. 2010) have in-
Ag3PO4 nanocomposite as catalyst under similar reaction condi- vestigated the effect of light intensity on photodegradation of
tions (Anwer and Park 2018). The highest degradation (97%) Fast Green dye. They have reported a twofold increase in the
was achieved with a catalyst dose of 0.25 g/L. The higher catalyst rate of reaction with increase in light intensity from 10 to 70
doses cause a decrease in degradation efficiency. The increased mWcm−2. Laouedj and Ahmed (2011) have reported an in-
scattering and reduced penetration of light were reported as major crease in rate of reaction up to light intensity of 80 J cm−2 and
factors for decreased degradation efficiency at higher catalyst decrease in rate of reaction with 90 J cm−2. The decrease in
dosages. rate of reaction with higher light intensity is due to thermal
effect due to rise in temperature.
Adsorption of dyes
Adsorption of dyes on the surface of photocatalysts signifi- Classification of photocatalysts

cantly affects the performance of photocatalytic degradation
of dyes. The adsorption of dyes on the surface of catalysts is This study is focused on metal oxides as photocatalysts for the
due to binding affinities and electrostatic interactions between degradation of organic pollutants. The metal oxide
the catalyst surface and dye molecules. The adsorption of photocatalysts have been classified as first-generation
dyes on the surface of the catalysts is a fundamental step photocatalysts, second-generation photocatalysts, and third-
in photodegradation of dyes. Both the strong adsorption generation photocatalysts as given in Figure 5.
and weak adsorption of dyes result in decreases in photo-
catalytic performance of the catalysts. Strong adsorption First-generation photocatalysts
causes the poisoning of the catalysts while weak adsorption
does lead to attachment of dyes to the surface of catalyst for The single-component metal oxides, metal phosphates, metal
photodegradation reaction. High adsorption of dyes on the nitrides, and metal sulfides are termed first-generation
surface of catalysts results in coverage of the surface with photocatalysts. These photocatalysts are characterized by va-
dyes which inhibits the access of photons to the surface of lence band and conduction band separated by an energy gap
catalyst. Hence, strong adsorption decreases the photocata- called bandgap energy. The photocatalytic reaction consists of
lytic performance. According to Sabatier principle, the absorption of photons with energy equal to or greater than the
binding of the dye molecules to the surface of the catalysts material’s resulting in the excitation of an electron from the
should be neither strong nor weak for best photocatalytic valence band to the conduction band of semiconductor metal
activity. The moderate is beneficial due to synergy between oxide which leads to the formation of pair of electron and
photocatalysis and adsorption for excellent positive hole. These photoinduced positive holes and elec-
photodegradation performance (Ajmal et al. 2014; Anwer trons undergo a series of reactions and finally produce hydrox-
and Park 2018; Nguyen-Phan et al. 2011). yl (OH) radicals. The hydroxyl radicals are the strong non-
selective oxidizing agent that degrades the organic pollutants
Intensity of light and leads to complete mineralization (Intarasuwan et al. 2017;
Yang et al. 2005).
The performance of photocatalytic degradation of dyes signif- Titanium dioxide (TiO2) is a common and most famous
icantly depends on the energy provided by irradiation of light. example of a first-generation photocatalyst. Fujishima and
As a result of energy provided by irradiation, positive holes Honda employed titanium dioxide (TiO2) as a photocatalyst
and electrons are formed in the valence band and conduction for the water-splitting reaction for the first time in 1972
band of the photocatalysts. The formation of positive holes (Fujishima 1972). Later, the photocatalytic application of
and electrons can only be produced when the energy of radi- TiO2 has been extended towards the degradation of organic
ations is greater than or equal to the band gap energy of the pollutants, solar cells, and hydrogen production (Teets and
Figure 5 Classification of photocatalysts
Nocera 2012). However, TiO2 cannot be employed as a photocatalysts (Wang et al. 2010; Vinodgopal and Kamat
photocatalyst under visible light irradiation. TiO2 has a wide 1995; Pouretedal et al. 2009; Daneshvar et al. 2004). ZnO is
bandgap (~ 3.2 eV), therefore is used as a catalyst only under also among the metal oxides widely used as photocatalysts for
UV irradiation (250–350 nm). Despite this limitation, TiO2 photodegradation of organic pollutants in wastewater due to
has been used as photocatalysts for a wide range of reactions its ability to absorb a wide radiation spectrum, low cost, and
due to its ready availability, high stability, and non-toxic na- high stability. The lattice and surface defects present in ZnO
ture. TiO 2 has been used as a photocatalyst for the greatly affect the photocatalytic activity of ZnO towards the
photodegradation of cationic dyes, anionic dyes, and dyes photodegradation of organic pollutants. The photodegradation
with different types of chromophores (Atarod et al. 2016). of acid red, acid orange, and methyl in the presence of ZnO
For example, TiO2 has been used for the degradation of cat- under UV radiation has been reported (Liu et al. 2013).
ionic dyes like rhodamine B, crystal violet, basic violet 2, Table 3 shows a literature survey of TiO2 and ZnO cata-
methyl red, methylene blue, and malachite green (Kyzas lyzed photodegradation of dyes.
et al. 2015; Fil et al. 2013). The first-generation photocatalysts (single-component
TiO2 exists in two allotropic forms: (1) anatase phase, (2) metal oxides) have a band gap >3 eV. This large bandgap is
rutile phase. The anatase phase and rutile phase have the a drawback because these catalysts require ultraviolet light for
bandgaps 3.2 eV and 3.0 eV respectively. Although the ana- the excitation of electrons from the valence band to the con-
tase phase has a wide bandgap compared to the rutile phase, duction band. Furthermore, these metal oxides have a single
yet it is preferred as a photocatalyst as it has a high affinity for valence band and conduction band. As a result, the probability
adsorption of dyes. Furthermore, it is more crystalline and has of recombination of photoinduced positive holes and electrons
higher photocatalytic activity due to comparatively slow re- is high. Hence, the positive holes and electrons recombine
combination of photoinduced positive holes and electrons and rather than secondary reactions that lead to the formation of
valence band and conduction band (Huo et al. 2014; Kim et al. OH radicals and ROSs. Ultimately, the over photocatalytic
2014). Other metal oxides like ZnO, NiO, SnO2, ZnS, ZrO2, activity of single-component metal oxides is lower (Tahir
MnO2, and Co2O3 have been also used as first-generation and Amin 2015; Li et al. 2015). In response to the drawback,
Table 3 Literature survey of

TiO2 and ZnO catalyzed No. Catalyst/ Dye Time (min) Activity (%) Reference
photodegradation of dyes light
1 TiO2/UV Reactive black 5 300 64 (Aguedach et al. 2005)

2 TiO2/UV Patent blue VF 80 93 (Saquib et al. 2008)
3 TiO2/UV Fast green FCF 80 93 (Saquib et al. 2008)
4 TiO2/UV Methyl blue 120 98 (Lachheb et al. 2002)
5 TiO2/UV Congo red 120 95 (Lachheb et al. 2002)
6 TiO2/UV Crocein orange 120 98 (Lachheb et al. 2002)
7 TiO2/UV Alizarin 120 99 (Lachheb et al. 2002)
8 TiO2/UV Methyl red 120 99 (Lachheb et al. 2002)
9 TiO2/UV Acid orange 2 120 98 (Chen et al. 2001)
10 TiO2/Visible Acid orange 7 60 75 (Chen et al. 2001)
11 ZnO/Visible Reactive red 4 480 85 (Neppolian et al. 2002)
12 ZnO/UV Reactive blue 4 180 29 (Neppolian et al. 2002)
13 ZnO/UV Reactive yellow 17 300 40 (Neppolian et al. 2002)
14 ZnO/UV Reactive red 2 60 49 (Neppolian et al. 2002)
15 ZnO/UV Rhodamine 6G 180 98 (Kansal et al. 2007)
16 ZnO/UV Methyl orange 120 98 (Tian et al. 2012)
17 ZnO/UV Rhodamine B 80 98 (Nagaraja et al. 2012)
18 ZnO/UV C.I. Yellow 23 60 90 (Behnajady et al. 2006)
19 ZnO/UV Acid red 14 120 70 (Daneshvar et al. 2004)
20 ZnO/Visible Acid brown 14 120 85 (Sakthivel et al. 2003)
doping has emerged as a potential solution leading to the photocatalysts, the single-component metal oxides, should
development of second-generation materials. have different band gaps and the bandgap of resulted
second-generation photocatalyst, the heterojunction,
Second-generation photocatalysts should lie in the visible region. The band gaps are of
two types: direct bandgap and indirect bandgap. The di-
The major drawback of single component first-generation rect bandgap is desirable in the construction of
photocatalysts is their wide separation between the va- heterojunctions. The highest energy level of VB and low-
lence band and conduction (bandgap >3 eV) and fast re- est energy level of CB align with one another concerning
combination of photoinduced positive holes and electrons momentum in direct bandgap materials (Mahadadalkar
leading to lowered catalytic activity. Various modifica- et al. 2018; Wang et al. 2014a; Etacheri et al. 2013). In
tions have been implemented to overcome the cited draw- heterojunction photocatalysts, the photo-induced electrons
backs. These modifications include the construction of are confined in the conduction band of one metal oxide
heterojunction, loading of co-catalyst, sensitization with while the positive holes are confined in the valence band
quantum dots, and doping of metal oxide with metal and of another metal oxide as shown in Figure 4. This results
non-metals. The construction of heterojunctions, the in separation between electrons and holes which leads to a
second-generation photocatalysts, is the best alternative decrease in the rate of recombination of charge carriers
for active photocatalysts towards photodegradation of or- and ultimately generates active centers for degradation
ganic pollutants (Zhang et al. 2010a). A heterojunction is of pollutants. The heterojunctions absorb radiation in the
a multi-component photocatalyst that exhibits significant- visible region (λ ≥ 420 nm) due to narrowband gaps com-
ly improved catalytic activity by suppressing the recom- pared to single component first-generation metal oxide
bination of charge carriers (Luo et al. 2021; Liu et al. catalysts (Yan et al. 2016).
2021; Sun et al. 2021). It consists of stacking up two The heterostructures or heterojunctions are not only
first-generation photocatalysts with different bandgaps. used as photocatalysts for the degradation of pollutants
The blend of multiple heterojunctions is said to be a but also used for other applications like in solar cells,
heterostructure. It is necessary that the first-generation diodes, transistors, lasers, fuel cells, and more. The
photocatalytic applications of heterojunctions in wastewa- Ag3VO4/g-C3N4 heterojunction was attributed to its opti-
ter treatment and the generation of hydrogen and oxygen mal band edge positions. It was reported that the potential
as fuel in fuel cells are two important applications of of the valence band of Ag3VO4 (2.24 eV) efficiently gen-
heterojunction. Several heterojunctions have been report- erated the hydroxyl radicals (·OH). Similarly, the conduc-
ed in the literature. The graphitic carbon nitride (g-C3N4)– tion band potential of C3N4 (−0.73 eV) efficiently gener-
based heterojunctions, the second-generation ated the superoxide radicals (·O2−). The Ag3VO4/g-C3N4
photocatalysts, have attracted attention due to the easy heterojunction exhibited higher catalytic performance due
synthesis and low cost of graphitic carbon nitride (g- to the formation of the reactive ROSs. Table 4 shows a
C3N4). Theoretically, the bandgap of second-generation comprehensive literature survey of various second-
photocatalyst should be < 2.8 eV. The graphitic carbon generation photocatalysts used for the degradation of dyes.
nitride (g-C3N4) has a bandgap energy of 2.65 eV, which Second-generation photocatalysts have also some limita-
makes it a suitable candidate for second-generation tions as discussed below (Munshi et al. 2017; Cole-
photocatalysts. Therefore, the graphitic carbon nitride (g- Hamilton 2003):
C3N4)–based heterojunctions have been studies extensive-
ly as photocatalyst for the degradation of organic pollut- 1. The separation and recovery of the second-generation
ants. Wang et al. (2014) have reported Ag3VO4/g-C3N4 photocatalysts require equipment and energy which in-
heterojunction as a second-generation photocatalyst for creases the cost of wastewater treatment with second-
the treatment of a textile effluent (Wang et al. 2014b). generation photocatalysts. For example, high temperature
The photocatalytic activity of Ag3VO4/g-C3N4 or pressure is needed for membrane filtration. High tem-
heterojunction was evaluated for photodegradation of perature or pressure may disintegrate the photocatalyst
crystal violet, basic fuchsine, and malachite green dyes. assembly.
The Ag3VO4/g-C3N4 heterojunction exhibited 75%, 96%, 2. The second-generation photocatalysts can be completely
and 97% activity towards visible light–assisted removed from the aqueous medium which leads to
photodegradation of crystal violet, basic fuchsine, and leaching of the catalysts to the aqueous medium.
malachite green dye within 2.5, 2.5, and 1 h respectively. 3. The recycled second-generation photocatalysts have a
The enhanced visible light–assisted catalytic activity of certain loss in photocatalytic activity.
Table 4 Literature survey of

second-generation photocatalysts No. Heterojunction Dye Time (min) Activity (%) Reference
used for photodegradation of dyes
under visible irradiation 1 BiVO4/Ag3VO4 Methyl red 40 78 (Yan et al. 2016)
2 BiVO4/Ag3VO4 Methylene blue 40 70 (Yan et al. 2016)
3 BiVO4/Ag3VO4 Rhodamine B 20 96 (Yan et al. 2016)
4 BiVO4/Ag3VO4 Methyl violet 40 95 (Yan et al. 2016)
5 Bi2O2CO3/Bi2S Rhodamine B 180 98 (Wang et al. 2013)
6 BiOI/ZnTiO3 Rhodamine 6G 180 82 (Reddy et al. 2013)
7 Bi2S3/TiO2/RG Methylene blue 90 99 (Liu et al. 2017)
8 SnO2/g-C3N Rhodamine B 80 99 (He et al. 2015)
9 Bi2O2CO3/BiO Rhodamine B 15 99 (Liang et al. 2014)
10 Co3O4-g-C3N4 Methyl orange 180 99 (Han et al. 2014)
11 WO3/NiWO Methylene blue 400 92 (Mohamed et al. 2014)
12 BiPO4/C3N4 Methyl orange 120 96 (Li et al. 2014)
13 BiOI/Ag3VO4 Crystal violet 120 85 (Wang et al. 2015)
14 BiOI/Ag3VO4 Malachite green 120 92 (Wang et al. 2015)
15 BiOI/Ag3VO4 Basic fuchsin 120 97 (Wang et al. 2015)
16 g-C3N4/BiOI Methylene blue 60 99 (Di et al. 2014)
17 g-C3N4/BiOI Rhodamine B 50 99 (Di et al. 2014)
18 g-C3N4/Ag3VO4 Malachite green 120 97 (Wang et al. 2014b)
19 g-C3N4/Ag3VO4 Basic fuchsin 150 95 (Wang et al. 2014b)
20 g-C3N4/Ag3VO4 Crystal violet 150 75 (Wang et al. 2014b)
Third-generation photocatalysts used colloidal silica as a binder for the immobilization of Ag

on TiO2. The prepared composite was used as the catalyst for
The photocatalysts immobilized on various solid inert supports the photodegradation of methylene blue. Organic binders can
or substrates are called third-generation photocatalysts. The also be used for the immobilization of catalysts on solid sup-
third-generation photocatalysts can be easily separated from ports. The organic binders strongly immobilize the catalysts
the reaction mixture resolving the problem of post-separation. on supports compared to inorganic binders. However, inor-
The third-generation photocatalysts are comprised of boron ni- ganic binders are preferable due to their hydrophilic nature.
trides, carbon nitrides, metal oxides, metallic nanocrystals, and The hydrophilic nature of inorganic binders assists the solid-
many others deposited on various substrates. Some of the third- liquid interaction. For example, the binding strength of the
generation photocatalysts are given in Table 5. epoxy binder, an organic binder, is sevenfold higher than the
Two approaches are used for the deposition of boron nitrides, binding strength of potassium and sodium silicates binders,
carbon nitrides, metal oxides, and metallic nanocrystals on var- the inorganic binders, for deposition of TiO2 on a glass sub-
ious substrates: the binder-through and binder-less approaches. strate. Although the epoxy binder has higher binding strength,
Organic and inorganic binders are used for the deposition it is not suitable for application in wastewater treatment due to
of catalytic substance on support in the binder-through ap- its hydrophobic nature (Park et al. 2010). Furthermore, the
proach. A wide range of third-generation photocatalysts can susceptible nature of organic binders to photooxidation under-
be prepared by deposition of first- and second-generation ma- mines long-term stability. Similarly, methylcellulose has been
terial on various support by binder-through approach. reported as an organic binder for the immobilization of Ag/
However, the use of binders causes a decrease in active cen- TiO2 composite on a glass substrate (Habibi and Nasr-
ters and surface area of the catalysts. Gao et al. have used the Esfahani 2008). The catalyst prepared with methylcellulose
binder-through approach for immobilization of Ag on binder showed 90% degradation of methyl orange within
fluorine-doped tin oxide substrate (Gao et al. 2015). They
Table 5 A literature survey of

third-generation photocatalysts No. Catalyst (light) Dye Time Activity Reference
(min) (%)
1 Al/ZnO (UV) Methyl orange 180 89 (Wang et al. 2012)

2 Si/TiO2 (UV) Methylene blue 240 89 (Gao and Liu 2005)
3 FTO/WO3–ZnO Methylene blue 60 82 (Zheng et al. 2015)
(UV)
4 Steel/TiO2–WO3 Methylene blue 240 91 (Zhan et al. 2013)
(UV)
5 TiO2 film (UV) Methyl orange 900 99 (Arconada et al. 2010)
6 Ni/TiO2 (UV) Methyl orange 120 85 (Zhang et al. 2010b)
7 FTO/BiOBr (Vis) Methyl orange 300 48 (Liu et al. 2014)
8 Ti/BiOCl (Vis) Rhodamine B 180 94 (Li et al. 2013a)
9 Ti/BiOCl (UV) Rhodamine B 120 98 (Li et al. 2013a)
10 Bi/BiOCl (Vis) Rhodamine B 210 98 (Zhang et al. 2016b)
11 FTO/BiOCl–TiO2 Rhodamine B 180 99 (Shen et al. 2017)
(UV)
12 Glass/P–TiO2 (Vis) Butyl benzyl 240 99 (Mohamed and Aazam
phthalate 2013)
13 Ce/TiO2 (UV) Basic blue 180 90 (Rapsomanikis et al.
2014)
14 Ag/Al2O3 Methylene blue 120 92 (Saeed et al. 2019b)
15 Ag/MnO2 Rhodamine B 120 88 [6]
16 Ag/TiO2 Rhodamine B 120 90 (Saeed et al. 2019c)
17 Pt/Al2O3 Methyl orange 120 80 (Saeed et al. 2017b)
18 Ag/Co3O4 Rhodamine B 120 93 (Saeed et al., 2018)
19 Ag/Co3O4 Methyl orange 120 87 (Saeed et al. 2019a)
20 Ag/Co3O4 Crystal violet 120 92 (Saeed et al. 2021a)
150 min; however, the recycling of the catalyst showed a of the catalysts from reaction mixture can be overcome by use
significant loss in catalytic activity due to its instability. of magnetically separable semiconductors photocatalysts. The
The drawbacks like hydrophobicity engaged reactive sites, and magnetically separable semiconductor photocatalysts can be
low surface area associated with third-generation photocatalysts easily recovered from reaction mixture using a strong magnet.
prepared by binder-through approaches can be overcome by the The doping of semiconductor metal oxides with iron or iron
preparation of photocatalysts by binder-less approaches. The oxide leads to the development of photocatalysts that can be
binder-less approaches include direct hydrolysis, electrophoretic easily separated from reaction mixture with a magnet. The re-
deposition, spray pyrolysis, chemical vapor deposition, and many search on semiconductors like ZnO and TiO2 doped with Fe or
more. The photocatalysts prepared by binder-less methods offer oxides of Fe has got much attention recently (Kiwi and Rtimi
higher reaction sites and surface area. Shen et al. (2017) have 2021). The oxides of iron like Fe2O3 (magnetite, hematite,
reported the deposition of BiOCl/TiO2 composite on FTO glass maghemite) and FeOOH (geothite) can absorb visible light;
by binder-less approach. The prepared catalyst was employed for hence, these oxides can be used for development of visible
visible light–assisted photodegradation of rhodamine B dye. They light–driven photocatalysts (Bandara et al. 2001). However,
reported a 99% degradation of rhodamine B dye within 3h. Fe2O3 is not suitable for photocatalytic applications due to its
Although the binder-less approach is superior to the binder- photo-corrosion. The photo-corrosion of Fe2O3 arises due to its
through approach, yet it has some limitations as well. A multi- reaction of photo induced positive holes as given below.
step approach is required for the deposition of multi-component
heterojunction catalysts on substrates. For instance, the deposition 2Fe2 O3 þ 12hþ
VB →4FeðaqÞ þ 3O2
3þ
of heterojunction on a substrate by the hydrothermal deposition

method consists of multiple and complex chemical routes. Alternately, FeOx has got attention for the development of
Similarly, a single component photocatalyst can be deposited on corrosion-resistant photocatalysts for photodegradation of pol-
the substrate in a single cycle by electrophoretic or chemical vapor lutants in aqueous medium. Kiwi and Rtimi (2021) have re-
methods; however, multiple cycles are needed for deposition of ported as extensive study on FeOx and ferrite-based magnetic
heterojunction on these approaches. These limitations in turn offer photocatalysts for enhanced photodegradation of pollutants and
opportunities for researchers to find better binder-less approaches selected bacteria. Similarly, Mangayayam and co-workers
that can practically overcome these undermining factors. (Mangayayam et al. 2017) have used Ag–TiO2–FeOx as cata-
Zeghioud et al. (2019a) have reported high-power impulse mag- lyst for inactivation of E. coli bacteria under irradiation of sun-
netron sputtering (HiPIMS) as new technique for the preparation light. They attributed the enhanced photocatalytic performance
of CuxO–TiO2 catalyst. They used the prepared material as cata- to synergistic effect between Ag and Fe in Ag–TiO2–FeOx.
lyst for degradation of reactive green dye. They studied the effect
of various species including inorganic ions, oxidants, and Degradation mechanism
scavengers on photodegradation of dyes. Rtimi et al. (2015) have
developed an efficient photocatalyst by deposition of TiO2 on The mechanism of photocatalytic degradation consists of the
polyethylene by sputtering technique. The sputtering of TiO2 on formation of electrons and holes in the energy bands of
polyethylene was accomplished by magnetron sputtering in the photocatalyst under irradiations. Then, these photo-induced
presence of oxygen. The third-generation photocatalysts are con- holes and electrons generate radicals by reactions with reduc-
sidered superior to metal oxide nano catalysts. The nano catalysts tants and oxidants, respectively. Finally, the radicals react
are associated with many issues. The most significant issue with with molecules of the pollutants and produce CO2, H2O, and
nano catalysts is the recovery of the catalysts from the reaction other small inorganic molecules by degradation of the pollut-
mixture. ants. It has been reported that the formation of electrons and
holes is the key step in the photocatalytic degradation of pol-
lutants. Therefore, several mechanisms have been proposed
Challenges in photocatalysis for the formation and separation of electrons and holes by
the transport of these carriers across the heterojunction.
Although the photocatalytic treatment of dye-contaminated However, there is no clear way to show how the photocata-
wastewater has been researched extensively during the last lytic reactions proceed in an actual reactor. Generally, indirect
decades, yet the real applications face some challenges and methods such as electron spin resonance, radical trapping, and
limitations, as highlighted below. radical scavenging tests have been used for the investigation
of degradation mechanisms (Xu et al. 2015; Ma et al. 2017;
Recovery of photocatalysts Dariani et al. 2016). For precise and detailed knowledge of
degradation mechanism, it is needed to develop a direct meth-
The recovery of the catalysts from reaction mixture is a signif- od for verification of pathway of charge migration and iden-
icant issue associated with catalysis. The problem of recovery tification sites on catalyst surface for degradation process. The
precise and detailed knowledge of degradation mechanisms degradation of pollutants consists of excitation of an electron
will facilitate the development of better photocatalytic appli- from the valence band to the conduction band of the catalysts
cations for the photodegradation of pollutants. under the irradiation of light having energy equal to or greater
than the bandgap of the photocatalyst. However, the accurate
Intermediate species determination of the bandgap energy of the photocatalyst (par-
ticularly the composite material) is quite difficult. Hence, it
Ideally, the water, carbon dioxide, and other small inor- would be difficult to select an appropriate light source due to
ganic molecules should be the final products of photo- the ambiguous bandgap energy of the photocatalyst. The se-
catalytic degradation of organic pollutants. As the or- lection of an inappropriate light source may lead to inefficient
ganic dyes have large and complex structures, so the photocatalytic performance, waste of energy, and unnecessary
photocatalytic degradation of these dyes may lead to cost of treatment processes.
the formation of several small intermediates/segments
during degradation reactions. Usually, the formation of
intermediates in photocatalytic treatment is not moni-
tored. It is possible that the intermediates formed may Conclusions
be more harmful than the original dyes. For example,
catechol has been reported as a by-product in the pho- Herein, we reviewed the photocatalysts used for
tocatalytic degradation of phenol. The catechol is more photodegradation of dyes in the aqueous medium. The
toxic for animals than phenol itself (Mena et al. 2017; photocatalysts used have been categorized into three genera-
Chen et al. 2002; Bui et al. 2010; Naeher et al. 2007). tions. The single-component photocatalysts like ZnO and TiO2
Therefore, intensive investigation of the nature and fate are categorized as first-generation photocatalysts. The first-
of intermediates formed during photocatalytic treatment generation photocatalysts are inefficient for the
is needed. photodegradation of dyes due to their wide band gaps and
interfacial charge recombination. The multiple component
Electron–hole recombination semiconductor metal oxides like ZnO–TiO2 and Bi2O3–ZnO
are categorized as second-generation photocatalysts. The
As discussed, the formation and recombination of elec- second-generation photocatalysts are efficient towards
trons and positive holes affect the performance of pho- photodegradation of dyes due to their visible light utilization,
tocatalytic degradation of organic pollutants. The improved charge separation, and high quantum yields. The
photoluminescence analysis is commonly used for the evalu- photocatalysts dispersed on an inert solid substrate like Ag–
ation of the rate of recombination of electrons and positive Al 2 O 3 and ZnO–C are classified as third-generation
holes. In this technique, the intensity of light emitted from photocatalysts. Furthermore, the underlying mechanism of
the photocatalyst is inversely related to the rate of recombina- photocatalytic degradation of dyes has been elaborated on in
tion of electrons and positive holes. The emission of radiations this review article. The effects of various experimental param-
from the photocatalyst occurs by the deactivation of electrons eters like the initial concentration of dyes, pH of the solution,
from the conduction band to the valence band of the and catalyst dosage on the performance of photocatalytic deg-
photocatalyst. However, if the photocatalyst absorbs or scat- radation have been discussed. Finally, the challenges associated
ters light due to the presence of some component like quantum with photocatalytic degradation of dyes have been highlighted.
dots and graphene oxide, then the intensity of emitted radia-
tion would not provide accurate and precise information about
the rate of recombination of electrons and positive holes. Availability of data and materials Available on request
Similarly, the radical scavenging and open-circuit
Code availability Not applicable
potentiometry techniques are also used for the measurement
of the rate of recombination of electrons and positive holes. Author contribution Muhammad Saeed is the principal author. He has
None of these techniques provide absolute and correct infor- drafted the manuscript.
mation (He et al. 2017). Therefore, it is needed to develop Majid Muneer has contribution in drafting and reviewing of the
manuscript.
methods for the prediction of the accurate rate of recombina-
Atta ul Haq has contributed to writing the manuscript.
tion of electron and positive holes. Nadia Akram has contributed to reviewing the manuscript.
Bandgap Declarations
As discussed in the “General mechanism of photocatalytic Conflict of interest The authors declare no competing interests.
degradation of dyes” section, the mechanism of photocatalytic
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Photocatalysis: an effective tool for photodegradation of dyes—a review

Article in Environmental Science and Pollution Research · January 2022

Muhammad Saeed Majid Muneer

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Photocatalysis: an effective tool for photodegradation

Keywords Dyes . Wastewater . Photocatalysts . Photodegradation

Introduction color of the aqueous body imparted by dyes inhibits the

Table 1 Classification of dyes

Polyazo compounds Hemicyanine Azo compounds Metallic azo Anthraquinone

Table 2 Main advanced oxidation processes (AOPs)

No. AOP Oxidant Merits Demerits

1 Photocatalyst UV Low energy requirement than other AOPs. Requirement of pre-treatment.

Figure 3 Mechanism of photocatalytic treatment of pollutants

e−Metal oxide þ O2 →O−2

Rate of reaction∝Pad O2 ðadÞ I

Rate of reaction∝Paq O2 ðadÞ I

Under constant irradiation and partial pressure of oxygen,

Rate of reaction ¼ k r Pad

Adsorption of dyes on the surface of photocatalysts signifi- Classification of photocatalysts

Figure 5 Classification of photocatalysts

Table 3 Literature survey of

1 TiO2/UV Reactive black 5 300 64 (Aguedach et al. 2005)

Table 4 Literature survey of

Third-generation photocatalysts used colloidal silica as a binder for the immobilization of Ag

Table 5 A literature survey of

1 Al/ZnO (UV) Methyl orange 180 89 (Wang et al. 2012)

of heterojunction on a substrate by the hydrothermal deposition

References dyes. Toxicological and Environmental Chemistry 88:35–44.

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