Review Article

ISSN 1998-0124 CN 11-5974/O4

2019, 12(5): 955–972 https://doi.org/10.1007/s12274-019-2287-0

Photocatalysts for degradation of dyes in industrial effluents:

Opportunities and challenges
Hassan Anwer1,§, Asad Mahmood1,§, Jechan Lee2,§, Ki-Hyun Kim1 (), Jae-Woo Park1 (), and Alex C. K. Yip3
1
Department of Civil and Environmental Engineering, Hanyang University, 222 Wangsimni-ro, Seoul 04763, Republic of Korea
2
Department of Environmental and Safety Engineering, Ajou University, Suwon 16499, Republic of Korea
3
Department of Chemical and Process Engineering, University of Canterbury, Christchurch 8041, New Zealand
§
Hassan Anwer, Asad Mahmood, and Jechan Lee contributed equally to this work.

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019
Received: 22 September 2018 / Revised: 27 December 2018 / Accepted: 3 January 2019

ABSTRACT
Discharging dye contaminants into water is a major concern around the world. Among a variety of methods to treat dye-contaminated water,
photocatalytic degradation has gained attention as a tool for treating the colored water. Herein, we review the recent advancements in
photocatalysis for dye degradation in industrial effluents by categorizing photocatalyst materials into three generations. First generation
photocatalysts are composed of single-component materials (e.g., TiO2, ZnO, and CdS), while second generation photocatalysts are composed
of multiple components in a suspension (e.g., WO3/NiWO4, BiOI/ZnTiO3, and C3N4/Ag3VO4). Photocatalysts immobilized on solid substrates are
regarded as third generation materials (e.g., FTO/WO3-ZnO, Steel/TiO2-WO3, and Glass/P-TiO2). Photocatalytic degradation mechanisms,
factors affecting the dye degradation, and the lesser-debated uncertainties related to the photocatalysis are also discussed to offer better
insights into environmental applications. Furthermore, quantum yields of different photocatalysts are calculated, and a performance evaluation
method is proposed to compare photocatalyst systems for dye degradation. Finally, we discuss the present limitations of photocatalytic dye
degradation for field applications and the future of the technology.

KEYWORDS
photocatalyst, dye wastewater, degradation mechanism, performance evaluation

1 Introduction
Recently, water contamination by dye discharges from various
industries (e.g., paper making, textile dyeing, cosmetics, paints, food
processing, etc.) has attracted significant attention due to hazards to
public health and ecosystems [1]. The current global colorant market
is 32 billion USD and is estimated to increase to 42 billion USD
by 2021 [2]. The annual total production of synthetic dyes is over
700,000 tons [3, 4]. More than 15% of these synthetic colorants are
discharged into water annually [5]. The dye contaminants in water
are toxic, carcinogenic, and xenobiotic [6].
Dyes are classified based on chromophore structure into reactive
dyes, solvent dyes, basic dyes, direct dyes, and vat dyes, as shown in
Fig. 1. Only 47% of synthetic dyes are biodegradable [7]. Conventional
wastewater treatment technologies (e.g., adsorption, coagulation/
flocculation, and precipitation) generally require a long operation
time and produce secondary sludge, which is costly to dispose of [7].
Advanced oxidation processes (AOPs) are effective techniques to
degrade organic compounds by producing reactive oxygen species  
(ROS). Hydroxyl (·OH) and superoxide (·O2−) radicals are well known Figure 1 Classification of dyes based on chromophore structure.
ROSs with oxidation potentials of 2.7 and −2.3 eV, respectively [8].
The oxidation potential of organic compounds varies from −1 to AOPs and of a conventional chemical treatment was conducted [10].
2 eV. Due to the difference in potential between ROS and organic The chemical treatment eliminated 60% of the chemical oxygen
species, an organic species entering a reactor containing ROS will demand (COD) from wastewater, while AOP removed 90% of COD.
either gain or lose electrons immediately and transform into two Moreover, AOP removed 95% of colored compounds, whereas the
or more smaller constituent parts [9]. The high redox potential of conventional ferrous sulfate treatment removed 49% of the colored
ROS provides the basis for the superior removal performance of compounds from dye wastewater. Some AOP technologies are listed
photocatalytic systems. A comparison of the degradation potential of in Table 1 along with their generated ROSs [11].
Address correspondence to Ki-Hyun Kim, kkim61@hanyang.ac.kr; Jae-Woo Park, jaewoopark@hanyang.ac.kr
956 Nano Res. 2019, 12(5): 955–972

Table 1 Major AOP technologies and brief descriptions thereof [8]

Order AOP technology Oxidant hierarchy Advantages Disadvantages
1 O3 ·OH Established technology for remediation. May require ozone off-gas treatment.
O3 Supplementary disinfectant.
2 O3/H2O2 ·OH Effective for high concentrations of MTBE in water. Potential for bromate formation.
·O2− Supplementary disinfectant. May require removing excess H2O2.
O3 Established technology for remediation.
Established technology for remediation.
H2O2 More effective than O3 or H2O2 alone.
3 O3/UV ·OH Supplementary disinfectant. Energy and cost intensive.
·O2− More effective than O3 or UV alone. Potential for bromate formation.
O3 Generates more ·OH than H2O2/UV. UV light penetration is inhibited by turbidity.
UV UV lamp failure can potentially contaminate water.
4 H2O2/UV ·OH Bromate formation suppressed. UV light penetration is inhibited by turbidity.
·O2− Can oxidize more MTBE compared to UV or H2O2 alone. UV lamp failure can potentially contaminate water.
UV No off-gas treatment required. Interfering compounds can absorb UV.
H2O2
5 Electron beam ·OH Bromate formation suppressed. No full-scale application exists.
eaq Bromate might be reduced. Energy and cost intensive.
·H Can help in disinfection. Requires skilled professionals for operation.
H2O2 Minimal effect of turbidity.
No off-gas treatment.
6 Cavitation ·OH Minimal maintenance cost. No full-scale application exists.
·H Less energy usage than UV. Low efficiency and supplementary oxidants are
No bromate formation. required.
No off-gas treatment.
7 Photocatalyst/UV ·OH No bromate formation. Pre-treatment required.
·O2− Less energy consumption than other AOPs. Loss of photocatalyst activity with usage.
UV Can utilize solar irradiation. Performance might be pH dependent.
HO2· No off-gas treatment.
8 Fenton’s reaction ·OH No bromate formation. Iron extraction system required.
·O2− Less energy intensive than ozone and UV alone. Works in low pH only.
No off-gas treatment needed. Higher maintenance costs.

Among AOPs, photocatalysis has emerged as a strong candidate

for practical field applications. The process does not rely on the use
of any chemicals or gases that could increase the risk of secondary
pollution. In addition, the oxidation capacity of the photocatalytic
process is sufficient to break down resilient pollutants into their
corresponding simpler forms [12]. The basic mechanism of
photocatalytic degradation is illustrated in Fig. 2. Photocatalysis
starts with the transport of contaminants from the surroundings to
the photocatalyst surface. The dye compounds are first adsorbed
onto the surface on which oxidation–reduction reactions occur.
These redox reactions are forced by photogenerated electrons in the
conduction band (CB) and holes in valence band (VB). The products
are then desorbed from the surface and transported back into the
fluid phase [13]. The reactions responsible for the photocatalytic
dye degradation can be summarized as follows
Photocatalyst + hν → hVB+ + eCB (1)
hVB
+
+ eCB → Energy (heat) (2)
H2O + h VB
+
→ ·OH (hydroxyl radical) + H +
(3)
O2 + eCB → ·O2 (superoxide radical) (4)
·OH + Pollutant → Intermediates → H2O + CO2 (5)  
Figure 2 Basic degradation mechanism of photocatalysis.
·O2 + Pollutant → Intermediates → H2O + CO2 (6)
A number of studies have established the notion that photocatalysis that azo dyes belong to the largest group of industrial colorants,
is a robust and effective way to degrade colorants in water, as shown representing more than 50% of all dyes and pigments. However,
in Table 2 and Fig. 3 [14–22]. The photodecomposition of dyes available only 7% of the total publications addressed the remediation challenges
in previous literature is listed in Table 2. The corresponding percentage associated with azo dye-contaminated wastewater [24].
of each in the literature is also presented in Fig. 3. It is evident that Despite many efforts, the fundamental principles of how
thiazine dyes are the most researched group of colorants, which photocatalysis works are still not well understood [25]. The present
includes methylene blue. Xanthanes form the second highest-studied article reviews different photocatalytic dye degradation technologies
group of dyes, which are dominated by rhodamine B [23]. Note for treating wastewater. To this end, important photocatalytic

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Table 2 Photodecomposition of dyes in wastewater [23] more reliable and robust processes. Finally, we establish a perfor-
mance evaluation method and assess the feasibility of various
Order Dye class UV light Visible light Percentage
source source photocatalytic dye degradation systems for practical applications.
Overall, this review will help provide a better understanding of
1 Anthraquinone 238 390 1.3%
photocatalysis for dye degradation in industrial wastewater and
2 Azo dyes 1,285 2,006 6.8% highlight the current challenges for commercializing the process.
3 Natural dyes 187 303 1.0%
4 Thiazine 7,496 13,471 43.4% 2 Nanomaterials for photocatalysis
5 Triarylmethanes 1,439 2,758 8.7%
A variety of photocatalysts (e.g., metals, metal oxides, semiconductors,
6 Xanthanes 5,625 12,244 37.0%
carbon-based nanostructures, quantum dots, metal–organic frame-
7 Others 303 557 1.8% works (MOFs), magnetic cored dendrimer, and other materials)
have been extensively studied for degradation of dyes in wastewater
[26–32]. Among the various materials, we will focus on metal oxide
photocatalysts classified into three generations, as shown in Fig. 4.
Each generation of material will be discussed in detail in the
following subsections.

2.1 First generation photocatalysts

 
Figure 3 Major segments indicating the number of publications on the
photodecomposition of colorants in industrial effluents.
degradation mechanisms and operation parameters affecting dye
degradation are discussed in detail. In addition, we highlight some
doubts associated with photocatalytic phenomena that need further
investigation. A clear understanding of the photocatalytic phenomena
could help us design more active and selective photocatalysts for
First generation photocatalysts are single component oxides, sulfides,
nitrides, and phosphates. These materials have a CB–VB pair and
rely on electron–hole generation for their operation [33, 34]. The
materials absorb UV or visible light, promoting electrons from the
VB to the CB with the formation of holes that oxidize dye molecules.
Titanium dioxide (TiO2), one of the most famous photocatalysts,
was first investigated for the water splitting reaction [35]. Later, its
applications have been extended to hydrogen production, solar cells,
pollutant photooxidation, and dye removal in liquid and gaseous
phases [36]. However, the TiO2-photocatalytic systems are operated
only under UV irradiation (250–350 nm) due to their large band
gap (~ 3.2 eV). Despite this limitation, TiO2 is widely used due to
its non-toxic nature, high chemical stability, and ready availability
[37]. Anionic dyes, cationic dyes, and dyes with different types of
chromophores are degraded using TiO2. For example, basic cationic
dyes with –NH3+ or NR2+ functional groups (e.g., basic violet 2, crystal
violet, and Rhodamine B) are used for dyeing substrates with negatively
charged end groups [38]. Malachite green, methylene blue, basic
violet, and methyl red are well-known cationic dyes that are degraded

 
Figure 4 The three generations of photocatalysts.

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958 Nano Res. 2019, 12(5): 955–972

using TiO2 [39]. Basic dyes with a large molecular weight are susceptible
to attack by ·OH and ·O2− radicals generated by TiO2. Once the dye
compounds are in proximity to the photocatalyst surface, they are
decomposed by the high potential ROS on the surface. Note that
TiO2 exists in two major phases (anatase and rutile). The anatase
phase has a larger band gap (3.2 eV) than the rutile (3.0 eV);
however, anatase is preferred due to its better adsorptive affinity
for dyes. Additionally, anatase is also favorable to lower charge
recombination rates and higher photocatalytic activity due to its
highly crystalline nature [40, 41].
Other than TiO2, ZnO, ZrO2, ZnS, SnO2, and NiO have been
considered as single component photocatalytic materials [42–45].
Among them, ZnO has been widely employed as a photocatalytic
material for decolorization of wastewater, because of its chemical
stability, low cost and larger light absorption spectrum than that of
TiO2. The effect of defects in the ZnO lattice on the degradation
of anionic dyes was investigated [46]. Methyl orange, acid orange,
and acid red were degraded using ZnO under UV illumination
(365 nm). The observed degradation rates for the dyes followed the
order: acid red > acid orange > methyl orange. ZnO catalysts that
had a number of higher defect states exhibited better dye adsorption
but a low photocatalytic activity.
The drawback of the first generation photocatalysts like TiO2,
ZnO, and ZrO2 is their large band gap (ranging from 3 to 5 eV) that
requires UV irradiation for electron excitation. These materials
consist of a single CB and a single VB. Multiple energy bands are
absent, increasing the probability that electrons fall back into the
VB without generating ROSs. As recombination of charge carriers
reduces the generation of reactive species for dye degradation, the
overall performance of the photocatalytic system decreases [47, 48].
In response to the drawback, doping has emerged as a potential
solution leading to the development of second generation materials.
A summary of TiO2 and ZnO mediated photocatalytic systems for
dye degradation are given in Table 3.
2.2 Second generation photocatalysts
Heterojunction materials were developed to improve the
photocatalytic performance of the first generation materials [49].
The multi-component photocatalytic systems showed significant
improvement by suppressing charge carrier recombination [50]. In
heterojunction photocatalysts, electrons are confined in the CB of
one semiconductor, and the holes are confined in the VB of the
other. This spatial distance between the charge carriers overwhelms
the recombination, thereby generating active sites at which degradation
of dye molecules occurs [51]. The second generation photocatalytic
materials show light absorbance in the visible region (λ ≥ 420 nm)
accompanied with lower band gap energies than first generation
photocatalytic materials. Representative second generation photo-
catalysts are summarized in Table 4. Among the second generation
photocatalysts, graphitic carbon nitride (g-C3N4) has attracted
attention due to its low cost and facile synthesis. Theoretically, the
band gap energy of a visible light active photocatalyst should be
less than 2.8 eV. The band gap energy of g-C3N4 is 2.65 eV, which
makes it a visible light-active photocatalyst [52]. Thus, g-C3N4-based
photocatalysts have been studied for dye degradation. A heterojunction
composite of Ag3VO4/g-C3N4 was reported for the treatment of a
textile effluent [53]. Performance of the composite was evaluated
for degradation of three colorants: malachite green, basic fuchsine,
and crystal violet. Under visible irradiation (420 nm < λ < 700 nm),
97% of malachite green was degraded in 1 h with the composite.
The rates of degradation of basic fuchsine and crystal violet were
slower than that of malachite green. Within 2.5 h, the composite
degraded 96% of basic fuchsine and 75% of crystal violet. The high
performance of the Ag3VO4/g-C3N4 photocatalyst was attributed to
its optimal band edge positions. The potential of the CB of C3N4
was sufficiently high (−0.73 eV) to generate superoxide radicals
(·O2−). Similarly, the VB of Ag3VO4 (2.24 eV) has the potential to
generate hydroxyl radicals (·OH). The high performance of the
Ag3VO4/g-C3N4 photocatalyst was likely due to the formation of the
reactive ROSs.
2.3 Third generation photocatalysts
Extra equipment and energy required for separating the second
generation photocatalyst from the suspension systems increase
the cost of the effluent treatment. Moreover, the separation process
cannot completely remove the catalyst, leading to leaching of the

Table 3 First generation titania and zinc oxide photocatalysts for dye degradation
Order Photocatalyst Dyes Light source Time (min) Degradation (%) References
1 TiO2 Acid orange 7 Vis 60 75 [108]
2 TiO2 Acid orange 2 UV 120 98 [109]
3 TiO2 Methyl red UV 120 99 [110]
4 TiO2 Alizarin UV 120 99 [110]
5 TiO2 Crocein orange UV 120 98 [110]
6 TiO2 Congo red UV 120 95 [110]
7 TiO2 Methyl blue UV 120 98 [110]
8 TiO2 Fast green FCF UV 80 93 [111]
9 TiO2 Patent blue VF UV 80 93 [111]
10 TiO2 Reactive black 5 UV 300 64 [112]
11 ZnO Acid red 14 UV 210 70 [45]
12 ZnO Acid brown 14 Solar light 120 85 [113]
13 ZnO C.I. Yellow 23 UV 60 90 [114]
14 ZnO Rhodamine B UV 80 98 [115]
15 ZnO Methyl orange UV 120 98 [116]
16 ZnO Rhodamine 6G UV 180 98 [117]
17 ZnO Reactive yellow 17 UV 300 40 [118]
18 ZnO Reactive red 2 UV 60 49 [118]
19 ZnO Reactive blue 4 UV 180 29 [118]
20 ZnO Reactive red 4 Solar light 480 85 [118]

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catalyst into water [54]. Loss in photocatalytic activity of the recycled
composite is another problem associated with separation techniques.
For instance, membrane filtration requires high pressure or tem-
perature that disintegrates the photocatalyst assembly. Metallic
photocatalysts can attach to organic functional groups of membranes,
which could lead to leaching problems [55]. Thus, studies have
recently focused on immobilizing photocatalysts on different substrates
or supports. The third generation photocatalyst materials provide a
viable solution to post-separation problems. Representative third
generation photocatalysts are listed in Table 5. Semiconductor, metallic
nanocrystals, metal oxides, carbon/boron nitrides, and many other
composites are deposited on different substrates for photocatalytic
dye degradation. Two approaches used for immobilization of first
and second generation photocatalysts onto different substrates are
the binder-through and binder-less approaches [56]. The binder-
through approach uses organic and inorganic binders for the
formation of films on the catalyst surface. Using this approach, a
wide range of first and second generation materials can be deposited
onto substrates. However, deposition using binders leads to a decrease
in surface area and active sites for photooxidation of contaminants.
The binder-through approach was used by Fengquan et al. for
depositing a TiO2/Ag composite onto a fluorine-doped tin oxide
(FTO) substrate [57]. The authors used colloidal silica binder and
a spin coating technique for fabricating a fine film on the FTO
glass. The photocatalytic activity of the composite was evaluated
by monitoring a methylene blue degradation pattern under UV
illumination. The composite showed good performance in the
suspension form; however, the photocatalyst film needed a long
operation time (3 h) to degrade 90% of the pollutant after
deposition.
Organic binders were also used for immobilizing photocatalysts
on catalyst support. The average binding strength of organic binders
is higher than that of inorganic binders; however, the latter is more
hydrophilic, which is essential for solid–liquid interactions. The
binding strength of organic epoxy binder was seven times higher
than that of inorganic sodium and potassium silicate binders
for depositing a TiO2 photocatalyst on a glass substrate. However,
the epoxy binder was more hydrophobic than the silicate binders,

Table 4 Second generation photocatalysts for dye degradation

Order Photocatalyst Dyes Light source Time (min) Degradation (%) References
1 WO3/NiWO4 Methylene blue UV 400 92 [119]
2 Co3O4-g-C3N4 Methyl orange Vis 180 99 [120]
3 Bi2O2CO3/BiOI Rhodamine B Vis 15 99 [121]
4 SnO2/g-C3N4 Rhodamine B Vis 80 99 [122]
5 Bi2S3/TiO2/RGO Methylene blue Vis 90 99 [123]
6 BiOI/ZnTiO3 Rhodamine 6G Vis 180 82 [124]
7 Bi2O2CO3/Bi2S3 Rhodamine B Vis 180 98 [125]
8 BiVO4/Ag3VO4 Rhodamine B Vis 20 96 [51]
9 BiVO4/Ag3VO4 Methylene blue Vis 40 70 [51]
10 BiVO4/Ag3VO4 Methyl red Vis 40 78 [51]
11 BiVO4/Ag3VO4 Methyl violet Vis 40 95 [51]
12 g-C3N4/Ag3VO4 Crystal violet Vis 150 75 [53]
13 g-C3N4/Ag3VO4 Basic fuchsin Vis 150 95 [53]
14 g-C3N4/Ag3VO4 Malachite green Vis 150 97 [53]
15 g-C3N4/BiOI Rhodamine B Vis 50 99 [126]
16 g-C3N4/BiOI Methylene blue Vis 60 99 [126]
17 BiOI/Ag3VO4 Basic fuchsin Vis 120 97 [127]
18 BiOI/Ag3VO4 Malachite green Vis 120 92 [127]
19 BiOI/Ag3VO4 Crystal violet Vis 120 85 [127]
20 BiPO4/C3N4 Methyl orange Vis 120 96 [128]

Table 5 Third generation materials for dye degradation

Order Photocatalyst Dyes Light source Time (min) Degradation (%) References
1 Steel/TiO2-WO3 Methylene blue UV 240 91 [129]
2 FTO/WO3-ZnO Methylene blue UV 60 82 [130]
3 Si/TiO2 Methylene blue UV 240 89 [131]
4 Al/ZnO Methyl orange UV 180 98 [132]
5 FTO/BiOBr Methyl orange Vis 300 48 [133]
6 Ni/TiO2 Methyl orange UV 120 85 [134]
7 TiO2 film Methyl orange UV 900 99 [135]
8 FTO/BiOCl-TiO2 Rhodamine B Vis 180 99 [60]
9 Bi/BiOCl Rhodamine B Vis 210 98 [136]
10 Ti/BiOCl Rhodamine B UV 120 98 [137]
11 Ti/BiOCl Rhodamine B Vis 180 94 [137]
12 Ce/TiO2 Basic blue UV 180 90 [138]
13 Glass/P-TiO2 Butyl benzyl phthalate Vis 240 99 [139]

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960
making it unsuitable for dye wastewater applications [58]. The
organic binder was susceptible to photooxidation, undermining the
long-term stability. Methyl cellulose was used as an organic binder
to deposit a TiO2/Ag composite on a glass substrate [59]. The
photocatalyst film degraded more than 90% of methyl orange in
150 min. However, no reusability test was performed to assess the
stability of the photocatalyst film. The drawbacks of binder-through
approaches (e.g., low surface area, engaged reactive sites, and decreased
hydrophilicity) could be overcome using binder-less approaches.
These methods (e.g., chemical vapor deposition, spray pyrolysis,
electrophoretic deposition, and direct hydrolysis) use fewer chemical
reagents and solvents. Photocatalyst films deposited by binder-less
methods offer higher surface area and reaction sites, which are
engaged with binders in binder-through deposition methods [56].
The binder-less method was used to deposit a BiOCl/TiO2 composite
on FTO glass [60]. The composite film was used to degrade
Rhodamine B dye under visible irradiation (λ > 420 nm). Dye
molecules were adsorbed and degraded on the film surface, resulting
in 99% dye removal in 3 h. Based on a degradation performance
perspective, the binder-less methods are superior to the binder-through
methods. However, deposition of multi-component heterojunction
photocatalysts on substrates is challenging as it requires a multi-step
synthesis approach. For instance, the use of chemical vapor or
electrophoretic methods is recommended to achieve the deposition
of a single photocatalyst in one cycle. Subsequently, two or more
deposition cycles are required to fabricate a heterojunction based
on these approaches. Similarly, hydrothermal deposition involves
complex chemical routes and multiple steps to assemble a hetero-
junction on a substrate. These limitations in turn offer opportunities
for researchers to find better binder-less approaches that can
practically overcome these undermining factors.
3 Photocatalytic degradation mechanisms
The general mechanism of photocatalysis involves photo-absorption
and excitation of electrons from the VB to the CB of a semiconductor
material. Based on the band gap theory, researchers have proposed
several mechanisms for electron–hole formation, their transfer
across the valence, conduction, and forbidden energy bands,
and their recombination [61]. Some well-accepted mechanisms
for photocatalytic dye degradation are discussed in the following
subsections.
3.1 Heterogeneous pairing
A heterogeneous combination of semiconductors (e.g., SnO2/ZnO,
WO3/NiWO4, and Sb2S3/TiO2) was introduced to suppress electron–
hole recombination for effective dye degradation [49]. The formation
of multiple junctions in such materials changes the energy levels
where electrons can reside. The proposed mechanism suggested
that electrons shift from the CB of a material having a high Fermi
level to the CB of a second material having a low Fermi level. By
contrast, holes move from the VB of one material having a low Fermi
level to the VB of a second material having a high Fermi level [62].
A heterogeneous junction between g-C3N4 and BiOClBr was
synthesized and investigated for its degradation potential for the
photooxidation of Rhodamine B [63]. Results showed that 95% of
the dye was degraded in 1 h under visible light. The band gaps of
g-C3N4 and BiOClBr are 2.67 and 2.14 eV, respectively. Under visible
light, the excited electrons in the CB of g-C3N4 were transported
into the CB of BiOClBr. On the other hand, the holes were
transferred from the VB of BiOClBr to the VB of g-C3N4 (Fig. 5).
This heterogeneous coupling separates charge carriers from the
junctions to effectively degrade Rhodamine B. Other examples of
semiconductor pairs that operate using this mechanism are listed in
Table 6. All heterojunction composites showed a staggered band
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Nano Res. 2019, 12(5): 955–972
 
Figure 5 Heterogeneous pairing between g-C3N4/BiOClBr for Rhodamine B
degradation under visible irradiation (reprinted with permission from Ref. [63],
© Elsevier B.V. 2014).
gap alignment. In this context, the VB of the first semiconductor
material is at a higher potential than that of the second semiconductor
material. On the other hand, the CB of the second material occupies
a higher potential than that of the first material. Charge-carrier
generation and separation by photocatalysts with straddled and
broken band gaps were reported. The staggered type of band alignment
is appropriate for charge transfer among the three types of band gap
alignments [64]. Heterogeneous coupling with the staggered band
gap was used for molecular fusion synthesis of a graphene quantum
dot (GQD)/TiO2 composite [65]. The composite was activated
in visible illumination (λ > 420 nm). The graphene quantum dots
acted as photosensitizers and injected electrons into the CB of TiO2.
Additionally, holes accumulated in the VB of GQDs. The ROS
generated via charge carriers effectively degraded 95% of methyl
orange in 2 h. However, TiO2 or GQDs without the heterojunction
coupling degraded only 20% of methyl orange. This indicates the
advantages of additional energy bands and charge separation in
heterojunction coupling.
3.2 p–n junctions
A p–n junction between two semiconductors leading to charge
carrier separation is described in Fig. 6. The VB and CB of silver
phosphate (Ag3PO4) and cerium oxide (CeO2) have a straddling
band gap alignment. The band edge positions are determined by
Mulliken electronegativity theory, which is the geometric mean of
the electronegativity of the constituent atoms. Once the heterojunction
is formed between two semiconductors, the electron transfer occurs
until equilibrium. This establishes an internal electric field across
the p–n junction. These electrostatic forces result in effective
separation of charge carriers, thereby reducing the recombination
rate and improving the catalytic performance [66]. Well-known
p–n junction-based degradation mechanisms are listed in Table 7.
Most composite materials following the p–n junction mechanism
are designed to operate under visible irradiation, which is useful for
practical applications. As shown in Table 7, the band gap alignment
in p–n junction photocatalysts is overlapping type, which changes
after a connection is established between two materials. This band
gap offset was studied using a BiOI/Bi2Sn2O7 nanocomposite [67].
The BiOI with a lower Fermi level acted as a p-type semiconductor,
whereas Bi2Sn2O7 (with a higher Fermi level) acted as an n-type
semiconductor. After a contact was established, the electrons
moved from n-type to p-type. This raised the potential of the BiOI
energy bands, resulting in the formation of a virtual staggered band
alignment. At equilibrium, an electrostatic field was established,
which prevented further crossing of electrons and holes across the
photocatalyst junction. Under the conditions of visible irradiation
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Table 6 Heterogeneous pairing of photocatalyst materials, their degradation mechanisms, and applications
No. Heterogeneous system Application Light source Mechanism References
1. SnO2-ZnO Methylene blue UV [140]

 
2. WO3/NiWO4 Methylene blue UV [119]

 
3. TiO2/GQDs Methyl orange Visible [65]

 
4. Sb2S3/TiO2 p-hydroxyazobenzene Visible [141]

 
5. g-C3N4/ZnTcPc Rhodamine B Visible [142]

(λ > 420 nm), the electrons moved from p- to n-type of CB, while
holes are transferred from n- to p-type of VB. Rhodamine B
molecules were adsorbed on the catalyst surface, where degradation
of the dye occurs. The charge separation caused by the p–n junction
in the BiOI/Bi2Sn2O7 composite resulted in 99% degradation of the
dye in 6 h. The dye degradation performance of the composite was
superior to that of BiOI or Bi2Sn2O7. The increase in photocatalytic
activity after the p–n junction formed between two semiconductor
materials highlights the importance of the p–n junction for
photocatalytic dye degradation.

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962 Nano Res. 2019, 12(5): 955–972

forces; however, the redox potential of the holes and electrons

Figure 6 p–n junction mechanism for contaminant degradation (reprinted
with permission from Ref. [66], © Zhang, W. et al. 2016).
3.3 Z-scheme mechanism
The p–n junctions offer charge carrier separation by electrostatic
is reduced [68]. The Z-scheme mechanism describes changes in
oxidation/reduction during the light reactions of photosynthesis,
which can help solve the problem of reduced redox potential in p–n
junctions [69]. The photoexcitation process in the Z-scheme occurs
in two steps. First, electrons in the highest occupied molecular
orbital (HOMO) of the first material are transferred to the HOMO
of the second material. Electrons then move from the HOMO of
the second material to the lowest unoccupied molecular orbital
(LUMO) of the second material. As a result, holes are created in the
HOMO of the first material. This naturally occurring phenomenon
does not necessarily reduce the redox potential of holes and electrons.
The reactive oxygen species generated at the HOMO and LUMO
of semiconductors degrade the dye molecules. Representative
photocatalytic systems with the Z-scheme dye degradation mechanism
are summarized in Table 8. Like the p–n junction mechanism, most
composite materials using the Z-scheme mechanism operate under
visible irradiation. For instance, the Z-scheme dye degradation

Table 7 p–n junction degradation mechanisms

No. p–n junction Application Light source Mechanism References
1. CuO-BiVO4 Rhodamine B Visible [143]

 
2. BiOI/Bi2Sn2O7 Rhodamine B Visible [67]

 
3. Cu3SnS4/TiO2 Methyl orange Visible [144]

 
4. BiOI/Bi4O5I2/Bi2O2CO3 Methylene blue Visible [145]

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(Continued)
No. p–n junction Application Light source Mechanism References
5. TiO2/ZnO Methyl orange Visible [146]

Table 8 Photocatalyst systems with Z-scheme mechanisms

No. p–n junction Application Light source Mechanism References
1. g-C3N4/Ag2WO4 Methyl orange Visible [147]

 
2. g-C3N4/RGO/Bi2MoO6 Rhodamine B Visible [70]

 
3. MoO3–g-C3N4 Methyl orange Visible [148]

 
4. SnO2−x–g-C3N4 Rhodamine B Visible [122]

 
5. Ag3PO4–MoS2 Methylene blue Visible [149]

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964
mechanism in a g-C3N4/reduced graphene oxide (RGO)/Bi2MoO6
photocatalyst was recently investigated [70]. The Z-scheme mechanism
in the composite material was verified using scavenging tests.
Electrons migrated to the CB of g-C3N4 under visible irradiation,
while the holes were restricted to the VB of Bi2MoO6. The electron
migration resulted in 97% degradation of Rhodamine B dye in 2 h,
which was due to the electron mediation of graphene oxide and
charge separation by the Z-scheme mechanism.
4 Key factors controlling dye degradation
Performance of photocatalytic degradation of dyes depends on
several parameters such as pH, light intensity, the ratio of catalyst to
dye, and the presence of interfering compounds (e.g., bromides, anti-
scaling agents, bicarbonates, phosphates, and radical scavengers) [71].
The effects of these factors on the dye degradation performance
will be discussed in the following subsections.
4.1 Effect of pH
The pH of wastewater containing dye determines the electrostatic
interaction between catalyst surfaces, substrates, and radicals
during the degradation process. Surface charge and aggregation of
the catalysts are associated with wastewater pH [71, 72]. Gaya et al.
investigated the effect of pH on the photocatalytic oxidation
capability of TiO2 [73]. They observed that TiO2 shows a strong
oxidation performance at a pH of less than 2. However, the reaction
rate decreased when pH became less than 2. The effect of pH on the
decomposition of methyl orange was studied [74]. Table 9 shows
the change in reaction rate as a function of pH. The first-order
reaction rate was 25 times higher at pH 2 than at pH 9. The reaction
rate decreased from 1.42 to 0.86 min−1 as the pH increased from
2 to 3. A rapid drop in the reaction rate was observed when pH
further increased from 3 to 9, confirming the sensitivity of dye
degradation to the pH of the reaction mixture.
4.2 Pollutant/photocatalyst adsorption
The adsorption of dyes on the photocatalyst surface is dependent
on the electrostatic interactions and binding affinity between the
dye molecule and the catalyst surface [5]. Moderate adsorption of dye
molecules on the photocatalyst surface is beneficial for degradation
performance based on the synergy between adsorption and
photocatalysis. The adsorption of dye molecules onto the catalyst
surface is an essential step for effective degradation. Composite
materials with good adsorption properties utilize this synergy principle
for simultaneous adsorption and degradation of dye molecules [75].
The synergy between the two mechanisms has been reported for
methylene blue degradation [76]. Accordingly, graphene oxide
incorporated with TiO2 resulted in a 50% enhancement in the dye
degradation relative to TiO2 alone. Although adsorption of dye
on the surface is important for photocatalytic dye degradation,
it may also be disadvantageous beyond a certain limit. A very high
adsorption of dye molecules on the catalyst surface suppresses the
number of photons reaching surface-active sites. In addition, dye
molecules may also act as sensitizers that can absorb electrons and
Table 9 First-rate constants of methyl orange degradation at different initial
pHs [74]
Initial pH of reaction mixture Kapp. × 102
2.02 1.42
3.00 0.86
5.02 0.26
7.04 0.11
9.01 0.06
Normal experiment, pH = 6.3 0.15
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Nano Res. 2019, 12(5): 955–972
scatter them in undesirable directions [77].
4.3 Effect of light intensity
Photocatalytic phenomena rely on the energy supplied by light
quanta. Electron–hole pairs are generated in the CB and VB of a
photocatalytic material when they receive photons with energy
equal to or greater than the band gap of the material [78, 79]. The
light intensity plays a critical role in photocatalytic dye removal
[80]. The effect of light intensity on photocatalytic dye degradation
has been extensively studied. As an example, the effect of light
intensity on the degradation and decolorization of wastewater
containing reactive yellow azo dye (RY14) is shown in Fig. 7 [81].
When the radiation intensity increased from 16 to 62 W, 33% more
dye decolorization was observed. An increase in irradiation intensity
led to improvements in the penetration of light and to an increase
in the rate of generation of ROSs. However, the increase in light
intensity improves photocatalytic performance only up to a certain
limit. As shown in Fig. 7, dye removal increases significantly when
irradiation power shifts from 16 to 32 W. A subsequent increase from
32 to 48 W yielded a small change in dye removal. After that, the
dye removal becomes independent of the irradiation intensity. The
effect of light intensity on kinetic rate constant in the degradation
of Fast Green dye was investigated [82]. A linear rise in dye
degradation rate was observed with an increase in the light intensity.
The results showed that dye removal rate almost doubled as the
light intensity increased from 10 to 70 mW·cm−2. In another study,
a negative effect of light intensity on Congo Red dye degradation
rate was observed when the light intensity varied from 50 to
90 J·cm−2 [83]. It was seen that the dye removal rate increased
with the light intensity up to 80 J·cm−2. However, at 90 J·cm−2, the
degradation rate began to drop which should be ascribed to the
thermal effects associated with the rise in temperature of the dye
contaminated solution.
4.4 Effect of photocatalyst loading
The mass of photocatalyst in a wastewater suspension has a
significant effect on the reaction rate and total dye degradation
capability. Lu et al. reported that the ratio of Rhodamine B removal
increased with increasing loading of a CdS/graphene composite
photocatalyst. The removal ratio increased from 49.1% to 84.5%
with an increase in the photocatalyst loading from 200 to 1,800 mg·L−1
[84]. Increasing the photocatalyst loading generates more electron–
hole pairs, resulting in higher and faster degradation of dye molecules.
However, the turbidity of wastewater increases at very high con-
centrations of composites, thereby increasing light scattering and
reducing its penetration in the reaction mixture [31, 71]. Recently,
the negative effect of composite dosage on degradation performance
was reported [75]. Degradation of para-nitrophenol (PNP) was
monitored against initial composite dosage concentrations of 0.05,
0.15, 0.25, 0.35, and 0.45 g·L−1. The best removal performance (97%)
was achieved at a composite dosage of 0.25 g·L−1. The degradation
Figure 7 Effect of UV radiation intensity on the decolorization and degradation
of RY14 (reprinted with permission from Ref. [81], © Elsevier 2006).
Nano Res. 2019, 12(5): 955–972
capability dropped when composite concentration increased to 0.35
or 0.45 g·L−1. The decrease in removal performance was associated
with reduced penetration and increased light scattering due to a
high composite density per unit volume.
4.5 Effect of dye loading
The interaction between a photocatalyst substrate and a dye
molecule is related to the nature of the functional groups of the dye
molecules as well as their abundance in the reactor. The optimal
concentration of dye molecules for a photocatalytic reaction is
highly dependent on the kind of dye. In general, as the initial dye
pollutant concentration increases, the photocatalytic degradation
efficiency decreases because more dye molecules compete for limited
active sites. Increasing photocatalyst loading leads to increased
turbidity. Furthermore, a high dye concentration makes the dye
itself absorb more light than a photocatalyst, thereby deteriorating
photocatalytic degradation performance [85]. A higher initial con-
centration of methyl orange made fewer photons reach the catalyst
surface due to the reduction of light penetration [86]. The effect
of the initial concentration of acid red dye on the photocatalytic
degradation performance was also investigated. The degradation
rate decreased when the dye concentration increased from 20 to
40 mg·L−1. The increase in dye loading prevented the photons from
reaching the catalyst surface, inhibiting the generation of ROSs. It
was reported that the decrease in dye removal efficiency is chiefly
due to a lower concentration of ROSs in the photocatalytic reactor.
In addition to the factors discussed above, the presence of
inorganic metal ions in dye-contaminated solution can also affect
the photocatalyst’s performance. In this regard, depending upon the
ionic nature of dye molecules, the metal ions may either accelerate
or decelerate the dye degradation. Generally, metal ions are adsorbed
on to the photocatalyst’s surface to make the catalyst electro-neutral
or slightly positively charge. As this effect reduces the electrostatic
repulsion for anionic dyes, they can be adsorbed and degraded
readily in the presence of metal ions. On the contrary, a retarding
effect can also be observed for cationic dyes due to the decrease in
attraction between positively charged dye molecules and neutral/
slightly positive catalyst surface [87].
5 Uncertainties and challenges
Even though researchers have made tremendous progress in the
field of photocatalysis, some doubts remain about the process and
operation of photocatalysts in real applications. Therefore, in this
section, we attempt to highlight uncertainties and ambiguities
regarding photocatalytic dye degradation.
5.1 Degradation mechanisms
A photocatalyst absorbs light photons to generate electrons and
holes in its energy bands. The photon-derived electrons and holes
react with available oxidants and reductants, respectively. Subsequently,
the radicals generated from electron–hole pairs react with dye
molecules to form H2O and CO2 [88]. Several mechanisms for
electron–hole pair formation and separation have already been
discussed. Nevertheless, there is no clear way to show how the
photocatalytic reactions proceed in an actual reactor. Researchers
have proposed different mechanisms for electron–hole transport
across the heterojunctions in photocatalysts; however, the transport
and degradation mechanism at photocatalytic active sites could be
explained in more than one way [67, 70]. The degradation mechanism
is usually studied via indirect methods such as scavenging, radical
trapping, and electron spin resonance tests [89, 90]. However, a direct
method is needed that could verify the charge migration pathway
and identify actual degradation sites on the photocatalyst surface.
Detailed and precise knowledge about the photocatalytic mechanism
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965
will help to design better photocatalyst materials for dye degradation
applications.
5.2 Intermediate species
Ideally, the photocatalytic reaction under UV light irradiation should
yield carbon dioxide and water as final products [91]. The organic
dyes have large structures that are broken into smaller segments
during photocatalytic degradation. It is possible that the intermediates
formed during this process could have more detrimental effects
than the parent dye compound. However, the intermediates formed
during photocatalysis are generally not monitored or studied.
There was an effort to explore transitional products formed in dye
degradation. Chen et al. identified intermediates with a different
number of N-ethyl groups in the photocatalytic degradation of
N,N,N,N-tetraethylsulforhodamine-B dye [92]. The intermediate
products generated during the breakdown of dye molecules were
not radically different from the parent dye molecules. However, it
would be wrong to assume this safe scenario is the case for all other
intermediates formed during dye degradation. The intermediates
formed during photocatalytic degradation of dye can be more
dangerous than the original dye. For instance, catechol is one of
the by-products of phenol degradation via photooxidation. The
possibility of experiencing hypertension and convulsions in animals
from catechol are higher than for phenol [93, 94]. Therefore, intensive
investigation is required to determine the nature of transitional
products and the fate of the intermediate pollutants produced when
treating the dye-containing wastewater.
5.3 Electron–hole recombination
Recombination of an electron and a hole in a photocatalyst, if it
occurs, reduces the quantum efficiency of a photocatalytic reaction.
The most common method to evaluate the recombination rate
is photoluminescence analysis. In this analysis, it is assumed that
the emission intensity of light from a photocatalyst is inversely
proportional to the electron–hole recombination [95]. Photo-
luminescence emission occurs when energy is released from
radiative decay of an electron from the CB to the VB. However, if
a photocatalyst has some component that scatters or absorbs light
(e.g., reduced graphene oxide and quantum dots), the emission
intensity could then be completely misleading [96]. There are other
indirect methods to measure the electron–hole recombination, such
as open circuit potentiometry and radical scavenging, but no absolute
method is available for assessing the recombination. To overcome
this deficiency, investigations are needed to find better methods that
provide an accurate prediction of the electron–hole recombination
rate.
5.4 Band gap
In a semiconducting material, electrons are excited from the VB to
the CB when irradiated by photons having an energy level greater
than their corresponding band gap. This inter-band excitation
occurs among three bands: the CB, the forbidden band, and the
VB. There are several approaches to find band gaps of different
semiconductor materials. However, it is hard to find the accurate
position of the VB and the CB and band gap energy, particularly in
composite materials. Given that the selection of light source highly
depends on the band gap energy, an ambiguous band gap position
makes the selection of the light source (and light intensity) difficult.
Choosing an inappropriate light source could lead to energy waste
and add to the total cost of dye wastewater treatment.
5.5 Structure and dopant distribution
Doping refers to the introduction of impurities/foreign atoms in
to the basic structure of a parent material that can improve
photocatalytic performance for dye degradation. An accurate and
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966 Nano Res. 2019, 12(5): 955–972

precise understanding of the dopant distribution in the parent
structure is crucial. Characterizations using scanning electron
microscopy (SEM) and transmission electron microscopy (TEM)
only provide information about a small representative part of
the bulk material. The composition and dopant distribution in a
representative part of the sample could be different from the bulk
phase. Hence, it is unsafe to assume that the bulk material will
have same properties as the representative sample. This erroneous
assumption demands extensive investigation for developing reliable
methods for analyzing bulk materials. Similarly, the determination
of the structure, density, and three-dimensional distribution of
doped materials in the bulk phase is challenging.
6 Performance evaluation
A wide range of colorants, including organic, inorganic, cationic,
anionic, and amphoteric dyes, can be photocatalytically decomposed.
Nevertheless, it is often hard to validate the performance of a
photocatalyst by simply monitoring its performance of degrading
a specific dye. The difficulty is because a photocatalyst showing an
outstanding performance under a specific set of conditions might
perform very poorly under different circumstances. The conditions
affecting photocatalytic activity are highly dependent on the type of
catalysts and kind of dye; thus, a direct comparison of different
photocatalysts operating at different conditions is very difficult and
not reasonable.
The quantum yield (QY) is important to photocatalytic reactions.
QY quantifies the ability of a photocatalyst to absorb photons and
shows how effectively the absorbed photons are used for photocatalytic
degradation. The definition and calculation method for QY may
vary between different application fields. For instance, the QY for
solar-driven systems was described in terms of “electrical energy
per order” or “electrical energy per unit mass” [97]. In an industrial
approach, QY was also defined as the monitoring the amount of
product obtained per unit of energy supplied [98]. Likewise, in this
research, the QY for the photocatalysts was calculated using the
method reported previously [99, 100]
Decay rate (molecules per second)
QY = (7)
Photon flux (photons per second)
The QY for photocatalytic systems was also assessed through the
evaluation of the degradation capacity between different nano-
materials [101–103]. However, QY alone cannot be used as a standard
metric to allow performance comparison between different
photocatalytic systems, unless all operational parameters are used
on parallel basis. Hence, we established an evaluation method
that can be used to assess, quantify, and compare the performance
of different photocatalysts. The method is based on operational
parameters that are critical for selecting photocatalysts for practical
applications. Recently, the validity of these parameters was investigated
experimentally [75, 104]. The selection criteria included the quantity
of dye-wastewater processed, catalyst mass, time, and energy con-
sumption for photodegradation. Using these parameters at the same
time, a figure of merit (FOM) was calculated as
FOM =
Product obtained (L)
Catalyst dosage (g⋅L1 ) ´ Time (h) ´Energy consumption (Wh ⋅ μmol 1 )
(8)
Chlorophyll, a natural photocatalyst with a QY of 0.04–0.06, was
used as a benchmark for normalizing the QYs of all photocatalyst
systems [105]. For easy interpretation, the highest obtained FOM
was set to 100, and the conversion factor was used to calculate
the FOMs for other photocatalyst systems. Important operational
parameters, QYs, and modified FOMs of 85 different photocatalytic
systems are listed in Table 10. As discussed earlier, the QY of
photocatalyst systems presented only one aspect of the degradation
potential. However, the FOM quantified the overall performance of
all systems based on four selected parameters. Some photocatalytic

Table 10 Performance evaluation and FOM of photocatalyst systems

Order Photocatalyst Genera- Dyes Light Time Energy Product Catalyst QY FOM Remarksa References
tion source (h) consumption obtained dosage (mol·photon−1)
(Wh·μmol−1) (L) (g·L−1)
1 TiO2 1st Fast green FCF UV 1.3 92.5 0.25 1.0 1.89 × 10−5 5.18 Average [111]
st −5
2 TiO2 1 Patent blue VF UV 1.3 22.9 0.25 1.0 7.64 × 10 20.88 Good [111]
3 TiO2 1st Reactive black 5 UV 5.0 9.7 0.50 2.0 1.96 × 10−4 13.18 Good [112]
4 TiO2 1st Reactive yellow 145 UV 5.0 10.4 0.50 2.0 1.84 × 10−4 12.34 Good [112]
5 ZnO 1st Acid red 14 UV 3.5 74.9 0.05 0.6 3.50 × 10−5 0.81 Below average [45]
st −5
6 ZnO 1 Rhodamine B UV 1.3 81.5 0.10 2.0 2.34 × 10 1.18 Average [115]
7 ZnO 1st Methyl orange UV 2.0 25.1 0.04 1.3 7.28 × 10−5 1.63 Average [116]
8 ZnO 1st Rhodamine 6G UV 3.0 88.0 0.10 0.5 2.07 × 10−5 1.94 Average [117]
9 ZnS 1st Methylene blue UV 1.5 412.7 0.05 1.0 4.61 × 10−6 0.21 Below average [150]
st −5
10 ZnS 1 Methyl orange UV 1.0 43.6 0.08 1.0 6.00 × 10 4.39 Average [81]
11 ZnS 1st Bromophenol blue UV 3.0 618.4 0.10 2.5 3.08 × 10−6 0.06 Below average [151]
12 WO3 1st Malachite green Vis 5.8 373.3 0.03 0.2 3.24 × 10−6 0.23 Below average [152]
st
13 WO3 1 Rhodamine B Vis 0.2 1,774.1 0.03 1.3 6.82 × 10−7 0.19 Below average [153]
14 WO3 1st Methylene blue Vis 2.0 1,023.5 0.10 1.0 1.27 × 10−6 0.12 Below average [154]
st −7
15 WO3 1 Orange G Vis 2.0 1,447.6 0.10 1.0 9.02 × 10 0.09 Below average [154]
16 TiO2 1st Reactive black 5 UV 3.0 60.2 0.50 2.0 3.16 × 10−5 3.53 Average [155]
17 CdS 1st Reactive black 5 UV 3.0 54.2 0.50 2.0 3.50 × 10−5 3.93 Average [155]
18 CdS 1st Eosin red Vis 1.7 951.0 0.10 0.5 1.27 × 10−6 0.32 Below average [156]
st −7
19 CdS 1 Congo red Vis 2.0 1,211.6 0.10 0.5 9.98 × 10 0.21 Below average [156]
20 CdS 1st Methylene blue Vis 3.0 903.1 0.10 0.5 1.34 × 10−6 0.19 Below average [156]
21 CdS 1st Methylene blue UV 3.0 38.6 0.20 1.0 4.26 × 10−5 4.41 Average [157]

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(Continued)
a
Order Photocatalyst Genera- Dyes Light Time Energy Product Catalyst QY FOM Remarks References
tion source (h) consumption obtained dosage (mol·photon−1)
(Wh·μmol−1) (L) −1
(g·L )
22 CdS 1st Phenol red UV 3.0 47.3 0.20 1.0 3.48 × 10−5 3.60 Average [157]
st −5
23 CdS 1 Methyl red UV 3.0 35.1 0.20 1.0 4.68 × 10 4.85 Average [157]
24 CdS 1st Methylene blue Vis 6.0 533.1 0.60 0.1 2.26 × 10−6 4.79 Average [158]
25 ZnS 1st Methylene blue Vis 6.0 253.9 0.60 0.1 4.76 × 10−6 10.06 Good [158]
26 Fe-doped TiO2 2nd Methyl orange UV 1.3 103.6 0.05 1.0 1.89 × 10−5 0.99 Below average [159]
27 Fe-doped TiO2 2nd Methyl orange Vis 6.0 818.3 0.05 1.0 1.48 × 10−6 0.03 Below average [159]
nd −5
28 Ag2CO3/C3N4 2 Methyl orange Vis 0.2 62.0 0.05 1.0 1.95 × 10 12.36 Good [160]
29 Graphene/TiO2 2nd Methyl orange UV 0.3 34.6 0.08 0.6 3.52 × 10−5 28.13 Good [161]
30 Graphene/TiO2 2nd Methyl orange Vis 3.0 17.9 0.08 2.5 3.90 × 10−5 1.52 Average [161]
31 BN/CdS 2nd Rhodamine B Vis 1.5 14.1 0.16 0.6 1.13 × 10−4 30.68 Best [106]
32 RGO/Bi2MoO6 2nd Rhodamine B Vis 1.0 96.8 0.25 1.0 1.22 × 10−5 6.60 Average [70]
nd −5
33 Ag3PO4/CeO2 2 Rhodamine B Vis 1.0 65.3 0.25 0.4 1.85 × 10 24.45 Good [66]
34 Ta2O5/g-C3N4 2nd Rhodamine B Vis 2.0 299.0 0.05 1.0 4.04 × 10−6 0.21 Below average [162]
35 Graphene/TiO2 2nd Rhodamine B Vis 3.0 300.3 0.05 0.3 3.98 × 10−6 0.47 Below average [163]
36 RGO/TiO2 2nd Methylene blue UV 1.0 94.1 0.05 0.2 2.00 × 10−5 6.79 Average [164]
37 RGO/TiO2 2nd Methylene blue Vis 1.0 228.5 0.05 0.2 5.34 × 10−6 2.80 Average [164]
nd
38 CdS/CoFe2O4 2 Methylene blue Vis 2.0 85.3 0.25 0.4 1.42 × 10−5 9.36 Average [165]
39 Ni-doped TiO2 2nd Methylene blue Vis 3.0 575.1 0.20 1.2 2.10 × 10−6 0.25 Below average [166]
40 WO3/g-C3N4 2nd Methylene blue Vis 1.5 29.5 0.10 0.5 2.00 × 10−5 11.55 Good [107]
41 WO3/NiWO4 2nd Methylene blue UV 6.7 41.2 0.35 0.6 4.62 × 10−5 5.70 Average [119]
nd −6
42 Co3O4-g-C3N4 2 Methyl orange Vis 3.0 245.5 0.10 1.0 4.92 × 10 0.35 Below average [120]
43 Bi2O2CO3/BiOI 2nd Rhodamine B Vis 0.3 437.5 0.10 0.5 2.76 × 10−6 4.67 Average [121]
44 SnO2/g-C3N4 2nd Rhodamine B Vis 0.8 139.7 0.10 1.0 8.66 × 10−6 2.19 Average [122]
nd
45 Bi2S3/TiO2/RGO 2 Methylene blue Vis 1.5 39.3 0.50 0.4 3.08 × 10−5 54.24 Best [123]
46 BiOI/ZnTiO3 2nd Rhodamine 6G Vis 3.0 525.8 0.02 1.0 2.30 × 10−6 0.03 Below average [124]
nd −6
47 Bi2O2CO3/Bi2S3 2 Rhodamine B Vis 3.0 231.8 0.10 1.0 5.22 × 10 0.37 Below average [125]
48 BiVO4/Ag3VO4 2nd Rhodamine B Vis 0.3 41.6 0.10 1.0 2.90 × 10−5 18.41 Good [51]
49 BiVO4/Ag3VO4 2nd Methylene blue Vis 0.7 82.9 0.10 1.0 1.46 × 10−5 4.62 Average [51]
50 BiVO4/Ag3VO4 2nd Methyl red Vis 0.7 63.1 0.10 1.0 1.92 × 10−5 6.07 Average [51]
nd −5
51 BiVO4/Ag3VO4 2 Methyl violet Vis 0.7 72.5 0.10 1.0 1.67 × 10 5.29 Average [51]
52 BiPO4/mg-C3N4 2nd Methyl orange Vis 2.0 99.2 0.10 1.0 1.22 × 10−5 1.29 Average [128]
53 g-C3N4/Ag3VO4 2nd Basic fuchsin Vis 2.5 426.1 0.05 1.0 2.84 × 10−6 0.12 Below average [53]
nd
54 g-C3N4/Ag3VO4 2 Malachite green Vis 1.0 188.1 0.05 1.0 6.42 × 10−6 0.68 Below average [53]
55 g-C3N4/Ag3VO4 2nd Crystal violet Vis 2.5 680.0 0.05 1.0 1.78 × 10−6 0.08 Below average [53]
nd −5
56 g-C3N4/BiOI 2 Rhodamine B Vis 0.8 121.0 0.10 0.1 1.00 × 10 25.34 Good [126]
57 g-C3N4/BiOI 2nd Methylene blue Vis 1.0 96.9 0.10 0.2 1.25 × 10−5 13.18 Good [126]
58 BiOI/Ag3VO4 2nd Basic fuchsin Vis 2.0 267.1 0.05 1.0 4.52 × 10−6 0.24 Below average [127]
59 BiOI/Ag3VO4 2nd Malachite green Vis 2.0 317.3 0.05 1.0 3.82 × 10−6 0.20 Below average [127]
60 BiOI/Ag3VO4 2nd Crystal violet Vis 2.0 384.0 0.05 1.0 3.14 × 10−6 0.17 Below average [127]
nd −6
61 C3N4/CdS 2 Rhodamine B Vis 2.8 135.7 0.25 0.4 8.92 × 10 4.15 Average [167]
62 RGO/CdS 2nd Rhodamine B Vis 2.5 119.8 0.25 0.4 1.01 × 10−5 5.33 Average [167]
63 C3N4/CdS/RGO 2nd Rhodamine B Vis 1.0 47.9 0.25 0.4 2.52 × 10−5 33.33 Best [167]
64 C3N4/RGO 2nd Rhodamine B Vis 2.0 95.8 0.25 0.4 1.26 × 10−5 8.33 Average [167]
65 C3N4/CdS 2nd Rhodamine B UV 0.7 95.8 0.25 0.4 1.98 × 10−5 25.00 Good [167]
nd −5
66 RGO/CdS 2 Rhodamine B UV 0.7 95.8 0.25 0.4 1.98 × 10 25.00 Good [167]
67 C3N4/RGO 2nd Rhodamine B UV 0.5 71.9 0.25 0.4 2.64 × 10−5 44.44 Best [167]
68 C3N4/CdS/RGO 2nd Rhodamine B UV 0.3 47.9 0.25 0.4 3.96 × 10−5 100.00 Best [167]
69 ZnS/CdS 2nd Methylene blue Vis 3.0 148.1 0.60 0.1 8.16 × 10−6 34.50 Best [158]
70 SnO2−x/g-C3N4 2nd Rhodamine B Vis 0.7 111.8 0.10 1.0 1.08 × 10−5 3.43 Average [122]
nd
71 SnO2−x/g-C3N4 2 Methyl orange Vis 1.5 171.9 0.10 1.0 7.04 × 10−6 0.99 Below average [122]
72 SnO2−x/g-C3N4 2nd Methylene blue Vis 0.7 74.6 0.10 1.0 1.62 × 10−5 5.13 Average [122]
73 Steel/TiO2-WO3 3rd Methylene blue UV 4.0 12,794.0 0.01 3.0 1.58 × 10−7 0.00 Below average [129]

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968 Nano Res. 2019, 12(5): 955–972

(Continued)
a
Order Photocatalyst Genera- Dyes Light Time Energy Product Catalyst QY FOM Remarks References
tion source (h) consumption obtained dosage (mol·photon−1)
(Wh·μmol−1) (L) −1
(g·L )
74 FTO/WO3-ZnO 3rd Methylene blue UV 1.0 61.0 0.20 0.3 4.20 × 10−5 33.50 Best [130]
rd −5
75 TiO2 3 Methylene blue UV 0.8 103.0 0.05 1.0 1.76 × 10 1.49 Average [131]
76 Al/ZnO 3rd Methyl orange UV 3.0 3,131.0 0.02 0.5 5.80 × 10−7 0.01 Below average [132]
77 FTO/BiOBr 3rd Methyl orange Vis 5.0 4,088.0 0.01 4.0 3.60 × 10−7 0.00 Below average [133]
78 Ni/TiO2 3rd Methyl Orange UV 2.0 8.0 0.95 2.0 3.40 × 10−4 75.05 Best [134]
79 TiO2 3rd Methyl Orange UV 15.0 255.0 0.05 6.4 7.20 × 10−6 0.01 Below average [135]
rd −6
80 FTO/BiOCl-TiO2 3 Rhodamine B Vis 3.0 871.0 0.10 2.1 1.52 × 10 0.05 Below average [60]
81 Bi/BiOCl 3rd Rhodamine B Vis 3.5 593.0 0.10 0.6 2.60 × 10−6 0.21 Below average [136]
82 Ti/BiOCl 3rd Rhodamine B UV 2.0 43.0 0.05 8.8 6.20 × 10−5 0.17 Below average [137]
83 Ti/BiOCl 3rd Rhodamine B Vis 3.0 908.0 0.05 8.8 2.00 × 10−6 0.01 Below average [137]
84 Ce/TiO2 3rd Basic blue UV 3.0 26.0 0.08 7.5 9.20 × 10−5 0.35 Below average [138]
rd −5
85 Glass/P-TiO2 3 Benzyl butyl phthalate Vis 4.0 95.0 0.20 0.6 1.76 × 10 2.24 Average [139]
a
FOM classification: best (100–30), good (30–10), average (10–1), below average (less than 1).

systems exhibited higher QYs but lower FOM, indicating their
deficiency in at least one of the four parameters selected for FOM.
Photocatalytic systems were categorized in to four classes based
on the FOM values: best, good, average, and below average.
The percentage share of FOM classes in different generations of
photocatalyst materials is shown in Fig. 8. The first generation
materials failed to qualify for the best FOM class: 40% of the first
generation materials exhibited a FOM less than one, which was
classified as below average. Thirteen percent of the second generation
materials were in the best category of FOMs. It is worth mentioning
that the best materials contained RGO/- or carbon nitride (C3N4) in
their hybrid structure. Therefore, it is safe to assume that RGO/- or
C3N4 could play a pivotal role in designing potentially efficient
photocatalyst materials for dye degradation. Better performance of
these materials is associated with their high adsorption capacity
that incorporates adsorption-photocatalysis synergy for improved
dye degradation [106, 107]. Two photocatalytic systems with third
generation materials showed the best FOMs. In both these systems, the
support material was a conductive substrate that enhanced the electron
mobility along the horizontal film surface. The increased carrier
mobility suppressed the undesirable electron–hole recombination,
which resulted in better overall performance. Third generation
materials address post-separation problems, but most of the currently
available systems are still unsuitable for field applications, and further
research is required to advance this technology.
7 Conclusions and prospects
We summarized the advancement in photocatalysis to remedy the
dye-contaminated industrial effluent by categorizing the photocatalysts
in to three generations. First generation photocatalysts proved to be
inadequate for dye removal as they were limited by their large band
gaps and interfacial charge recombination. With the progress in this
research field, a better knowledge on diverse functional properties
(e.g., the optoelectronic, physical, and band gap characteristics)
opened a new avenue to develop a second generation of photocatalysts.
Among photocatalysts, the second generation materials were studied
most extensively due to their excellent charge separation, faster
reaction kinetics, visible light utilization, and remarkable QYs
for dye degradation. To expand the photocatalyst applications to
industrial scale, the post separation problems associated with the
first and second generation materials were addressed by the third
generation photocatalysts. The low QYs of the third generation
photocatalysts (e.g., due to reduced surface area and reaction sites
after deposition) presented a new opportunity to develop or improve
immobilization technologies.
Besides the design of photocatalysts, the underlying mechanisms
that govern the degradation process are of immense importance.
In this regard, the Z-scheme mechanism that replicates the natural
degradation process of chlorophyll is ideal for designing photocatalysts
for dye degradation. Moderate reusability and low catalyst dosage
(100–200 g·m−3) are also advantageous to wastewater treatment.
The ambiguities regarding process parameters, material design, and
functioning in real wastewater create an impression of skepticism
towards photocatalysts. However, the limitations and challenges
that currently undermine the industrial applications of photocatalysts
can be resolved. In conclusion, the third generation materials hold a
tremendous potential for the future of dye wastewater treatment on
an industrial scale.

 
Figure 8 Performance evaluation results for photocatalyst materials consisting
of first, second, and third generation materials.
Acknowledgements
K. H. K. and J. W. P. acknowledge support made by the Basic Science
Research Program through the National Research Foundation of
Korea (NRF) funded by the Ministry of Science, ICT, & Future Plan-
ning Grant Nos. 2016R1E1A1A01940995 and 2018R1A2A1A05023555,
respectively.

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Nano Res. 2019, 12(5): 955–972
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