Chemosphere 276 (2021) 130201

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Recent advances in photocatalytic decomposition of water and

pollutants for sustainable application
Yujie Zhao a, Yan Li a, *, Lidong Sun b, **
a
School of Materials Science and Engineering, Beihang Unviersity, Beijing, 100191, China
b
School of Materials Science and Engineering, Chongqing University, Chongqing, 400044, China

h i g h l i g h t s

Recent developments in photoinduced reduction for water splitting are reviewed.

Mechanism aspects on cocatalysts, sacrificial agents and heterojunctions are discussed.

Recent advances in photoinduced oxidation for organic degradation are summarized.

Emerging pollutants of organic dyes, pharmaceuticals and organic volatile compounds are discussed.

Key challenges and perspectives are highlighted for future development.

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

Article history: Photoinduced reduction and oxidation, the important processes in photocatalytic water splitting and
Received 17 November 2020 organic degradation, have generated increasing interest to address the energy and environmental issues.
Received in revised form In this review, the recent developments in bandgap and interfacial engineering for enhanced light ab-
3 March 2021
sorption, efficient charge separation and interfacial reaction are focused toward the applications in
Accepted 4 March 2021
Available online 6 March 2021
photocatalytic water splitting and organic degradation. In photoinduced reduction for hydrogen evolu-
tion, three major strategies are discussed: cocatalysts, sacrificial agents and heterojunctions. In photo-
Handling Editor: Derek Muir induced oxidation for organic degradation, three types of emerging pollutants of current concerns are
highlighted: organic dyes, pharmaceuticals and volatile organic compounds. The key challenges of
Keywords: promising photocatalysts are discussed for future development and practical application.
Sustainability © 2021 Elsevier Ltd. All rights reserved.
Photocatalysis
Water splitting
Photodegradation
Organic pollutant

Credit author statement renewable energy sources and the treatment of environmental
pollutions (Jin et al., 2018; Xia et al., 2020; Ye et al., 2020). The solar
Yujie Zhao: Methodology, Date curation and Writing-Original energy is regarded as a competent and promising candidate to
Draft; Yan Li: Writing-Review&Editing and Funding acquisition; manage the urgent and global challenges.
Lidong Sun: Methodology, Writing-Review&Editing and Funding
acquisition.
1.1. Photocatalysis for a sustainable world
1. Introduction
Solar energy is the largest source of renewable energy on the
planet, and therefore has been intensively studied for a wide
The energy and environmental issues have been the worldwide
spectrum of applications (Sun et al., 2011; Xiang et al., 2019; Zhao
focus toward a sustainable world. This motivates the exploration of
et al., 2019). Photocatalysis is a typical process that converts solar
energy into chemical fuels or environmental-friendly products. It
* Corresponding author.
has generated increasing interest in light of its cost-effective,
** Corresponding author. renewable, and clean features. An emerging trend of current con-
E-mail addresses: [email protected] (Y. Li), [email protected] (L. Sun). cerns is the solar-driven water spitting and organic decomposition.

https://doi.org/10.1016/j.chemosphere.2021.130201
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
Y. Zhao, Y. Li and L. Sun Chemosphere 276 (2021) 130201

This includes hydrogen production (Barba-Nieto et al., 2020b; reactive oxygen species (ROSs) interact with the organic com-
Jimenez-Calvo et al., 2020; Spanu et al., 2020; Zhou et al., 2021), pounds in water or air to ultimately produce organic oxygenates,
pollutant decomposition (Brueger et al., 2020; Chen et al., 2020b; carbon dioxide, or other species (Wu et al., 2020b). When the
Kaur et al., 2020; Li et al., 2020c, 2020d; Medhi et al., 2020; Qin semiconductor renders a more positive potential relative to 1.23 eV
et al., 2020; Ramachandran et al., 2020; Zhang et al., 2020b; Tang (vs. NHE), oxygen can also be generated.
et al., 2021), air/water purification (Mamaghani et al., 2020; Nasir This review discusses the photoinduced reduction for water
et al., 2020a; Padmanabhan et al., 2021), organic synthesis (Fukui spitting first. It focuses on three major strategies for efficiency
et al., 2020; He et al., 2020b; Liu et al., 2020b; Vu et al., 2020; enhancement, i.e., cocatalysts, sacrificial agents and hetero-
Zhang et al., 2020f), CO2 reduction (Dehkordi et al., 2020; He et al., junctions, based on recent advances in the field. The key influ-
2020b; Wang et al., 2021), self-cleaning (Mokhtarifar et al., 2020), encing factors and challenges are summarized. The second part
anti-bacterial (Helmy et al., 2020; Raja et al., 2020) and anti-viral introduces the photoinduced oxidation for organic degradation. It
(Wu et al., 2020a) applications. includes three major types of emerging pollutants, i.e., organic
dyes, pharmaceuticals and volatile organic compounds. The chal-
lenges are also presented. Perspectives on future development are
1.2. Photoinduced reduction and oxidation discussed at the end.

Photocatalytic decomposition of water was first reported by

2. Photoinduced reduction for water splitting
Fujishima and Honda in 1972. When irradiating a TiO2 electrode
with a xenon lamp, the water was decomposed into hydrogen and
Currently, the solar-driven hydrogen production is restricted by
oxygen (Fujishima and Honda, 1972). This triggered the rapid
a number of limitations, where an efficient and cost-effective
development of semiconductor photocatalysis technology.
photocatalyst is required. Fig. 2a illustrates a typical photo-
The photocatalytic reactions generally proceed by (1) the gen-
catalytic process. The photon energy that is greater than the
eration of charge carriers upon light absorption, (2) the transport of
bandgap energy of a semiconductor is first harvested to generate
charge carriers to the photocatalyst surface, and (3) the reaction
electronehole pairs; the photogenerated electrons and holes then
with targeting molecules. In this process, the recombination of
separate and transport to the semiconductor surface; the active
charge carriers should be avoided. The photocatalysis efficiency is
species drive the surface redox reactions. The overall efficiency is
closely related to the thermodynamic and kinetic features of the
highly associated with the thermodynamic and kinetic compromise
aforementioned steps.
of each step (Gao and Yan, 2019; Rahman et al., 2020). Fig. 2b
Accordingly, two kinds of reactions are rationalized with refer-
summarizes the bandgap alignment of typical semiconductors for
ence to the photogenerated charge carriers, i.e., photoinduced
hydrogen production. Many of the semiconductor photocatalysts
reduction and oxidation (Fig. 1). In this process, the electrons and
suffer from low absorption or serious recombination issues. A
holes are of major concerns, respectively, which move to the
number of strategies have been employed to address these prob-
catalyst surface and participate in interface reactions.
lems, such as the use of cocatalysts, sacrificial agents and well-
In the case of photoinduced reduction, the reduction ability is
designed heterojunctions, as is discussed below.
closely related to the chemical potential of the semiconductors.
When the semiconductor bears a more negative potential relative
to 0 V (vs. normal hydrogen electrode, NHE), hydrogen can be 2.1. Cocatalysts
produced by the photocatalyst under light irradiation. Besides, it is
also possible to reduce the carbon dioxide (CO2) to methane (CH4), An appropriate cocatalyst can increase the charge transfer rate
formaldehyde (CH2O), and carbon monoxide (CO) (Zeng et al., and survival time of the photogenerated charge carriers, as pre-
2020) with well-designed photocatalysts. sented in Fig. 3 (Gao and Yan, 2019; Xiao et al., 2020). The reactivity
In the case of photoinduced oxidation, the photogenerated holes of the photocatalysts is thus improved. Some cocatalysts can also
react with the H2O/OH to generate hydroxyl radicals (OH$). These improve the visible light absorption because of the localized surface

Fig. 1. The photoinduced reduction and oxidation with a catalyst under solar irradiation.

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Fig. 2. The photocatalytic water splitting with a semiconductor (a). Band alignment of typical semiconductors for water splitting (b). Reproduced with permission from ref. (Li et al.,
2020d), Copyright 2020, the Royal Society of Chemistry.

recombination, and thereby promotes the separation and trans-

portation of charge carriers. Besides, the cocatalysts can protect
semiconductors from photocorrosion by serving as electron sinks
and proton-reduction sites (Ombaka et al., 2020). For example,
some metal sulfides are easy to be oxidized and exhibit poor sta-
bility (Wu et al., 2016; Wu, 2018). After cocatalyst loading, the
consumption of the photoexcited holes suppresses the decompo-
sition of sulfides.
A Schottky junction generally forms at the metal/semiconductor
interface. This produces the band bending at the semiconductor
side and facilitates the charge separation process. The primary
shortcoming of metal cocatalysts, e.g., Cu and Ni, is their chemical
stability. The Cu and Ni cocatalysts may suffer from significant
changes at ambient and under photocatalytic conditions, such as
the particle morphology, valance state, and crystallinity. For
example, Irie and co-workers (Irie et al., 2009) reported that the
Cu2þ species on the TiO2 surface were reduced to Cuþ species
through electron capture. This is because the redox potential of the
Cu2þ/Cuþ is less positive than the conduction band minima of TiO2.
Fig. 3. The photocatalytic water splitting with cocatalysts. Reproduced with permis- The Ni cocatalyst behaves in a similar manner, where the oxidized
sion from ref. (Xiao et al., 2020), Copyright 2020, Elsevier Ltd. species can be reduced to metals via electron capture. Operando X-
ray absorption spectroscopy (XAS) was used to directly observe the
chemical state of cocatalysts in fluorescence mode (Spanu et al.,
plasmon resonance (e.g. Au and Cu) (Kuang et al., 2017; Reddy et al., 2020). The photocatalytic performance was effectively enhanced
2017; Jimenez-Calvo et al., 2020; Xiao et al., 2020; Yao et al., 2020). by depositing nanoparticles of noble metals on semiconductor
During photocatalytic water splitting, the charge separation is surface to form Schottky junctions (Rao et al., 2019; Zhong et al.,
determined by two factors: the transportation to and reaction on 2020). However, the metal cocatalysts are usually expensive and
the surface. The trapping effect of the cocatalyst restricts the charge

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Y. Zhao, Y. Li and L. Sun Chemosphere 276 (2021) 130201

limited by their natural reserves on the earth (Allam, 2011; Reddy

et al., 2017; Barba-Nieto et al., 2020a; Li et al., 2020b; Spanu
et al., 2020; Wang et al., 2020a). This drives the efforts to identify
alternative earth-abundant cocatalysts.
A Type II heterojunction can form between two semiconductors
with suitable band alignment, and therefore promotes the charge
separation. Fig. 4 displays a typical example where the CdS nano-
particles deposited on TiO2 hollow spheres to develop the Type II
heterojunction. Some Au nanoparticles on the surface contact
directly with CdS because of AueS affinity. As such, the photo-
generated electrons in CdS transfer to the conduction band of TiO2,
and subsequently to Au for hydrogen evolution, while the holes are
consumed by agents S2 and SO2 3 . This results in efficient charge
separation with the Type II heterojunction. To this end,
environmental-friendly semiconductors are more favorable toward
practical applications. Nasir and co-authors studied the SnSe2/TiO2
nanofiber photocatalysts (Nasir et al., 2020c) and the g-C3N4
quantum dots loaded SnSe2/TiO2 nanofiber composites (Nasir et al.,
2020b). The SnSe2 increases the carrier lifetime and participates in
the hydrogen-producing reaction. As compared to the metal co- Fig. 5. The water splitting mechanism with sacrificial agents. Reproduced with
catalysts, the semiconductor deposits are also capable of absorbing permission from ref. (Xiao et al., 2020), Copyright 2020, Elsevier Ltd.
photon energy over a wide spectrum and with a tailorable feature
induced by the quantum confinement effect (Sun et al., 2013; Sun
and Wang, 2014; Sun, 2016). Kumaravel et al., 2019; Li et al., 2019, 2020a; Zhang et al., 2019;
Melillo et al., 2020). The oxidation of the sacrificial agents generates
C1 products and hydrogen. For example, under the activation of
2.2. Sacrificial agents photogenerated holes or OH$, the methanol converts into formal-
dehyde, formic acid, carbon dioxide, and hydrogen in sequence
Sacrificial agents are essential in hydrogen evolution in light of (Salcedo-Abraira et al., 2020). However, all of those reactions can
the uphill reaction (DH0 ¼ 286 kJ mol1) for water splitting. In the release hydrogen, making the measured hydrogen yield higher
case of an aqueous solution that includes a sacrificial agent (e.g., than the actual value. In addition, the intermediate species (such as
methanol and sulfide ions), the photoexcited holes can oxidize the alkoxy radicals) produced by the oxidation of alcohol also exhibit
sacrificial agent instead of recombine with the electrons, as pre- reducing properties and hence participate in the half-reactions.
sented in Fig. 5. This is beneficial for feasible hydrogen production This indirectly promotes the hydrogen evolution. A few sacrificial
provided that the biomass or abundant compounds are employed agents, such as phosphorous acid and S2, give rise to protonation
as the sacrificial agents. Most of the agents oxidized by hþ (OH$, O2) in water. The protonated ions combine with the photogenerated
can also release Hþ or H2, giving rise to a higher H2 evolution yield holes to generate hydrogen (Hao et al., 2019; Pei et al., 2019; Zhang
than the photocatalyst alone. et al., 2020d). Glucose can be oxidized easily by O2 and subse-
Typical electron donor sacrificial agents include methanol, quently developed into formic acid and H2 (Bellardita et al., 2016).
ethanol, isopropanol, triethanolamine, formic acid, ascorbic acid, N, Consequently, the H2 evolution yield is affected by the reaction
N-dimethylformamide, and glucose in photocatalytic reactions between the sacrificial agents and holes or ROSs.
(Vaiano et al., 2015; Hafeez et al., 2019; Huang et al., 2019; Apart from the H2 production activity, the long-term stability of
photocatalyst is another concern with the sacrificial agents. It is
reported that the P25 photocatalyst deactivates in long-term
recycle tests in electrolytes with sacrificial agents, as presented in
Fig. 6a. It is thus crucial to understand the deactivation mechanism
for improved lifetime. Unexpected irreversible reactions may arise
in the photocatalyst under light irradiation, where the accumula-
tion of photogenerated charge carriers causes the deactivation
(Huang et al., 2020). For example, by using methanol as a sacrificial
agent, Huang and co-workers revealed that the intermediate
products of formaldehyde and formic acid were responsible for the
catalyst deactivation through in-situ spectroscopy. The formic acid
could destroy the Pt cocatalyst, while the formaldehyde simulta-
neously suppressed the Pt and TiO2 catalysts and played a major
role in the deactivation (Fig. 6c). The rutile TiO2 was the bottleneck
that resisted to the deactivated intermediate. The catalytic activity
could be restored by approximately 80% through washing away the
deactivated catalysts (Fig. 6b and d). As such, it is necessary to
investigate the long-term stability and reusability of photocatalysts,
and to understand the reaction mechanism of the catalyst with
sacrificial agents.
Besides the organic sacrificial agents, organic compounds with
functional groups can also facilitate the charge separation. For
Fig. 4. The illustration of Mie resonance, light harvesting, and charge separation.
Reproduced with permission from ref.(Yao et al., 2020), Copyright 2020, Elsevier Ltd.
example, the electron-rich microenvironment produced by eNH2

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Y. Zhao, Y. Li and L. Sun Chemosphere 276 (2021) 130201

Fig. 6. (a) Hydrogen evolution with Pt/P25 in methanol-water solution. (b) Hydrogen evolution with non-deactivated Pt/P25, deactivated Pt/P25, and reactivated Pt/P25. Schematic
illustrations of the proposed deteriorative mechanism (c) and the water wash mechanism (d). Reproduced with permission from ref.(Huang et al., 2020), Copyright 2020, Elsevier
Ltd.

from the highest occupied molecular orbital of chitosan can attract

the holes in the valance band of CdS. This gives rise to the charge
separation and prevents the CdS from photocorrosion, as presented
in Fig. 7 (Zhang et al., 2020e). Similar to the chitosan, the ethyl-
enediamine (EDA) is used to modifyTiO2 surface for enhanced light
absorption (Fig. 8a). The electron-rich environment generated by
EDA on the photocatalyst surface weakens the attraction between
the electrons in the CB and the holes in the VB (Hu et al., 2020).
Thus, the separation efficiency is enhanced (Fig. 8b). The density
functional theory (DFT) calculation results explained that the H2O
and Hþ were not adsorbed at the EDA surface or the EDA/TiO2
interface, but the TiO2 surface that far from the EDA. This result
suggested that the hydrogen production site was at the TiO2 surface
rather than the EDA deposition site (Hu et al., 2020). The study
provided a deep understanding on the mechanism of the photo-
catalytic reaction and surface reactive sites. However, it requires
further study on the long-term stability and solar-to-hydrogen
conversion performances.

2.3. Heterojunctions
Fig. 7. Schematic illustration of reduced photocorrosion mechanism on sacrificial
Heterojunction photocatalysts are designed for extended light agent modified Chitosan@CdS. Reproduced with permission from ref. (Zhang et al.,
absorption and efficient charge separation. The semiconductors 2020e), Copyright 2020, Elsevier Ltd.

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Y. Zhao, Y. Li and L. Sun Chemosphere 276 (2021) 130201

Fig. 8. (a) The procedure to prepare the TiO2-EDA photocatalyst and (b) the hydrogen evolution mechanism. Reproduced with permission from ref. (Hu et al., 2020), Copyright 2020,
Elsevier Ltd.

should exhibit suitable band structures to establish favorable band electrons and holes accumulate on semiconductor B. When two
alignment. Fig. 9 illustrates four typical heterojunctions, i.e., Type I, semiconductors exhibit stepped energy band alignment, a Type II
Type II, Z-scheme, and Schottky junction. When the CB and VB of heterojunction system is formed (Fig. 9b). In the photocatalytic
semiconductor A span that of semiconductor B, a Type I hetero- process, the electrons in the CB of semiconductor A transfer to that
junction is developed (Fig. 9a). In this scenario, both of the of semiconductor B, while the holes in the VB of semiconductor B

Fig. 9. Schematic illustrations of different heterojunctions: (a) Type I, (b) Type II, (c) Z-scheme, and (d) Schottky junction. Reproduced with permission from ref. (Hou and Zhang,
2020), Copyright 2020, Elsevier Ltd.

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Y. Zhao, Y. Li and L. Sun Chemosphere 276 (2021) 130201

transfer to that of semiconductor A. Such a heterojunction is [apparent quantum efficiency (AQE)] of 5-PCT and 10-HCT was
favorable for efficient charge separation. The band alignment in a Z- investigated (Fig. 11). The Type II heterojunctions exhibited higher
scheme heterojunction is similar to that of a Type II heterojunction, AQE under full-spectrum light irradiation. Further studies are
where the charge transfer pathways are different. As presented in necessary to disclose the active sites for H2 evolution and to further
Fig. 9c, the holes in the VB of semiconductor A combine with the understand the mechanism for progressive enhancement.
electrons that migrate from the CB of semiconductor B. When a The solar spectrum is currently underutilized, as most of the
metal is coupled with a semiconductor, the Schottky junction forms studies make use of only UV and/or visible light irradiation. How-
at the semiconductor/metal interface, which is discussed in Section ever, the UVevisible light accounts for a limited proportion of the
2.1. The charge transfer route of Z-scheme heterojunction improves full spectrum. It is appealing to explore the utilization of infrared
the charge separation and maintains the redox capability. However, (IR) radiation of more than 50% solar energy. Active IR-harvested
most of the current Z-scheme photocatalysts still have a narrow photocatalysts of cobalt titanate nanorods layered double hydrox-
light-response range. Their quantum efficiency and durability for ide (CTN-LDH) were prepared using chloride-based precursors
practical applications are far from satisfactory. Therefore, it remains (Mostafa et al., 2020). The narrow bandgap (1.4 eV) and specific
great challenge to explore more effective Z-scheme photocatalysts. nanostructure were responsible for high IR photocatalytic activity
Miodynska and co-workers constructed a heterojunction by and active site distribution (Fig. 12a and c). The recycling experi-
using lanthanide-doped Bi2S3 and TiO2 (Miodynska et al., 2020). ments indicated that the CTN-LDH displayed good structural and
Bi2O3 was developed in the doping process, and formed a type II photocatalytic stability under IR irradiation (Fig. 12b). This study
heterojunction with TiO2. The theoretical calculations revealed that provided an opportunity to explore IR-excited photocatalysts for H2
the Er/Yb doping could introduce defects into the Bi2S3 lattice and evolution. Further direct experimental evidences could be explored
form new energy levels. This extended the light absorption, accel- by in situ observation technology in order to understand the role of
erated the charge transport and inhibited the charge recombination CO2
3 in the photocatalytic process.
during photocatalytic reactions. By engineering the band structure
of CdS with different phases, Luo and co-workers fabricated a Type
II heterojunction with hexagonal CdS/TiO2 (PCT) and a Type I het- 2.4. Key factors and challenges
erojunction with cubic CdS/TiO2 (HCT) (Luo et al., 2020). The
bandgap energy of CdS in 5-PCT (2.52 eV) was increased compared Currently, the photocatalytic water splitting still exhibits low
with that in photodeposited CdS, because of quantum confinement solar-to-hydrogen conversion efficiency. It is of paramount impor-
effect induced by the ultrasmall particles (6 nm). The bandgap tance to explore novel catalysts and further understand the cata-
energy of CdS in 10-HCT (2.30 eV) was the same as that in hydro- lytic mechanisms. To this end, advanced techniques in operando
thermal CdS, in agreement with the large particle size (50 nm). The conditions are effective means to disclose the dynamics of catalytic
Type II catalysts significantly outperformed the Type I counterparts process with direct experimental evidences. Although rapid
because of the higher activity of electrons in the CB of CdS and holes development has been achieved for photocatalytic water splitting
in the VB of TiO2, as illustrated in Fig. 10 (Luo et al., 2020). Poly- over the last decade, it is still far from the practical application.
vinylpyrrolidone (PVP) was used to modify the catalysts for light Many drawbacks and obstacles remain, such as high costs, limited
corrosion resistance. The solar-to-hydrogen conversion efficiency long-term stability, suitable reactors and protocols. This should be
further addressed in the near future. Moreover, it is essential to

Fig. 10. The mechanism of different CdSeTiO2 heterojunctions under visible and full spectrum light irradiation. Reproduced with permission from ref.(Luo et al., 2020), Copyright
2020, Elsevier Ltd.

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Y. Zhao, Y. Li and L. Sun Chemosphere 276 (2021) 130201

Fig. 11. (a) Hydrogen evolution yields of TiO2 and different CdSeTiO2 heterojunctions; (b) Hydrogen evolution yields of CdS from the corresponding heterojunctions under visible
light irradiation; AQE of 5-PCT (c) and 10-HCT (d) at different wavelength. Reproduced with permission from ref.(Luo et al., 2020), Copyright 2020, Elsevier Ltd.

establish evaluation standards to compare the solar-to-hydrogen 2020d). Recently, the pharmaceutical pollutions in groundwater
conversion performances in different labs. and soil have become prominent, originated from the pharma-
ceutical industry, hospitals, expired drugs, and pesticides
(Ahmadpour et al., 2020; Bang et al., 2020; Jandi et al., 2020; Wu
3. Photoinduced oxidation for organic degradation et al., 2020a). Substantial quantities of these organic pollutants
are constantly being discovered in various water resources,
The main sources of water pollution have historically been the threatening the health of humans and aquatic organisms (Jandi
contaminants from industrial effluents and heavy metal ions (Yuan et al., 2020; Wang et al., 2020d). Conventional treatments are
et al., 2014; Liang et al., 2015; Kadam et al., 2020; Wang et al.,
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Y. Zhao, Y. Li and L. Sun Chemosphere 276 (2021) 130201

Fig. 12. (a) Bandgap diagram of CTN-LDH. (b) The recycling performances. (c) The mechanism of water splitting. Reproduced with permission from ref.(Mostafa et al., 2020),
Copyright 2020, Elsevier Ltd.

difficult to remove durable organic pollutants, such as phenols and 2020b; Zhang et al., 2020c; Zhao et al., 2020).
pharmaceutical residues, from contaminated water (Zhang et al., The common organic pollutants [e.g., methylene orange (MO),
2020f; Zhou et al., 2020a). Advanced semiconductor photo- methylene blue (MB), rhodamine B (RhB), acid orange 7 azo dye
catalysts have been considered as a promising and energy-efficient (AO7) and phenol], pharmaceuticals (e.g., ibuprofen, tetracycline,
method for pollutant removal under solar irradiation (Kumari et al., doxycycline, oxytetracycline, and naproxen) and VOCs (e.g.,
2020). A large number of semiconductors have been employed as toluene, benzene, o-xylene, ethylene, isopropyl alcohol, and form-
the photocatalysts to decompose the organic pollutants, such as aldehyde) have attracted considerable attention in the related fields
TiO2, ZnO, CdS, and BiOCl (Mishra and Chun, 2015; Kim et al., 2020; (Ahmadpour et al., 2020; Bang et al., 2020; Chen et al., 2020a; He
Raju et al., 2020; Sun et al., 2020; Wu et al., 2020a; Mokhtar et al., et al., 2020a; Liu et al., 2020a; Mamaghani et al., 2020; Mancuso
2021). et al., 2020; Wang et al., 2020b; Yang et al., 2020; Zhang et al.,
Volatile organic compounds (VOCs) that usually exist in the 2020a, 2020c; Zhao et al., 2020).
indoor and urban air, are harmful to the health and living envi-
ronment of human beings. Several techniques based on the 3.1. Mechanism
adsorption, nonthermal plasma, and catalytic oxidation, have been
exploited to improve the air quality (Boulamanti and The mechanism of photocatalytic degradation is similar to the
Philippopoulos, 2009; Cui et al., 2020; Mamaghani et al., 2020; conventional photocatalysis process. Upon light absorption, the
Minella and Minero, 2021). However, these processes generally photoexcited charge carriers move to the catalyst surface and
consume considerable amounts of energy (e.g., heat and electricity) participate in the redox reactions. The degradation of an organic
and may produce secondary pollution and waste. Thus, it is urgent pollutant is associated with four factors: (1) the organic pollutant
to develop environmental-friendly technologies. Photocatalytic should adsorb onto the catalyst surface for reactions; (2) the active
degradation is an effective way to remove the VOCs of low con- charge carriers should be sufficient; (3) the intermediates of
centration from the indoor environments, because of the mild degraded pollutant should be quickly desorbed; and (4) the cata-
conditions and the environmental-friendly products (Wang et al., lysts should be stable during the entire process. Accordingly, the
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Y. Zhao, Y. Li and L. Sun Chemosphere 276 (2021) 130201

morphological control of catalysts aims at porous structure for large 2020). Hydroxyl radicals played a major role, and superoxide ions
surface area to meet Factor (1). Bandgap and facet engineering, and holes also participated in the catalytic reaction. The CB and VB
such as doping, plasmonic modification, and heterojunction con- positions suggested a Z-scheme heterojunction, which promoted
struction (Sun et al., 2018, 2019a, 2019b), are effective in broad- the charge separation (Fig. 13). The C, N, and S co-doped TiO2 with
ening the light absorption and facilitating the charge separation yellow color was synthesized by mixing expired eggs and tetrabutyl
toward Factor (2). Intermediates attached to the surface can deac- titanate for RhB degradation (Kadam et al., 2020). The results
tivate catalysts, which requires further exploration to achieve effi- indicated that the superoxide ions were the main active radicals in
cient energy conversion in terms of Factor (3). The stability is the the catalytic reaction, and both OH$ and holes participated in the
key factor for practical application and requires systematic study. photocatalysis. In addition, no hydrogen peroxide (Fenton reaction)
was detected, suggesting that no hydroxyl radicals were produced
3.2. Organic dyes in the reaction between the holes and water. Dye molecules could
also absorb light and generate holes, which reacted with water or
The photocatalysts usually exist in the form of powders for high hydroxide to produce OH$. This further improved the degradation
surface area. As such, substrate supporters are required for recy- rate ((Chen et al., 2002; Wang et al., 2015; Wu et al., 2019).
clable treatments, such as carbon nanofibers, carbon clothes, filter
papers, and indium tin oxide glasses (Cao et al., 2020; Mpelane 3.3. Pharmaceuticals
et al., 2020; Wang et al., 2020c; Wu et al., 2020a; Zhao et al.,
2020). The suspensible materials, such as Marimo gel beads, can Pharmaceuticals are persistent pollutants that are harmful to
also be used as the supporters (Kaur et al., 2020). humans and aquatic organisms (Miranda et al., 2016). A number of
The TiO2 based catalysts have been widely employed for their heterojunctions have been explored for pharmaceutical degrada-
high stability. Zhou and co-workers synthesized the methyl-capped tion. The Co3O4/TiO2 heterojunction was prepared by growing
Janus TiO2eSiO2 particles (MJTSs) with superior stability and Co3O4 nanodots on TiO2 nanosheet to degrade the enrofloxacin
emulsification ability (Zhou et al., 2020b). The MJTSs exhibited high (ENR) (Figs. 14 and 15). The Z-scheme heterojunction suppressed
photocatalytic activity for MB decomposition while maintaining charge recombination and facilitated charge transportation,
the Pickering emulsion stability under UV light irradiation. How- thereby providing more active species for photocatalytic degrada-
ever, the separation of photocatalysts from water remains a tion (Wang et al., 2020d). The OH$ played a major role in the
shortcoming in practical applications. Other robust photocatalysts photocatalytic process. Possible degradation routes are presented
were prepared by coating SiO2, TiO2, and SiO2/TiO2 onto reusable in Fig. 15. The final products were CO2, H2O, and NHþ 4 after miner-
Fe3O4 magnetic particles (Sultana et al., 2020). The photocatalysts alization. Photocatalytic activity decreased because of the incom-
with a TiO2 topcoat rendered higher catalytic activity than that plete collection of catalysts during each run in four recycling tests.
with SiO2 counterparts because of better light harvesting ability. Therefore, it is essential to explore reusable catalysts, such as films
Catalytic performance decreased by only 1.5% after 10 cycles, that can be collected and reused easily. In addition, the long-term
indicating the robustness of the structure. recycling tests should be conducted to study the effects of in-
The active species provide major contributions to the catalytic termediates on photocatalytic activity (Sun et al., 2019c).
process. Sun and co-workers studied the degradation of bisphenol Similar to the aforementioned studies, the CdS/Fe3O4/TiO2 het-
A, 2,6-dichlorophenol, and 2,4,5-trichlorophenol under visible light erojunction was prepared hydrothermally and applied to the
irradiation using CdS/ZnO1-x-TiO2-x heterojunctions (Sun et al., degradation of ibuprofen under visible light (Zhou et al., 2020a).

Fig. 13. The proposed photocatalytic degradation process of CdS/ZnO1-x-TiO2-x under visible light. Reproduced with permission from ref (Sun et al., 2020). Copyright 2020, Elsevier
Ltd.

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Y. Zhao, Y. Li and L. Sun Chemosphere 276 (2021) 130201

Fig. 14. The schematic illustration of Co3O4/TiO2 and Z-scheme heterojunction system. Reproduced with permission from ref. (Wang et al., 2020d), Copyright 2020, Elsevier Ltd.

Holes and OH$ had prominent contributions to the photocatalytic the CdS photocorrosion. The degradation rate was approximately
reactions. No O
2 $ radicals were observed during the entire reaction. 75% after four recycling tests.
The photocatalyst could be separated magnetically from water
because of the Fe3O4 species. The Fe3O4 could capture the photo-
3.4. Volatile organic compounds
generated electrons and holes in light of the Fe3þ/Fe2þ redox cou-
ples, thereby improving the separation efficiency and suppressing
Aromatic hydrocarbons are typical volatile organic compounds

Fig. 15. Proposed photodegradation pathways of ENR with Co3O4/TiO2 under light irradiation. Reproduced with permission from ref. (Wang et al., 2020d), Copyright 2020, Elsevier
Ltd.

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Y. Zhao, Y. Li and L. Sun Chemosphere 276 (2021) 130201

Fig. 16. (a) Gibbs energy of ring-opening reaction by DFT calculation. (b) The role of methyl number in photocatalytic decomposition of benzene, toluene and o-xylene. Reproduced
with permission from ref. (Chen et al., 2020a), Copyright 2020, Elsevier Ltd.

and difficult to decompose naturally because of the presence of et al., 1974). Oxygen tends to attack the carbon atom with the
stable benzene rings. Therefore, the ring-opening reaction is the highest electron density and the least steric obstruction. According
key to a complete decomposition of aromatic VOCs (Fig. 16). Ac- to the alkane oxidation mechanism, the alcoholic intermediates
cording to previous reports, the conjugated p system could be usually develop on the Cprim, Csec and Ctert atoms and are oxidized
broken by the oxidation of OH$ in the benzene rings (Chen et al., into aldehyde or ketone. In the case of Csec and Ctert atoms, the
2020a). The distribution of the delocalized electrons in the conju- intermediates may be first dehydrated into an olefin. In addition, a
gated p system was tailored by the presence of methyl on the high degradation efficiency was observed with the increasing
benzene rings. The bond order of carbonecarbon bonds on the molecular chain (He et al., 2020a). The presence of heteroatoms
aromatic rings was thus weakened, thereby affecting the efficiency affects the photocatalyst deactivation. The influence of VOC func-
of ring-opening reactions. The DFT calculation and experimental tional group on the deactivation efficiency was however insuffi-
results demonstrated a relationship between the degradation effi- ciently studied.
ciency and structural stability of the aromatic VOCs with different
methyl numbers (Chen et al., 2020a). The N-doped graphite carbon 3.5. Key factors and challenges
(GC-N)emodified TiO2 was prepared by pyrolyzing zeolitic imida-
zolate frameworke8 with a hydrothermal method (Qin et al., 2020). Photocatalytic degradation shows great potential to convert
The resulting GC-N-TiO2 exhibited an enhanced activity toward organic pollutants, pharmaceuticals, and VOCs into environmental-
toluene degradation compared with Pt counterparts. The photo- friendly products. However, some major challenges still exist and
catalysts displayed high durability with stable activity after 20 re- limit the practical application. The intermediates or products that
cycles, ascribed to the high conductivity and stability. In addition, are adsorbed on the catalyst surface gradually deactivate photo-
the N-doped graphite carbon was rich in pyridinic N, promoting the catalysts. This reduces the long-term stability and activity of the
transportation of electrons and improving the generation of ROSs. photocatalysts. Systematic studies are required to well understand
As the VOC degradation takes place at the solid/gas interface, the mechanism and develop novel alternatives. Besides, the toxicity
the intermediate products generally compete with the VOCs on of the byproducts during the pollutant degradation should also be
photocatalyst surface. The catalytic activity can be reduced or even considered toward a completely sustainable route.
deactivated by the formation and accumulation of intermediates on Most of the studies employ simulated water instead of real
the catalyst surface. The accumulation accelerates with the waste water; in this case, the effects of natural and dissolved
incomplete reaction, thereby inhibiting the ROS generation. Zhang organic species, inorganic salts, and suspended solid particles may
and co-workers identified three possible reasons for the coke be ignored during photocatalytic degradation. This gap should be
involvement in the superficial state changes of photocatalysts addressed to expand the applicability of photocatalysts. Currently,
(Zhang et al., 2020c). Firstly, the coke on the surface might reduce the photocatalysts that offer promising performance are limited to
the VOC adsorption and light absorption. Secondly, the coke might the laboratory scale. The use of UV lamps and solar simulators
serve as the centers for charge recombination because of the un- promotes the total cost. The activity, stability and scalability of
stable structure and impurities. Finally, the mineralization of coke promising catalysts should be tested especially under natural
might compete with the VOCs and weaken their degradation. sunlight.
Clearly, the accumulation of intermediates is a crucial factor
affecting the photocatalytic activity. As such, the adsorption per-
4. Summary and outlook
formance of intermediates should be systematically studied for
efficient VOC degradation. In this regard, sacrificial agents could be
In summary, two photocatalytic processes are highlighted
developed to adsorb the intermediates, hence releasing the active
herein: photoinduced reduction for water splitting and photoin-
sites on the photocatalyst surface.
duced oxidation for organic degradation. For water splitting, three
The number of carbon atoms and heteroatoms, molecular ste-
general ways are focused based on the state-of-the-art reports, i.e.,
reochemical structures, and functional group types might also
cocatalyst loading, sacrificial agent employment, and hetero-
affect the deactivation behaviors (Chen et al., 2020a; He et al.,
junction construction. Bandgap and interfacial engineering are
2020a). It was reported that the reactivity of tertiary carbon
deployed to improve light absorption, charge separation and sur-
(Ctert) was the highest, with the quaternary, secondary, and primary
face reaction for enhanced H2 evolution. It is essential to develop
carbon (Cquat, Csec, Cprim) being decreased in sequence (Djeghri
stable photocatalysts suitable for visible and infrared light
12
Y. Zhao, Y. Li and L. Sun Chemosphere 276 (2021) 130201

harvesting. Further mechanistic studies should be conducted to g-C3N4@TiO2 hollow spheres for enhanced visible-light induced catalytic CO2
reduction. Sol. Energy 205, 465e473.
reveal the active sites on the catalyst surfaces using advanced
Djeghri, N., Formenti, M., Juillet, F., Teichner, S.J., 1974. Photointeraction on the
techniques. Earth-abundant and environmental-friendly materials surface of titanium dioxide between oxygen and alkanes. Faraday Discuss.
are favorable for cost-effective and pollution-free photocatalysts. Chem. Soc. 58, 185e193.
For organic degradation, three major kinds of targeting pollut- Fujishima, A., Honda, K., 1972. Electrochemical photolysis of water at a semi-
conductor electrode. Nature 238, 37e38.
ants are discussed based on recent emerging trends, i.e, organic Fukui, M., Koshida, W., Tanaka, A., Hashimoto, K., Kominami, H., 2020. Photo-
dyes, pharmaceuticals, and volatile organic compounds. The deac- catalytic hydrogenation of nitrobenzenes to anilines over noble metal-free TiO2
tivation mechanism, long-term stability, scalability of the photo- utilizing methylamine as a hydrogen donor. Appl. Catal. B Environ. 268, 118446.
Gao, R., Yan, D., 2019. Recent development of Ni/Fe-based micro/nanostructures
catalysts are critical issues to be addressed for practical toward photo/electrochemical water oxidation. Adv. Energy Mater. 10, 1900954.
applications. Hafeez, H.Y., Lakhera, S.K., Ashokkumar, M., Neppolian, B., 2019. Ultrasound assisted
The extended applications of photocatalysts for organic syn- synthesis of reduced graphene oxide (rGO) supported InVO4-TiO2 nano-
composite for efficient hydrogen production. Ultrason. Sonochem. 53, 1e10.
thesis have generated increasing interest. Well-designed photo- Hao, X., Hu, Y., Cui, Z., Zhou, J., Wang, Y., Zou, Z., 2019. Self-constructed facet
catalysts of high activity and selectivity are crucial for further junctions on hexagonal CdS single crystals with high photoactivity and pho-
development. To this end, catalytic process and mechanism should tostability for water splitting. Appl. Catal. B Environ. 244, 694e703.
He, F., Muliane, U., Weon, S., Choi, W., 2020a. Substrate-specific mineralization and
be systematically studied to disclose the active and critical species. deactivation behaviors of TiO2 as an air-cleaning photocatalyst. Appl. Catal. B
Environ. 275, 119145.
He, F., Zhu, B., Cheng, B., Yu, J., Ho, W., Macyk, W., 2020b. 2D/2D/0D TiO2/C3N4/
Declaration of competing interest
Ti3C2 MXene composite S-scheme photocatalyst with enhanced CO2 reduction
activity. Appl. Catal. B Environ. 272, 119006.
The authors declare no conflicts of interest. Helmy, E.T., Abouellef, E.M., Soliman, U.A., Pan, J.H., 2020. Novel green synthesis of
S-doped TiO2 nanoparticles using Malva parviflora plant extract and their
photocatalytic, antimicrobial and antioxidant activities under sunlight illumi-
Acknowledgement nation. Chemosphere 271, 129524.
Hou, H.L., Zhang, X.W., 2020. Rational design of 1D/2D heterostructured photo-
catalyst for energy and environmental applications. Chem. Eng. J. 395, 125030.
The authors are grateful for the financial support from the Na- Hu, J., Xie, J., Jia, W., Zhang, S., Wang, S., Wang, K., Cao, Y., 2020. Interesting molecule
tional Natural Science Fundation of China (No. 51771011 and adsorption strategy induced energy band tuning: boosts 43 times photo-
51871037), the National Key Research and Development Program of catalytic Water splitting ability for commercial TiO2. Appl. Catal. B Environ. 268,
118753.
China (No. 2020YFF0421893), and the Chongqing Youth Talents Huang, H., Feng, J., Zhang, S., Zhang, H., Wang, X., Yu, T., Chen, C., Yi, Z., Ye, J., Li, Z.,
Program (No. CQYC201905023). Zou, Z., 2020. Molecular-level understanding of the deactivation pathways
during methanol photo-reforming on Pt-decorated TiO2. Appl. Catal. B Environ.
272, 118980.
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