Received: 19 October 2021 | Revised: 26 November 2021 | Accepted: 27 November 2021

DOI: 10.1002/cey2.179

REVIEW

Advances in Z‐scheme semiconductor photocatalysts

for the photoelectrochemical applications: A review

Jiaxin Li1 | Hao Yuan1 | Wenjie Zhang1 | Bingjun Jin2 | Qi Feng2 |

Jan Huang2 | Zhengbo Jiao1

1
Institute of Materials for Energy and
Environment, and College of Material
Science and Engineering, Qingdao
University, Qingdao, P. R. China
2
School of Applied Physics and Materials,
Wuyi University, Jiangmen, P. R. China
Correspondence
Bingjun Jin, School of Applied Physics
and Materials, Wuyi University,
Jiangmen 529020, P. R. China.
Email: zhmjbj2008@163.com
Zhengbo Jiao, Institute of Materials for
Energy and Environment, and College of
Material Science and Engineering,
Qingdao University, Qingdao 266071,
P. R. China.
Email: jiaozhb@qdu.edu.cn
Funding information
Natural Science Foundation
of Shandong Province of China,
Grant/Award Number: ZR2019MB006;
Natural Science Foundation of
Guangdong Province,
Grant/Award Number: 2018A030313460
Abstract
With continuous consumption of nonrenewable energy, solar energy has been
predicted to play an essential role in meeting the energy demands and miti-
gating environmental issues in the future. Despite being green, clean and
pollution‐free energy, solar energy cannot be adopted directly as it cannot
provide sufficiently high energy density to work in the absence of machinery.
Thus, it is necessary to develop an effective strategy to convert and store
solar energy into chemical energy to achieve social sustainable development
using solar energy as the main power source. Photocatalysis, in which semi-
conductor photocatalysts play a key role, is one of the most promising can-
didates for realising the effective utilisation of sunlight in a green, low‐cost and
environmentally friendly method. The photocatalytic efficiency of photo-
catalysts is considerably influenced by their compositions. Among the various
heterostructures, Z‐scheme heterojunction is one of the most interesting ar-
chitecture due to its outstanding performance and excellent artificial imitation
of photosynthesis. Z‐scheme photocatalysts have attracted considerable at-
tention in the past few decades. Herein, we review contemporary Z‐scheme
systems, with a particular focus on mechanistic breakthroughs, and highlight
current state‐of‐the‐art systems. Z‐type photocatalysts are classified as tradi-
tional, all‐solid‐state, direct Z‐schemes and S‐scheme photocatalysts. The
morphology, characterisation and working mechanism of each type of
Z‐scheme are discussed in detail. Furthermore, the applications of Z‐scheme
in photoelectrochemical water splitting, nitrogen fixation, pollutant degrada-
tion and carbon dioxide reduction are illustrated. Finally, we outline the main
challenges and potential advances in Z‐scheme architectures, as well as their
future development directions.

KEYWORDS
heterostructure, photocatalysis, photoelectrochemical, water splitting, Z‐scheme

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
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© 2022 The Authors. Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.

294 | wileyonlinelibrary.com/journal/cey2 Carbon Energy. 2022;4:294–331.

LI ET AL.
1 | INTRODUCTION
The consumption of fossil fuels has increased rapidly in
contemporary times, which has brought on severe energy
and environmental issues. The development of new
green energy is necessary because contemporary sources
of energy, such as oil, natural gas and coal, are non-
renewable.1 The reserves of these fuels on Earth are
diminishing due to their constant consumption, ne-
cessitating sustainable energy sources for development.
Excessive use of fossil fuels has also led to the green-
house effect, which has prompted the development of
synthetic, clean and renewable energy. Thus, there has
been considerable research interest in exploring sus-
tainable energy sources and developing environmentally
friendly technology. Hydrogen is such a new secondary
energy source that can satisfy this purpose, and thus,
related technology has advanced greatly in the past sev-
eral decades.2–4 Photocatalytic water splitting driven by
solar energy is a green and economical strategy for ob-
taining hydrogen energy, in which photocatalysts with
high activity and stability become the essential factors.
As a typical n‐type photocatalyst, titanium dioxide
has received widespread attention as Fujishima and
Honda reported, in Nature, for the first time, that it
exhibits the ability to split water in the presence of ul-
traviolet light.5 This breakthrough has stimulated en-
thusiasm in photocatalysis. Photocatalytic technology is
also used to decompose organic wastes or reduce CO2 for
small molecular organics as the electrons and holes in
semiconductor materials are excited by light.6 In the past
several decades, environmentally friendly photocatalysis
technologies have developed rapidly as a new discipline.7
When a semiconductor is irradiated by solar light with
energy larger than its band gap, a photogenerated elec-
tron transition orbit is formed between the valence band
(VB) and the conduction band (CB) and free electrons
(e−) move between these bands. At the same time, po-
sitively charged holes (h+) are left in the VB. Electrons
assembled in the CB lead to a reduction reaction, and the
holes participate in the oxidation reaction. Under light
irradiation, a photocatalytic reaction occurs on the sur-
face of a photocatalyst, which is similar to photosynth-
esis, producing free hydroxyl groups and active oxygen
with strong oxidising ability. Photocatalysts exhibit
strong photoredox performance, and they can oxidise and
decompose various organic compounds. Some inorganic
substances can kill bacteria and viruses by destroying
their cell membranes and the protein content, respec-
tively, or decompose organic pollutants to produce non‐
polluted water and carbon dioxide. Owing to their merits,
photocatalysts are widely used in various fields, such as
air purification,8,9 water purification,10 N2 fixation,11–13
| 295
CO2 reduction14,15 and hydrogen production.16–18 Thus,
there has been extensive research interest in photo-
catalytic technologies to provide insights for advance-
ments in the field of energy and the environment.
However, the photocatalytic efficiency largely depends
on the choice of semiconductor materials; the positions of
the CB and VB determine the oxidation–reduction ability of
the photocatalyst, directly affecting the photocatalytic effi-
ciency. The main requirement for photocatalyst perfor-
mance is designing and synthesising nanomaterials with
high strength, coordinated chemical activity, specificity
and selectivity. Excellent photocatalysts should be en-
vironmentally friendly and exhibit strong light stability and
low price. Studies have shown that while light‐induced
electrons can transfer steadily, it is hard to extract electrons
because the rate of transfer of holes is approximately 2–4
times of magnitude slower than that of transfer of electrons.
Therefore, the removal of holes is considered a key step that
influences the efficiency of O2 and H2 evolution. Single‐
component photocatalysts have not been widely applied
due to their low exchange efficiencies, narrow absorption
ranges, poor stabilities and weak redox abilities. Moreover,
photogenerated carriers in the excited state are easily re-
combined, which results in a low photocatalytic conversion
rate. Therefore, composite photocatalysts comprising two or
more types of semiconductors are preferred over single‐
component photocatalysts as they can increase catalytic
efficiency. When two semiconductors are connected, a
channel is formed between individual semiconductors;
holes in the first photocatalyst combine with electrons in
the second photocatalyst, with the band energy of the two
photocatalysts being similar, resulting in remarkable redox
ability. This photocatalyst scheme is known as Z‐scheme,
and it is attributed to the heterojunction of carriers moving
as they form the letter ‘Z’.19 It is worth noting that the
construction of artificial Z‐scheme photocatalysts inspired
by natural photosynthesis provides a feasible strategy to
overcome these bottlenecks.20 As for the difference between
S‐scheme and Z‐scheme photocatalyst, the S‐scheme pho-
tocatalyst is usually composed of two n‐type semi-
conductors, while the Z‐scheme is usually composed of
n‐type and p‐type semiconductors. In addition, the con-
struction of the Z‐scheme photocatalyst is inspired by the
natural photosynthesis process and the S‐scheme photo-
catalyst is named for its staggered band structure.
Besides, it is emphasised that the two semiconductors
constituting S‐scheme photocatalyst are referred to as oxi-
dation photocatalysts and reduction photocatalysts. The S‐
scheme photocatalyst works by the joint effort of the built‐
in electric field, Coulomb interaction and band energy
bending. According to the band gap and electronic energy
levels of semiconductors, semiconductor heterojunctions
can be primarily classified into five types, namely straddling
296 | LI
alignment (type‐I),21 staggered alignment (type‐II),22,23
Z‐scheme system, p‐n heterojunctions24–26 and
27
homojunctions. Among these types, type‐II and Z‐scheme
heterojunctions have been extensively studied. In type‐II
heterojunctions, it is hard to separate photogenerated
electrons and holes. Moreover, the transfer mode weakens
the overall redox capability of the type‐II heterojunction, as
shown in Figure 1A.28 Interface Coulomb resistance is
not conducive to charge transfer. However, unlike the
electron–hole transfer mode of traditional type‐II hetero-
junctions, Z‐scheme heterojunctions retain the strong
reduction ability of photogenerated electrons in the photo-
catalyst (PC) I component CB and the strong oxidation
ability of photogenerated holes in the PC II component VB,
as illustrated in Figure 1B. When PC I and PC II are in
contact, the free electrons of PC I will be transferred to PC
II until their Fermi levels reach equilibrium. Therefore, the
PC I side is positively charged, and the PC II side is nega-
tively charged at the interface. As a result, a built‐in electric
field is formed and band edge bending occurs. Photo-
generated electrons in PC II can easily combine with the
photoexcited holes in PC I in Z‐scheme systems. Thus,
Z‐scheme heterojunctions can improve the separation effi-
ciency of photogenerated carriers while retaining the
oxidation–reduction ability of the catalyst.29
In the past several years, the research on Z‐scheme
systems has attracted more and more interest due to the
large advances in its production and the further under-
standing of its mechanism. It is thus of great importance to
summarise the recent achievements in Z‐scheme photo-
catalysts. This review summarises the recent advances in
Z‐scheme photocatalysts and their various applications.
Moreover, most contemporary reviews have proposed
synthesis strategies and specific photocatalytic reactions
using specific bases or applications of Z‐scheme photo-
catalysts. However, rare studies have summarised the
comprehensive photoelectrochemical (PEC) characteristics
of Z‐scheme photocatalysts. The present review classifies
Z‐scheme photocatalysts based on different criteria, and
ET AL.
the PEC characteristics and applications of Z‐scheme
have been discussed in detail. It will also provide insights
into advances in Z‐scheme photocatalysts, which may
contribute to the development of this architecture.
2 | CLASSIFICATION
Z‐scheme photocatalysts are typically categorised accord-
ing to various criteria. According to the different transport
media, Z‐scheme photocatalysts are divided into tradi-
tional Z‐scheme photocatalysts, all‐solid‐state Z‐scheme
photocatalysts and direct Z‐scheme photocatalysts.
2.1 | Traditional Z‐scheme
photocatalysts
Traditional Z‐scheme photocatalysts comprise two
photocatalysts and a pair of acceptors/donors, which are
called shuttle redox mediators. Ionic Z‐scheme photo-
catalyst materials, as typical Z‐scheme photocatalysts,
have been studied since 1997.19 Their reactions rely on
the charge transport of redox electronic media. Common
redox media include the following types: Fe3+/Fe2+,
I−/IO3− and others; recent advancements of traditional
Z‐scheme photocatalysts are highlighted in Table 1. The
charge‐transfer mechanism of ionic Z‐scheme photo-
catalytic reactions is illustrated in Figure 2. The VB of PC
II is excited by light and electrons transition to the CB.
The holes in the VB of PC II can oxidise H2O to O2 and
generate H+. Excited‐state electrons in the CB of PC II
react with high‐valence ions in the redox electron med-
ium. The VB of PC I is excited by light and the electrons
transition to the CB to reduce H+ to hydrogen. The holes
in the VB of PC I react with low‐valent ions in the redox
electron medium to generate high‐valent ions.
Li's study30 reported a unique shuttle redox mediator for
removing holes in photocatalysts to efficiently produce O2.
F I G U R E 1 Schematic illustration of the
charge carrier transfer for (A) type‐II and
(B) Z‐scheme heterojunctions
LI ET AL.
TABLE 1 Summary of representative traditional Z‐scheme photocatalyst
Catalyst Mediator
−
mpg‐C3N4/Ag/AgCl Cl /Cl·
VI VI VI 4− V 5−
K4[SiW11 Mo O40] [SiW11Mo O40] /[SiW11Mo O40]
− 3−
GaN:ZnO–Ni/NiO I /IO
SrTiO3:Rh/Sb Fe3+/Fe2+
TaON/Ta3N5 I−/IO3−
− −
Sm2Ti2S2O5/H‐Cs‐WO3 I /IO
F I G U R E 2 Schematic illustration of charge transfer
mechanism in traditional Z‐scheme photocatalyst, where A and D
represent electron acceptor and donor, respectively
Their system has three components: mesoporous graphite
carbon nitride (mpg‐C3N4) as the photocatalyst, silver ni-
trate as the sacrificial electron acceptor and La2O3 as the
pH buffer solution for O2 generation. Figure 3A,B shows
the high‐resolution transmission electron microscope
(HRTEM) images of precipitation after photoillumination
and Ag/AgCl heterojunction, respectively, demonstrating
that Ag and AgCl nanoparticles were uniformly dis-
tributed on the surface of mpg‐C3N4. The formation of Ag/
AgCl heterostructure indicates that the in situ generated
Ag nanoparticles were in close contact with the AgCl
semiconductor. The release rate of O2 increased sig-
nificantly under 450 nm radiation after KCl was in-
troduced into an aqueous solution, which was more than
10 times faster than that recorded on mpg‐C3N4 without
Cl−. KCl solutions of different concentrations were used to
test the photocatalytic activity of the samples at room
temperature, and the results are shown in Figure 3C. The
photocatalyst mpg‐C3N4/Ag/AgCl that is formed in situ
allows Cl− to remove holes in the VB of AgCl to form Cl
radicals that can oxidise hydroxide (OH)− ions for direct
O2 production, which is accompanied by the regeneration
of Cl− (Figure 3D).
Ionic photocatalysts are prone to side reactions, and
at the same time, high‐valence ions easily react with the
CB electrons of PC I. Low‐valence ions can also undergo
similar reactions. However, the application of ionic
| 297
Synthesis method Application References
Deposition‐precipitation O2 evolution [30]
Deposition‐precipitation Water splitting [31,32]
Calcination Hydrogenation of CO2 [33]
Hydrothermal Water splitting [34]
Deposition Water splitting [35]
Flux method Water splitting [36]
Z‐scheme photocatalysts is limited because these photo-
catalysts require an aqueous solution for their applica-
tion. Due to defects of the redox electronic medium, the
traditional Z‐scheme photocatalyst has been gradually
replaced by the solid Z‐scheme photocatalyst.
2.2 | All‐solid‐state Z‐scheme
photocatalysts
Depending on the presence or absence of electronic con-
ductors, all‐solid‐state Z‐scheme photocatalysts are classified
into PC I–conductor–PC II and PC I–PC II,36 whose me-
chanisms are also different, as shown in Figure 4A and 4B,
respectively. The purpose of all‐solid‐state Z‐scheme pho-
tocatalysts is to eliminate the use of redox pairs by replacing
them with nanoconductors and expand the range of appli-
cation. However, the charge‐transfer route in the all‐solid‐
state Z‐scheme is completely different from the one it gen-
erates. The electrons in the photocatalyst with a higher CB
potential are preferentially transferred to the photocatalyst
with a lower VB potential through the conductor, which is
due to the greater driving force generated by the higher
potential difference. If the conductor is not completely lo-
cated between the two photocatalysts, electrons can also be
transferred to the surface through the conductor.
There are many types of electronic media, such as
metals, carbon quantum dots, oxides and nonoxides. Based
on the electronic media composition, PC I–conductor–PC II
photocatalysts can be further categorised.
Noble metal nanoparticles have attracted attention as a
new high‐efficiency medium that is suitable for collecting
light energy for chemical processes because they have
high optical absorption in a wide range of sunlight spectra,
including visible light and ultraviolet light. The localised
surface plasmon resonance effect exists in noble metal
nanoparticles that couple the light flux to the conductive
electrons of those metal nanoparticles. The excited elec-
trons and enhanced electric fields near nanoparticles can
assist the conversion of solar energy into chemical energy
through photocatalytic reactions driven by photons.
298 | LI ET AL.

F I G U R E 3 (A) HRTEM images of precipitation after photoillumination; (B) HRTEM images of Ag/AgCl heterojunction; (C) kinetics of
photochemical O2 evolution with different concentration of KCl measured using the Clark electrode, mpg‐C3N4 0.5 mg, La2O3 4 mg, AgNO3
3.5 mg, deionised (DI) H2O 2 mL, illumination with 450 nm LED; (D) in situ formed mpg‐C3N4/Ag/AgCl ternary photocatalyst for the
acceleration of hole transfer and improved O2 evolution. Reproduced with permission: Copyright 2017, Wiley.30 HRTEM, high resolution
transmission microscopy; LED, light‐emitting diode30

F I G U R E 4 Schematic illustration of charge

carrier transfer in (A) PC I–conductor–PC II and
(B) PC I–PC II

Among noble metals, gold has the lowest Fermi level.
When gold is used as an electronic conductor between
CdS and TiO2, both CdS and TiO2 transfer electrons to Au,
balancing the interface charges of the three components
and redistributing the Fermi levels. A Schottky hetero-
junction is formed between Au and CdS or TiO2 that
hinders the successive migration of photogenerated elec-
trons from TiO2 to Au and then to CdS. Thus, gold is not
suitable as the mediator between TiO2 and CdS, and noble
metal nanoparticles are usually used for electronic con-
ductors as they can act as mediator transferring carriers.37
Silver, a typical noble metal, is often used in photo-
catalysis as an electronic conductor. Silver nanoparticles
have great application value in nano‐electronic devices,
biomedical composites and high‐efficiency catalysts due
to their small particle size, large specific surface area and
unique physical and chemical properties, and they have
received widespread attention. Studies have shown that
the optical, electrical and catalytic activities of silver
nanoparticles are strongly dependent on the size, mor-
phology and structures of the particles.
To overcome the disadvantages of pure g‐C3N4, such as
a small specific surface area and a high recombination rate
of light‐induced electron–hole (e−/h+) pairs, which result
in low visible light‐induced photocatalytic performance,
Lu's group presented a highly efficient method for deposi-
tion of Ag nanoparticles to form a Z‐scheme hetero-
structure. In a g‐C3N4/Ag/MoS2 system, silver nanoparticles
LI ET AL. | 299

are fixed on MoS2 nanoflowers, and their photocatalytic
performance is better than that of the corresponding single‐
component and two‐component systems.38 The mechanism
of the system illustrated in Figure 5A shows that the
properties of MoS2 and g‐C3N4 considerably influence the
conduction of Ag nanoparticles, forming a synergy to assist
rapid separation of photo‐induced electron–hole pairs and
suppress the recombination rate, leading to excellent pho-
tocatalytic activity. MoS2 is synthesised to form a three‐
dimensional flower‐like microstructure and g‐C3N4 is
formed into nanosheets, as shown in Figure 5B,C. Detailed
morphology of the g‐C3N4/Ag/MoS2 system is presented in
Figure 5D–G, which clearly shows that MoS2, g‐C3N4 and
Ag coexist in the composites.
Studies have investigated the PEC performance of as‐
prepared samples under on‐ and off‐light conditions; the
g‐C3N4/Ag/MoS2 composites exhibited the highest pho-
tocurrent, which is several times that of other samples
(Figure 6A). A high photocurrent indicates that the se-
paration of light‐induced e−/h+ pairs on the interface is
more effective and leads to a low recombination rate. The
global environmental pollution caused by organic dyes
has become an issue of concern with the development of
human society. The g‐C3N4/Ag/MoS2 composite exhibits

F I G U R E 5 (A) Schematic for the separation and transfer of photogenerated charges in g‐C3N4/Ag/MoS2 nanocomposites; SEM images
of (B) MoS2, (C) g‐C3N4 and (D) g‐C3N4/Ag/MoS2; (E, F) TEM images and (G) SEAD pattern of g‐C3N4/Ag/MoS2. Reproduced with
permission: Copyright 2017, American Chemical Society.38 SEM, scanning electron microscopy; TEM, transmission electron microscopy;
SEAD, selected‐area electron diffraction
300 | LI ET AL.

F I G U R E 6 (A) Surface photocurrent curves a–e: MoS2, Ag/MoS2, g‐C3N4, g‐C3N4/MoS2 and g‐C3N4/Ag/MoS2, respectively; visible
light‐induced photocatalytic degradation of (B) Rhodamine B (RhB), (C) methylene blue (MB) and (D) methyl orange (MO) for different
samples. Reproduced with permission: Copyright 2017, American Chemical Society38

a strong ability to degrade organic dyes, such as RhB, MO
and MB, as shown in Figure 6B–D. Thus, comparative
experiments have demonstrated the excellent perfor-
mance of the g‐C3N4/Ag/MoS2 system.
Nano‐carbon materials have at least one dimension of
<100 nm in the dispersed phase. The dispersed phase com-
prises carbon atoms, heterogeneous atoms (non‐carbon
atoms) or nanopores. Nano‐carbon materials mainly in-
clude three types, namely carbon quantum dots, graphene
and carbon nanotubes. Carbon quantum dots are mono-
dispersed fluorescent carbon nanomaterials (size < 10 nm),
and their geometric shapes are almost spherical, with stable
and adjustable photoluminescence properties. Carbon
quantum dots have a wide absorption range, up‐conversion
luminescence behaviour and good electron transport prop-
erties. The hydroxyl and carboxyl groups on the surface can
be used as nucleation sites for the reaction, forming a
composite system with the photocatalyst through strong in-
terface bonding. The introduction of nitrogen, sulphur and
other doping elements into carbon quantum dots results in
diverse functional groups on the surface, with better water
solubility, biocompatibility and more stable luminescence
properties. When nitrogen combines with carbon to form a
bond, the emission intensity of carbon quantum dots im-
proves. Moreover, the presence of additional electron pairs
due to the defects, which are introduced by the doping of
nitrogen and sulphur elements, provides additional active
sites and improves the local chemical activity of carbon na-
nomaterials. Carbon quantum dots are typically introduced
into photocatalyst systems as electron mediators.
In 2017, Wu's group39 used a hydrothermal method to
design and synthesise a Z‐scheme photocatalyst that works
with carbon quantum dots as a solid conductor. Cadmium
sulphide (CdS) can also be used as an electron transfer
medium to significantly improve the photoelectric conver-
sion efficiency. Carbon quantum dots are first introduced
into BiVO4 nanoparticles through hydrothermal methods,
and thereafter, CdS is introduced into the photocatalyst
system through a facile precipitation method. The accurate
morphology of the synthetic sample, BiVO4/CDs/CdS, is
shown in Figure 7A,B; it promotes charge transport
and photocatalytic activity. The high‐resolution X‐ray
LI ET AL. | 301

(A) (B) (C) 405.6 Cd 3d

412.4

Intensity (a.u.)
402 405 408 411 414 417
Binding energy (eV)
(D) (E) (F)
161.2 CdS
Bi 4f
158.5 BiVO4
S 2p Absorbance (a.u.) BCC50
162.4

Intensity (a.u.)
Intensity (a.u.)

163.8

CdS
BiVO4
BCC50

156 158 160 162 164 166 300 400 500 600 700 450 500 550 600 650
Binding energy (eV) Wavelength (nm) Wavelength (nm)

F I G U R E 7 (A) TEM and (B) HRTEM images of BCC50; high‐resolution XPS spectra of (C) Cd 3d, and (D) Bi 4f and S 2p; (E) UV‐Vis
diffuse reflection spectra (DRS) of BiVO4, CdS and BCC50; (F) PL spectra of BCC50, BiVO4 and CdS. Reproduced with permission:
Copyright 2017, Elsevier,39 TEM, transmission electron microscopy; HRTEM, high‐resolution transmission electron microscopy; XPS, X‐ray
photoelectron spectroscopy; PL, photoluminescence

photoelectron spectroscopy spectra of Cd 3d and Bi 4f & S
2p are shown in Figure 7C,D, which show that Cd species
exist as +2 and Bi species exist as +3. The optical properties
of BiVO4, CdS, and BCC50 (the weight ratio of BiVO4 to
CdS in BiVO4/CDs/CdS is 50) were examined using UV‐Vis
diffuse reflectance spectra (Figure 7E). Photoluminescence
(PL) spectra can show the recombining ability of photo-
generated electron–hole pairs of a photocatalyst. As shown
in Figure 7F, BCC50 samples have the lowest PL intensity
compared with CdS and BiVO4.
As shown in Figure 8A, the VB energies (EVB) of BiVO4
and CdS are 7.23 and 6.73 eV, respectively. The CB energies
(ECB) of BiVO4 and CdS were 4.79 and 4.35 eV, respectively,
which were calculated using the formula Eg = EVB − ECB.
Figure 8B displays the band structures of BiVO4 and CdS.
The Ec level of BiVO4 is more positive than the reduction
level of H+/H2 (0 V vs. RHE), and the Ev level is more
positive than the oxidation level of H2O/O2 (1.23 eV vs.
RHE); as a result, theoretically, H2O is oxidised into O2 by
holes in the VB of BiVO4. Similarly, the ECB level of CdS is
more negative than the reduction energy level of H+/H2.
Thus, Z‐scheme BiVO4/CDs/CdS photocatalysts can split
water to form O2 and H2. The photoresponse performance
of samples can be evaluated using transient photocurrent
technologies. The value of photocurrent reflects the
separation efficiency of electron–hole pairs. The higher the
value, the better is the separation efficiency.
The prepared photocatalysts were placed in a Pyrex
glass photoreactor and irradiated with 420‐nm light through
gas chromatography to determine the H2 and O2 production
rates, which were found to be approximately 1.24 and
0.61 μmol h−1, respectively (Figure 9A). Figure 9B shows
that the H2 and O2 evolution rates were the highest in the
BCC50 system among the samples. PEC measurement re-
sults show that BCC50 exhibited excellent characteristics
with relatively low resistance and high photocurrent, as
presented in Figure 9C,D. In addition to the aforemen-
tioned findings, BCC50 also exhibited excellent stability, as
determined through cycle tests (Figure 9E). In the ultra-
violet spectrum, both BiVO4 and CdS can absorb visible
light under visible light irradiation accompanied by elec-
trons in CB and holes in VB that are generated due to
photoexcitation. Due to the photo‐induced electron transfer
characteristics of carbon quantum dots and the close con-
tact among the three components, as shown in Figure 9F,
photogenerated electrons can quickly migrate from CB in
BiVO4 crystals to the surface of carbon quantum dots and
further transfer to the holes of CdS.
Studies have demonstrated that graphene oxide (GO)
with high electron mobility can act as an electron trap and
302 | LI ET AL.

F I G U R E 8 (A) UPS spectra of BiVO4 and CdS; (B) band structure diagram of BiVO4 and CdS. Reproduced with permission: Copyright
2017, Elsevier.39 UPS, ultraviolet photoelectron spectroscopy

F I G U R E 9 (A) Photocatalytic activity of BCC50 under visible light irradiation for splitting water into H2 and O2; (B) H2 and O2
evolution rates determined using various as‐prepared samples as photocatalysts under visible light irradiation; (C) EIS of BiVO4, CdS and
BCC50; (D) I–t curves of BiVO4, CdS and BCC50; (E) stability of photocatalytic water splitting determined using BCC50 as the photocatalyst;
(F) possible photocatalytic water splitting mechanism of Z‐scheme BiVO4/CDs/CdS photocatalyst. Reproduced with permission: Copyright
2017, Elsevier.39 EIS, electrochemical impedance spectroscopy

reduce carrier recombination. The introduction of GO with
dense atomic and functional groups in Fe‐based MILs can
enhance the adsorption of pollutant molecules, thereby
improving the photocatalytic activity. At the same time, it is
worth noting that GO can be functionalised with magnetic
nanoparticles and facilitate the separation process at the
end of the photocatalytic operation. In the study by Fakhri's
group,40 magnetic GO was proposed to modify MIL‐101
(Fe); in this study, GO with layer morphology was used as a
host for iron nanoparticles. After visible light irradiation,
AFG@MIL‐101(Fe) was excited to generate electron–hole
pairs (Figure 10). The Fenton reaction was initiated by
photoreduction, changing Fe3+ to Fe2+. Thereafter, the
photogenerated electrons migrated to the core of Fe3O4
through the oxide layer. GO enhanced the efficiency of
Fe3+ conversion to Fe2+, which is ideal for generating more
·OH radicals. In the photocatalytic system, the generated
electrons and holes could participate in reduction and
oxidation reactions, respectively, due to their high redox
abilities. Since the CB of MIL‐101 (Fe) is more negative
than the potential of O2/·O2−, the generated electrons can
reduce O2 to ·O2−. By contrast, ·OH radical is another
LI ET AL. | 303

effective group in photocatalytic systems derived from the
oxidant component (H2O2). Finally, active free radicals
excited by light will decompose pesticide structures and
subsequently transform pollutants to H2O and CO2.
F I G U R E 10 Proposed mechanism pathway under visible light
irradiation. Reproduced with permission: Copyright 2020, Elsevier40
Carbon nanotubes (CNTs) are one‐dimensional hollow
tubular structures. Owing to their unique electrical and
mechanical properties and large specific surface areas, they
play an important role in the process of catalysis. When used
as an electron acceptor, electrons can move freely along the
axis of the CNTs owing to the quantum confinement effect.
The carrier migration rate of CNTs is also superior compared
with the characteristics of ballistic transport. Additionally,
their use in combination with other semiconductors through
nanotechnology can lower the band gap and width of CNTs,
significantly improving the photocatalytic performance of
the composite material. Naffati's group synthesised CNT‐Pt/
TiO2 through a one‐pot oxidation/hydrothermal route by
using different amounts of CNTs and titanium dioxide and
used them to produce hydrogen from aqueous methanol and
glycerol solutions under UV‐LED irradiation41; platinum
nanoparticles were used as a cocatalyst in the system. The
introduction of CNTs enhanced the photoresponse of TiO2 to
the visible light region, reduced its band gap, improved
charge mobility and reduced the recombination rate of
electrons and holes. Moreover, CNTs have also been used in
combination with other semiconductors, such as BiVO4,
CdS, g‐C3N4, and BiOI. Some representative all‐solid‐state

TABLE 2 Summary of representative all‐solid‐state Z‐scheme photocatalysts

Catalyst Mediator Synthesis method Application References
BiVO4/CDs/CdS CDs Deposition‐precipitation H2 and O2 evolution [39]
BiVO4/N‐CQDs/Ag3PO4 N‐CQDs Solvothermal‐precipitation Enhanced antibiotic degradation [42]
Zn0.5Cd0.5S‐ MWCNT Coating and hydrothermal Hydrogen evolution [43]
MWCNT‐TiO2
g‐C3N4/GO/AgBr GO In situ growth Degradation of RhB [44,45]
AgBr/GO/Bi2WO6 GO In situ deposition Removal of tetracycline hydrochloride [45]
g‐C3N4/RGO/Bi2WO6 RGO Hydrothermal Degradation of 3,5,6‐trichloro‐2‐ [46]
pyridinol (TCP)
BiVO4/MoS2/RGO RGO Calcination Water splitting [47]
WO3/g‐C3N4/Bi2O3 g‐C3N4 Cocalcination Degradation of refractory pollutant [48]
WO3@Cu@PDI Cu Water bath Degradation of tetracycline [49]
hydrochloride (TC)
BiVO4/Au@CdS Au Hydrothermal and photodeposition Degradation of RhB [50]
BiOCl‐Au‐CdS Au Deposition Degrading water dyes and antibiotics [51]
NaNbO3‐Au‐Sn3O4 Au Ultrasonic dispersion and calcination Degradation of carbofuran [52]
ZnO–Au–SnO2 Au Precipitation Water splitting [53]
BiVO4‐W‐WO3 W Calcination PEC performance [54]
Ag/AgBr/g‐C3N4 Ag Hydrothermal and photoreduction Simultaneous Cr (VI) reduction and [55]
ciprofloxacin oxidation
g‐C3N4/Ag/Ag3PO4 Ag NaCl template‐assisted strategy plus Removal of NO [56]
selective deposition
Ag3PO4/Co3(PO4)2@Ag Ag Precipitation‐photoreduction Degradation activity of tetracycline [57]
Abbreviations: PEC, photoelectrocatalysis; TC, tetracycline hydrochloride; TCP, 3,5,6‐trichloro‐2‐pyridinol.
304 | LI ET AL.

Z‐scheme photocatalysts with different mediators, such as

References
CDs, GO, Cu and Ag, are listed in Table 2.

[67]
[68]
[69]
[70]

[71]
[72]
[73]
[74]
2.3 | Direct Z‐scheme photocatalysts

Traditional photocatalysts require the presence of liquid

hydrogen evolution, CO2 reduction

media, whereas all‐solid‐state photocatalysts require elec-

Degrading water dyes and antibiotics

tronic media with a light‐shielding effect. As a result,
direct Z‐scheme photocatalysts can not only retain the

Photocatalytic degradation,
advantages of the abovementioned Z‐scheme photo-
catalysts but also utilise sunlight effectively and improve

Degradation of RhB
the separation efficiency of electron–hole pairs, realising

Degradation of GF

N2 photofixation
the spatial separation of electrons and holes, as well as

H2 production

H2 production
H2 production
Application
optimised redox capacity. The absence of electronic media
also remarkably reduces the costs, makes the preparation
process easier, and avoids light‐shielding effects.
In solid Z‐scheme catalysts without conductive media,
carriers are directly transported through the interface be-
tween the two semiconductors, which reduces the transport

Smooth surface with tunnel

distance and improves the photocatalytic efficiency. These

Hierarchical microspheres
materials are called direct Z‐scheme photocatalysts, which
Hexahedral structure
contain holes and electrons are the primary conductive
carriers. In direct Z‐scheme photocatalysts, the two semi-

Nanodomains
Microspheres
Morphology

conductors adhere closely through diverse synthesis strate-

Nanosheets

Nanofibers
Nanorods
gies. Photogenerated electron–hole pairs on the surface of a
semiconductor are separated by the electrical field of the
semiconductor–electrolyte junction. Thereafter, the electron–
hole pairs participate in an oxidation–reduction reaction
Summary of representative TiO2‐based direct Z‐scheme photocatalysts

with ions in the solution, which is called the PEC reaction.

Successive ionic layer adsorption and reaction

Semiconductor photoelectrodes are used in PEC cells that

convert light energy into chemical energy, and they are used
Hydrothermal and ultrasonic dispersion

in light absorption and photocatalysis. n‐ and p‐type semi-

conductors comprise a photoanode and a photocathode,
Electrospinning and hydrothermal

which catalyse the oxidation and reduction reactions, re-

Hydrothermal or solvothermal
Hydrothermal and calcination

Annealing and hydrothermal

spectively. Direct Z‐scheme photocatalysts are classified into

Chemical vapour deposition
Solvothermal calcination

several types based on different properties, such as those

based on g‐C3N4, TiO2, BiVO4 and sulphides (CdS)58,59 and
Synthesis method

metal oxides (such as WO3,60–63 ZnO64,65 and Fe2O366).

2.3.1 | TiO2‐based direct Z‐scheme

photocatalysts

TiO2 is an n‐type metal oxide semiconductor with high

chemical stability, corrosion resistance and high
TiO2/(CdS, CdSe, CdSeS)

oxidation–reduction potential. It has a strong driving

TiO2 QDs/Bi12TiO20

force for photocatalytic reactions. However, the band gap

of TiO2 is wide and the utilisation efficiency of solar
ZnFe2O4/TiO2
Ag3PO4/TiO2

CoTiO3/TiO2

energy is low. Moreover, the photogenerated carriers

MoS2/TiO2
TABLE 3

TiO2/CdS

TiO2/NiS
Catalyst

easily recombine, and the quantum yield is low. Several

studies have attempted to improve the characteristics of
TiO2 (listed in Table 3); combination with another
LI ET AL. | 305

suitable semiconductor, such as ZnFe2O4, CdS and visible light absorption zone. At the same time, the low PL
Ag3PO4, is the most common method. intensity reveals the combination of carriers.
Modified TiO2 (MT) was combined with ZnFe2O4 Nitrogen is a key nutrient whose deficiency restricts
(ZFO) by using the solvothermal calcination method de- plant growth. Carbon and oxygen are also essential;
scribed by Rong.72 As shown in Figure 11A, some mi- however, plants can easily obtain these nutrients from
crospheres (MT, diameter = 1 μm) loaded with a large soil and air. Air contains 78% nitrogen, though this ni-
number of nanoparticles (ZFO) were observed. Figure 11B trogen is an unusable nutrient because nitrogen mole-
shows a high magnification scanning electron microscope cules in the atmosphere are bound by strong triple bonds.
image of a single microsphere, which has a regular Nitrogen must be ‘fixed’, that is, it should be converted
spherical structure and a highly rough surface with a into a bioavailable form or man‐made processes. In the
mesoporous structure. In this study, TiO2 comprised a early 20th century, in Germany, Fritz Haber and Karl
large number of nanoparticles with a particle size of ap- Bosch developed the first practical process for converting
proximately 100 nm, and the interparticle voids formed atmospheric nitrogen into nutrient ammonia. Compared
mesopores, as shown in Figure 11C. Combined with with the Haber–Bosch method, the semiconductor‐based
analysis, the curve of MT/ZFO calcined at 400°C in nitrogen–ammonia light fixing method has received
Figure 11D shows a nitrogen adsorption–desorption iso- more attention because it is environmentally friendly, is
therm of type IV, which indicates that the samples have driven by a light source, does not emit carbon dioxide,
mesoporous structures. Figure 11E,F presents the UV‐Vis consumes less energy, and can operate safely under
diffuse reflection spectra and PL spectra of as‐prepared normal temperature and pressure.
composited photocatalysts. MT exhibits strong absorption Figure 12A shows that the photocurrent response of
in the UV range, whereas ZFO exhibits strong absorption MT/ZFO is considerably better than that of MT under
in a wide wavelength range from UV to visible light. light irradiation, which implies that the MT/ZFO com-
Compared with a pure metal TiO2 photocatalyst, the ab- posite performs a more effective separation of electrons
sorption spectrum of a metal–ZFO photocatalyst extends and holes. The charge‐transfer resistance and separation
to the visible light range, indicating that the addition of efficiency were further studied through electrochemical
ZFO considerably influences the optical properties of the impedance spectroscopy. Figure 12B shows the plot of

(A) (B) (C)

(D) (E) 2.0

(F)
Quantity adsorbed (cm3/g,STP)

280 500
400 1.6
Absorbance (a.u.)

240 300
Intensity (a.u.)

200
200 1.2
Physical mixing ZFO
160
0.8
120 MT/ZFO
MT
80 0.4
MT MT/ZFO
40
0.0
0.0 0.2 0.4 0.6 0.8 1.0 200 300 400 500 600 700 800 350 400 450 500 550
Relative pressure (P/P4) Wavelength (nm) Wavelength (nm)

F I G U R E 11 (A) SEM images of MT/ZFO and (B) mesoporous TiO2 microspheres; (C) TEM images of mesoporous TiO2 microspheres;
(D) N2 adsorption–desorption isotherm of MT/ZFO calcined at different temperatures; (E) UV‐Vis DRS spectra; (F) PL spectra of as‐
prepared composite photocatalysts. Reproduced with permission: Copyright 2019, Elsevier.72 SEM, scanning electron microscopy; TEM,
transmission electron microscopy; DRS, diffuse reflection spectra; PL, photoluminescence; MT, modified TiO2; ZFO, ZnFe2O4
306 | LI ET AL.

the electrochemical impedance spectrum of the prepared shown in Figure 12C, NH3 yield increases with an in-
sample. Under light irradiation, the spectral arc radius of crease in irradiation time when ZFO and MT/ZFO are
MT/ZFO is smaller than that of single MT and ZFO, used as samples, whereas NH3 is not produced when
reflecting that the composite photocatalyst has small pure TiO2 is used as the sample. As shown in Figure 12D,
interface layer resistance and high charge‐transfer effi- using the MT/ZFO sample excited by photoreduction,
ciency. ZFO can also prevent the transformation of the NH3 generation rate could reach approximately
anatase TiO2 into rutile TiO2 during calcination. As 1.48 μmol L−1 min−1. The rate could be maintained for

(A) (B)
600
8
500
MT/ZFO
6
Current (μA.cm-2)

400
On Off On

-Z" (Ohm)
300
4

200
2
MT MT
100 ZFO
MT/ZFO
0
0

140 150 160 170 180 190 200 210 0 400 800 1200 1600 2000
Times (s) Z' (Ohm)

(C) (D)
160 2.0
Ammonia generation rate (μmol/L/min)
Concentration of ammonia (μmol/L)

140
MT/ZFO 1.6
120
ZFO
100 MT
1.2
80

60
0.8
40

20 0.4
0

-20 0.0
0 20 40 60 80 100 0 100 200 300 400 500 600
Time (min) Time (min)

(E) (F)
160 160
Concentration of ammonia (μmol/L)

Concentration of ammonia (μmol/L)

140 140

120
120
100
100
80
80
60
60
40
40
20
20 0
1st 2nd 3rd 4th 5th
0 -20
None O2 CH3OH TA Recycle runs

F I G U R E 12 (A) Transient photocurrent responses and (B) electrochemical impedance spectra; (C) N2 photofixation ability using
as‐prepared samples; (D) ammonia generation rate by photoreduction of N2 over MT/ZFO; (E) stability evaluation on the ability of N2
photofixation for MT/ZFO; (F) effect of active species trapped on the ability of N2 photofixation for MT/ZFO. Reproduced with permission:
Copyright 2019, Elsevier.72 MT, modified TiO2; ZFO, ZnFe2O4
LI ET AL. | 307

>600 min, demonstrating excellent catalytic stability. As
shown in Figure 12E, the stability of the MT/ZFO sample
was further examined through a cycle experiment, which
showed high N2O light fixing ability after five cycles.
Thus, capture experiments of electrons (e−), holes (h+)
and hydroxyl radicals (·OH) were performed to study the
active species during N2 photofixation under 100 mL/min
nitrogen bubbling. As shown in Figure 12F, under only
N2 bubbling or addition of TA (a ·OH quencher), N2
photofixation was not affected. However, when O2 (a
e− quencher) was bubbled at 100 mL/min, the N2 fixation
capacity decreased considerably. After the addition of
CH3OH (a h+ quencher), the light‐induced holes in VB
could be used for photocatalytic decomposition of
CH3OH, considerably enhancing the photofixation abil-
ity of N2, which improved the effective separation of
electron–hole pairs. Based on the findings of the active
species capture experiment, it can be considered that the
electrons photo‐induced in the CB are the main active
species for N2 photofixation in an aqueous solution under
visible light irradiation.
2.3.2 | g‐C3N4‐based direct Z‐scheme
photocatalysts
g‐C3N4 is a typical polymer semiconductor with a sui-
table position of band edge. The C and N atoms in this
structure is sp2 hybridised to form a highly delocalised
π‐conjugated system. g‐C3N4 has a band gap of approxi-
mately 2.7 eV because of which it can absorb light with a
wavelength of <475 nm in the solar spectrum. In addi-
tion, compared with traditional TiO2 photocatalysts, g‐
C3N4 can effectively activate molecular oxygen and gen-
erate superoxide radicals for photocatalytic conversion of
organic functional groups and photocatalytic degradation
of organic pollutants. The use of exfoliated 2D g‐C3N4
nanosheets is a crucial step for overcoming these short-
comings as it provides abundant reaction sites. Further-
more, the unique 2D g‐C3N4 plate provides a large and
accessible surface platform for small nanoparticles to
load on it. As observed in several studies, g‐C3N4 can be
integrated with metal oxides (such as Co3O4, ZnO, WO3
and MnO2) and metal sulphides (such as CdS and MoS2).
The rapid development of g‐C3N4‐based photocatalysts
has been achieved using diverse materials to be com-
posited with, as summarised in Table 4.
Metal oxides are considered as promising functional
materials; they are ionic compounds comprising metal
cations and oxygen anions. The electrostatic interaction
between a metal cation and an oxygen anion forms a
strong solid ionic bond. Metal oxides responsive to visible
light are an important class of semiconductor materials.
The preparation of 0D quantum dots/2D nanosheet het-
erostructures is one of the methods for developing high‐
efficiency photocatalysts. In 2018, 0D metal oxide

TABLE 4 Summary of representative g‐C3N4 direct Z‐scheme photocatalysts

Catalyst Synthesis method Morphology Application References
MoS2/g‐C3N4 Impregnation Nanosheets with quantum dots H2 evolution [75]
g‐C3N4/FeWO4 Hydrothermal and mixing Flake with particles Degradation of RhB [76]
g‐C3N4/Ag2WO4 In situ precipitation Nanosheets with particles Degradation of MO [77]
Fe2O3/g‐C3N4 Electrostatically assembling Hexagonal nanoplates attached with H2 evolution [78]
nanosheets
g‑C3N4/MnO2 Wet‐chemical Layered Degradation of RhB [79]
Ag2CrO4/ Self‐assembly precipitation Irregular folding sheets with CO2 reduction [80]
g‐C3N4 particles
CdS/g‐C3N4 Chemical deposition Nanosheet H2 evolution [81]
g‐C3N4/WO3 Calcination Layers with nanocuboids H2 evolution [82]
g‐C3N4/ZnO Electrostatic self‐assembly Microspheres CO2 reduction [83]
g‐C3N4/m‐Bi2O4 Hydrothermal Lamellar Inactivation of Escherichia coli [84]
CdMoO4/ One‐pot in situ Nanosheets Oxygen evolution reaction [85]
g‐C3N4 hydrothermal (OER) and photocatalytic dye
degradation
Bi2O3/g‐C3N4 Photoreductive deposition Submicron particles Degradation of phenol [86]
V2O5/g‐C3N4 In situ growth Layers with agglomeration Degradation of RhB and TC [87]
nanoparticles
Abbreviations: OER, oxygen evolution reaction; TC, tetracycline hydrochloride.
308 | LI ET AL.

nanocrystal‐2D ultrafine g‐C3N4 nanosheet (Co3O4/
CNNS) heterostructures were synthesised by Gao's
group.88 Co3O4 has an ultrafine structure
(diameter = ~2.2–3.2 nm), and it is attached uniformly
and closely to the surface of g‐C3N4 nanosheets, as shown
in Figure 13A. A large number of tiny nanocrystals
(~1–5 nm) are evenly and tightly anchored on CNNS,
forming a Co3O4/CNNS heterojunction, as the exposed
area of the active site is greatly increased. High crystal-
lisation and ultra‐small particle size accelerate the dif-
fusion of photogenerated carriers to the surface,
enhancing the photocatalytic activity of the material.
Moreover, the close contact of Co3O4 quantum dots and
CNNS at the interface forms a heterojunction, effectively
impeding the recombination of photogenerated
electron–hole pairs. Samples with different CNS contents
also influence the removal efficiency of tetracycline hy-
drochloride. As shown in Figure 13B, the number of
Co3O4/CNNS heterojunctions increases with an increase
in the CNNS content, and a large number of photo-
generated charge carriers are effectively transferred and
separated by Co3O4/CNNS heterojunctions. The sample,
Co3O4/CNNS‐1100, showed the highest degradation
among all the samples. Compared with pure CNNS,
Co3O4/CNNS‐700 and Co3O4/CNNS‐1100 exhibit sig-
nificantly enhanced current densities, approximately 3.1
and 4.4 times, respectively, higher than pure CNNS, as
shown in Figure 13C,D, indicating that the introduction
of Co3O4 quantum dots in CNNS can effectively suppress
the recombination of photogenerated carriers.
The metal sulphide photocatalyst has been primarily
studied in the field of photocatalysis and is composed of
metal cations with a d10 electronic configuration. This
configuration possesses a higher VB top position and a
more negative CB bottom position than those of metal
oxides, thus rendering the sulphide suitable for proton
reduction. Furthermore, owing to their electronic con-
figuration, metal sulphides usually exhibit a relatively
narrower band gap and superior sunlight response.
However, the excellent visible light response and reduc-
tion ability resulting from photocatalytic reaction hinge
on the oxidising ability of sulphides. CdS, a direct semi-
conductor with a band gap of 2.4 eV, is the most attrac-
tive visible light‐responsive photocatalyst among
numerous other metal sulphides. From a thermodynamic
perspective, the positions of the VBs and CBs of a
semiconductor photocatalyst determine the redox ability
of its photogenerated carriers. The redox ability, in turn,
significantly influences the photocatalytic reaction ac-
tivity. The CB and VB of CdS are located at −0.52 and
1.88 V versus NHE, respectively, fully meeting the ther-
modynamic requirements of major photocatalytic reac-
tions, including the production of hydrogen through
water splitting, reduction of carbon dioxide to produce
hydrocarbon fuel and dye degradation. Photocorrosion is
another key factor that impedes the practical application

F I G U R E 13 (A) TEM images of Co3O4/CNNS‐1100 heterojunction; (B) the effect of CNNS contents on the removal efficiency of TC; (C)
transient photocurrent response; (D) electrochemical impedance spectroscopy of different catalysts. Reproduced with permission: Copyright
2018, Wiley.88 TEM, transmission electron microscopy; TC, tetracycline hydrochloride
LI ET AL.
of CdS semiconductor photocatalysts. Photocorrosion
involves the oxidisation of sulphide ions on the surface of
CdS through the formation of photogenerated holes, thus
rendering CdS unstable in the photocatalytic reaction.
Therefore, it is necessary to promote rapid separation of
charge carriers, avoid the accumulation of holes on the
surface of CdS and optimise its photocatalytic activity
and stability. The combination of g‐C3N4 and CdS is a
superior choice for achieving this goal.
A study reported that CdS nanoparticles can be de-
posited on g‐C3N4 nanosheets by using methods, such as
photodeposition and chemical deposition.81 The two
composite materials exhibit different photocatalytic ac-
tivities and stabilities. Photoelectric positioning is a
common method that involves the deposition of a Pt
promoter on the catalyst to enhance electron transfer to
Pt nanoparticles. Therefore, photodeposition technology
can be utilised to manipulate the direction of electron
transfer. Jiang's group81 constructed two systems by ad-
justing the direction of excited electron flow, exploiting
the existence of different electron transfer pathways.
Figure 14A displays the CdS/g‐C3N4 synthesised through
chemical deposition, with 0.35 g of cadmium nitrate as
the raw material. Charge transfer herein occurred ac-
cording to the Z‐scheme mechanism. Figure 14B also
shows the transformation routes of the composites
photo‐deposited at 25°C. Therefore, the photocatalytic
performances and the composite photocatalyst stabilities
of g‐C3N4, CdS, chemical deposition of CdS onto g‐C3N4
nanosheets (c‐CSCN, 10%) and photodeposition of CdS
onto g‐C3N4 nanosheets (p‐CSCN, 25%) were studied
under the following conditions: light source was a 300 W
Xe lamp with λ > 420 nm, the reaction solution was
100 mL of Na2S (0.05 mol L−1)–Na2SO3 (0.1 mol L−1)
aqueous solution and the catalyst dosage was 25 mg.
Figure 15A,B presents the photocatalytic activities of
F I G U R E 14 Energy‐level diagrams and charge‐transfer routes of (A) c‐CSCN‐10% and (B) p‐CSCN‐25. Reproduced with permission:
Copyright 2018, American Chemical Society.81 c‐CSCN, chemical deposition of CdS onto g‐C3N4 nanosheets; p‐CSCN, photodeposition of
CdS onto g‐C3N4 nanosheets
| 309
g‐C3N4, CdS, c‐CSCN and p‐CSCN loaded with 1.0%
by weight Pt nanoparticles in a Na2S–Na2SO3 buffer
solution. The pure 25 mg g‐C3N4 exhibited weak photo-
catalytic activity (0.65 μmol h−1). For comparison, in the
case of CdS prepared using the hydrothermal method for
25 mg of photocatalyst, the photocatalytic H2 release rate
was 1.96 μmol h−1. Meanwhile, c‐CSCN‐10% exhibited a
photocatalytic activity of 14.9 μmol h−1, which was
higher than that observed for any single component. In
the case of p‐CSCN‐25, the photocatalytic rate reached
56.9 μmol h−1, which was the highest among the studied
samples. Figure 15C,D exhibits the stability of the
c‐CSCN‐10% and p‐CSCN‐25 samples. The stability of
c‐CSCN‐10% and p‐CSCN‐25 was tested for four repeated
photocatalytic H2O2 production cycles in Na2S‐Na2SO3
buffer solution. After four cycles, the activity of c‐CSCN‐
10% diminished considerably (by 50%), implying that
c‐CSCN‐10% was corroded by light during the H2 pro-
duction process. Generally, photoetching occurs due to
the oxidation of sulphides by holes, which can be sup-
pressed by rapidly transferring holes from sulphide.
Conversely, p‐CSCN‐25 exhibited better stability during
photocatalytic H2 evolution. This clearly indicates the
transfer of holes from sulphide.
2.3.3 | BiVO4‐based direct Z‐scheme
photocatalyst
BiVO4 is an n‐type semiconductor with a band gap of
2.4 eV, and it exhibits appreciable chemical stability and
photostability. BiVO4 is a crucial candidate for capturing
solar energy, owing to its unique electronic structure and
excellent visible light catalytic performance. However,
due to the extremely facile recombination of electrons
and holes caused by the narrow band gap, its
310 | LI ET AL.

F I G U R E 15 (A) Amount of H2 generated by g‐C3N4, CdS, c‐CSCN‐25 and p‐CSCN‐10% under visible light (λ > 420 nm) for 25 mg of the
photocatalyst in 0.05 M Na2S–0.1 M Na2SO3 aqueous solution for 5 h. (B) Their photocatalytic H2 production rate. Cycling test of
photocatalytic H2 evolution for (C) c‐CSCN‐10% and (D) p‐CSCN‐25 composites with 1.0 wt% cocatalyst Pt nanoparticles. Reproduced with
permission: Copyright 2018, American Chemical Society.81 c‐CSCN, chemical deposition of CdS onto g‐C3N4 nanosheets; p‐CSCN,
photodeposition of CdS onto g‐C3N4 nanosheets

photocatalytic performance requires considerable im-
provement. Significant effort has been directed towards
separating the photogenerated charge carriers. One of the
most commonly employed methods is to prepare com-
posite photocatalysts by compounding oxides or sul-
phides with BiVO4, as shown in Table 5.
In 2019, Zhao's90 group successfully synthesised a
novel 3D‐microsphere direct Z‐scheme Ag3VO4/BiVO4
heterojunction photocatalyst. From Figure 16A,B, it is
evident that the BiVO4 microspheres in the sample exhibit
uniform, flower‐like structures, whereas Ag3VO4 exists in
the form of nanosheets. Figure 16C presents the trans-
mission electron microscope of the 0.24‐Ag3VO4/BiVO4
photocatalyst. Furthermore, HRTEM results clearly in-
dicate a close connection between Ag3VO4 and BiVO4. As
shown in the HRTEM images in Figure 16D,E, the in-
terplanar spacings corresponding to the BiVO4 (121) and
Ag3VO4 (220) crystal planes are 0.312 and 0.191 nm, re-
spectively. The ultraviolet‐visible absorption spectrum of
the sample is shown in Figure 16F. As the loading dosage
of Ag3VO4 increases, the absorption edge of Ag3VO4/
BiVO4 exhibits a slight red shift. In addition, the PL
spectra in Figure 16G indicate an effective charge transfer
between Ag3VO4 and BiVO4, with an intensity lower than
that of BiVO4.
The carrier transport efficiency was studied based on the
PEC properties. The photocurrent of the composite photo-
catalyst Ag3VO4/BiVO4 is obviously higher than that of the
single component, as shown in Figure 17A. Figure 17B
shows the photocatalytic reduction of Cr6+ and the oxidation
of bisphenol S (BPS) on different samples in a dark ad-
sorption experiment. The BiVO4 particles exhibit lower
photocatalytic activity than the flower‐shaped BiVO4 mi-
crospheres, which may be attributed to their relatively small
specific surface area. As a result, the photocatalytic perfor-
mance of Ag3VO4/BiVO4 is higher than that of Ag3VO4 and
BiVO4. Among the prepared Ag3VO4/BiVO4 samples con-
taining different amounts of Ag3VO4, 0.24‐Ag3VO4/BiVO4
exhibited the highest photocatalytic performance. After
150 min of visible light irradiation, the photocatalytic
LI ET AL. | 311

reduction and oxidation efficiency of 0.24‐Ag3VO4/BiVO4

References could reach 74.9% and 94.8%, respectively.
[89]
In addition, the photocatalytic activity stability of

[90]

[91]
[92]
[93]
Ag3VO4/BiVO4 was studied (Figure 17C), and the results
indicated that the sample is sufficiently stable. The hetero-
junction of Ag3VO4/BiVO4 follows the typical direct
Z‐scheme charge carrier migration mechanism, as shown in
6+

and oxidation of bisphenol S

Figure 17D. After light irradiation, the photo‐induced elec-

Photocatalytic reduction of Cr

trons in the CB of BiVO4 are transferred to the VB of

Ag3VO4. Compared with the potential of H2O/HO radicals,
Degradation of benzene

Degradation of gaseous

the positive potential of BiVO4 can oxidise H2O into HO·

radicals. This is more conducive to the generation of HO·
formaldehyde
Water splitting

radicals. In addition, the Fermi level of Ag3VO4 is higher

Application
H2 evolution

than that of BiVO4, which results in the flow of electrons

from Ag3VO4 to BiVO4. As a result, the Fermi level of
Ag3VO4 goes down and the Fermi level of BiVO4 goes up
until equilibrium is achieved. Due to electron transfer, when
the two components reach an equilibrium Fermi level, a
built‐in electric field from Ag3VO4 to the surface of BiVO4 is
established. Furthermore, the existence of the built‐in po-
Three‐dimensional flower‐like
Nanowires with nanoparticles

tential at the interface facilitates the separation of photo-

Triangular nanoparticles

generated charge carriers through the Z‐scheme charge‐

transfer mechanism, thereby inhibiting recombination and
improving the photocatalytic activity of heterostructures.
microspheres
Nanoparticles
Morphology

Nanosheets

2.4 | S‐scheme photocatalyst

In a traditional type‐II heterojunction, electrons and holes

migrate to different semiconductors, realising effective se-
paration. However, it comes at the cost of reducing the
Summary of representative BiVO4 direct Z‐scheme photocatalysts

Hydrothermal and ultrasonic dispersion

redox potential of the semiconductor. The Z‐scheme me-

chanism was proposed to counter this phenomenon.19 The
Z‐scheme heterojunction induces efficient separation of the
charge carriers while maintaining a high redox potential.
Electrostatically assemble

With developments in the field of photocatalysis, Z‐scheme

Stirring and centrifuging

has its inevitable shortcomings, such as the intricate sys-

Synthesis method

tematisation. Furthermore, it is difficult to define the

charge migration mechanism, rendering the Z‐scheme
Hydrothermal

Hydrothermal

unfavourable for unification. To counter this limitation

and unify the Z‐scheme photocatalyst classification, the S‐
scheme mechanism was proposed by Yu's group in 2018.94
The S‐scheme pertains to the link between two n‐type
semiconductors. Generally, the work function of the oxi-
dation photocatalyst is higher, although its Fermi level is
lower; in contrast, the reduction photocatalyst exhibits a
Black Phosphorus/BiVO4

low work function and a high Fermi level. In addition, the

Triangular Ag/BiVO4

S‐scheme photocatalyst works through the synergistic effect

of the built‐in electric field, Coulomb interaction and band
Ag3VO4/BiVO4

BiVO4/TiO2

energy bending. The S‐scheme mechanism exploits the

CdS/BiVO4
TABLE 5
Catalyst

merits of the type‐II and Z‐scheme photocatalyst, such that

the heterostructure enables efficient separation and clearly
elucidates the mechanism of charge transfer.
312 | LI ET AL.

F I G U R E 16 (A) SEM images of the Ag3VO4 and (B) 0.24‐Ag3VO4/BiVO4 photocatalysts; (C) TEM image and (D,E) HRTEM image of
the 0.24‐Ag3VO4/BiVO4 photocatalyst; (F) UV‐Vis absorption spectra of the as‐prepared samples; (G) PL spectra of the as‐prepared samples.
Reproduced with permission: Copyright 2019, Elsevier.90 SEM, scanning electron microscopy; TEM, transmission electron microscopy;
HRTEM, high‐resolution transmission electron microscopy; PL, photoluminescence

Various S‐scheme novel heterojunction structures
have been developed in the past year. The synthesis
methods and the applications of S‐scheme photocatalyst
are summarised in Table 6.
The 2D/2D WO3/g‐C3N4 photocatalyst is a typical
S‐scheme heterostructure.94 The ultrathin WO3 and
g‐C3N4 nanosheets were synthesised by electrostatic‐
assisted ultrasonic exfoliation of bulk WO3 and the
two‐step thermal‐etching of bulk g‐C3N4, respectively.
Generally, g‐C3N4 is a reduction photocatalyst with a
relatively low work function and high Fermi level. By
contrast, WO3 is an oxidation‐type photocatalyst with a
high work function and a low Fermi level, as illustrated
in Figure 18A. When g‐C3N4 and WO3 are in close con-
tact, electrons in g‐C3N4 are spontaneously transferred to
WO3 through the interface, until the Fermi levels become
similar, as shown in Figure 18B. Therefore, g‐C3N4 loses
electrons and is positively charged, while WO3 gains
LI ET AL. | 313

F I G U R E 17 (A) Photocurrent of the as‐prepared samples; (B) photocatalytic activities of the as‐prepared photocatalysts for Cr6+ and
bisphenol S (BPS) degradation, Sample 1: BiVO4 particles, Sample 2: Ag3VO4, Sample 3: BiVO4 microspheres, Sample 4: 0.06‐Ag3VO4/
BiVO4, Sample 5: 0.12‐Ag3VO4/BiVO4, Sample 6: 0.24‐Ag3VO4/BiVO4, Sample 7: 0.36‐Ag3VO4/BiVO4; (C) recycling runs of Cr6+ and BPS
degradation; (D) photocatalysis enhancement mechanism of the Z‐scheme Ag3VO4/BiVO4 photocatalyst. Reproduced with permission:
Copyright 2019, Elsevier90

electrons and is negatively charged at the interface,
naturally generating an internal electric field at the in-
terface. Simultaneously, the band edge of g‐C3N4 bends
upward due to the loss of electrons, while the band edge
of WO3 bends downward due to the accumulation of
electrons. Under light irradiation, electrons are excited
from the VBs of WO3 and g‐C3N4 to their CBs. The in-
ternal electric field, band edge bending, and Coulomb
interaction accelerate the recombination of some elec-
trons (CB from WO3) and holes (VB from g‐C3N4), while
inhibiting other electrons (CB from g‐C3N4) and holes
(VB from WO3), as shown in Figure 18C.
2.5 | Perovskite‐based photocatalysts
Perovskite refers to a class of ceramic oxides with a
molecular formula of ABO3. The perovskite‐type com-
posite oxide ABO3 is a new type of inorganic nonmetallic
material with unique physical and chemical properties.
This oxide is named after the perovskite ore from which
it was first discovered in the form of a calcium titanate
(CaTiO3) compound. Perovskite can exist in numerous
forms, such as simple perovskite, double perovskite and
layered perovskite structures, as shown in Figure 19A,B.110
The A site in ABO3 is generally occupied by rare earth or
alkaline earth element ions, whereas the B site houses a
transition element ion; in addition, both A and B sites can
be occupied by other metal ions with similar radii, which
are partially substituted to keep their crystal structure
stable. Therefore, in theory, ABO3 is an ideal sample for
studying catalyst surfaces and catalytic performance. The
stable crystal structures of these compounds lead to unique
electromagnetic properties, high redox potential, hydro-
genolysis, isomerisation and electrocatalysis, among others.
The new type of functional materials is utilised in the fields
of environmental protection and industrial catalysis. The
properties of the materials are largely dependent on their
preparation method. The synthesis pathways of perovskite
structure‐type compounds mainly include the traditional
high‐temperature solid‐phase method (ceramic process
method), sol‐gel method, hydrothermal synthesis method,
high energy ball milling in addition to vapour deposition,
supercritical drying, microemulsion and self‐propagating
314 | LI ET AL.

TABLE 6 Summary of representative S‐scheme photocatalysts

Catalyst Cocatalyst Synthesis method Activity Application References
−1
Bi2MoO6/g‐C3N4 Au Photoreduction and 0.0808 min Photodegradation RhB [95]
hydrothermal (0.5 mg L−1)
TiO2/C3N4 Ti3C2 QD Thermal deposition and CO: 4.39 μmol g−1 h−1 CH4: CO2 reduction [96]
electrostatically 1.20 μmol g−1 h−1
assemble
BiOBr/ No Coprecipitation RhB: 99.4% Photodegradation RhB [97]
BiOAc1 −xBrx and TC
TC: 99.2%
Bi2S3/g‐C3N4 No Solvothermal 3394.1 μmol g−1 h−1 H2 evolution [98]
−1
g‐C3N4/BiVO4 Bi Substrate directed liquid‐ RhB: 0.067 min Photodegradation RhB [99]
phase deposition (10 mg L−1) and CO2
CO: 1.25 μmol g−1 h−1
reduction
CdS/MoO3 − x No Coprecipitation 7.44 mmol g−1 h−1 H2 evolution [100]
g‐C3N4/ZrO2 No Calcination 82% of RhB, 50% of MO and Degradation RhB, [101]
98% of AO II degraded in
MO and AO II
150 min
CeO2/PCN No In situ wet chemistry Bacteria removal Inactivation of bacteria [102]
with subsequent heat efficiency 88.1%
treatment
CoO/PCN No Solvothermal 40.31 μmol g−1 h−1 CO2 reduction [103]
−1
CdS/UiO‐66 No Photodeposition 0.234 min Reduction 4‐nitroaniline [104]
−1
In2O3 − x(OH)y/ No Calcination Cr (VI): 0.0338 min Reduction of Cr(VI) and [105]
Bi2MoO6 degradation of RhB
RhB: 0.0745 min−1
AgI/I‐BiOAc No One‐pot milling Methyl violet: 0.047 min−1 Degradation of methyl [106]
−1 violet and bisphenol A
Bisphenol A: 0.215 h
Sb2WO6/BiOBr No Precipitation‐deposition Ratio of: 52.9% NO removal [107]
−1
BP/BiOBr No Liquid‐phase ultrasound TC: 0.021 min Tetracycline removal and [108]
and solvothermal −1 −1 oxygen evolution
O2: 89.5 μmol g h
−1
SnNb2O6/Ag3VO4 No Hydrothermal 0.2256 min Degradation of MB [109]
Abbreviations: TC, tetracycline hydrochloride.

F I G U R E 18 (A) Work functions of g‐C3N4

and WO3; (B) internal electric field and band
edge bending at the interface of WO3/g‐C3N4;
(C) S‐scheme charge‐transfer mechanism
between WO3 and g‐C3N4 under light
irradiation. Reproduced with permission:
Copyright 2019, Elsevier94

high‐temperature combustion synthesis methods, among emphasis on state‐of‐the‐art developments in the appli-
others. cation of perovskite oxides and their modifications for
To date, numerous studies have delved into the pro- photocatalytic reactions. Among these studies, a study
mising perspectives of perovskite photocatalysis, with an by Kanhere investigated perovskite‐based photocatalysts
LI ET AL. | 315

F I G U R E 19 Crystal structure of simple perovskite, (A) BaTiO3 and (B) double perovskite Na2Ta2O6 (red: oxygen; green and purple:
A‐site cation; grey and blue: BO6 octahedra). Reproduced under the terms of the Creative Commons Attribution 4.0 International license:
Copyright 2014, MDPI110

with visible light activity.110 The perovskite photocatalysts

could be used for the degradation of volatile organic
compounds in the environment, sterilisation and anti-
microbial action in medicine, decolourisation of dyes in
industries, nitrogen fixation in agriculture and removal of
NOx/SOx pollutants in the air (Figure 20).111 In terms
of photocatalytic applications, perovskite has some
advantages over binary oxides. For example, it has suffi-
cient cathode CB energy for hydrogen evolution. Fur-
thermore, it is possible to combine properties, such as
ferroelectricity or piezoelectricity, with the photocatalytic
effect to improve photocatalytic activity. The perovskite
photocatalysts can be classified into the following
categories: titanates, SrTiO3112–118 and BaTiO3119–123; tan-
talates, LiTaO3,124 NaTaO3125–132 and KTaO3133–137;
F I G U R E 20 Applications of perovskite photocatalysts.
niobates, LiNbO3,138,139 NaNbO3140–147 and KNbO3148–153;
Reproduced with permission: Copyright 2020, American Chemical
vanadates, AgVO3154–162; and ferrites, LaFeO3,164–169
Society111
BiFeO3170–176 and GaFeO3.177 These compounds show
great potential for application in visible light‐driven
photoreactions.
To the best of our knowledge, only a few studies have titanate has good light stability and corrosion resistance
investigated combined semiconductors derived from ha- in aqueous solutions. In Yoshino's research, SrTiO3
lide perovskites, including inorganic and hybrid, though doped in Rh was synthesised with BiVO4 by using a solid‐
these semiconductors have witnessed extraordinary de- state reaction to form a Z‐scheme photocatalyst, which
velopment over the past few years. Titanate perovskites could enhance the efficiency of CO2 to reduce to CO.15
have been studied for photocatalytic applications for a The Z‐scheme photocatalyst uses SrTiO3:Rh as the re-
long time. Most titanate perovskites have band gap en- duction photocatalyst and BiVO4 as the O2 evolution
ergy values greater than 3.0 eV; however, they exhibit photocatalyst. Through electron transfer between parti-
excellent photocatalytic performance under ultraviolet cles without the use of an electronic medium, CO2 is
radiation. By employing these titanates as the host ma- reduced to CO under visible light, with water as an
terials, doping is widely used to modify optical properties electron donor, as shown in Figure 21A. In the Z‐scheme
and induce visible light absorption. The band gap of system, the combination of SrTiO3:Rh and BiVO4 effec-
titanium dioxide (anatase) is 3.2–3.4 eV, and its CB po- tively decomposes water into H2 and O2. Notably, the
tential is 0.3–0.6 eV higher than the water reduction Z‐scheme system works through the interparticle elec-
level. Certain perovskite titanates have more negative tron transfer between SrTiO3:Rh and BiVO4 without an
chemical energy than titanium dioxide, rendering them electronic medium. Figure 21B shows the products of
more suitable for hydrogen production. Furthermore, CO2 reduction through interparticle electron transfer by
316 | LI ET AL.

F I G U R E 21 (A) Z‐scheme photocatalyst system for CO2 reduction by using SrTiO3:Rh and BiVO4, with water as an electron donor
driven under visible light; (B) Z‐scheme CO2 reduction using Au (0.4 wt%)‐loaded SrTiO3:Rh (1%) and BiVO4 photocatalysts under visible
light irradiation. Reproduced with permission: Copyright 2020, American Chemical Society15

using the Au/SrTiO3:Rh and BiVO4 photocatalysts under
visible light irradiation, with water as the only electron
donor. Within 10 h of visible light irradiation, the evo-
lution of H2 and O2 occurs due to the splitting of water.
Therefore, research groups have successfully constructed
a new Z‐schematic CO2 reduction system solely by using
the metal oxide photocatalyst to enhance response to
visible light.
Traditional perovskite materials have some short-
comings, such as large band gap, carrier recombination,
small specific surface area and poor selectivity.
Therefore, in recent years, double perovskites (general
formula: A2B2O6), such as Sr2FeNbO6, La2FeTiO6 and
Ba2LaBiO6, have gained the attention of scientists. The
crystal structure of double perovskites is similar to that of
simple perovskites. The basic skeleton of double per-
ovskite is BO6 octahedrons containing cations; however,
the connectivity of octahedrons with different structures
may be different. Double perovskite can accommodate
different cations at the A or/and B sites, with the general
formula AAʹBBʹO6. The attachment of different cations
at the A and B sites markedly alters the photophysical
properties of the compound. Properties of double per-
ovskites, such as good stability and high light‐excited
charge mobility, can enable better use of light energy.110
Photoelectrocatalysis has triggered ripples of excite-
ment in the fields of environmental protection and en-
ergy conversion due to its potential applications in the
degradation of organic pollutants and evolution of H2
and O2 through H2O splitting and reduction of CO2 by
utilising solar energy. Over the past 3 years, halide per-
ovskites, which inculcate extraordinary charge transport
capability in solar cells, have witnessed extensive devel-
opment in photocatalysis applications compared with
conventional oxide perovskites.178,179 This type of
perovskite possesses a small surface area, limited light
utilisation and high carrier recombination, which result
in inadequate reactant contact on catalyst surfaces and
decreased catalytic activity.
The review further discusses the progress of halide
perovskites, from their fundamental properties to their
applications in light‐driven reactions, with a focus on
crystal dimensions, toxicity and stability. In addition,
computational studies on halide perovskites, ranging
from electronic properties to catalytic mechanisms, are
presented to provide a foundation for future research and
advancement in this field. Lastly, critical insights into
the current limitations and favourable prospects are
provided.
As an efficient and stable photocatalytic material,
perovskite oxides and their derivatives have been ex-
tensively studied in numerous energy conversion reac-
tions and environmental treatments. In the past decade,
more than 100 relevant papers have been published on
the efficient photocatalytic CO2 reduction reaction of
perovskite oxide‐based materials. However, due to the
complexity of the CO2 reduction reaction process and the
high tunability of the perovskite structure, elucidating
the relationship between its internal structure and ac-
tivity remains a challenge.
3 | PEC A PPLICATIONS
Photocatalysts have a fatal disadvantage, namely the high
recombination rate of photogenerated hole–electron
pairs. Therefore, the key to improving photocatalytic ef-
ficiency is to reduce the recombination rate of photo-
generated holes and electrons. PEC is a photocatalytic
technology assisted by an external electric field.
LI ET AL.
3.1 | Water splitting
Solar energy is the most abundant and the cleanest en-
ergy on the planet. Because of its renewable, nonpollut-
ing characteristics, it is projected to be critical for solving
the inevitable energy and environmental crises in the
future. Every year, approximately 100,000 TW of solar
energy reaches Earth, of which only ~36,000 TW reaches
land. This implies that only 1% of the Earth's land area
needs to be covered with 10% high‐efficiency PEC cells to
generate 36 TW of energy per year, which will suffice to
meet the projected annual global energy consumption in
2050.180 In addition, artificial photosynthesis is a pro-
mising technology that can not only harvest solar energy
but also serve as a storage method to produce energy‐rich
chemical fuels such as hydrogen or hydrocarbons
through technological processes, such as water splitting
and CO2 utilisation. Hydrogen is clean energy with a
high energy density to storage ratio. Among various
chemical fuels, the mass‐energy density of hydrogen is
three to four times higher than that of gasoline and can
be used by the direct combustion or hydrogen fuel cells.
Currently, hydrogen is mainly obtained by reforming
traditional fossil fuels, such as coal and natural gas,
which will inevitably aggravate energy depletion and is-
sues pertaining to environmental pollution. The use of
light, water and semiconductors to produce hydrogen
through photocatalytic decomposition of water has re-
ceived widespread attention ever since the finding that
TiO2 photoelectrode splits water, reported by Professor
Fujishima and Honda in 1972; this process has realised
the effective conversion of solar energy to chemical en-
ergy.181 The efficiency of photocatalytic water splitting
largely depends on the choice of semiconductors. The
positions of the CB and VB determine the oxidation–
reduction ability of semiconductors, which directly af-
fects the efficiency of photocatalytic water splitting.
Owing to the limitations of thermodynamics and
kinetics, photocatalytic total water splitting is extremely
challenging. Furthermore, the oxygen production process
is complicated, and activation is difficult under normal
circumstances. This is one of the main reasons for lim-
itations in the efficiency of photocatalytic total water
splitting. Therefore, the photocatalytic total water split-
ting system requires that the semiconductor photo-
catalyst should have a suitable energy band structure to
achieve a strong redox capability and a high photo-
generated carrier separation efficiency.
In this regard, Z‐scheme photocatalysts exhibit
significant potential for achieving high photocatalytic
performance inspired by natural photosynthesis.
Z‐scheme photocatalysts are usually composed of two
semiconductors—an oxidation photocatalyst and a
| 317
reduction photocatalyst. The oxidising photocatalyst has
a lower VB position and exhibits a strong oxidising
ability, whereas the reducing photocatalyst has a high CB
position and exhibits a high reduction performance.
Based on the unique charge‐transfer method, the Z‐
scheme photocatalyst possesses the following character-
istics: (1) simultaneous strong oxidation and reduction
capabilities of the catalyst; (2) spatial separation of oxi-
dation and reduction active sites; (3) photogenerated
carrier separation efficiency with strong redox capability;
(4) a wide‐spectrum response range that can be con-
structed. Z‐scheme photocatalysts can be divided, based
on whether an intermediate medium is involved in the
charge transfer and the type of intermediate medium,
into ionic Z‐scheme photocatalysts, all‐solid‐state Z‐
scheme photocatalysts and direct Z‐scheme photo-
catalysts. These three photocatalysts exhibit differences
in synthesis strategy, mechanism of action, properties
and applications.
Unlike a photocatalyst system, water reduction and
oxidation reactions in the photoelectric catalytic water
splitting system are carried out on two physically sepa-
rated electrodes. This allows H2 and O2 to be produced
separately, avoiding the re‐formation of the two gases
into water which is one of the main defects of the PS
system. In addition, another advantage of the PEC sys-
tem is that fixing the photocatalyst on the conductive
substrate will facilitate the facile removal of the photo-
catalyst and its subsequent separation from water. The
basic photovoltaic system comprises a light‐absorbing
component and a counter electrode. Theoretically, due to
the electric field at the cross section, the photo‐induced
minority carriers in the semiconductor are driven to the
semiconductor–electrolyte interface, while the minority
carriers are transported to the counter electrode through
the external circuit. For example, when the working
electrode is an n‐type semiconductor, electrons are
transferred as majority carriers to the counter electrode
to reduce water to H2. Meanwhile, minority carriers
(holes) oxidise water on the surface of the semi-
conductor, and O2 is generated. Therefore, the n‐type
semiconductor acts as a photoanode in the PEC system.
By contrast, a p‐type semiconductor acts as a photo-
cathode in which water is reduced on the surface of the
semiconductor and oxidised on the counter electrode.
Table 7 presents examples of Z‐scheme photocatalysts
employed for the PEC application of water splitting.
In a study, g‐C3N4 was proposed in the Z‐scheme
configuration, which increased the performance of
BiVO4 by fourfold.184 The experimental observation re-
sults in the study were cross‐checked by carrying out a
density functional theory simulation. The FESEM cross‐
sectional images of this photoelectrode are shown in
318 | LI ET AL.

Figure 22A. The 3D illustration represents photoanodes

References composed of pristine thin films (Figure 22B). When
[182]
the bias of g‐C3N4/BiVO4 is 1.23 V versus RHE, the

[183]

[184]
[185]
[186]
[66]
photocurrent is 0.42 mA cm−2, which is the highest
among g‐C3N4‐based Z‐scheme heterojunction devices,
as shown in Figure 22D. For the g‐C3N4‐based hetero-
Type of heterostructure

junction, lower charge‐transfer resistance, higher light

All‐solid‐state Z‐scheme
All‐solid‐state Z‐scheme
absorption and more oxygen vacancies are observed. The
simulation results prove that g‐C3N4 and BiVO4 form a
Direct Z‐scheme

Direct Z‐scheme
Direct Z‐scheme

Direct Z‐scheme
van der Waals heterojunction, and the internal electric
field promotes the separation of electron/hole pairs on
the g‐C3N4/BiVO4 interface, thereby limiting further re-
Type‐II

combination of carriers. The valence state and CB edge

position of g‐C3N4 and BiVO4 all vary with the Fermi
level, as shown in Figure 22C.
Products and activity

−1
h
−1

−1

3.2 | N2 fixation
H2: 2518 μmol h

H2: 1.7 mmol g

Nitrogen is a key mineral nutrient that aids in plant

growth. Carbon and oxygen are also critical; however,
they are easily accessible to plants from soil and air.
Although the air contains 78% nitrogen, this atmospheric
Summary of representative Z‐scheme photocatalysts for the PEC application of water splitting

nitrogen is an unusable nutrient because the nitrogen

Photocurrent

−2

0.15 mA cm−2
−2

molecules in the atmosphere are held together with

0.42 mA cm
−2

−2

−2

0.34 μA cm
−2

strong triple bonds. Nitrogen must be ‘fixed’, that is,

50 μA cm
80 μA cm

15 μA cm
8 μA cm

converted into a bioavailable form through natural or

man‐made processes. N2 can be converted into many
forms, such as ammonia, nitrate and urea. Therefore,
ensuring efficient fixation of nitrogen under mild con-
Hydrothermal and electrophoretic deposition
Electrophoretic deposition and spin casting

ditions in the environment is a critical subject in the

fields of chemistry and catalysis.187,188
Ammonia (NH3), one of the most important che-
micals and carbon‐free energy sources, has a global
annual output of 150 million tons. It is mainly produced
by the traditional high‐temperature and pressure
Haber–Bosch process, which consumes a considerable
Synthesis method

amount of energy. In this process, high‐purity nitrogen

Electrodeposition

gas (N2) reacts with hydrogen gas (H2) in the presence

Freeze‐drying
Self‐assembly
Calcination

Calcination

of iron or ruthenium‐based catalysts at high tempera-

ture (~500°C) and pressure (200–300 atm). This process
accounts for approximately 1% of the world's annual
energy consumption. In addition to the energy required
for heating and pumping, the high‐purity H2 used in
this process is mainly produced by the steam reforming
ZnO1 − x (10 wt%)/Zn0.2Cd0.8S

of natural gas, a fossil fuel. This process produces a large

Zn‐AgIn5S8 QDs/α‐Fe2O3

amount of greenhouse gases. Therefore, the formulation

of a green and sustainable strategy for NH3 production
FeVO4/RGO/ZnO
Bi5O7I/RGO/ZnO

is essential. Electrocatalysis and PEC are considered to

g‐C3N4/BiVO4
WO3/g‐C3N4
g‐C3N4/WO3

be energy‐saving and environmentally friendly methods

TABLE 7
Catalyst

for producing NH3 because these methods can be per-

formed using renewable solar and wind energies under
environmental conditions. Recently, the electrocatalytic
LI ET AL. | 319

F I G U R E 22 (A) FESEM cross‐sectional images of g‐C3N4/BiVO4; (B) 3D illustration of g‐C3N4/BiVO4; (C) energy‐level diagram of the
band edge positions of BiVO4 (001), g‐C3N4 and g‐C3N4/BiVO4; (D) g‐C3N4/BiVO4 and TiO2/BiVO4 heterojunction photoanodes under
chopped illumination. Reproduced with permission: Copyright 2018, Elsevier.184 FESEM, field‐emission scanning electron microscopy

and photoelectrocatalytic reduction of N2O to NH3 has
received considerable attention as it can be carried out
using renewable energy under environmental condi-
tions. The overall performance of these electrocatalytic
and photoelectrocatalytic systems largely depends on
their core components, that is, catalysts. This view fa-
cilitates the reasonable design of electrocatalysts and
photocatalysts to reduce N2O to NH3 under environ-
mental conditions.189
Therefore, coupling semiconductor catalysts with other
narrow band gap semiconductors to construct heterojunc-
tion photocatalysts is much sought after in various devel-
opment strategies, which will extend the light response range
to visible light and effectively suppress photo‐induced
electron–hole pairs through a charge‐transfer complex. For
example, in Guan's work,190 a highly efficient p‐type Cu3P/n‐
type g‐C3N4 heterojunction photocatalyst was synthesised in
situ. The results showed that Cu3P nanoparticles were highly
dispersed onto the g‐C3N4 surface, which obviously promotes
the separation of electrons and holes. The charge transfer
between Cu3P and g‐C3N4 follows the Z‐scheme mechanism.
Furthermore, the as‐prepared Cu3P/g‐C3N4 heterojunction
photocatalyst exhibited an ammonium‐ion production rate
of 7.5 mg L−1 h−1 g−1cat, which was 28.8 times that of neat g‐
C3N4, along with appreciable catalytic stability.190 Jiang and
co‐workers191 prepared an all‐solid‐state Z‐scheme hetero-
junction– 3,4‐dihydroxybenzaldehyde functionalised Ga2O3/
graphitic carbon nitride (Ga2O3‐DBD/g‐C3N4) (Figure 23A).
The photocatalytic performance of the nitrogen fixation rate
on Ga2O3‐DBD/g‐C3N4 was 3.37 times faster than that of g‐
C3N4. A photocatalytic mechanism exploration suggested
that aromatic rings with high conductivity acted as electron
mediators during the transformation of nitrogen
(Figure 23B). Methanol was oxidised to •CO2− by active
oxygen species, thus facilitating the reduction of N2 to NH3.
3.3 | Degradation of pollutants
Photocatalytic degradation refers to the use of radiation
and photocatalysts to generate extremely active free ra-
dicals in the reaction system. Following this, through the
process of addition, substitution and electron transfer
between free radicals and organic pollutants, all the
pollutants are degraded into inorganic substances. Spe-
cifically, the redox mechanism of the photocatalyst
mainly involves the following steps: the catalyst is irra-
diated by light, absorbs light energy, undergoes electronic
320 | LI
F I G U R E 23 (A) The fabrication process of Ga2O3‐DBD/g‐C3N4 and (B) its charge transfer mechanism under light illumination.
Reproduced with permission: Copyright 2017, Elsevier191
F I G U R E 24 Schematic of the photocatalytic Z‐scheme
mechanism of Ag/CN/BTO composites. Reproduced with
permission: Copyright 2019, Elsevier192
transitions, generates electron–hole pairs and directly
reduces the pollutants adsorbed on the surface or oxi-
dises the hydroxide (OH−) adsorbed on the surface.
Subsequently, strong ·OH radicals would be generated to
oxidise the pollutants.
Ao et al.192 reported a ternary Ag/g‐C3N4 (CN)/Bi3TaO7
(BTO) photocatalyst for the photodegradation of sulfa-
methoxazole. They found the activity of the two components
Z‐scheme photocatalyst (CN/BTO) could be greatly en-
hanced by the addition of trace amount Ag. During the
photocatalytic process, Ag has two functions on the en-
hanced performance, namely serving as transmission‐bridges
of charge carriers and extending light absorption range
through SPR effect (Figure 24). In another study, Z‐scheme
TiO2/g‐C3N4 photocatalyst‐supported MoS2 nanosheets were
prepared using the wet impregnation method.193 The ex-
foliated two‐dimensional g‐C3N4 and MoS2 nanosheets were
utilised for the preparation of Z‐scheme nanocomposites.
ET AL.
Compared with other photocatalysts, some MoS2‐supported
Z‐scheme TiO2/g‐C3N4 photocatalysts exhibit extended ab-
sorption in the visible light region. The pure Z‐scheme and
composite Z‐scheme photocatalysts were used to study the
photocatalytic degradation of methylene blue (a common
dye) and atrazine (an effective herbicide) in aqueous
media. The 10 wt% g‐C3N4‐supported TiO2 exhibited
higher degradation performance than other g‐C3N4‐
supported bare photocatalysts. This enhanced degradation
is attributed to the improved electron/hole pair separation
at the TiO2/g‐C3N4 interface of the Z‐scheme electron
transfer. In addition, compared with all other photo-
catalysts, the MoS2 nanosheets loaded with the Z‐scheme
TiO2/g‐C3N4 photocatalyst displayed excellent degradation
performance. Some Z‐scheme composite photocatalysts
have a layer of MoS2, which acts as an electron acceptor/
promoter to enhance photocatalytic activity. A suitable
mechanism for improving the charge separation perfor-
mance by using PL analysis, and the charged potential of
the photocatalyst was proposed.193
Various types of Z‐scheme photocatalysts have been
synthesised to fix nitrogen and degrade pollutants, as
shown in Table 8.
3.4 | CO2 reduction
With the increasing consumption of fossil fuels for energy
supplies, the concentration of CO2 rises in the atmosphere,
which results in a worldwide concern of greenhouse effect
and global warming. Photocatalytic CO2 reduction into
hydrocarbon fuels and chemicals, including CH4, CH3OH,
HCHO and HCOOH is an effective and promising
method for solving the environmental challenges and si-
multaneously supplying sustainable energy. Among the
LI ET AL. | 321

TABLE 8 Summary of representative Z‐scheme photocatalysts utilised in the other applications

Catalyst Synthesis method Application Type of heterostructure References
CdTe‐Bi2S3 Hydrothermal and electrostatic Detection of microcystin‐LR Direct Z‐scheme [194]
g‐C3N4‐WO3‐ Hydrothermal and thermo Degradation of methyl orange and All‐solid‐state Z‐scheme [195]
Bi2WO6 polymerisation phenol
NaNbO3‐Au‐Sn3O4 Ultrasonic dispersion and Degradation of carbofuran All‐solid‐state Z‐scheme [52]
calcination
BiOBr/UMOFNs Deposition‐precipitation Degradation of phenol Direct Z‐scheme [196]
TiO2/g‐C3N4 Wetness impregnation Degradation of organic water Direct Z‐scheme [193]
pollutants
CdS/Fe3O4/TiO2 Hydrothermal Degradation of ibuprofen All‐solid‐state Z‐scheme [197]
CdTe/TiO2 Hydrothermal Degradation of antibiotic Direct Z‐scheme [198]
wastewater
Ag/g‐C3N4/Bi3TaO7 Hydrothermal and Degradation of sulfamethoxazole All‐solid‐state Z‐scheme [192]
photodeposition
Ag3PO4/g‐C3N4 In situ precipitation Degradation of sulfamethoxazole Direct Z‐scheme [199]
ZnMoO4/ Ultrasonication Degradation of All‐solid‐state Z‐scheme [200]
BiFeWO6/rGO anthraquinonic dye
g‐C3N4/ZnFe2O4 Solvothermal N2 fixation Direct Z‐scheme [201]
Cu3P/g‐C3N4 In situ N2 fixation Direct Z‐scheme [190]
Ga2O3‐DBD/g‐C3N4 Postgrafting N2 fixation All‐solid‐state Z‐scheme [191]
TiO2/ZnFe2O4 Calcination N2 fixation Direct Z‐scheme [72]

various strategies to enhance the photocatalytic efficiency,
the construction of the Z‐scheme system is a powerful
option due to its own characteristics, such as maintaining
the strong redox capacity and eliminating the weak electron
–hole pairs through the ‘Z’ letter like charge transfer route.
In the above classification of Z‐scheme photocatalysts, in-
cluding S‐scheme and perovskite‐based photocatalysts, we
have interspersed with some research on CO2 reduction.
Although the photocatalytic CO2 reduction based on pow-
der Z‐scheme systems has been widely investigated during
the past decades, and there are many literatures to review
the application of Z‐scheme in photocatalytic CO2 reduc-
tion.202 However, the PEC reduction of CO2 is still in its
infancy due to the difficulties in both experimental and
theoretical facets. The PEC CO2 reduction system have
several different configurations depending on the light‐
absorbing photoelectrode, such as photoanode, photo-
cathode or both. As shown in Figure 25, J. S. Lee et al.203
reported the BiVO4/WO3 photoanodes to drive the PEC
reduction of CO2 on a Cu cathode in which cobalt carbo-
nate was used as the oxygen evolution electrocatalyst. It can
be seen that the high photocurrent density corresponds to
more PEC CO2 reduction products and high Faradaic effi-
ciency. In most cases, the PEC experiments were utilised to
explore the charge‐transfer mechanism and energy band
analysis. H. Huang et al.204 constructed a Bi2O2(NO3)(OH)/
g‐C3N4 Z‐scheme structure by an electrostatic self‐assembly
method, which exhibits enormously promoted CO2 reduc-
tion ability under solar light irradiation. The PEC experi-
ments demonstrated that the Z‐scheme junction facilitates
charge transfer and separation. K. Maeda and coworkers205
performed the Z‐scheme CO2 reduction on a metal
complex–semiconductor hybrid photocatalysts. To explore
the CB potential of GaN:ZnO samples, which could criti-
cally affect the photocatalytic activity, its flat band potential
was obtained from the photocurrent onset in the PEC tests.
Thereby, PEC experiments could contribute to the ex-
ploration of the photocatalytic mechanism. With the de-
velopment of Z‐scheme theories and the breakthrough of
efficient photocatalysts, the Z‐scheme PEC reduction of
CO2 would arouse more interest in the near future.
The Z‐scheme photocatalysts used in CO2 reduction
in recent years are summarised in Table 9.
4 | CONCLUSION AND
PERSPEC TIVES
Research on Z‐scheme photocatalyst has enriched our
understanding of its basic principles, preparation meth-
ods and environmental and energy‐related applications.
Furthermore, in recent years, PEC technology has
322 | LI ET AL.

F I G U R E 25 (A) Illustration of a photoelectrochemical system for solar fuel production by CO2 reduction. (B) Energy diagram and
reactions involved on Co‐Ci/BiVO4/WO3 photoanode for oxygen evolution and on Cu cathode for CO2 reduction. (C) Chronoamperometry
for the PA‐Cu cathode photoelectrochemical CO2 reduction. (D) Amounts of CH4 produced. (E) Faradaic efficiency at 60 min. (F) Faradaic
efficiency × charge at 60 min. Reproduced with permission: Copyright 2015, Elsevier203

emerged as one of the most promising research fields,
and the current photocatalytic technology is based
mainly on single‐component semiconductors. However,
this technology is limited by several factors, such as low
quantum yield, low solar energy utilisation and difficult
recovery. These technical difficulties have greatly re-
stricted the wide application of PEC technology in the
industry. The reasonable designing of semiconductor
photocatalysts is a promising method for solving current
issues pertaining to energy and the environment because
it can utilise sunlight to stimulate various photocatalytic
reactions. The constructed Z‐scheme photocatalyst,
which simulates natural photosynthesis, has the ad-
vantages of increased daylighting, spatial separation
of reduction and oxidation active sites and good pre-
servation of redox capacity, which are all beneficial to
improving the photocatalytic performance. The present
study reviews the latest advances in the preparation,
modification and main PEC applications of Z‐scheme
photocatalysts. The application of Z‐scheme photo-
catalysts includes water splitting, pollutant degradation,
N2 fixation and CO2 reduction. The future challenges in-
volve the impedance of the development prospects of
Z‐scheme photocatalytic systems, owing to the charge‐
LI ET AL. | 323

TABLE 9 Summary of representative Z‐scheme photocatalysts utilised in CO2 reduction

Type of
Catalyst Synthesis method Products and activity heterostructure References
−1
g‐C3N4/SnS2 One‐step hydrothermal CH3OH: 2.24 μmol g Direct Z‐scheme [202]
−1 −1
g‐C3N4/Sn2S3‐DETA Hydrothermal and CH4: 4.84 μmol g h All‐solid‐state Z‐scheme [206]
electrophoretic deposition −1 −1
CH3OH: 1.35 μmol g h
−1
ZnO/g‐C3N4 Calcination CO: 70 μmol g Direct Z‐scheme [207]
−1
CH4: 47 μmol g
Ag2CrO4/g‐C3N4/GO Self‐assembly CH3OH: 0.5 μmol g−1 All‐solid‐state Z‐scheme [80]
−1
α‐Fe2O3/LaTiO2N Calcination CO: 29.0 μmol g Direct Z‐scheme [208]
−1
CH4: 38.0 μmol g
GaPO4/α‐MoC/Ga2O3 Hydrothermal CO: 2.5 μmol g−1 h−1 All‐solid‐state Z‐scheme [209]
−1 −1
WO3/LaTiO2N Hydrothermal CO: 2.21 μmol g h Direct Z‐scheme [210]
−1 −1
CH4: 0.36 μmol g h

transfer dynamics in the entire Z‐scheme system. Factors
such as appropriate mediators, pH values, doping with
other elements and different morphologies could greatly
influence catalytic reactions. Efficient carrier transmission
and a low recombination rate of electron–hole pairs
further establish the superiority of the PEC performance
and improve the photocatalytic activity. Poor under-
standing of the aforementioned issues is a factor that
limits the development of the Z‐scheme system; thus,
more efforts should be directed towards resolving this
issue in the future.
Firstly, the construction of Z‐scheme photoelectrodes
is still at an early stage compared with the numerous
photocatalysts in photocatalytic applications, including
water splitting, CO2 reduction, pollutant eliminating
and N2 conversion. The main challenge is that the charge
transfer direction in a photoelectrode is fixed and only
the special migration manner can improve the PEC
performances, which is intrinsically different with the
powder photocatalyst that can be dispersed randomly in
the reaction systems. In view of this, the aligned na-
noarrays structure has the natural advantage of charge
directional transformation. However, the design and
fabrication of Z‐scheme architecture on aligned na-
noarrays would be a delicate and complex process.
Therefore, paying more attention to the directional array
structure and looking for a facile and universal strategy
to construct Z‐scheme systems on it should be a key
direction for expanding PEC applications.
Secondly, the physical and chemical properties of
the individual semiconductor in the Z‐scheme photo-
electrode should be optimised. However, the con-
struction of the semiconductor on the substrate firmly
needs to resolve many technological issues. The
morphology, dimension and even physical properties
of the semiconductors would all influence their growth
on the photoelectrode substrate. Much work is needed
to optimise the physical and chemical properties of
each semiconductor. And many attempts are necessary
to achieve the successful construction of the Z‐scheme
on the conductive substrate. Moreover, the decoration
of the second semiconductor on the Z‐scheme photo-
electrode also involves many scientific and technical
issues. The energy band of the second semiconductor
must meet the specific requirements of charge direc-
tional transfer and the contact interfaces between the
two semiconductors in the Z‐scheme should be ra-
tionally controlled. Optimising each detail is the key
problem in the fabrication of efficient Z‐scheme
photoelectrode.
Finally, the photocatalytic mechanism in powder
Z‐scheme system is comparatively simple based on the
free radical identification methods. For example, super-
oxide radical, hydroxyl radical and holes could be re-
spectively captured by benzoquinone, tertiary butanol
and ethylene diamine tetra acetic acid, and thus confirm
the decisive factors in photocatalytic experiments.
Nevertheless, the photoelectrodes have a different
working mechanism and would be influenced by many
factors, involving the quantity of the second semi-
conductor, the working condition of the PEC cell and the
introduction of bias voltage. All of these factors influence
the exploration of working principles that cannot be
completely copied from the traditional Z‐scheme pow-
ders, and thus would consume much time and attention
for the exploration of the charge transfer mechanism.
The in‐depth understanding of the photocatalytic me-
chanism of Z‐scheme photoelectrodes is beneficial for
324 | LI
optimising the charge separation efficiency and tunning
their architecture. The investigation, therefore, would be
a very difficult but important process, which may affect
the application fields of PEC systems.
We believe that the future exploration of Z‐scheme
architectures would definitely stimulate the rapid devel-
opment of PEC applications in both practice and theory.
With breakthroughs in the resolution of the above issues,
the practical applications of nano‐photocatalytic materi-
als will be realised in the near future, resulting in an
improved living environment and high quality of living
standard in our daily lives.
AC K N O WL E D G E M E NTS
This study was financially supported by the Natural
Science Foundation of Shandong Province of China
(ZR2019MB006), National Natural Science Foundation
of China (21303232) and Natural Science Foundation of
Guangdong Province (2018A030313460).
CONFLI CT OF I NTER EST
The authors declare no conflict of interest.
ORCID
Bingjun Jin http://orcid.org/0000-0002-6444-583X
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AU T HO R B I O G R A P HI E S
Jiaxin Li was born in Henan, China in
1998. She obtained her bachelor's degree
in Changsha University of Science &
Technology in 2019. She is pursuing her
master's degree in Qingdao University,
majoring in Materials Science. Her re-
search interests mainly focus on the fabrication and
LI ET AL. | 331

utilisation of semiconductor photocatalysts in photo- research fellow in National University of Singa-

electrochemical field.
Bingjun Jin received his PhD degree
from Yonsei University, South Korea, in
2020 and then worked as a research
fellow in Yonsei University. He is cur-
rently an assistant professor in School of
Applied Physics and Materials at Wuyi
University, China. His research interests mainly focus
on the synthesis and modification of nanomaterials
for solar energy conversion and storage.
pore, Singapore. He is currently an associate
professor in College of Material Science and
Engineering in Qingdao University, China. His
research interests focus on the design and regula-
tion of novel nanostructures for solar energy
utilisation, and the corresponding theoretical
calculations.

How to cite this article: Li J, Yuan H, Zhang W,

Zhengbo Jiao received his PhD de-
et al. Advances in Z‐scheme semiconductor
gree from Shandong University in
photocatalysts for the photoelectrochemical
2011, then worked as an associate
applications: a review. Carbon Energy. 2022;4:
professor in Lanzhou Institute of
294‐331. doi:10.1002/cey2.179
Chemical Physics, Chinese Academy
of Sciences (CAS), China, following a