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Heterojunction Photocatalysts
Review

Jingxiang Low, Jiaguo Yu,* Mietek Jaroniec, Swelm Wageh, and Ahmed A. Al-Ghamdi

applications.[8–10] However, the practical

Semiconductor-based photocatalysis attracts wide attention because of its applications of photocatalysis are still lim-
ability to directly utilize solar energy for production of solar fuels, such as ited by its low photocatalytic activity.[11–14]
hydrogen and hydrocarbon fuels and for degradation of various pollutants. In simple terms, a photocatalytic reac-
tion on a semiconductor includes at least
However, the efficiency of photocatalytic reactions remains low due to the
five main steps: i) light absorption by the
fast electron–hole recombination and low light utilization. Therefore, enor- semiconductor, ii) formation of photogen-
mous efforts have been undertaken to solve these problems. Particularly, erated electron–hole pairs, iii) migration
properly engineered heterojunction photocatalysts are shown to be able to and recombination of the photogenerated
possess higher photocatalytic activity because of spatial separation of photo­ electron–hole pairs, iv) adsorption of reac-
tants and desorption of products, and
generated electron–hole pairs. Here, the basic principles of various hetero-
v) occurrence of redox reactions on the
junction photocatalysts are systematically discussed. Recent efforts toward semiconductor surface (see Figure 1).
the development of heterojunction photocatalysts for various photocatalytic Among them, the recombination of elec-
applications are also presented and appraised. Finally, a brief summary and tron–hole pairs plays a negative role in
perspectives on the challenges and future directions in the area of hetero- the photocatalytic processes.[15–17] During
junction photocatalysts are also provided. photocatalytic reaction, the photogenerated
electron–hole pairs can either transfer to
the photocatalyst surface and initiate redox
reactions, or recombine and create useless
1. Introduction heat. To better understand this process, let us illustrate it by a
somewhat similar situation: the effect of the gravitational force
A fast-growing industry and the rising global population in on a man jumping off the ground (see Figure 2a,b). The expres-
recent years are the key factors contributing to the energy sions for both the gravitational force acting on a man jumping
shortage and environmental pollution. Thus, to assure a long- off the ground and the Coulomb force acting between the elec-
term and sustainable development of human society, there tron and the hole have similar forms:
is an urgent need for the development of environmentally
friendly and renewable technologies for green energy produc- Mm
Fg = G (1)
tion and environmental remediation. Among the various pro- R2 
posed technologies, semiconductor-based photocatalysis has
great potential because it directly utilizes solar energy both for qe q h
Fc = k
the production of valuable chemical fuels, such as hydrogen r2  (2)
and hydrocarbon fuels, and for the degradation of harmful
pollutants.[1–6] Since the pioneering work on photocatalysis by In Equation (1) and (2), Fg is the gravitational force, G is the
Honda and Fujishima in 1972,[7] many semiconductors have gravitational constant, M is the Earth’s mass, m is the mass of
been investigated and developed for various photocatalytic the man, R is the distance between the center of the Earth and
the man, Fc is the Coulombic force, k is the Coulomb constant,
qe and qh are the charge magnitudes of the electron and the
J. X. Low, Prof. J. G. Yu
State Key Laboratory of Advanced Technology for
hole, respectively, and r is the distance between the centers of
Materials Synthesis and Processing these charges. When the man (cf. the electron) jumps from the
Wuhan University of Technology ground (cf. from the valence band) into the air (cf. the conduc-
122 Luoshi Road, Wuhan 430070, P. R. China tion band), he will fall back to the ground rapidly (cf. recom-
E-mail: yujiaguo93@whut.edu.cn; jiaguoyu@yahoo.com bine with the hole) because of the action of gravitational force
Prof. J. G. Yu, Prof. S. Wageh, Prof. A. A. Al-Ghamdi (cf. the Coulombic force between the electron and the hole).
Department of Physics
Faculty of Science In order to keep the man off the ground (cf. to separate the
King Abdulaziz University photogenerated electron–hole pairs), a stool (cf. the conduc-
Jeddah 21589, Saudi Arabia tion band of the semiconductor B) is provided (see Figure 2c,d);
Prof. M. Jaroniec then, the aforementioned man will land again on the stool and
Department of Chemistry and Biochemistry be kept off the ground (cf. the electron and hole pairs can be
Kent State University
Kent, Ohio 44242, USA
separated). Moreover, it should be noted that the value of the
Coulomb constant (8.99 × 109 N m2 C−2) is much larger than
DOI: 10.1002/adma.201601694 that of the gravitational constant (6.67 × 10−11 N m2 kg−2). Thus,

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Review
Jingxiang Low obtained
his B.Eng. (Hons) from
Multimedia University,
Malaysia in 2011 and his
M.S. in materials science
from Wuhan University of
Technology. He is a now a
Ph.D. candidate under the
supervision of Prof. Jiaguo Yu
at the State Key Laboratory
of Advanced Technology
for Materials Synthesis and
Processing, Wuhan University of Technology. His current
research includes photocatalytic H2 production and CO2
reduction.
Figure 1.  Schematic illustration of the typical photocatalytic processes
on a semiconductor.
Jiaguo Yu received his B.S.
the aforementioned man will fall back to the ground on the and M.S. in chemistry
timescale of seconds, while electron–hole pairs will recombine from Central China Normal
much faster, i.e., in the range of nanoseconds. Therefore, the University and Xi’an Jiaotong
separation of photogenerated electron–hole pairs on the sur- University, respectively, and
face of a photocatalyst is very difficult to achieve. Although pre- his Ph.D. in materials sci-
venting electron–hole recombination is a very challenging task, ence in 2000 from Wuhan
it can be accomplished by the proper design of a photocatalyst. University of Technology. In
Various strategies have been proposed to efficiently sepa- 2000, he became a Professor
rate the photogenerated electron–hole pairs in semiconductor at Wuhan University of
photocatalysts, for instance by doping,[18,19] metal loading,[20,21] Technology. He was a post-
and/or introducing heterojunctions.[22,23] Among the proposed doctoral fellow at the Chinese
strategies, engineering heterojunctions in photocatalysts has University of Hong Kong from 2001 to 2004, a visiting sci-
been proved to be one of the most promising ways for the entist from 2005 to 2006 at the University of Bristol, and a
preparation of advanced photocatalysts because of its feasibility visiting scholar from 2007 to 2008 at the University of Texas
and effectiveness for the spatial separation of electron–hole at Austin. His current research interests include semicon-
pairs (see Figure 2d). Basically, five different heterojunctions ductor photocatalysis, photocatalytic hydrogen production,
have been mainly investigated by our group at Wuhan Univer- CO2 reduction to hydrocarbon fuels, and so on.
sity of Technology (WUT) as well as by others and proved to
be efficient for enhancing the activity of photocatalysts; these
are conventional type-II heterojunctions,[24–27] p–n heterojunc- Mietek Jaroniec received his
tions,[28–30] surface heterojunctions,[31–34] direct Z-scheme heter- M.S. and Ph.D. from
ojunctions,[35,36] and semiconductor–graphene (SC–graphene) M. Curie-Sklodowska
heterojunctions.[37,38] University (Poland) in 1972
In the past 15 years, many studies have been published by and 1976; afterward, he was
our group on the development of advanced heterojunction pho- appointed as a faculty at
tocatalysts for various applications. As shown in Table 1, the the same University. Since
conventional type-II heterojunction mechanism was studied by 1991, he has been Professor
our group in 2001 to explain the high photocatalytic activity of of Chemistry at Kent State
anatase–brookite TiO2.[24,25] Then, the p–n heterojunction was University, Kent, Ohio (USA).
found to be more effective for enhancing the photocatalytic His research interests include
activity than the aforementioned conventional type-II hetero- interfacial chemistry and
junction.[39] Thereafter, two new heterojunction concepts were the chemistry of materials, especially adsorption at the
firstly proposed by our group, which were the direct Z-scheme gas/solid and liquid/solid interfaces and nanoporous
heterojunction in 2013[35] and the surface heterojunction in materials. At Kent State, he has established a vigorous
2014,[31] to further improve the photocatalytic activity. Recently, research program in the area of nanomaterials, such as
two-dimensional (2D) graphene nanosheets have been widely ordered mesoporous silicas, organosilicas, inorganic
used by our group to prepare advanced sc–graphene hetero- oxides, carbon nanostructures, and nanostructured cata-
junction photocatalysts with enhanced activity due to the fas- lysts/photocatalysts, focusing on their synthesis, character-
cinating properties of graphene, such as its high conductivity, ization, and environmental and energy-related applications.
large specific surface area, and high photostability.

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This review represents an appraisal of the

Review

recent efforts in engineering various het-

erojunction photocatalysts and highlights
their application in photocatalysis, including
hydrogen production, CO2 reduction, and
pollutant degradation. The above-mentioned
five important types of heterojunctions in
photocatalysts are reviewed and discussed.
Finally, the current status, opportunities,
and future directions of these heterojunction
photocatalysts are presented. We hope that
this review can provide some useful guide-
lines and shed some light toward the devel-
opment of highly efficient heterojunction
photocatalysts for different applications.

2. Conventional Heterojunctions
A heterojunction, in general, is defined as
the interface between two different semicon-
ductors with unequal band structure, which
can result in band alignments.[47,48] Typically,
there are three types of conventional hetero-
junction photocatalysts, those with a strad-
dling gap (type-I), those with a staggered
gap (type-II), and those with a broken gap
(type-III) (see Figure 3). For the type-I het-
Figure 2.  Schematic illustration of: a) the effect of gravitational force on a man who jumps erojunction photocatalyst (see Figure 3a), the
off the ground, b) electron–hole recombination on a single photocatalyst, c) use of a conduction band (CB) and the valence band
stool to keep a man off the ground, and d) electron–hole separation on a heterojunction (VB) of semiconductor A are respectively
photocatalyst. higher and lower than the corresponding

Table 1.  List of heterojunction photocatalysts studied by our group at WUT for various photocatalytic applications.

Sample Heterojunction type Application Year Ref.

Anatase–brookite TiO2 Conventional type-II Acetone degradation 2001 [24]

Anatase–brookite TiO2 Conventional type-II Acetone degradation 2003 [25]

Ag–multiphase TiO2 Conventional type-II Methyl orange (MO) degradation 2005 [40]

SnO–TiO2 Conventional type-II Rhodamine B (RhB) degradation 2008 [41]

NiO–TiO2 p–n p-Chlorophenol degradation 2010 [42]

BIOI–TiO2 p–n MO degradation 2011 [28]

NiS–CdS p–n Hydrogen production 2013 [29]

{001} and {101} TiO2 Surface CO2 reduction 2014 [31]

N-doped {001} and {101}TiO2 Surface CO2 reduction 2015 [32]

g-C3N4–TiO2 Direct Z-scheme HCHO decomposition 2013 [35]

Anatase–rutile TiO2 Direct Z-scheme Hydrogen production 2014 [43]

Ag2CrO4–graphene oxide Direct Z-scheme MB degradation 2015 [36]

CdS–WO3 Direct Z-scheme CO2 reduction 2015 [44]

Reduced graphene oxide–CdS SC–graphene Hydrogen production 2011 [37]

g-C3N4–graphene SC–graphene Hydrogen production 2011 [45]

Graphene–TiO2 nanosheets SC–graphene Hydrogen production 2011 [38]

CdS–graphene SC–graphene CO2 reduction 2014 [46]

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Review
Figure 3.  Schematic illustration of the three different types of separation of electron–hole pairs in the case of conventional light-responsive heterojunc-
tion photocatalysts: a) type-I, b) type-II, and c) type-III heterojunctions.

bands of semiconductor B.[49] Therefore, under light irradia- to prepare different type-II heterojunction photocatalysts, such
tion, the electrons and holes will accumulate at the CB and the as TiO2/g-C3N4,[55] BiVO4/WO3,[56] g-C3N4–WO3,[57] g-C3N4–
VB levels of semiconductor B, respectively. Since both electrons BiPO4,[58] and so on, for enhancing the photocatalytic activity.
and holes accumulate on the same semiconductor, the elec- Generally, type-II heterojunction photocatalysts exhibit good
tron–hole pairs cannot be effectively separated for the type-I electron–hole separation efficiency, wide light-absorption range,
heterojunction photocatalyst. Moreover, a redox reaction takes and fast mass transfer.[59]
place on the semiconductor with the lower redox potential, For example, Zhou et al. prepared a SnO2/TiO2 type-II heter-
thereby significantly reducing the redox ability of the hetero- ojunction photocatalyst by an electrophoretic-deposition (EPD)–
junction photocatalyst. For the type-II heterojunction photocata- calcination method for photocatalytic RhB degradation.[41] Spe-
lyst (see Figure 3b), the CB and the VB levels of semiconductor cifically, a commercial TiO2 was first electrophoretically depos-
A are higher than the corresponding levels of the semicon- ited on F-doped SnO2-coated glass, followed by calcination at
ductor B. Thus, the photogenerated electrons will transfer to 200, 300, 400, 500 and 600 °C to obtain crystallized SnO2/TiO2
semiconductor B, while the photogenerated holes will migrate type-II heterojunction photocatalyst films. It was found that all
to semiconductor A under light irradiation, resulting in a spa- the prepared samples show good photocatalytic activities due
tial separation of electron–hole pairs.[50–52] Similar to the type-I to the fast electron–hole separation through the type-II het-
heterojunction, the redox ability of the type-II heterojunction erojunction between the TiO2 and the SnO2. Particularly, the
photocatalyst will be also reduced because the reduction reac- sample prepared at 400 °C exhibited the highest photocatalytic
tion and the oxidation reaction take place on semiconductor B activity among all the samples studied. This high activity could
with lower reduction potential and on semiconductor A with be attributed to the optimal crystallinity and specific surface
lower oxidation potential, respectively. As shown in Figure 3c, area, which can reduce the number of recombination centers
the architecture of the type-III heterojunction photocatalyst is on the sample and provide larger surface area with active sites
similar to that of the type-II heterojunction photocatalyst except for photocatalytic reaction.
that the staggered gap becomes so extreme that the bandgaps Meanwhile, Wetchakun et al. reported a hydrothermal syn-
do not overlap.[53,54] Therefore, the electron–hole migration and thesis of BiVO4/CeO2 type-II heterojunction photocatalysts for
separation between the two semiconductors cannot occur for the the photocatalytic degradation of methylene blue (MB), methyl
type-III heterojunction, making it unsuitable for enhancing the orange (MO), and a mixture of MB and MO.[60] It was found
separation of electron–hole pairs. Among the aforementioned that the the BiVO4 and the CeO2 possessed different isoelectric
conventional heterojunctions, it is obvious that the type-II het- points, located at pH values of 4.56 and 7.33 respectively. The
erojunction is the most effective conventional heterojunction isoelectric-point difference for these two semiconductors was
to be used for improving photocatalytic activity because of its shown to be beneficial for adsorbing both cationic and anionic
suitable structure for spatial separation of electron–hole pairs. dyes simultaneously. Specifically, the BiVO4 and the CeO2 can
In the past several decades, enormous efforts have been made preferentially respectively adsorb cationic MB and anionic MO

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Review

Figure 4. Schematic illustration of the photocatalytic-activity enhancement mechanism of: (a) Ag/AgCl/pCN type-I, and b) Ag/AgBr/pCN type-II
heterojunction photocatalysts under light irradiation. Reproduced with permission.[61] Copyright 2014, Elsevier.

during degradation reactions. As a result, the BiVO4/CeO2 Moreover, the morphology tuning of heterojunction pho-
composite exhibited higher photocatalytic-degradation activity tocatalysts is also critical for optimizing the performance of
toward the mixture of MB and MO as compared with the single type-II heterojunction photocatalysts. For example, Shen and
BiVO4 or CeO2 photocatalysts, which were not active toward the co-workers reported visible-light-active CdS/ZnO core/shell
photocatalytic degradation of the anionic MO and the cationic nanofibers with a type-II heterojunction (see Figure 5a,b), with
MB, respectively, due to the electrostatic repulsion between good photocatalytic activity toward hydrogen production.[10] The
their surface charges and the charges of the dye molecules. This type-II heterojunction significantly facilitated the electron–hole
remarkable activity of the composite photocatalyst is attributed separation efficiency between the ZnO and the CdS. Mean-
to the enhanced electron–hole separation efficiency and strong while, the core–shell structure of the CdS/ZnO featured a large
electrostatic attraction between the composite and the dye contact interface, which can further enhance the separation
molecules. This study suggests that the proper coupling of two efficiency of electron–hole pairs. As a result, the photocatalytic
different semiconductors can not only enhance the electron– hydrogen-production efficiency of ZnO/CdS was higher than
hole separation efficiency but can also afford photocatalysts with that of the single ZnO and CdS compounds.
good adsorption ability toward both anionic and cationic dyes. Furthermore, type-II heterojunction photocatalysts can
Ong et al. systematically investigated the photocatalytic be also created between two different phases of a semicon-
activity of type-I Ag/AgCl/g-C3N4 and type-II Ag/AgBr/g- ductor.[62–64] For instance, the mixed phase of TiO2, i.e., P25
C3N4 heterojunction photocatalysts for photocatalytic CO2 (consisting of anatase and rutile TiO2), has been commercial-
reduction.[61] It was found that both Ag/AgCl/g-C3N4 and Ag/ ized and has attracted wide attention for various photocatalytic
AgBr/g-C3N4 exhibited good photocatalytic CO2-reduction per- applications due to its efficient charge-carrier separation. In
formance toward CH4 production due to the presence of the detail, the CB and VB levels of anatase TiO2 are higher than
heterojunction, which may improve the charge-carrier sepa- the corresponding levels of rutile TiO2. Therefore, a type-II
ration in these photocatalysts. Notably, the
photocatalytic CO2 reduction activity of Ag/
AgBr/g-C3N4 toward CH4 production was
much higher than that of Ag/AgCl/g-C3N4.
This was ascribed to the formation of the
type II-heterojunction instead of the type-I
heterojunction in the case of Ag/AgBr/g-
C3N4, which can lead to the spatial separa-
tion of electrons and holes by accumulating
them in the Ag/AgBr and the g-C3N4, respec-
tively (see Figure 4). This study proved that
the type-II heterojunction in photocatalysts
is more effective than the type-I heterojunc- Figure 5.  a,b) Scanning electron microscopy (SEM) (a) and transmission electron microscopy
tion for improving their photocatalytic CO2- (TEM) (b) images of CdS/ZnO core/shell nanofibers with a type-II heterojunction. Reproduced
reduction activity. with permission.[10] Copyright 2013, The Royal Society of Chemistry.

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Review
Figure 7.  Schematic illustration for the transfer and separation of charge
carriers on an anatase/rutile/Ag heterojunction photocatalyst under light
irradiation.

was found that the optimal Ag–TiO2 (0.05 M of AgNO3) sample

exhibited very high photocatalytic activity for MO degradation.
This is due to the formation of multiphase type-II heterojunc-
tions, such as anatase/rutile, anatase/brookite and rutile/
brookite, which can greatly enhance the electron–hole separa-
Figure 6.  Comparison of the rate constant of anatase–brookite compos- tion efficiency. Moreover, Ag loading can also further enhance
ites: with 80% anatase and 20% brookite (A), with 92% anatase and 8% the charge-carrier separation in the Ag–TiO2 composite. Taking
brookite (B), with 100% anatase (C); as well as P25, in the photocatalytic
anatase/rutile/Ag as an example (see Figure 7), the photogen-
degradation of acetone in air. Reproduced with permission.[24] Copyright
2001, The Royal Society of Chemistry. erated electrons and holes can be spatially separated in rutile
and anatase TiO2, respectively, through the type-II heterojunc-
tion. Meanwhile, the electrons on the rutile TiO2 can further
heterojunction photocatalyst can be formed by combining the migrate to Ag nanoparticles (NPs) through the Schottky junc-
anatase and rutile TiO2 in P25, which results in an enhance- tions between the Ag and the rutile TiO2, thus achieving high
ment of the electron–hole separation. Also, in 2001 our group electron–hole separation efficiency.
reported an anatase–brookite dual-phase type-II heterojunction Although type-II heterojunction photocatalysts possess good
photocatalyst by hydrolysis of titanium tetraisopropoxide in electron–hole separation efficiency, there are still some prob-
water or 1:1 ethanol–H2O solution.[24] It was found that the con- lems that limit their practical applications. For example, the
tent of brookite in the composite was reduced in the presence reduction and oxidation reactions on the type-II heterojunction
of ethanol because the latter can suppress the hydrolysis of the photocatalysts take place on the semiconductors with the lower
titanium alkoxide and inhibit the rapid crystallization of the reduction and oxidation potentials, respectively, thereby greatly
TiO2 nanoparticles into brookite by adsorbing on the surface of suppressing their redox ability (see Figure 3b). Moreover, the
the TiO2. Notably, the photocatalytic activity of the sample con- migration of electrons from semiconductor A to the electron-
sisting of anatase and brookite toward degradation of acetone rich CB of semiconductor B or the corresponding migration
was higher than that of one consisting of pure anatase (see of holes from semiconductor B to the hole-rich VB of semi-
Figure 6). This is due to the formation of a type-II heterojunc- conductor A are physically unfavorable because of the electro-
tion between the brookite and the anatase, which can greatly static repulsion between electron and electron or hole and hole,
enhance the separation efficiency of the electron–hole pairs. respectively. Therefore, the development of more effective het-
In order to further enhance the photocatalytic activity of the erojunctions in photocatalysts is urgently needed.
multi-phase type-II heterojunction photocatalysts, an Ag–TiO2
multiphase composite was designed and synthesized by Yu
et al.[40] It was found that the silver precursor, AgNO3, has a 3. p–n Heterojunctions
great influence on the crystallization of the TiO2. The phase
composition of the TiO2 changed with changing AgNO3 con- Although the type-II heterojunction can ideally separate elec-
centration. Particularly, brookite TiO2 started to appear and tron–hole pairs in space, the achieved enhancement in the
steadily grow, starting from a AgNO3 concentration of 0.02 M, electron–hole separation across a type-II heterojunction is not
because the AgNO3 facilitates and catalyzes the formation of sufficient to overcome the ultrafast electron–hole recombination
brookite TiO2. Meanwhile, the rutile TiO2 began to be formed on the semiconductor. Thus, a p–n heterojunction photo­catalyst
at a AgNO3 concentration of 0.03 M. Notably, the phase-trans- concept was proposed, which is able to accelerate the electron–
formation temperature of TiO2 from anatase to rutile was sig- hole migration across the heterojunction for improving the
nificantly reduced from 700 °C to 500 °C due to the presence photocatalytic performance by providing an additional electric
of AgNO3. Thus, AgNO3 can suppress the growth of anatase field.[65–67] Specifically, an effective p–n heterojunction photo-
domains and thus increase the total boundary energy of TiO2 catalyst can be obtained by combining p-type and n-type semi-
by promoting the phase transformation of anatase to rutile. It conductors. Before light irradiation, the electrons on the n-type

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equal to or higher than their bandgap value, both p-type and

Review

n-type semiconductors can be excited, generating electron–hole

pairs. The photogenerated electrons and holes in the p-type and
n-type semiconductors will migrate under the influence of the
internal electric field to the CB of the n-type semiconductor and
the VB of the p-type semiconductor, respectively, which results
in the spatial separation of the electron–hole pairs. It should
be noted that this electron–hole separation process is also ther-
modynamically feasible because both the CB and the VB of the
p-type semiconductor are normally located higher than those of
the n-type semiconductor in a p–n heterojunction photocata-
lyst.[75,76] As a result, the electron–hole separation efficiency in
p–n heterojunction photocatalysts is faster than that of type-II
heterojunction photocatalysts due to the synergy between the
internal electric field and the band alignment.[42]
For example, our group has demonstrated that the design
of NiS/CdS nanorods with p–n heterojunctions can greatly
improve the photocatalytic hydrogen-production efficiency of
Figure 8. Schematic illustration of the electron–hole separation under the CdS.[29] NiS NPs with sizes of 10–30 nm were uniformly
the influence of the internal electric field of a p–n heterojunction photo- dispersed on the surface of CdS nanorods, thereby providing
catalyst under light irradiation.
larger contact interface for creating p–n heterojunctions
between the NiS and the CdS (see Figure 9a). The formation of
semiconductor near the p–n interface tend to diffuse into the p–n heterojunctions can facilitate charge transfer between the
p-type semiconductor, leaving a positively charged species (see NiS and the CdS and suppress the charge-carrier recombination
Figure 8).[68–71] Meanwhile, the holes on the p-type semicon- (see Figure 9b,c). Meanwhile, the CdS nanorods can enhance
ductor near the p–n interface tend to diffuse into the n-type electron transport because of their one-dimensional (1D) struc-
semiconductor, leaving a negatively charged species. The elec- ture. As a result, the photocatalytic hydrogen-production rate
tron–hole diffusion will continue until the Fermi level equilib- on the NiS/CdS nanorods with p–n heterojunctions, having
rium of the system is achieved. As a result, the region close to 5 wt% NiS (56.6 µmol h−1) is much higher than that of the pure
the p–n interface is charged, creating a “charged” space or the CdS (2.8 µmol h−1) and 1 wt% Pt-loaded CdS (36.3 µmol h−1)
so-called internal electric field.[72–74] When the p-type and n-type (see Figure 9d). However, a further increase in the NiS loading
semiconductors are irradiated by incident light with an energy on the CdS causes a decrease in the photocatalytic activity

Figure 9.  a) SEM image of 5 wt% NiS-loaded CdS. b,c) Schematic illustration of the charge-carrier separation on the NiS/CdS nanorods with p–n
heterojunctions (b) and across the NiS/CdS p–n heterojunction (c). d) Comparison of the photocatalytic activity of CdS with different NiS loadings:
Ni0 (0 wt% NiS), Ni0.5 (0.5 wt% NiS), Ni1 (1 wt% NiS), Ni3 (3 wt% NiS), Ni5 (5 wt% NiS), Ni10 (10 wt% NiS), 1 wt% Pt–CdS, and pure NiS under
visible-light irradiation. Reproduced with permission.[29] Copyright 2013, The Royal Society of Chemistry.

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4. Surface Heterojunctions

Review
In 2014, our group proposed the concept of
the surface heterojunction to explain the
unique electron–hole separation phenom-
enon observed on the crystal facets of a single
semiconductor.[31] It is well-known that the dif-
ferent crystal facets on a single semiconductor
can have different band structures.[31,78] Since
a heterojunction is formed by combining
two semiconducting materials with different
band structures, it is possible to create a het-
Figure 10.  a,b) SEM images of flower-like NiO (a), and a flower-like NiO/TiO2 p–n heterojunc-
tion photocatalyst (b) with the inset showing high resolution. Reproduced with permission.[42]
erojunction between two crystal facets of a
Copyright 2010, Wiley-VCH. single semiconductor, namely a surface het-
erojunction.[31,79,80] In our work, a series of
because the shielding effect of the NiS may reduce the number anatase TiO2 samples with different ratios of the exposed {001}
of active sites on the surface and thus the light-absorption and {101} facets was reported. These samples were prepared
ability of the CdS. by a F−-ions-assisted hydrothermal method. The photocatalytic
Furthermore, Feng and co-workers reported a MoS2/CdS activity of the sample with 55:45 ratio of the exposed {001} and
p–n heterojunction photocatalyst for enhancing photocata- {101} facets was much higher than that of the samples domi-
lytic hydrogen-production efficiency,[77] which was simply pre- nated either by exposed {001} or {101} facets. According to den-
pared by a one-pot solvothermal method. It was shown that a sity functional theory (DFT) calculations (see Figure 11a), the
“V-shaped” Mott–Schottky plot can be obtained by performing observed enhancement in the photocatalytic activity was due to
electrochemical testing, which suggests the formation of p–n the formation of surface heterojunctions between the {001} and
heterojunctions by the combination of the p-type MoS2 and the {101} facets. In fact, the basic principle of the surface hetero-
n-type CdS. It was found that the n-type CdS is uniformly dis- junction is similar to that of the type-II heterojunction, in which
persed on the surface of nanosheets of the p-type MoS2, which the CB and VB levels of the {001} facets are higher than the cor-
results in a larger contact interface between the CdS and the responding levels of the {101} facets of anatase TiO2. Thus, elec-
MoS2, being beneficial for accelerating charge transfer and sep- trons and holes can be spatially separated on the {101} facets
aration. Therefore, the MoS2/CdS p–n heterojunction photocat- for reduction reactions and on the {001} facets for oxidation
alyst exhibited an excellent electron–hole separation efficiency reactions, respectively (see Figure 11b). This finding enables the
due to its large contact interface and rapid electron–hole sepa- design of heterojunction systems into the surface of single nan-
ration through the formed p–n heterojunctions. Consequently, oparticle. In addition, the fabrication cost of the resulting het-
the 2D MoS2/CdS p–n heterojunction photocatalyst exhibited a erojunction photocatalysts can be greatly reduced because only
hydrogen-production rate of 137 µmol h−1, which is 10 times one semiconductor is used. Notably, the redox potential loss of
higher than that obtained for pure CdS. This work shows a type-II heterojunction photocatalyst can be also minimized
that an enlarged contact interface on the p–n heterojunction by creating a surface heterojunction, because the difference in
photocatalysts is beneficial for enhancing their photo­catalytic the band structures between the {001} and {101} facets of TiO2
performance. is small. Therefore, the photocatalytic CO2 reduction activity of
The morphology of the p–n heterojunction photocatalysts anatase TiO2 with an optimal ratio of exposed {001} and {101}
can be tuned for achieving large specific surface area and an facets was 3.5 times higher than that of commercial TiO2, i.e.,
abundant number of surface active sites, which has been P25 (Figure 11c). Furthermore, it was observed that the over-
proved to be effective for further improvement of the photocata- exposed {101} or {001} facets on the TiO2 caused an overflow
lytic activity of p–n heterojunction photocatalysts. Recently, our effect of holes and electrons (see Figure 12a,c), respectively, and
group showed that a flower-like NiO/TiO2 p–n heterojunction consequently reduced the photogenerated electron–hole separa-
photocatalyst exhibited an exceptional photocatalytic activity tion efficiency. Apparently, the fabrication of anatase TiO2 with
toward degradation of p-chlorophenol.[42] The flower-like NiO/ the optimal ratio of the exposed {001} and {101} facets is crucial
TiO2 p–n heterojunction was afforded by a simple hydrothermal for enhancing the photocatalytic activity of the anatase TiO2 (see
method. Specifically, TiO2 NPs were uniformly deposited on Figure 12b).[31,81–84]
the surface of flower-like NiO particles, which resulted in the Selective deposition of oxidation and reduction co-catalysts
formation of a NiO/TiO2 p–n heterojunction photocatalyst (see on a semiconductor has been widely applied to confirm the type
Figure 10a,b). The resulting photocatalyst featured a large spe- of oxidation and reduction sites thereon.[85] Recently, Liu et al.
cific surface, which assured the abundance of surface active reported that the spatial separation of electrons and holes on the
sites for photocatalytic reactions and enhanced the adsorption different facets of a single anatase TiO2 crystal can be confirmed
ability for dye molecules. In addition, it was shown that the for- by photo-deposition of Pt NPs. Specifically, Pt NPs were selec-
mation of p–n heterojunctions in NiO/TiO2 can improve the tively loaded on the surface of the electron-rich {101} facets due
electron–hole separation rate. As a result, the NiO/TiO2 photo­ to the spatial separation of electrons and holes on the anatase
catalyst exhibited a superior photocatalytic activity toward the TiO2.[86] Moreover, they found that an optimal ratio of the {001}
degradation of p-chlorophenol. and {101} facets is also an important issue for photocatalytic

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photocatalytic activity. Specifically, 1, 2, and

Review

4 mL of H2PtCl6 solution were used to pre-

pare a series of TiO2/Pt photocatalysts, named
as TP1, TP2, and TP4, respectively. Interest-
ingly, Pt NPs were selectively deposited on
the surface of the {101} and {010} facets of
anatase, which was due to the formation of
surface heterojunctions. Particularly, {001}
and {110} have a higher CB value, while {101}
and {010} have a lower VB value. The elec-
trons and holes tend to migrate to the {101}
and {010} facets for reduction reactions and
to {001} and {110} facets for oxidation reac-
tions, respectively. Therefore, the Pt ions are
accumulated on the {101} and {010} facets
and reduced into Pt NPs by photogenerated
electrons during the photoreduction process.
Due to the synergistic effect of surface hetero-
junctions and Schottky junctions, the photo-
catalytic activity of the resulting TP1 toward
the degradation of phenol was much higher
than that of pure TiO2. However, a further
increase in the loading of Pt NPs (e.g., sam-
ples TP2 and TP4) led to the light-shielding
effect, which may significantly reduce the
photocatalytic activity of these samples.
Furthermore, Li et al. reported BiVO4 with
co-exposed {010} and {110} facets for the spa-
tial separation of photogenerated electrons
and holes.[87] It was found that the {010} and
{110} facets exhibited different band struc-
tures, in which the CB of the {110} facets is
Figure 11.  a) Density of states (DOS) plots of the {101} and {001} facets of anatase TiO2, higher than that of the {010} facets, while
where O 2P, Ti 3d, and TDOS are the partial DOS of O2P, partial DOS of Ti 3d, and total DOS, the VB of the {010} facets is lower than that
respectively. b) Electron–hole separation on the surface heterojunction of anatase TiO2 with an of the {110} facets. Therefore, electrons and
optimal ratio of the exposed {001} and {101} facets (55:45). c) Comparison of the photocata- holes tend to migrate to the {010} and {110}
lytic CH4 production activity of P25, HF0 (anatase TiO2 with a ratio of the exposed {001} and facets, respectively, resulting in their spa-
{101} facets equal to 11:89), HF3 (anatase TiO2 with the ratio of 49:51), HF4.5 (anatase TiO2 tial separation. In order to further improve
the ratio of 55:45), HF6 (anatase TiO2 with the ratio of 72:28), and HF9 (anatase TiO2 with the
[31]
ratio of 83:17). Reproduced with permission. Copyright 2014, American Chemical Society.
the photocatalytic activity of such samples,
reduction (Pt) and oxidation (MnOx) co-
catalysts were loaded onto BiVO4 by the
hydrogen production by water splitting. Namely, the photo- photo-deposition method. It was found that Pt and MnOx co-
catalytic hydrogen-production activity of the sample with an catalysts are preferably loaded on the {010} and {110} facets
optimal ratio of the exposed {001} and {101} facets and 0.5% (see Figure 13a,b), respectively. This is because Pt and MnOx
loading of Pt was ca. 9 times higher than
that of the corresponding sample dominated
by {101} facets. Furthermore, Gao et al. pre-
pared anatase TiO2 with exposed {101}, {010},
{001}, and {110} facets by using a simple
hydrothermal method to create surface het-
erojunctions on the anatase TiO2 for photo-
catalytic phenol degradation.[33] Transmission
electron microscopy (TEM) images of these
samples suggested that the anatase TiO2
with exposed {101}, {010}, {001}, and {110}
Figure 12.  Schematic illustrations of: a) overflow effect of holes on the anatase TiO2 dominated
facets was successfully fabricated. Then, dif-
by {101} facets, b) spatial separation of electrons and holes on anatase TiO2 with an optimal
ferent amounts of Pt NPs were loaded on the ratio of the exposed {001} and {101} facets, and c) overflow effect of electrons on anatase
as-prepared anatase TiO2 to form Schottky TiO2 dominated by {001} facets. Reproduced with permission.[31] Copyright 2014, American
junctions for further improvement of the Chemical Society.

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Review
Figure 13.  a,b) SEM images of BiVO4 with deposited Pt (a) and MnOx (b). Reproduced with permission.[87] Copyright 2013, Nature Publishing Group.

can be easily formed on the photogenerated electron-rich sur- in the liquid phase, thereby limiting their wide application in
face of the {010} facets and the photogenerated hole-rich sur- photocatalysis.
face of the {110} facets, respectively. By adjusting the loadings In 2006, Tada et al. proposed the concept of an all-solid-
of the reduction and oxidation co-catalysts, the electrons on the state Z-scheme photocatalyst, which consisted of two different
{010} facets and the holes on the {110} facets of the BiVO4 can semiconductors (PS I and PS II) and a solid electron mediator
further migrate to Pt and MnOx, respectively, which results in between them.[93] As shown in Figure 15, electrons on the VB
accelerating the electron–hole separation. Due to the spatial of the PS II are firstly excited to the CB under light irradiation,
separation of the electron–hole pairs and the proper loading of leaving holes on the VB. Then, the photogenerated electrons on
reduction and oxidation co-catalysts, the resulting photocatalyst the PS II migrate to the VB of the PS I via an electron mediator
exhibited a high photocatalytic activity for water oxidation. (such as Pt, Ag, and Au), and are further excited to the CB of
PS I. As a result, photogenerated holes and electrons are accu-
mulated in the PS II, with a higher oxidation potential, and in
5. Direct Z-Scheme Heterojunctions the PS I, with a higher reduction potential, respectively, which
results in the spatial electron–hole separation and optimiza-
Although all the above-mentioned heterojunction photocata- tion of the redox potential. Moreover, all-solid-state Z-scheme
lysts are efficient for enhancing electron–hole separation, the photocatalysts can be used in solution, gas, and solid media,
redox ability of the photocatalyst is sacrificed because the reduc- thereby extending their photocatalytic applications.[94–96] How-
tion and oxidation processes occur on the semiconductor with ever, electron mediators required for improving the migration
the lower reduction and oxidation potentials, respectively.[88–91] path for electrons in the all-solid-state Z-scheme photocatalysts
In order to overcome this problem, the Z-scheme photocata- are expensive and rare, which limits large-scale applications of
lytic concept was proposed by Bard et al. in 1979 to maximize these photocatalysts.
the redox potential of the heterojunction systems.[92] A conven- In 2013, our group proposed a direct Z-scheme heterojunc-
tional Z-scheme photocatalytic system is composed of two dif- tion photocatalyst concept. A direct Z-scheme photocatalyst
ferent semiconductors, photocatalyst I (PS I) and photocatalyst was prepared by combining two different semiconductors
II (PS II), and an acceptor/donor (A/D) pair (see Figure 14). PS without an electron mediator.[35] As shown in Figure 16, the
I and PS II are not in physical contact. During the photocata- construction of this direct Z-scheme heterojunction photocata-
lytic reaction, photogenerated electrons migrate from the CB of lyst is identical to that of conventional all-solid-state Z-scheme
the PS II to the VB of the PS I through an A/D pair via fol-
lowing redox reactions:

A + e− → D  (3)

D + h+ → A  (4)

Specifically, A is reduced into D by reacting with the pho-

togenerated electrons from the CB of the PS II. After that, the
D is oxidized into A by the photogenerated holes from the VB.
Since electrons accumulate on the PS I, with the higher reduc-
tion potential, and holes accumulate on the PS II, with the
higher oxidation potential, a spatial separation of electron–hole
pairs and an optimal redox ability can be achieved. However, Figure 14.  Schematic illustration of electron–hole separation on the con-
conventional Z-scheme photocatalysts can only be constructed ventional Z-scheme photocatalytic system under light irradiation.

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Review

Figure 16.  Schematic illustration of electron–hole separation on a direct

Figure 15.  Schematic illustration of the electron–hole separation on all-
Z-scheme heterojunction photocatalyst under light irradiation.
solid-state Z-scheme photocatalysts under light irradiation.

heterojunction photocatalysts, except that the rare and expen- at about 425 nm with increasing irradiation time is visible (see
sive electron mediators are not required in this system.[35,97–99] Figure 17b), indicating the generation of the •OH radical. If a
Similarly, electrons and holes are spatially separated on the type-II heterojunction is formed by coupling the g-C3N4 and the
semiconductor with the higher reduction potential and oxida- TiO2, instead of a direct Z-scheme heterojunction, no increase
tion potential of the direct Z-scheme heterojunction photocata- in the PL intensity should be observed because the photogen-
lyst, respectively.[100–102] Furthermore, the fabrication cost of erated holes are accumulated on the valence band of g-C3N4,
this direct Z-scheme heterojunction photocatalyst is low and which does not have sufficient oxidation power for producing
comparable to that of conventional type-II heterojunction sys- •OH radicals (see Figure 17c,d). The observed production of
tems.[103] Also, it shows other advantages; for instance, its redox •OH radicals confirms the accumulation of photogenerated
potential can be optimized for specific photocatalytic reactions. holes on the valence band of the TiO2, suggesting the forma-
Moreover, the charge transfer on the direct Z-scheme hetero- tion of the g-C3N4–TiO2 direct Z-scheme heterojunction. As a
junction photocatalyst is physically more favorable than that on result, the photocatalytic formaldehyde-decomposition activity
the type-II heterojunction photocatalyst because of the electro- of the optimized g-C3N4–TiO2 photocatalyst (12% g-C3N4-loaded
static attraction between electrons and holes. In particular, in TiO2) is 2.1 times higher than that of commercial TiO2, i.e., P25
the case of the direct Z-scheme photocatalysts, the migration of (see Figure 18a,b). Moreover, it was shown that the photocata-
photogenerated electrons from the CB of the PS II to the pho- lytic activity of the g-C3N4-TiO2 direct Z-scheme heterojunction
togenerated hole-rich VB of the PS I is easier, due to the elec- is greatly dependent on the amount of g-C3N4 loaded on the
trostatic attraction between the electrons and the holes. In con- TiO2. An overloading of g-C3N4 on the TiO2 led to a decrease
trast, for conventional type-II heterojunction photocatalysts, the in the photocatalytic activity (see Figure 18c,d). This is due to
migration of photogenerated electrons from the CB of semicon- the shielding effect of the g-C3N4 on the TiO2, which causes a
ductor A to the photogenerated electron-rich CB of semicon- reduction in the light-absorption ability of the TiO2 and inhibits
ductor B is apparently harder due to the electrostatic repulsion the reaction between the photogenerated holes in the TiO2 and
between electrons (see Figure 3b). Due to the aforementioned reactants.
advantages, direct Z-scheme heterojunction photocatalysts have In 2014, Katsumata et al. fabricated a WO3/g-C3N4 Z-scheme
recently attracted a lot of attention. heterojunction photocatalyst for hydrogen production under
For instance, our group reported the photocatalytic decompo- visible-light irradiation by a simple calcination method.[104]
sition of the major indoor pollutant formaldehyde on a g-C3N4– In this direct Z-scheme heterojunction system, the photogen-
TiO2 direct Z-scheme heterojunction photocatalyst.[35] Specifi- erated electrons migrated from the WO3 to the g-C3N4, while
cally, a series of the samples was prepared by calcining mix- the photogenerated holes were kept on the WO3 during the
tures of P25 titania with different amounts of urea. As can be photocatalytic reaction. Thus, the reduction and oxidation
seen from Figure 17a, the sizes of the TiO2 NPs were ca. 30 nm. reactions took place on the g-C3N4, having higher reduction
More interestingly, the TiO2 NPs were covered by g-C3N4. potential, and on the WO3, having higher oxidation potential,
Therefore, an intimate contact between the TiO2 and the g-C3N4 respectively, thereby optimizing the redox ability of the com-
was created, enabling a rapid transport of charge carriers across posite photocatalyst. As a result, the photocatalytic hydrogen-
the contact interface. The actual loading of g-C3N4 on TiO2 was production rate of the WO3/g-C3N4 Z-scheme heterojunction
further confirmed by TGA analysis. The pure TiO2 exhibited no photocatalyst is much higher than that of the pure WO3 and
weight loss on the TG curve, while the g-C3N4 was fully decom- g-C3N4 components.
posed at 600 °C. Furthermore, the U100 sample exhibited Very recently, our group reported the synthesis of a hierar-
about 12% loss at 600 °C, indicating that the actual loading of chical CdS–WO3 direct Z-scheme heterojunction photocatalyst
the g-C3N4 on the TiO2 was ca. 12%. Then, the presence of the in the form of hollow spheres (CdS–WO3 HSs) for photocata-
direct Z-scheme heterojunction was also confirmed by radical- lytic CO2 reduction.[44] According to the photocurrent charac-
trapping experiments. Specifically, an increase in the photolu- terization, the electron–hole separation efficiency of CdS–WO3
minescence intensity of 2-hydroxy-terephthalic acid (•OH-TA) HSs is higher than that of the pure CdS and WO3 HSs. This

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Review
Figure 17.  a) TEM image of g-C3N4–TiO2 direct Z-scheme heterojunction photocatalyst. b) •OH-TA PL spectral changes of the same photocatalyst in a
0.002 M NaOH solution in the presence of 0.0005 M terephthalic acid under UV irradiation. c) Schematic illustration of the band structures of g-C3N4
and TiO2 together with the OH−/•OH potential. d) The •OH radicals cannot be formed on the conventional g-C3N4–TiO2 heterojunction photocatalyst.
Reproduced with permission.[35] Copyright 2013, The Royal Society of Chemistry.

Figure 18.  a) Comparison of the photocatalytic HCHO decomposition activity of U0 (pure TiO2), U20 (TiO2 calcined with 20 wt% urea), U100 (TiO2 cal-
cined with 100 wt% urea), U200 (TiO2 calcined with 200 wt% urea), U500 (TiO2 calcined with 500 wt% urea), and pure g-C3N4 samples. b–d) Schematic
illustrations of the electron–hole separation on the g-C3N4-TiO2 direct Z-scheme heterojunction photocatalysts (b), g-C3N4-TiO2 with optimal loading
of g-C3N4 (c), g-C3N4-TiO2 with overloaded amount of g-C3N4 (d). Reproduced with permission.[35] Copyright 2013, The Royal Society of Chemistry.

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was used as a photocatalyst. It was shown that the thermally

Review

treated NP (TNP) was composed of hematite (Fe2O3) and pyrite

(FeS2). Notably, the resulting TNP exhibited good photocatalytic
activity for Escherichia coli disinfection in comparison to that
of the initial NP. This activity was attributed to the formation
of the direct Z-scheme heterojunction between the Fe2O3 and
the FeS2, greatly suppressing electron–hole recombination and
optimizing the redox ability of the system. In addition, during
thermal treatment, oxygen or sulfur vacancies can be gener-
ated and utilized as electron traps prohibiting the electron–hole
recombination. More interestingly, the presence of Fe2O3 in the
TNP direct Z-scheme heterojunction photocatalyst resulted in
its strong magnetic behavior, thereby enabling the simple mag-
netic recovery of the photocatalyst, which is beneficial for long-
term application.
More recently, Xu et al. showed that the direct Z-scheme
Figure 19.  Schematic illustration of the charge-transfer pathway of the heterojunction can also be constructed between two different
photogenerated electron–hole pairs on CdS–WO3 direct Z-scheme het- semiconductor phases. They successfully prepared an anatase/
erojunction photocatalyst under visible-light irradiation. rutile biphase electrospun TiO2 as a direct Z-scheme hetero-
junction photocatalyst through the rapid cooling of electrospun
is due to the spatial separation of the electrons and holes on TiO2 calcined at 500 °C (see Figure 21a,b).[43] As can be seen
the CB of the CdS and the VB of the g-C3N4, respectively (see from Figure 21b,c, TiO2 nanofibers with both rutile and anatase
Figure 19). Moreover, the formation of the CdS–WO3 HS direct phases were successfully prepared. Normally, the prepared TiO2
Z-scheme heterojunction can also promote electron accumu- nanofibers are dominated by anatase due to the fast transfor-
lation on the surface of the CdS, which is beneficial for the mation rate of rutile into anatase during slow cooling. Notably,
multielectron CO2-reduction reaction. Therefore, the main the proposed rapid-cooling method was shown to be effective
product of the photocatalytic CO2 reduction reaction on the for suppressing the transformation rate of rutile to anatase, and
CdS–WO3 HS Z-scheme heterojunction photocatalyst was CH4 thus the rutile TiO2 phase can be preserved after the cooling
(see Figure 20a). As a result, the photocatalytic CO2 reduction process. Moreover, it was shown that during the photo-deposi-
activity of the optimized CdS–WO3 HSs (0.1 µmol h−1 of CO2 tion process of Pt NPs, the Pt NPs were favorably deposited on
were reduced to CH4 on the catalyst with 5 mol% CdS) was 100 the surface of rutile instead of anatase (see Figure 21b), sug-
and 10 times higher than the corresponding values obtained gesting that the photogenerated electrons tend to migrate to
for the pure WO3 HS and CdS (see Figure 20b), respectively. the CB of the rutile phase due to the formation of the direct
However, an overloading of CdS led to a decrease in the photo- Z-scheme heterojunction. Furthermore, the electron–hole
catalytic CO2 activity, which can be also related to the observed separation efficiency of the sample prepared by a rapid cooling
decrease in the number of surface active sites on the WO3 HSs method was better than that of the TiO2 nanofiber prepared by
and the light-shielding effect. slow cooling because, in the former case, the direct Z-scheme
Furthermore, Wong and co-workers reported that a low-cost heterojunctions on the TiO2 nanofibers can greatly reduce the
natural mineral can be used for constructing a direct Z-scheme electron–hole-recombination rate. Since the reduction and oxi-
heterojunction photocatalyst.[105] Specifically, natural magnetic dation reactions occur on the semiconductors with the higher
pyrrhotite (NP) mineral, after thermal treatment at 600 °C, reduction and oxidation potentials, respectively, the redox ability

Figure 20.  a) Gas-chromatography spectra for the CO2 reduction on CdS–WO3 hollow spheres (HS) at different irradiation times. b) Photocatalytic CO2
reduction activity of C0 (pure WO3 HS), C1 (1 mol% of CdS loaded on WO3 HS), C2 (2 mol% of CdS loaded on WO3 HS), C5 (5 mol% of CdS loaded
on WO3 HS), C10 (10 mol% of CdS loaded on WO3 HS), C20 (20 mol% of CdS loaded on WO3 HS), C100 (pure CdS), and N5 (5 mol% CdS–WO3
nanoparticle composite) for CH4 production. Reproduced with permission.[44] Copyright 2015, Wiley-VCH.

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Figure 21.  a,b) TEM (a) and HRTEM (b) images of the mixed-phase composite of anatase and rutile TiO2 with photo-deposited Pt NPs. c) X-ray dif-
fraction (XRD) patterns of anatase–rutile composites: I (pure anatase), II (with 72% of anatase and 28% of rutile), III (with 55% of anatase and 45%
of rutile), and IV (pure rutile). d) Comparison of the photocatalytic-hydrogen-production activity of the anatase–rutile composites I, II, III, and IV.
Reproduced with permission.[43] Copyright 2014, Elsevier.

of the composite can be also optimized. As a result, the pho- the photocatalyst, thereby enabling the fast electron migration
tocatalytic hydrogen-production efficiency of TiO2 nanofibers from the photocatalyst to the graphene.[38] The use of graphene
prepared by the rapid-cooling method (324 µmol h−1) is higher in photocatalytic applications was firstly proposed by Zhang
than that of the TiO2 nanofibers prepared under slow-cooling et al. in 2010.[120] It was shown that the photocatalytic activity
conditions (188 µmol h−1) (see Figure 21d). of P25 titania toward MB degradation was greatly enhanced
by adding graphene, which was attributed to the rapid separa-
tion of charge carriers across the P25–graphene heterojunction.
6. Semiconductor/Graphene Heterojunctions Furthermore, the large specific surface area of graphene is also
beneficial for providing a greater number of surface active sites
Graphene, a 2D single layer sheet of sp2-hybridized carbon for photocatalytic reactions.
atoms with hexagonally packed structure, has attracted great In 2011, our group firstly reported the CdS–graphene het-
attention due to its extraordinary physical properties including erojunction system for photocatalytic hydrogen production.[37]
superior charge transport, unique optical properties, high Specifically, a CdS/reduced graphene oxide (CdS/RGO) com-
thermal conductivity, large theoretical specific surface area, and posite was prepared by the simple solvothermal method. Prior
good mechanical strength.[106–108] Since the discovery of single- to the reaction, graphene oxide (GO) and cadmium acetate
layer graphene nanosheets by Geim and Novoselov in 2004,[109] were mixed in dimethyl sulfoxide (DMSO). Since GO has a
graphene has been known as a perfect candidate for various negatively charged surface at pH = 7, the Cd+ ions from the
applications, including solar cells,[110–112] supercapacitors,[113,114] cadmium acetate in a DMSO solution can be adhered to the
batteries,[115,116] photocatalysis,[117–119] etc. Particularly, tre- surface of GO because of the electrostatic attraction between
mendous efforts have been made for coupling graphene with the Cd+ ions and the GO. Then, during the solvothermal pro-
other semiconductors to fabricate heterojunction photocata- cess, H2S is produced from the DMSO and reacts in situ with
lysts with improved photocatalytic activity. The ultrahigh elec- the Cd+ ions to create CdS NPs on the GO surface. Simulta-
tron conductivity of graphene allows the flow of electrons neously, in the presence of DMSO, GO can be reduced to
from the semiconductor to its surface, assuring efficient elec- RGO during the solvothermal process. The in situ growth of
tron–hole separation. Moreover, the potential of graphene/ CdS nano­particles on RGO can not only create an intimate
graphene− (−0.08 V vs standard hydrogen electrode (SHE), pH contact between the CdS and the RGO, assuring rapid migra-
= 0) is normally lower than the conduction-band potential of tion of electrons from the CdS to the RGO, but also limits the

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Figure 22.  a) TEM images of the graphene/TiO2 NS at low resolution and high resolution (inset). b) Light-absorption spectra of G0 (pure TiO2 NS),
G0.2 (0.2 wt% graphene on TiO2 NS), G0.5 (0.5 wt% graphene on TiO2 NS), G1.0 (1.0 wt% graphene on TiO2 NS), G2.0 (2.0 wt% graphene on TiO2
NS), and G5.0 (5.0 wt% graphene on TiO2 NS). c) Comparison of the photocatalytic-hydrogen-production activity of the G0, G0.2, G0.5, G1.0, G2.0,
G5.0, and P1.0 (1.0 wt% Pt on TiO2 NS). d) Schematic illustration of the photocatalytic mechanism on graphene/TiO2 NS. Reproduced with permis-
sion.[38] Copyright 2013, The Royal Society of Chemistry.

growth of CdS and consequently enlarges the specific surface all the sample studied, due to the rapid migration of elec-
area of the CdS/RGO composite. As a result, the photocatalytic trons from the TiO2 NSs to the graphene (see Figure 22c,d).
hydrogen-production activity of the CdS/RGO composite was However, if the graphene content is higher than 1.0 wt% in
4.87 times higher than that of CdS with added Pt. the composite, the photocatalytic activity of such composites
After that, our group further investigated the effect of gra- is drastically reduced, because the graphene overloading leads
phene on the photocatalytic activity of TiO2 by preparing gra- to the light-shielding effect, which greatly suppresses the light
phene/TiO2 nanosheet composites (graphene/TiO2 NS).[38] As absorption of TiO2 NS. Therefore, it should be noted that
shown in the TEM images of the sample (see Figure 22a), the finding the optimal content of graphene on the semiconductor
TiO2 NSs were face-to-face dispersed on the surface of the gra- is crucial for enhancing its photocatalytic activity.
phene, enabling the intimate contact between the TiO2 NSs In addition, a large π–π conjugation on the graphene sur-
and the graphene. Therefore, electrons can rapidly migrate face can be also utilized for the adsorption of different reac-
from the TiO2 NSs to the surface of the graphene. The light- tants during the photocatalytic reaction. For example, our
absorption ability of the TiO2 NSs was also greatly enhanced by group prepared a Bi2WO6/graphene/Ag (Bi2WO6/G/Ag)
adding graphene. The graphene/TiO2 NS composite exhibited composite for photocatalytic RhB degradation by a hydro-
a broad background absorption in the visible-light region (see thermal–photoreduction method.[20] It was shown that the
Figure 22b), which can be attributed to the 0 eV bandgap of gra- addition of graphene can significantly enhance adsorption of
phene. Although this enhanced light absorption by graphene the aforementioned dye pollutant. In particular, the adsorp-
cannot generate any active charge carriers for redox reaction, tion ability of the prepared samples was tested by analyzing
the absorbed light can be used for producing heat and creating the concentration changes of the RhB solution in the pres-
a unique photothermal effect around the photocatalyst surface. ence of the different samples, including Bi2WO6, Bi2WO6/Ag,
This effect is favorable for accelerating charge transport.[118] A Bi2WO6/G, and Bi2WO6/G/Ag, under dark conditions. It was
similar photothermal effect can be also observed in the case shown that the samples with added graphene exhibited higher
of the ZnxCd1−xS/graphene,[121] Cu2O/graphene,[122,123] g-C3N4/ RhB adsorption ability (see Figure 23a) due to a large π–π con-
graphene,[124] Bi2WO6/graphene,[125] and other composites. jugation on the graphene surface, which could easily adsorb
Therefore, the transient photocurrent density of graphene- RhB molecules through the strong π–π interactions between
loaded TiO2 NSs is higher than that of pure TiO2 NSs, indi- the graphene and the RhB molecules (see Figure 23b). Dye
cating high electron–hole separation efficiency on the former pollutants other than RhB, such as methylene blue, methyl
NSs. As a result, the 1.0 wt% graphene-loaded TiO2 NSs exhib- violet, methyl green, and so on, can be adsorbed on graphene
ited the highest photocatalytic activity (36.8 µmol h−1) among as well.[126–128]

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Figure 23.  a) RhB concentration changes with time in the presence of Bi2WO6, Bi2WO6/Ag, Bi2WO6/G, and Bi2WO6/G/Ag under dark conditions, where
C0 and C represent the initial and actual (at a given time) concentrations of the RhB solution. b) Schematic illustration of the π–π interactions between
graphene and RhB molecules. Reproduced with permission.[20] Copyright 2014, The Royal Society of Chemistry.

Meanwhile, the adsorption ability of the graphene toward significant changes in the specific surface area were observed
CO2 molecules was also confirmed by Yu et al.[46] Particularly, a for the CdS-nanorods/RGO composites in comparison with
CdS-nanorods/RGO composite was prepared for photocatalytic pure CdS nanorods. However, the CO2-adsorption ability of
CO2 reduction. The CdS nanorods were uniformly dispersed on the CdS-nanorods/RGO was shown to be higher than that of
the surface of RGO nanosheets, which was beneficial for cre- the pure CdS nanorods. This was attributed to the π–π conju-
ating a greater number of surface active sites (see Figure 24a). gation interaction between the CO2 molecules and the RGO.
As shown in Figure 24b, G0.5 exhibited a smaller semicircle Moreover, the π–π conjugation interaction between RGO and
in the Nyquist plot than pure CdS, indicating faster interfa- CO2 can also lead to the destabilization and activation of CO2
cial electron transfer on the G0.5 sample. Moreover, according molecules to facilitate their reduction. Thus, the photocata-
to the nitrogen adsorption–desorption measurements, no lytic CO2-reduction activity of CdS-nanorods/RGO toward CH4

Figure 24.  a) TEM image of optimized CdS-nanorods/RGO (G0.5). (Note: the weight percentage of RGO to CdS nanorods was varied from 0, 0.1, 0.25,
0.5, 1.0 and 2.0 wt%, the corresponding samples were labeled as G0, G0.1, G0.25, G0.5, G1.0 and G2.0, respectively.). b) Nyquist plots for G0 and G0.5.
c) Comparison of photocatalytic CO2 reduction activity of the G0, G0.1, G0.25, G0.5, G1.0, G2.0, N0.5 (0.5 wt% graphene on CdS nanoparticles), P0.5
(0.5 wt% Pt on CdS nanorods), and RGO for CH4 production. d) Schematic illustration of the mechanism for the enhancement of the photocatalytic
activity of the CdS-nanorods/RGO. Reproduced with permission.[46] Copyright 2014, The Royal Society of Chemistry.

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Figure 25.  Schematic illustration of the advantageous contact between

both components in 2D–2D composite photocatalysts in comparison to
0D–2D and 0D-1D composites. Reproduced with permission.[12] Copy-
right 2014, The Royal Society of Chemistry.

production was higher than that of pure CdS nanorods (see

Figure 24c,d) due to the high electron–hole separation effi-
ciency, strong CO2 adsorption, and unique CO2 destabilization.
Taking into account the 2D structure of graphene, its poten-
tial can be fully utilized in constructing graphene–semicon-
ductor 2D–2D heterojunction photocatalysts. Namely, the
contact interface in a 2D–2D (face contact) heterojunction
photocatalyst is larger than that in the zero-dimensional–2D
(0D–2D) (point contact) and 1D–2D (line contact) heterojunc-
tion photocatalysts, which facilitates the migration of charge
carriers across the the graphene–semiconductor heterojunc-
tion (see Figure 25).[12] Recently, our group reported a low-cost
2D–2D graphene–g-C3N4 composite prepared by an impregna-
tion–chemical-reduction method for photocatalytic hydrogen
production.[45] In the aforementioned composite, 2D layered
g-C3N4 was intimately coupled with graphene nanosheets to
form a 2D–2D layered composite (see Figure 26a,b). Moreover,
based on the nitrogen adsorption–desorption isotherms and Figure 26.  a,b) TEM images of graphene nanosheets (a) and graphene–
UV–vis absorption spectra, the specific surface area and light- g-C3N4 composite (b). c) Comparison of the photocatalytic activity of
absorption ability of g-C3N4 were enhanced by adding gra- GC0 (pure g-C3N4), GC0.25 (0.25 wt% graphene added to g-C3N4), GC0.5
(0.5 wt% graphene added to g-C3N4), GC1.0 (1.0 wt% graphene added to
phene. Meanwhile, the electron–hole recombination on g-C3N4 g-C3N4), GC2.0 (2.0 wt% graphene added to g-C3N4), GC5.0 (5.0 wt% gra-
was also greatly suppressed after graphene addition due to the phene added to g-C3N4), and N-doped TiO2 for photocatalytic hydrogen
fast electron–hole separation across the graphene–g-C3N4 heter- production. Reproduced with permission.[45] Copyright 2011, American
ojunction and a large contact interface of the 2D–2D graphene– Chemical Society.
g-C3N4 structure. Therefore, the photocatalytic activity of g-C3N4
increases with increasing graphene loading. The photo­catalytic heterojunction photocatalysts. For example, Babu et al. reported
activity of an optimized graphene–g-C3N4 composite (1.0 wt% a Cu2O/TiO2 p–n heterojunction photocatalyst with incorpo-
graphene) toward hydrogen production in methanol aqueous rated graphene oxide (GO) for enhancing its photocatalytic
solution was 3 times higher than that of g-C3N4 with Pt as a activity toward hydrogen production.[130] The electron–hole
co-catalyst (see Figure 26c). However, a further increase in gra- separation rate of Cu2O–TiO2 was higher than that of TiO2 due
phene loading to 2.0 wt% and 5.0 wt% resulted in a smaller to presence of the p–n heterojunction. The aforementioned
and smaller photocatalytic activity due to the overloading of electron–hole separation in this Cu2O–TiO2 p–n heterojunction
graphene on the g-C3N4, which can cause shielding effects and photocatalyst was further improved by adding GO to facilitate
greatly inhibits the light absorption ability of the g-C3N4. the migration of electrons from the space-charge region of the
Meanwhile, Liang et al. carefully investigated the photocata- Cu2O/TiO2 p–n heterojunction to GO. Incorporation of GO
lytic activity of 1D–2D single-wall carbon nanotubes (SWCNT)/ to this p–n heterojunction photocatalyst enhanced its photo-
TiO2 nanosheets and 2D–2D graphene/TiO2 nanosheets toward catalytic hydrogen efficiency under light irradiation, which was
CO2 reduction.[129] It was shown that both SWCNT and gra- 14 times higher than that of a pure TiO2. Moreover, Zhao et al.
phene can significantly enhance the photocatalytic CO2-reduc- showed that the photocatalytic hydrogen-production activity of
tion activity of the TiO2 nanosheets because of the improved the WO3/g-C3N4 direct Z-scheme heterojunction photocatalyst
electron–hole separation efficiency and enlarged specific sur- can be further improved by the loading of RGO as a metal-free
face area. However, the photocatalytic activity of graphene/TiO2 electron mediator.[131] Zhao’s group demonstrated that RGO
nanosheets was higher than that of SWCNTs/TiO2 because, in can improve the flow of electrons from WO3 to g-C3N4 and
the former, a 2D–2D structure was formed with a large contact suppress reverse migration of electrons to WO3. Therefore, the
interface for electron migration. photocatalytic activity of the WO3/g-C3N4 Z-scheme heterojunc-
In addition to the above-presented simple coupling of gra- tion photocatalyst was greatly enhanced after the incorporation
phene nanosheets with a single semiconductor, graphene can of RGO. Furthermore, Kuai et al. reported a low-cost direct
be utilized to further improve the photocatalytic activity of Z-scheme heterojunction CdS/RGO/TiO2 photocatalyst[132] and

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showed that this heterojunction photocatalyst can significantly great significance to find cost-effective and advanced mate-

Review
promote the separation and accumulation of electrons and rials to prepare heterojunction photocatalysts for practical
holes in the conduction band of the CdS and the valence band applications. A perfect material for engineering a hetero-
of the TiO2, respectively. Moreover, the presence of RGO can junction photocatalyst should fulfill several requirements,
accelerate the migration of electrons from the TiO2 to the CdS. such as visible-light activity, high solar-conversion effi-
Therefore, the CdS/RGO/TiO2 Z-scheme heterojunction photo­ ciency, proper bandgap structure for redox reactions, high
catalyst showed an exceptional photocatalytic CO2-reduction photostability for long-term applications, and scalability for
performance toward CH4 production, which was higher than commercialization.
that of CdS, CdS/TiO2, and CdS/RGO. These studies clearly
prove that combining graphene with other heterojunction In conclusion, we have summarized recent work related to
photocatalysts can greatly enhance their photocatalytic perfor- heterojunction photocatalysts and their application in photo­
mance, which is worthy of further exploration. catalysis. The preparation and investigation of heterojunction
photocatalysts provides a meritorious platform for accelerating
their practical applications. We hope that this review can stimu-
7. Conclusions and Future Perspectives late further exploration of the heterojunction systems in photo­
catalysis, solar cells, batteries, and other important research areas.
In the past several decades, many studies have been reported for
the preparation of various heterojunction photocatalysts. Here,
a concise appraisal of the current achievements in the field of Acknowledgments
heterojunction photocatalysts is presented, including the funda-
mental aspects in their design, synthesis, characterization, and This study was partially supported by the 973 program (2013CB632402),
applications, demonstrating that this research field is important, NSFC (21433007, 51320105001, 21573170, 51372190 and 51272199),
the Fundamental Research Funds for the Central Universities (2015-III-
exciting, and highly rewarding. However, the practical applica- 034), the Self-determined and Innovative Research Funds of SKLWUT
tions and commercialization of heterojunction photocatalysts (2015-ZD-1), and the Natural Science Foundation of Hubei Province of
require further substantial progress in the engineering of highly China (No. 2015CFA001)
efficient heterojunction photocatalysts. Future research direc-
tions in this field should be focused on the following aspects. Received: March 29, 2016
Revised: November 4, 2016
i) Significant challenges still remain in the development of Published online: February 21, 2017
facile, efficient, and economic methods for preparing high-
quality heterojunction photocatalysts at the large scale for
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