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Semiconductor heterojunction photocatalysts:

design, construction, and photocatalytic
Cite this: Chem. Soc. Rev., 2014,
43, 5234 performances
Huanli Wang,a Lisha Zhang,*a Zhigang Chen,b Junqing Hu,b Shijie Li,a
Zhaohui Wang,a Jianshe Liu*a and Xinchen Wang*c

Semiconductor-mediated photocatalysis has received tremendous attention as it holds great promise to

address the worldwide energy and environmental issues. To overcome the serious drawbacks of fast
charge recombination and the limited visible-light absorption of semiconductor photocatalysts, many
strategies have been developed in the past few decades and the most widely used one is to develop
photocatalytic heterojunctions. This review attempts to summarize the recent progress in the rational
design and fabrication of heterojunction photocatalysts, such as the semiconductor–semiconductor
heterojunction, the semiconductor–metal heterojunction, the semiconductor–carbon heterojunction
and the multicomponent heterojunction. The photocatalytic properties of the four junction systems
Received 8th April 2014 are also discussed in relation to the environmental and energy applications, such as degradation of
DOI: 10.1039/c4cs00126e pollutants, hydrogen generation and photocatalytic disinfection. This tutorial review ends with a
summary and some perspectives on the challenges and new directions in this exciting and still emerging
www.rsc.org/csr area of research.

Key learning points

(1) The fundamental principles of semiconductor photocatalysis
(2) The design and construction of semiconductor–semiconductor heterojunctions
(3) The design and construction of semiconductor–metal heterojunctions
(4) The design and construction of semiconductor–carbon heterojunctions
(5) The design and construction of multicomponent heterojunctions

1. Introduction of contaminants, under the illumination of sunlight under

ambient conditions.1 To date, the TiO2 semiconductor has
In recent years, energy shortages and environmental pollution undoubtedly proven to be one of the excellent photocatalysts
have become the focus of world attention. As one of the most for water splitting and the oxidative decomposition of many
promising solutions for these problems, semiconductor photo- organic compounds.2 However, due to its wide band-gap of 3.2 eV,
catalysis has attracted much attention, since it is a ‘‘green’’ TiO2 can only be excited by ultraviolet or near-ultraviolet radiation,
technology for decomposing water into hydrogen and oxygen, which occupies only 4% of the incoming solar light spectrum on
inactivating viruses and/or completely eliminating all kinds the earth.3 To efficiently utilize the visible region (l 4 400 nm)
which covers the largest proportion of the solar spectrum, the
a
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials,
development of visible-light-driven (VLD) photocatalysts is the
State Environmental Protection Engineering Center for Pollution Treatment and current trend. Many groups have reported some novel VLD photo-
Control in Textile Industry, College of Environmental Science and Engineering, catalysts, such as simple oxides (Bi2O34 and WO35), sulfides (CdS6),
Donghua University, Shanghai, 201620, China. E-mail: [email protected], complex oxides (Bi2WO67 and Zn:In(OH)ySz8) and nitrides (C3N49).
[email protected]; Fax: +86 21 67792522; Tel: +86 21 67792523
b
Up to date, although much efforts have been devoted to preparing
College of Materials Science and Engineering, Donghua University,
Shanghai 201620, China
different VLD photocatalysts, there are still some drawbacks
c
State Key Laboratory of Photocatalysis on Energy and Environment, College of hindering their practical application, such as short photogenerated
Chemistry, Fuzhou University, Fuzhou 350002, China. E-mail: [email protected] electron–hole pair lifetimes and the limited visible-light absorption.

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It is still necessary to design novel VLD photocatalyst systems to

improve photocatalytic efficiencies for the requirements of
future environmental and energy technologies.
During the past decade, a variety of strategies have been
employed to improve the photocatalytic efficiencies of photo-
catalysts, for example, via suitable textural design, doping, and
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forming a semiconductor heterojunction by combining them

with metal and/or other semiconductors. Among these, the
construction of a semiconductor heterojunction has attracted
a lot of attention due to its perfect effectiveness in improving
the photocatalytic activity. Many important findings have been
reported on the semiconductor heterojunction photocatalysts
(SHPs) during the past few years. We have also developed nano-
Cu2O–carbon nanotube composites,10 a C@TiO2 catalyst,11 an
AgBr–Ag–Bi2WO6 three-component nanojunction,12,13 Bi2WO6
superstructure decorated with Bi2O3 nanoparticles14 and
Fig. 1 Schematic illustration of the principle of semiconductor photo-
metal–C3N4 materials,15 for the degradation of organic pollu- catalysis: (I) the formation of charge carriers by a photon; (II) the charge
tants. Furthermore, a C3N4/sulfur-mediated C3N4 (CN/CNS) carrier recombination to liberate heat; (III) the initiation of a reductive
isotype heterojunction has also been developed for the degra- pathway by a conduction-band electron; (IV) the initiation of an oxidative
dation of organic pollutants or photocatalytic hydrogen evolu- pathway by a valence-band hole; (V) the further thermal (e.g., hydrolysis or
reaction with active oxygen species) and photocatalytic reactions to yield
tion.16 We believe that a comprehensive review on this subject
mineralization products; (VI) the trapping of a conduction band electron in
is timely to promote further developments in this exciting a dangling surficial bond; (VII) the trapping of a valence-band hole at the
and still emerging area of research. This review focuses on surface of the semiconductor.
the recent progress in the rational design, fabrication and
applications of semiconductor heterojunction photocatalysts,
while providing some stimulating perspectives on the future form of heat or emitted light (Fig. 1II). The recombination is
developments. often facilitated by a scavenger or crystalline defects which can
trap the electron or the hole. Therefore, a better crystallinity
with few defects can usually minimize the trapping states and
2. Fundamental principles of recombination sites, resulting in an increased efficiency in the
usage of the photogenerated carriers for desired photoreactions.
semiconductor photocatalysis Based on the fundamental principles of semiconductor photo-
2.1 Fundamental principles of semiconductor heterojunction catalysis, the recombination between the electron and the hole is
photocatalysts detrimental to the efficiency of a semiconductor photocatalyst.
From the point of view of semiconductor photochemistry, the For higher photocatalytic efficiency, the electron–hole pairs
role of photocatalysis is to initiate or accelerate specific should be efficiently separated, and charges should be rapidly
reduction and oxidation (redox) reactions in the presence of transferred across the surface/interface to restrain the recombi-
irradiated semiconductors. When the semiconductor catalyst is nation. To improve the photocatalytic performance, the approach
illuminated with photons whose energy is equal to or greater that has generally been applied is to form a semiconductor
than their band-gap energy (Eg), firstly, an electron (ecb ) is heterojunction by coupling with a secondary substance (noble
promoted from the valence band (VB) into the conduction band metal, other semiconductors and so on), which will be discussed
(CB), leaving a hole (hvb+) behind (see Fig. 1I).1 Secondly, the in detail in the following section.
excited electrons and holes migrate to the surface. Thirdly, the
electrons (ecb ) in the CB should have a chemical potential of 2.2 The categories of semiconductor heterojunction
+0.5 to 1.5 V versus the normal hydrogen electrode (NHE) and photocatalysts
exhibit a strong reduction capacity; while holes (hvb+) in the VB In recent years, considerable efforts have been placed on the
should have a chemical potential of +1.0 to +3.5 V versus the design and fabrication of heterojunctions for improving the
NHE and exhibit a strong oxidative potential. Electrons (ecb ) photocatalytic activity.17 Overall, there are four typical categories of
and holes (hvb+) can act as the reductant (Fig. 1III) and oxidant heterojunction photocatalysts, including: (1) the semiconductor–
(Fig. 1IV) to react with electron donors (D) and electron semiconductor (abbreviated as S–S) heterojunction; (2) the
acceptors (A) adsorbed on the semiconductor surface or within semiconductor–metal (abbreviated as S–M) heterojunction;
the surrounding electrical double layer of the charged particles, (3) the semiconductor–carbon group (abbreviated as S–C) hetero-
respectively. Besides, they can get trapped in metastable surface junction (carbon group: activated carbon, carbon nanotubes
states (Fig. 1VI and VII). It should be noted that, in the second (CNTs) and graphene); (4) the multicomponent heterojunction.
step, the excited state conduction-band electrons and valence- The design principle of the above-mentioned four categories of
band holes can recombine and dissipate the input energy in the SHPs will be discussed in detail in the following passage.

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3. The design and construction of incompatible reduction and oxidation reactions in nanospace.
semiconductor–semiconductor (S–S) All of these features endow the p–n type heterostructures with
an enhanced photocatalytic performance.
heterojunctions In addition to the p–n type heterostructure, there are also
3.1 The design principle of S–S heterojunctions other non-p–n type heterojunction systems, where the most
In general, the S–S heterojunction systems can be divided into suitable for photocatalytic applications is the staggered band-
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two different types: p–n semiconductor heterojunction (Fig. 2) gap type (Fig. 3). In this type, the semiconductors A and B with
and non-p–n heterojunction systems (Fig. 3). matching band potentials are tightly bonded to construct the
The semiconductor p–n junction is an effective architecture efficient heterostructure. When the CB level of semiconductor-B
for the highly efficient charge collection and separation. In is lower than that of semiconductor-A, electrons in the CB of
general, when the p- and n-type semiconductors are in contact, semiconductor-A can be transferred to that of semiconductor-B
they form a p–n junction with a space-charge region at the under visible light irradiation. If the VB level of semiconductor-B
interfaces due to the diffusion of electrons and holes, and thus is lower than that of semiconductor-A, holes in the VB of
create a built-in electrical potential that can direct the electrons semiconductor-B can be transferred to that of semiconductor-A.
and holes to travel in the opposite direction (Fig. 2). When the As a result, the separation and migration of photogenerated
p–n heterojunction is irradiated by photons with energy higher carriers can be promoted by the internal field, so less of a barrier
or equal to the bandgaps of the photocatalysts, the photo- exists. Therefore, the probability of electron–hole recombination can
generated electron–hole pairs can be quickly separated by the be reduced. A larger number of electrons on the semiconductor-B
built-in electric field within the space charge region. Driven by surface and holes on the semiconductor-A surface can, respectively,
the electric field, the electrons are transferred to the CB of the participate in photoredox reactions to directly or indirectly degrade
n-type semiconductors and the holes to the VB of the p-type organic pollution, and thus the photocatalytic reaction can be
semiconductors.18 In this p–n type heterostructure, several enhanced greatly.
advantages can be obtained: (1) a more effective charge separa- 3.2 Construction and performance of S–S heterojunctions
tion; (2) a rapid charge transfer to the catalyst; (3) a longer
lifetime of the charge carriers; and (4) a separation of locally During the past few years, many groups have reported different
types of S–S heterojunction photocatalysts. These research
studies greatly improve the efficiencies of the photocatalysts
and promote their applications in the energy production and
environmental protection. The following section will discuss
the highlighted findings in this subject.
3.2.1 TiO2 based S–S heterojunctions. In recent years,
tremendous efforts have been made in surface modification
of TiO2 nanomaterials with other semiconductors. Table 1
summarizes and compares the typical TiO2-based heterojunction
systems. Most of these systems possess high dye adsorption
capacity, an extended light absorption range, enhanced charge
separation, promoted mass-transfer and thus improved photo-
catalytic efficiency. For example, Wang’s group successfully
Fig. 2 Schematic diagram showing the energy band structure and electron– synthesized Bi2WO6–TiO2 hierarchical heterostructure through
hole pair separation in the p–n heterojunction. a simple and practical electrospinning-assisted route (Fig. 4A
and B).19 As shown in Fig. 4A, Bi2WO6 nanoplates grew aslant
on the primary TiO2 nanofibers. These three dimensional (3D)
Bi2WO6–TiO2 hierarchical heterostructures exhibited enhanced
VLD photocatalytic activity for the decomposition of CH3CHO,
which was almost 8 times higher than that of the Bi2WO6
sample, and the decomposition rate by the bare TiO2 could
be neglected under visible light irradiation. This high photo-
catalytic activity was ascribed to the reduced probability of
electron–hole recombination and the promoted migration of
photogenerated carriers. Similarly, Wang et al.20 fabricated
SnO2–TiO2 heterostructured photocatalysts based on TiO2 nano-
fibers by combining the electrospinning technique with the
hydrothermal method (Fig. 4C and D). This SnO2–TiO2 compo-
site possessed a high photocatalytic activity for the degrada-
Fig. 3 Schematic diagram showing the energy band structure and electron– tion of Rhodamine B (RhB) dye under UV light irradiation,
hole pair separation in the non-p–n heterojunction. which was almost 2.5 times higher than that of the bare TiO2.

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Table 1 Comparison of the typical TiO2-based heterojunction systems

Types Preparation Morphology The improved performances The proposed reasons Ref.
TiO2 (anatase)– Coating method Films 4.5 times than the sum of TiO2 (anatase) The increase in charge-separation 21
TiO2 (rutile) and (rutile) for the decomposition of efficiency resulting from interfacial
CH3CHO in 3 hours electron transfer from TiO2 (anatase)
to TiO2 (rutile)
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Bi2WO6–TiO2 Electrospinning- Bi2WO6 nanoplates 8 times than that of Bi2WO6 sample The reduced probability of electron– 19
assisted route grew aslant on TiO2 for the decomposition of CH3CHO in hole recombination
substrates 120 min under visible light, and the
decomposition rate by the bare TiO2
could be neglected under visible
light irradiation

SnO2–TiO2 Electrospinning SnO2 nanostructures About 2.5 times than that of TiO2 for The efficient charge separation 20
technique and grown on TiO2 the degradation of RhB in 60 min
hydrothermal nanofibers
method

CdS–TiO2 Microemulsion- Nanocrystals Almost 8 times than CdS for the decom- The efficient charge separation by 22
mediated position of methylene blue (MB) in minimizing the electron–hole
solvothermal method 60 min under UV-vis light irradiation recombination

amount of TCA was 20 mg) showed the highest performance, where

11 times higher performance than that of C3N4 was obtained.
Furthermore, the H2 produced amount increased steadily with
irradiation time, without a noticeable deactivation by four consecu-
tive cycle tests. The enhanced performance was attributed to the
promoted charge separation which arose from the band offsets.
Besides the S–S SHPs mentioned above, novel S–S SHPs with
tuned structure have also been proposed by taking into account
of both surface junctions and the texture engineering of the
photocatalysts,25–31 including multi-layer-film SHPs,23 and SHPs
with spatially separated co-catalysts31 (Table 2). For example, Hong
et al. fabricated WO3–BiVO4 heterojunction film electrodes by the
layer-by-layer deposition of WO3 and BiVO4 on a conducting
glass.23 The electrode with the optimal composition (four layers
of WO3 covered by a single layer of BiVO4) exhibited 1.74 and
7.3 times increase of photocurrent relative to bare WO3 and bare
Fig. 4 SEM (A) and HRTEM (B) images of Bi2WO6/TiO2 nanofiber from ref. 19; BiVO4, respectively, under simulated solar light. Furthermore, by
SEM (C) and HRTEM (D) images of SnO2/TiO2 heterostructures from ref. 20. taking BiVO4 as a model semiconductor, Prof. Li’s group con-
Reprinted with permission. Copyright 2009, American Chemical Society. firmed the existence of oxidation and reduction facets,29 and they
rationally designed and prepared a series of BiVO4-based SHPs
(M/MnOx/BiVO4 and M/Co3O4/BiVO4, M stands for noble metals)
The enhanced photocatalytic efficiency was attributed to the by selective deposition of reduction and oxidation cocatalysts on
improvement of the separation of photogenerated electrons the {010} and {110} facets of BiVO4.30 These SHPs exhibited
and holes as discussed in Section 3.1. remarkably enhanced photocatalytic activities for photocatalytic
3.2.2 Other S–S heterojunctions. Apart from TiO2 based water oxidation and photocatalytic degradation of methyl orange
S–S heterojunctions, other S–S heterojunctions have also been and RhB, which were not only due to the intrinsic nature of charge
reported, such as Bi2O3–Bi2WO6,14 WO3–BiVO423 and C3N4- separation between the {010} and {110} facets of BiVO4, but also
based heterojunctions.16 These S–S heterojunctions exhibited the synergistic effect of dual-cocatalysts deposited on different
excellent photocatalytic performances. For example, we have facets of BiVO4. Recently, Prof. Choi’s group reported BiVO4-based
reported C3N4-sulfur-modified-C3N416 and C3N4–MoS224 for SHPs by coupling two different oxygen evolution catalyst (OEC)
hydrogen-evolution. By coating trithiocyanuric acid (TCA) on the layers, FeOOH and NiOOH, for solar water splitting.26 The intro-
surface of C3N4, and then subjecting them to a heat treatment at duction of OEC can reduce the interface recombination at the
600 1C, an isotype C3N4-sulfur-modified-C3N4 heterojunction (termed BiVO4/OEC junction while creating a more favorable Helmholtz
the CN–CNS heterojunction) was fabricated.16 These CN–CNS layer potential drop at the OEC/electrolyte junction, resulting in the
heterojunctions exhibited an enhanced H2 evolution activity over improvement of the propensity for surface-reaching holes to insti-
their corresponding host substrates. The CN–CNS (the coating gate water-splitting chemistry. The resulting BiVO4/FeOOH/NiOOH

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Table 2 Comparison of the typical S–S heterojunction systems

Types Preparation Morphology The improved performances The proposed reasons Ref.
Bi2O3–Bi2WO6 Dip-coating- Flower-like 2.7 times than that of Bi2WO6 for the The great broadening of photo- 14
anneal method degradation of RhB in 60 min under absorption range and the existence of the
visible light irradiation p–n junction

C3N4-sulfur- Sheets covered 11 times higher hydrogen evolution rate The promoted charge separation which 16
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mediated C3N4 with paper-fold compared with C3N4 under visible light arose from the band offsets
thin layers irradiation

WO3–BiVO4 Layer-by-layer Films 1.74 and 7.3 times increase photocurrent The synergy of excellent charge transfer 23
deposition compared with bare WO3 and bare BiVO4 characteristics of WO3 and good light
respectively under UV light irradiation absorption capability of BiVO4

Pt/MnOx/BiVO4 Facet-selective Nanoparticles More than 65 and 30 times higher O2 Efficient charge separation 30
photo-deposition deposited on evolution rate compared with bare BiVO4
crystals and MnOx/BiVO4 under visible light
irradiation respectively

BiVO4/FeOOH/ Electrode position FeOOH and NiOOH Exhibited markedly better performance The reduced interface recombination at 26
NiOOH combined with layers deposited on for water oxidation than those of BiVO4/ the BiVO4/OEC junction and a more
photodeposition BiVO4 nanoporous FeOOH and BiVO4/NiOOH favorable Helmholtz layer potential drop
network created at the OEC/electrolyte junction

Ta3N5/Pt/IrO2 Stober method Core/shell More than 6 times higher H2 evolution The core/shell structure and the effective 31
combined with rate than that of bulk Ta3N5 separation and collection of the electrons
chemical vapor and holes at the respective cocatalysts
deposition

photoanode achieved a photocurrent density of 2.73 milliamps

per square centimeter at a potential as low as 0.6 V versus the
reversible hydrogen electrode (RHE).
Apart from promoting charge separation, coupling semi-
conductors with different gaps can also enhance the light
absorption, promote the surface reaction kinetics, and thus
improve the photocatalytic efficiency. For example, Prof. Ye’s
group prepared AgX/Ag3PO4 (X = Cl, Br, I) core–shell hetero-
structures with an unusual rhombic dodecahedral morphology
by a facile and general method.32 The pure Ag3PO4 rhombic
dodecahedrons absorb solar energy with a wavelength shorter
than 530 nm. After the growth of a thin AgCl and AgBr layer on Fig. 5 Schematic of the Schottky barrier.
their surface, the absorption edges of these heterocrystals were
drastically extended to around 550 nm and 560 nm respectively.
Moreover, their photocatalytic performance studies indicate that of the n-type semiconductor (such as TiO2), and electrons
that these core–shell heterostructures exhibited much higher will flow from the semiconductor into the metal to adjust the
photocatalytic activities, structural stabilities and photoelectric Fermi energy levels (Fig. 5). The formation of the Schottky barrier
conversion performances than the pure Ag3PO4 catalyst. results in the fact that the metal has excess negative charges and
the semiconductor has excess positive charges. In addition, the
Schottky barrier can serve as an efficient electron trap preventing
4. The design and construction of electron–hole recombination in photocatalysis, which often results
semiconductor–metal (S–M) in an enhanced photocatalytic performance.
heterojunctions 4.2 Construction and performance of S–M heterojunctions
4.1 The design principle of S–M heterojunctions In recent years, many S–M heterojunction photocatalysts have
Another effective method to create a space-charge separation been successfully prepared by different groups. Recently, Prof.
region (called the Schottky barrier) is to form a S–M junction. Antonietti’s group presented the latest progress in the synthesis
At the interface of the two materials, electrons flow from one and catalytic performances of S–M heterojunctions, including
material to the other (from the higher to the lower Fermi level) to N-doped carbon–metal and C3N4–metal heterojunctions.33 In
align the Fermi energy levels. The common case is the hetero- the present review, we focus on the advances in carbon-free S–M
junction based on the n-type semiconductor and metal, where heterojunctions, as demonstrated in Table 3. Obviously, after the
the ideal case is that the work function of the metal is higher than deposition of noble metal, the photocatalytic efficiencies of these

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Table 3 Comparison of the typical S–M heterojunction systems

Types Preparation Morphology The improved performances The proposed reasons Ref.
Au/TiO2 Multicomponent Mesoporous titania Almost 3 times higher than that of TiO2 Enhanced light absorption and 34
assembly approach photocatalyst by for phenol decomposition under UV-vis improved QE
embedding gold NPs irradiation

Ag–AgCl Ion-exchange reaction NPs 8 times than N-doped TiO2 for the The plasmon resonance and electron 35
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combined with decomposition of MO dye in solution conductivity of Ag

irradiating under
visible light

Ag–AgBr A one-step hydro- Colloids 13 times and 1.5 times than that of The enhanced separation and 36
thermal process N-TiO2 and AgBr respectively for the transportation of photogenerated
degradation of RhB under visible light charge

Ag–Ag3PO4 A modified polyol Necklace-like It can completely degrade RhB dye in The rapid electron export through Ag 37
process combined only 2 min, while the pure Ag3PO4 cubes nanowires as well as highly efficient
with a hetero-growth need about 8 min charge separation at the contact
process interfaces

semiconductors have been significantly enhanced. For example, activities for the phenol oxidation and chromium reduction,
Li et al.34 synthesized highly active mesoporous Au–TiO2 nano- which are almost 3 times higher than that of TiO2 when 0.5% of
composites by utilizing a multicomponent assembly approach, Au was doped. They believed that the enhanced light absorption
where surfactant, TiO2, and gold building clusters were coopera- and improved quantum efficiency (QE) are the main factors
tively assembled in a one-step process (Fig. 6A and B). These unique leading to the improved photocatalytic activity.
nanocomposites show significantly improved photocatalytic Plasmonic photocatalysts which were developed very recently
have attracted great attention as promising candidates for the
development of highly efficient and stable photocatalysts.35,36,38
Ag–AgX and Ag–Ag3PO4 are the most studied and widely used
plasmonic photocatalysts. For example, Wang and his coworkers
have prepared Ag–AgCl35 by depositing silver NPs directly onto the
surface of AgCl. These plasmonic photocatalysts have a strong
adsorption in the visible region. In addition, they also exhibited far
enhanced photo-oxidation capability for the decomposition of
methyl orange (MO) dye in solution compared with N-doped
TiO2, under visible light irradiation. However, the synthesis
procedures mentioned above for the Ag–AgX (Cl, Br) plasmonic
photocatalyst are complex or time-consuming. To solve these
problems, Lu et al.36 reported an effective strategy for one-step
preparation of Ag–AgBr by hydrothermal treatment of AgNO3
and NaBr in the presence of poly[(2-ethyldimethylammonioethyl-
ethacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)] (PQ11) (Fig. 6C
and D). These Ag–AgBr exhibited high efficiency for the degradation
of RhB under visible light illumination, which was about 13 times
and 1.5 times higher than that of N-TiO2 and AgBr respectively.
Similarly, Han et al.38 have also developed a simple hydrothermal-
photochemical process for the preparation of a cube-like Ag@AgCl
plasmonic photocatalyst (Fig. 6E). This Ag@AgCl photocatalyst
exhibited high photocatalytic activity for the photodegradation of
MO dye under visible light irradiation compared to N-doped TiO2,
which should be ascribed to the localized surface plasmon reso-
nance effect from the photogenerated Ag NPs, the well defined
interface, and the complexation between Ag+ ions and the nitrogen
Fig. 6 (A and B) Representative TEM images of (A) Au/TiO2, and (B) high- atoms in the MO dye. In addition, the photocatalytic activity of the
resolution image of Au/TiO2 from ref. 34; (C and D) typical SEM images of photocatalyst has no obvious loss even after four cycles of the
Ag–AgBr from ref. 36; inset: a HR-TEM image of one nanoparticle on AgBr;
photodegradation of MO dye solution.
(E) SEM images of Ag@AgCl from ref. 38 (inset: a surface SEM image of the
product); (F) SEM images of Ag/Ag3PO4 heterostructures from ref. 37.
In addition to the AgX (Cl, Br), another semiconductor coupled
Reprinted with permission. Copyright 2007, 2012 and 2012, American with Ag was the Ag3PO4 semiconductor. Ye’s group coupled Ag3PO4
Chemical Society, Wiley-VCH and Royal Society of Chemistry. submicro-cubes and highly conductive Ag nanowires into novel

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necklace-like coaxial heterostructures37 (Fig. 6F). With this

novel necklace-like Ag nanowire-Ag3PO4 cube heterostructure
as a photocatalyst, RhB dye can be completely degraded in only
2 min under visible light irradiation, while the pure Ag3PO4
cubes need about 8 min. This enhancement was attributed to
the rapid electron export through Ag nanowires as well as
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highly efficient charge separation at the contact interfaces

which was caused by the Fermi level equilibration.
S–M SHPs have also been applied in carbon dioxide (CO2)
photofixation.39,40 For example, Hinogami et al. prepared metal-
particle-coated p-Si electrodes for photoelectrochemical reduction
of CO2.40 This p-Si electrode modified with small metal (Cu, Ag,
or Au) particles generated a high photovoltage of ca. 0.5 V and Fig. 7 The proposed mechanisms for the TiO2–CNT heterojunction.
works as an effective electrode for the photoelectrochemical
reduction of CO2.
the space-charge regions are transferred into the CNTs until the
Fermi levels of the TiO2 and that of the CNTs are on the same
5. The design and construction of level, and holes remain on the TiO2 to take part in redox reactions.
semiconductor–carbon (S–C) 5.1.3 Semiconductor–graphene heterojunctions. Graphene is a
single layer of graphite which possesses a unique two-dimensional
heterojunctions structure, high conductivity, superior electron mobility and
5.1 The design principle of S–C heterojunctions extremely high specific surface area. It can be produced on a
For the construction of a S–C heterojunction, different types of large scale at low cost, nowadays. Thus, it has been regarded as an
carbons have been used, including activated carbon, CNTs and important guest/host component for making various functional
graphene. The design principles of S–C heterojunctions have materials. In particular, numerous attempts have been made to
slight differences, which will be discussed, respectively, in the combine graphene with photocatalysts to enhance their photo-
following section. catalytic performance.17,42 The graphene in the composites can
5.1.1 Semiconductor-activated carbon heterojunctions. promote the charge separation, restrain the hole–electron recom-
Activated carbon was initially used as a support for TiO2 in bination as well as provide a large surface/interface for hetero-
photodegradation studies,41 due to its very large specific surface geneous reactions at the interface, which results in an enhanced
area that is typically more than one order of magnitude larger photocatalytic activity. As shown in Fig. 8, electron–hole pairs are
than that of P25. Usually, the increase of the surface area leads to generated within the semiconductor upon light excitation, these
the improvement of the photocatalytic activity which can be photogenerated electrons tend to transfer to graphene sheets, and
concluded from the Langmuir–Hinshelwood mechanism. There- then scavenged by dissolved oxygen, facilitating the hole–electron
fore, it can be expected that combining semiconductors with the separation. Meanwhile, the holes leaving from the VB of the
activated carbon yields an increase in adsorbed amounts of semiconductor can either react with adsorbed water (or surface
pollutants and thus enhances their photocatalytic activity. hydroxyl) to form hydroxyl radicals or directly oxidize various
5.1.2 Semiconductor–CNT heterojunctions. CNTs also organic compounds.
provide a larger specific surface area and thus the coupling of
semiconductors on it can enhance the photocatalytic degradation
efficiency, as explained above. Furthermore, similar to the metals
above, CNTs also exhibit metallic conductivity as one of the
possible electronic structures and just like the semiconductor–
metal heterojunction system. Semiconductor–CNTs can form
a Schottky barrier junction which is an effective method of
increasing recombination time. Furthermore, CNTs have a large
electron-storage capacity and therefore can accept photon-excited
electrons in mixtures or nanocomposites with semiconductors,
thus retarding or hindering the recombination.1 Among the
semiconductor–CNT systems, the TiO2–CNT composite system
represents a good example illustrating the enhancement of the
photocatalytic properties of semiconductor–CNT heterojunctions.
Hoffmann et al.1 proposed a mechanism to explain the enhance-
ment of the photocatalytic properties of TiO2–CNT composites, as
shown in Fig. 7. A high-energy photon excites an electron from the
VB to the CB of anatase TiO2. Photogenerated electrons formed in Fig. 8 The schematic structure of semiconductor–graphene heterojunctions.

5240 | Chem. Soc. Rev., 2014, 43, 5234--5244 This journal is © The Royal Society of Chemistry 2014
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It is worth mentioning that in some cases, the electronic

interactions and charge equilibration between graphene and
the semiconductor can lead to a shift in the Fermi level and
decrease the CB potential of the semiconductor (Fig. 8). Thus,
the negative shift in the Fermi level of semiconductor–graphene
and the high migration efficiency of photoinduced electrons
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can suppress the charge recombination effectively, resulting in

the enhanced photocatalytic activity.

5.2 Construction and performance of S–C heterojunctions

S–C heterojunction systems are currently being considered for
many applications including their potential use to address
environmental problems. In particular, semiconductor–CNT
heterojunction systems have attracted much attention in photo-
catalytic applications. Recently, heterojunction systems of CNTs
and TiO2 have been reviewed.43 All of these heterojunction
systems exhibited improved photocatalytic efficiency compared
with bare TiO2. The enhancement was due to the slowed recombi-
Fig. 9 (A and B) TEM images and SAED pattern of graphene nanosheets
nation of photogenerated electron–hole pairs, the extended excita- decorated with CdS clusters from ref. 46; (C and D) TEM images of graphene
tion wavelength, as well as the increased surface-adsorbed amount decorated with Bi2WO6 composite from ref. 47. Reprinted with permission.
of reactant species.44 Copyright (2011), American Chemical Society and PCCP Owner Societies.
In addition, plenty of semiconductor–graphene heterojunctions
have also been developed, and most of the graphene-based
nanocomposites have been reviewed very recently.17,42 They have electron collector and transporter to efficiently lengthen the life-
given a detailed description of the design, fabrication, modifica- time of the photogenerated charge carriers from CdS NPs. Bi2WO6
tion and applications of these graphene-based semiconductor has also been coupled with graphene to enhance its photocatalytic
photocatalysts. Herein, several typical semiconductor–graphene efficiency. For example, Wang’s group47 prepared a graphene–
heterojunctions have been listed in Table 4. These hetero- Bi2WO6 composite via an in situ hydrothermal reaction (Fig. 9C
junctions have exhibited a significant enhancement of photo- and D). This graphene–Bi2WO6 photocatalyst showed significantly
catalytic efficiency compared with the bare semiconductors. For enhanced photocatalytic activity for the degradation of RhB under
example, Li et al.46 synthesized graphene nanosheets decorated visible light (l 4 420 nm), which was 3 times greater than that of
with CdS clusters through a solvothermal method in which the pure Bi2WO6. The enhanced photocatalytic activity could be
graphene oxide (GO) served as the support while cadmium acetate attributed to the negative shift in the Fermi level of graphene–
(Cd(Ac)2) as the CdS precursor (Fig. 9A and B). These nanosized Bi2WO6 and the high migration efficiency of photoinduced
composites exhibited a high H2-production rate of 1.12 mmol h 1 electrons; these electrons may not only be effectively involved
(which was about 4.87 times higher than that of pure CdS NPs) at in the oxygen reduction reaction but also suppress the charge
graphene content of 1.0 wt% and Pt 0.5 wt% under visible-light recombination, as revealed in Section 5.1.3.
irradiation. This high photocatalytic H2-production activity was Besides CNTs and graphene, other type carbons can also be used
mainly attributed to the presence of graphene, which serves as an to construct S–C heterojunctions. For example, carbon@TiO2 dyade

Table 4 Comparison of the typical graphene–S heterojunction systems

Types Preparation Morphology The improved performances The proposed reasons Ref.
TiO2– Self-assembly Macro-mesoporous solid 11 times higher MB degradation The improved mass transport, the reduced the 44
graphene method films rate than that of pure mesoporous length of the mesopore channel, the increased
titania films accessible surface area of the thin film and the
suppressed charge recombination

P25– A one-step P25 NPs deposited on 6 times than that of P25 for the Great adsorptivity of dyes, extended photorespond- 45
graphene hydrothermal graphene nanosheet degradation of MB under visible ing range, and enhanced charge separation and
reaction light transportation properties

CdS– A solvother- Graphene nanosheets 4.87 times higher H2-production The enhanced separation of photogenerated elec- 46
graphene mal method decorated with CdS rate than that of pure CdS NPs tron and hole pairs
clusters under visible-light irradiation

Bi2WO6– In situ hydro- Bi2WO6 NPs distributed on 3 times than that of Bi2WO6 for the The negative shift in the Fermi level of graphene– 47
graphene thermal the surface and edges of degradation of RhB under visible Bi2WO6 and the high migration efficiency of photo-
reaction the graphene sheets light induced electrons

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structure has been prepared by a solvothermal method.11 the VB of S-A escape from the pair recombination and are available
C@TiO2 has a high surface area and anatase structure and is to oxidize the pollutants or OH . On the other hand, since the
able to absorb a high amount of photoenergy in the visible energy level of metal is above the VB of S-B, holes in the VB of S-B
region, driving effectively photochemical degradation reactions. also easily flow into metal (electron transfer II: metal - S-B, see
The origin of photocatalytic activity under visible light is due to a Fig. 10), which is faster than the electron–hole recombination
direct optical charge transfer transition involving both the TiO2 between the VB and CB of S-B. More electrons with a strong reduc-
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and carbon phase, keeping the high reactivity of the photo- tion power in the CB of S-B can escape from the pair recombination
generated electron and hole. and are available to reduce some absorbed compounds (such as O2,
H+, etc.). Therefore, simultaneous electron transfer I and II (that is,
vectorial electron transfer of S-A - metal - S-B in Fig. 10) can
6. The design and construction of occur as a result of UV/visible-light excitation of both S-A and S-B. In
multicomponent heterojunctions these vectorial electron-transfer processes, metal in multicompo-
nent heterojunction systems acts as a storage and/or a recombina-
Up to date, although a variety of approaches have been developed tion center for electrons in the CB of S-A and holes in the VB of S-B,
to prepare many kinds of VLD SHPs, there are still some draw- and contributes to enhancing interfacial charge transfer and realiz-
backs, such as the limited region of visible-light photo-response. ing the complete separation of holes in the VB of S-A and electrons
To solve these problems, multicomponent heterojunction systems in the CB of S-B. So the multicomponent heterojunction systems
have been developed,48,49 in which two or more visible-light active can simultaneously and efficiently generate holes with a strong
components and an electron-transfer system are spatially inte- oxidation power in the VB of S-A and electrons with a strong
grated. The typical schematic structure of multicomponent hetero- reduction power in the CB of S-B, resulting in greatly enhanced
junction systems is shown in Fig. 10. photocatalytic activity, compared with the single semiconductor
First of all, since both semiconductor A (S-A) and semi- or semiconductor heterojunctions mentioned above.
conductor B (S-B) can be excited by UV/visible light and have In 2006, Tada et al.48 developed a CdS–Au–TiO2 three-
different photoabsorption ranges, the conjunction of their photo- component nanojunction system using a simple photochemical
absorption can broaden the range of UV/visible-light photo- technique (Fig. 11A and B). This CdS–Au–TiO2 nanojunction
response. Secondly, the photocatalytic reaction is initiated by the exhibited excellent photocatalytic activity, which was far higher
absorption of UV/visible-light photons with energy equal or higher than that of either the single component or two components
than the band-gap in both S-A and S-B, which results in the creation systems. For this photocatalytic CdS–Au–TiO2 nanojunction
of photogenerated holes in their VB and electrons in their CB. On system, 52.2% of methylviologen (MV2+) have been reduced in
the one hand, the electrons in the CB of S-A easily flow into metal 100 min, which are 1.6, 1.8 and 2.3 times than that of Au/TiO2,
(electron transfer I: S-A - metal) through the Schottky barrier CdS/TiO2 and TiO2 (calculated from the figure in the original
because the CB (or the Fermi level) of S-A is higher than that of the publication48).
loaded metal, which is consistent with the previous study on
electron transfer from the semiconductor (such as TiO2) to metal
(such as Ag, Au).48,50 This process of electron transfer I is faster than
the electron–hole recombination between the VB and the CB of S-A.
Thus, plenty of electrons in the CB of S-A can be stored in the metal
component. As a result, more holes with a strong oxidation power in

Fig. 11 TEM (A) and HRTEM (B) images of Au@CdS-TiO2 from ref. 48; SEM
(C) and HRTEM (D) images of the AgBr–Ag–Bi2WO6 nanojunction system
from ref. 12. Reprinted with permission. Copyright 2006 and 2009, Nature
Fig. 10 Schematic structure of multicomponent heterojunction systems. Publishing Group and Elsevier.

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Subsequently, an AgBr–Ag–Bi2WO6 nanojunction system Program for Changjiang Scholars and Innovative Research
was developed by a facile deposition–precipitation method Team in University (Grant No. IRT1221), Specialized Research
(Fig. 11C and D).12 This AgBr–Ag–Bi2WO6 nanojunction system Fund for the Doctoral Program of Higher Education (CUSF-DH-
shows much higher VLD photocatalytic activity than a photo- D-2013054), Innovation Program of Shanghai Municipal Educa-
catalyst with single visible-light response components, such tion Commission (Grant No. 13ZZ053), project of the Shanghai
as Bi2WO6 nanostructures, Ag–Bi2WO6 and AgBr–Ag–TiO2. For Committee of Science and Technology (13JC1400300), the
Published on 20 May 2014. Downloaded by UNIVERSIDAD DE BUENOS AIRES on 6/24/2018 11:33:55 AM.

example, with the AgBr–Ag–Bi2WO6 nanojunction system as the Shanghai Leading Academic Discipline Project (B604), the
photocatalyst, the MX-5B could be photocatalytically degraded Fundamental Research Funds for the Central Universities,
42.8 mg L 1 within 60 min under visible-light irradiation, which is and DHU Distinguished Young Professor Program.
higher than that by Bi2WO6 nanostructures (2.0 mg L 1),
Ag–Bi2WO6 (2.9 mg L 1) and AgBr–Ag–TiO2 (34.1 mg L 1).
Furthermore, 65% of pentachlorophenol could be mineralized References
within 4 h by AgBr–Ag–Bi2WO6, which is much higher than that
(34.5%) of the AgBr–Ag–TiO2 composite. This excellent VLD 1 M. R. Hoffmann, S. T. Martin, W. Choi and D. W. Bahnemann,
photocatalytic performance was mainly attributed to the vectorial Chem. Rev., 1995, 95, 69–96.
interparticle electron transfer driven by the two-step excitation of 2 M. Fujihira, Y. Satoh and T. Osa, Nature, 1981, 293, 206–208.
both VLD components (AgBr and Bi2WO6). 3 C. Chen, W. Cai, M. Long, B. Zhou, Y. Wu, D. Wu and
Y. Feng, ACS Nano, 2010, 4, 6425–6432.
4 L. S. Zhang, W. Z. Wang, J. O. Yang, Z. G. Chen, W. Q.
7. Conclusions and outlook Zhang, L. Zhou and S. W. Liu, Appl. Catal., A, 2006, 308,
105–110.
In summary, we have discussed the general strategies and recent
5 D. Chen and J. Ye, Adv. Funct. Mater., 2008, 18, 1922–1928.
progress in SHPs for developing highly efficient and stable photo-
6 N. Bao, L. Shen, T. Takata and K. Domen, Chem. Mater.,
catalysts, including: (1) the coupling of semiconductors with other
2007, 20, 110–117.
semiconductors to satisfy high absorption of solar energy and to
7 L. S. Zhang, W. Z. Wang, Z. G. Chen, L. Zhou, H. L. Xu and
create sufficient built-in potential for redox reactions; (2) the
W. Zhu, J. Mater. Chem., 2007, 17, 2526–2532.
formation of heterostructured junctions with carbon material to
8 L. S. Zhang, K. H. Wong, D. Q. Zhang, C. Hu, J. C. Yu,
effectively drive the separation and transportation of the electron–
C. Y. Chan and P. K. Wong, Environ. Sci. Technol., 2009, 43,
hole pairs; (3) the deposition of metal to enhance the utilization of
7883–7888.
sunlight or improve the separation and transportation of the
9 X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin,
electron–hole pairs; (4) the forming of multicomponent hetero-
J. M. Carlsson, K. Domen and M. Antonietti, Nat. Mater.,
junctions for enhancing the utilization of sunlight and improving
2008, 8, 76–80.
the separation/transportation of the electron–hole pairs. The
10 L. S. Zhang, J. L. Li, Z. G. Chen, Y. W. Tang and Y. Yu,
achieved progress in this field indicates that forming hetero-
Appl. Catal., A, 2006, 299, 292–297.
junctions affords a promising route to enhance the photo-
11 L. Zhao, X. Chen, X. Wang, Y. Zhang, W. Wei, Y. Sun,
catalytic efficiencies of photocatalytic semiconductors.
M. Antonietti and M. M. Titirici, Adv. Mater., 2010, 22,
To date, many kinds of semiconductor heterojunctions have
3317–3321.
been reported to improve photocatalytic efficiencies by enhan-
12 L. S. Zhang, K. H. Wong, Z. G. Chen, J. C. Yu, J. C. Zhao,
cing the utilization of sunlight or improving the separation/
C. Hu, C. Y. Chan and P. K. Wong, Appl. Catal., A, 2009, 363,
transportation of the electron–hole pairs, and some examples
221–229.
are highlighted in this review. However, the studies in this area
13 L. S. Zhang, K. H. Wong, H. Y. Yip, C. Hu, J. C. Yu,
are currently unsystematic, and the heterojunction systems
C. Y. Chan and P. K. Wong, Environ. Sci. Technol., 2010,
with high efficiency and stability are needed to be further
44, 1392–1398.
developed. Meanwhile, the heterogeneous photocatalysts have
14 H. Wang, S. Li, L. Zhang, Z. Chen, J. Hu, R. Zou, K. Xu,
been and will continue to be applied in solar water splitting and
G. Song, H. Zhao and J. Yang, CrystEngComm, 2013, 15,
environmental remediation, while the photocatalytic conversion
9011–9019.
of carbon dioxide to fuels and other useful chemicals is expected
15 X. Wang, X. Chen, A. Thomas, X. Fu and M. Antonietti,
to be a dominant area.
Adv. Mater., 2009, 21, 1609–1612.
16 J. Zhang, M. Zhang, R. Q. Sun and X. Wang, Angew. Chem.,
Acknowledgements Int. Ed., 2012, 124, 10292–10296.
17 Q. Xiang, J. Yu and M. Jaroniec, Chem. Soc. Rev., 2012, 41,
This work was financially supported by the National Basic 782–796.
Research Program of China (2013CB632405), the National Natural 18 L. Jiang, G. Zhou, J. Mi and Z. Wu, Catal. Commun., 2012, 24,
Science Foundation of China (Grant No. 21033003, 21007009, 48–51.
21107013, 21377023, 41273108, and 51272299), High-Tech Research 19 M. Shang, W. Wang, L. Zhang, S. Sun, L. Wang and L. Zhou,
and Development Program of China (Grant No. 2012AA030309), J. Phys. Chem. C, 2009, 113, 14727–14731.

This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev., 2014, 43, 5234--5244 | 5243
 View Article Online

Chem Soc Rev Tutorial Review

20 C. Wang, C. Shao, X. Zhang and Y. Liu, Inorg. Chem., 2009, 35 P. Wang, B. Huang, X. Qin, X. Zhang, Y. Dai, J. Wei and
48, 7261–7268. M. H. Whangbo, Angew. Chem., Int. Ed., 2008, 47, 7931–7933.
21 T. Kawahara, Y. Konishi, H. Tada, N. Tohge, J. Nishii and 36 W. Lu, X. Qin, H. Li, A. M. Asiri, A. O. Al-Youbi and X. Sun,
S. Ito, Angew. Chem., Int. Ed., 2002, 114, 2935–2937. Part. Part. Syst. Charact., 2013, 30, 67–71.
22 C. Y. Jimmy, L. Wu, J. Lin, P. Li and Q. Li, Chem. Commun., 37 Y. Bi, H. Hu, S. Ouyang, Z. Jiao, G. Lu and J. Ye, J. Mater.
2003, 1552–1553. Chem., 2012, 22, 14847–14850.
Published on 20 May 2014. Downloaded by UNIVERSIDAD DE BUENOS AIRES on 6/24/2018 11:33:55 AM.

23 S. J. Hong, S. Lee, J. S. Jang and J. S. Lee, Energy Environ. Sci., 38 L. Han, P. Wang, C. Zhu, Y. Zhai and S. Dong, Nanoscale,
2011, 4, 1781–1787. 2011, 3, 2931–2935.
24 Y. Hou, A. B. Laursen, J. Zhang, G. Zhang, Y. Zhu, X. Wang, 39 S. Yamamura, H. Kojima, J. Iyoda and W. Kawai, J. Electroanal.
S. Dahl and I. Chorkendorff, Angew. Chem., Int. Ed., 2013, Chem. Interfacial Electrochem., 1987, 225, 287–290.
52, 3621–3625. 40 R. Hinogami, Y. Nakamura, S. Yae and Y. Nakato, J. Phys.
25 J. Su, L. Guo, N. Bao and C. A. Grimes, Nano Lett., 2011, 11, Chem. B, 1998, 102, 974–980.
1928–1933. 41 J. F. Tanguay, S. L. Suib and R. W. Coughlin, J. Catal., 1989,
26 T. W. Kim and K.-S. Choi, Science, 2014, 343, 990–994. 117, 335–347.
27 K. Maeda, K. Teramura, D. Lu, T. Takata, N. Saito, Y. Inoue 42 X. Huang, X. Qi, F. Boey and H. Zhang, Chem. Soc. Rev.,
and K. Domen, Nature, 2006, 440, 295. 2012, 41, 666–686.
28 Y. Zheng, Y. Jiao, Y. Zhu, L. Li, Y. Han, Y. Chen, A. Du, 43 K. Woan, G. Pyrgiotakis and W. Sigmund, Adv. Mater., 2009,
M. Jaroniec and S. Qiao, Nat. Commun., 2014, 5, 3783, DOI: 21, 2233–2239.
10.1038/ncomms4783. 44 J. Du, X. Lai, N. Yang, J. Zhai, D. Kisailus, F. Su, D. Wang
29 R. Li, F. Zhang, D. Wang, J. Yang, M. Li, J. Zhu, X. Zhou, and L. Jiang, ACS Nano, 2010, 5, 590–596.
H. Han and C. Li, Nat. Commun., 2013, 4, 1432. 45 H. Zhang, X. Lv, Y. Li, Y. Wang and J. Li, ACS Nano, 2009, 4,
30 R. Li, H. Han, F. Zhang, D. Wang and C. Li, Energy Environ. 380–386.
Sci., 2014, 7, 1369–1376. 46 Q. Li, B. Guo, J. Yu, J. Ran, B. Zhang, H. Yan and J. R. Gong,
31 D. Wang, T. Hisatomi, T. Takata, C. Pan, M. Katayama, J. Am. Chem. Soc., 2011, 133, 10878–10884.
J. Kubota and K. Domen, Angew. Chem., Int. Ed., 2013, 52, 47 E. Gao, W. Wang, M. Shang and J. Xu, Phys. Chem. Chem.
11252–11256. Phys., 2011, 13, 2887–2893.
32 Y. Bi, S. Ouyang, J. Cao and J. Ye, Phys. Chem. Chem. Phys., 48 H. Tada, T. Mitsui, T. Kiyonaga, T. Akita and K. Tanaka,
2011, 13, 10071–10075. Nat. Mater., 2006, 5, 782–786.
33 X.-H. Li and M. Antonietti, Chem. Soc. Rev., 2013, 42, 49 M. R. Elahifard, S. Rahimnejad, S. Haghighi and M. R.
6593–6604. Gholami, J. Am. Chem. Soc., 2007, 129, 9552–9553.
34 H. Li, Z. Bian, J. Zhu, Y. Huo and Y. Lu, J. Am. Chem. Soc., 50 T. Hirakawa and P. V. Kamat, J. Am. Chem. Soc., 2005, 127,
2007, 129, 4538–4539. 3928–3934.

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