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Visible light driven type II heterostructures and their

enhanced photocatalysis properties: a review
Cite this: Nanoscale, 2013, 5, 8326
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Yajun Wang, Qisheng Wang, Xueying Zhan, Fengmei Wang, Muhammad Safdar
and Jun He*

Considerable efforts have been devoted to enhancing the photocatalytic activity and solar energy
utilization of photocatalysts. The fabrication of type II heterostructures plays an important role in
photocatalysts modification and has been extensively studied. In this review, we briefly trace the
application of type II heterostructured semiconductors in the area of environmental remediation and
water splitting, summarize major fabrication methods, describe some of the progress and resulting
achievements, and discuss the future prospects. The scope of this review covers a variety of type II
Received 30th March 2013
Accepted 19th May 2013
heterostructures, focusing particularly on TiO2 and ZnO based visible light driven type II 0D and 1D
heterostructured photocatalysts. Some other low dimensional nanomaterials which have shown high-
DOI: 10.1039/c3nr01577g
performance photocatalysis are also presented. We expect this review to provide a guideline for readers
www.rsc.org/nanoscale to gain a clear picture of fabrication and application of type II heterostructures.

1 Introduction series of environmental problems and public health crises due

to the burning of fossil fuel. In order to solve these severe
Environmental and energy issues are among the biggest chal- problems, China has set goals to mitigate its CO2 emission per
lenges in the new century. With the growth of worldwide unit of Gross Domestic Production (GDP) by 40–45% by 2020,
industry, severe environmental contaminations have become a with an interim target in the 12th 5-Year Plan of 17% by 2015.1
major concern of our society. The development of high effi- Among various strategies, nding renewable energy, instead
ciency, green energy sources and eco-friendly methods for of fossil fuel is the key measure. Hydrogen, as a clean and non-
environmental remediation has become an imperative task. carbon energy source, is of great potential in solving the envi-
Moreover, energy shortages and surging green-house gas (GHG) ronmental crisis and energy shortage. As a result, photo-
emissions have been two of the major challenges the world is catalysis, as one of the promising technologies in utilizing solar
facing today. For example, in China over 70% of domestic energy to solve environmental and energy issues, has attracted
energy originates from coal. As a result, China suffers from a considerable attention.
Fujishima and Honda rst reported the UV light induced
photo-assisted decomposition of water into hydrogen and
National Center for Nanoscience and Technology, Beijing 100190, P. R. China. E-mail:
[email protected] oxygen using a titanium dioxide photoanode in electrochemical

Yajun Wang received her BS Jun He received his PhD in

degree in Environmental Engi- physical chemistry from the
neering from Tsinghua Univer- Institute of Semiconductors,
sity in 2006. She received her Chinese Academy of Sciences in
PhD degree in Chemistry from 2003. Dr He is presently a
Tsinghua University in 2011. Professor of physical chemistry
Currently, she is an assistant of materials in the National
professor in National Center of Center for Nanoscience and
Nanoscience and Technology Technology, China, with
(NCNST), China. Her research research interests in low dimen-
interests include development sional semiconductor materials
and modication of photo- synthesis, characterization, and
catalysts for environmental devices.
purication and water splitting.

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cell in 1972.2 Since then, semiconductor photocatalysis has PEC water splitting at a semiconductor photoelectrode is
attracted widespread attention in scientic community due to calculated as 1.6–2.4 eV per electron–hole pair generated.6
its potential application in environmental remediation and Although semiconductor photocatalysis has made great
hydrogen production. The basic mechanisms of photocatalysis progress during the past three decades, there are still some
have been established and reported in many literature unsolved problems. Again, taking TiO2 as an example, TiO2 is
accounts.3,4 Taking TiO2 as an example, the mechanism of the known as the most widely investigated photocatalyst due to its
photocatalytic process is shown in Fig. 1. high oxidative efficiency, high chemical stability, nontoxicity
When the absorbed photon has an energy equaling or and low-cost.7–9 Presently, the photocatalytic degradation
exceeding the band gap energy (Eg) of TiO2, an electron in the activity and water splitting efficiency of TiO2 is still low, mainly
lled valence band (VB) is excited into the empty conduction due to the following two reasons: (1) slow reaction rate: the
band (CB), leaving behind a hole in VB (stage I). Stage II and photocatalytic reactions only occur when the photoinduced
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stage III occur in parallel, but the recombination process (stage electrons and holes transfer to the surface active sites of the
II) is much faster than the transportation process (stage III) as semiconductor. However, the recombination process is much
shown in Fig. 1. Aer the electrons and holes transfer to the faster than the transportation process, leading to low photo-
active sites of the surface of TiO2, they will act as reducing/ catalytic efficiency. (2) Poor solar energy utilization: TiO2 with a
oxidizing agents to drive reduction/oxidation on the surface bandgap of 3.2 eV can be only excited by photons with light
(stage VI and V). In detail, at stage VI and V, for photocatalytic wavelengths shorter than about 400 nm in the UV wavelength
degradation of pollutants, holes of VB can react with surface range, which accounts for about 4% of the solar radiation
adsorbed H2O to produce hydroxyl radicals. The hydroxyl radi- energy.10,11 Therefore, a great deal of effort has been devoted to
cals are strong oxidizing agents, which can oxidize almost all enhancing the efficiency of the photocatalytic process and
organic pollutants with no selectivity. Moreover, the holes can extending the light adsorption range of TiO2, such as formation
also directly oxidize the organic pollutants to form R+.3,5 For of semiconductor heterostructures,12,13 codeposition of noble
water splitting, water molecules are reduced by the photoin- metals,14,15 doping,16,17 surface hybridization18–20 and coupling
duced electrons to form H2 and are oxidized by the photoin- with other technology.19,20 Among these approaches, formation
duced holes to form O2. For effective water splitting, the bottom of semiconductor heterostructures is an effective way to
level of the CB of the semiconductor has to be more negative enhance the photoinduced charges separation efficiency and
than the redox potential of H+/H2 (0 V vs. NHE), while the top the photocatalytic performance, and has been extensively
level of the VB of the semiconductor should be more positive studied for the last decades. Depending on the bandgaps and
than the redox potential of O2/H2O (1.23 V vs. NHE). The the electronic affinity of semiconductors, semiconductor het-
minimum band gap for water splitting is 1.23 eV; theoretically, erostructures can be divided into three different cases: type-I,
all types of semiconductors that satisfy the above requirements type-II and type-III band alignment as shown in Fig. 2.
could be used as photocatalysts for water splitting. Particularly, In a type-II band alignment, the position of valance and
in a photoelectrochemical (PEC) cell, carriers in the semi- conduction bands of semiconductor 2 is higher than that of
conductor should travel to an electrode/liquid junction to drive semiconductor 1, and the steps in the conduction and valance
the hydrogen/oxygen evolution reaction. In electron-transfer bands go in the same direction. Importantly, the difference of
processes at semiconductor/liquid junctions, unavoidable los- chemical potential between semiconductor 1 and 2 causes band
ses are caused by concentration and kinetic overpotentials. bending at the interface of junction. The band bending induces a
Therefore, accounting for the losses, the energy required for built-in eld, which drives the photogenerated electrons and holes
to move in opposite directions, leading to a spatial separation of
the electrons and holes on different sides of heterojunction.21
Thus, the formation of type-II heterostructures is an effective
approach to enhance charge separation efficiency for improved
photocatalytic degradation activity and water splitting efficiency.
Moreover, a UV excited semiconductor (such as TiO2, ZnO,
ZnWO4) coupled with a visible light excited semiconductor

Fig. 1 Primary steps in the photocatalytic mechanism (TiO2): (I) formation of

electron (e
)–hole (h+) pairs by photoexcitation; (II) photoinduced charge
recombination; (III) photoinduced charge transportation; (IV) oxidation caused by
a valence band hole; (V) reduction caused by a conduction band electron Fig. 2 Schematic energy band diagram of three types of semiconductor
(adapted with permission from ref. 3, copyright 1995 American Chemical Society). heterojunctions.

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Fig. 3 Band edge position of several semiconductors, using the normal hydrogen electrode (NHE) as a reference (adapted with permission from ref. 23, copyright
2009 Royal Society of Chemistry).

(a narrow bandgap semiconductor such as CdS, CdSe, CdSSe, visible-light driven type II heterostructured photocatalysts have
C3N4) can effectively improve its solar energy utilization effi- attracted tremendous attention. Over the past decades, various
ciency because the synergic absorption of two semiconductors synthesis techniques, such as chemical vapor deposition,44
with different band gaps extends the light response range to the chemical deposition,45–47 electrodeposition, etc.,48 have been
whole solar spectrum. There are two prerequisite conditions to well developed and successfully used in preparing high-quality
prepare a visible light driven type II heterostructure: (1) the outer type II core/shell heterostructures.
shell material should have a strong visible light absorption Compared with the synthesis of the core material, the growth
(photo-sensitizer), and (2) the band alignment at the interface of outer shell material (sensitizer) is more complicated. For
between the outer shell material and inner core should satisfy example, different thicknesses of sensitizer may result in
the conditions of type II heterostructures. In addition, the crystal different photocatalytic properties.49 Therefore, in this section,
structure in the junction area of the heterostructure is found to we will focus our attention on methods for the synthesis of the
be important in enhancing the quantum efficiency of the pho- sensitizer. Considering the wide application of ZnO and TiO2 as
tocatalyst. A difference in lattice spacing between two semi- the photocatalysts, here we will mainly discuss the preparation
conductors is likely cause lattice mismatch. The lattice of sensitizers based on ZnO and TiO2 nanostructured material.
mismatch at the interface may cause defects, which trap the Other type II heterostructured photocatalysts prepared by
photogenerated carriers and thus prevent the diffusion of elec- special synthetic methods are also presented.
trons and holes. However, interface strain arising from the lattice
mismatch also alters the electronic structure. Indeed, lattice 2.1 Chemical vapor deposition
strain could induce an electric eld, which further improves the
Vapor-phase synthesis is probably the most extensively explored
separation efficiency of electrons and holes.22 Consequently,
careful selection of materials should be taken before preparing approach in the eld of nanofabrication. Chemical vapor
visible light driven type II heterostructures. Fig. 3 shows the band deposition (CVD) or chemical vapor transport (CVT) is very
commonly used for type II heterostructure synthesis. This
edge position of several widely used semiconductors.23 The type-
method has the ability to control the sensitizer composition,
II heterostructure has attracted widespread attention in fabri-
thickness and stability by controlling several processing
cation, study of its properties, and applications. Diverse type-II
parameters such as temperature, pressure, carrier gas, substrate
heterostructures have been explored, such as composite nano-
and evaporation time period. A number of type-II hetero-
particles,24–29 quantum dots in nanowires,30–32core/shell nano-
structured sensitizers, for example, CdSe, CdSSe, ZnxCd1
xSe,
wires,33–35 etc. Compared with pure semiconductors, these type-II
heterostructures, such as CdS/TiO2,36,37 CdS/ZnO,38,39 ZnSe/ ZnSxSe1
x, ZnSxSe1
x/ZnSe, ZnGa2O4 and ZnTe have been
ZnO,40 ZnS/ZnO,41 ZnO/TiO2/CuO,42 and SnO2/CdS43 have ach- deposited on ZnO cores via the CVD method.44,50–54 In most
cases, type II heterostructure can be obtained in two-step
ieved higher photocatalytic efficiency and solar energy utiliza-
growth procedure. Firstly, the inner core semiconductor nano-
tion. In this review, we briey trace the application of type II
structure is grown on a suitable substrate via CVD or another
heterostructured semiconductors in the area of environmental
synthetic technique. In the second step, the substrate with pre-
remediation and water splitting, summarize major fabrication
grown core nanostructure, is kept in a tube furnace to deposit
methods, describe some of the progress and resulting achieve-
the shell and under optimized conditions, controlled shell
ments, and discuss the future prospects.
materials can be obtained. Myung and co-workers have reported
10 nm and 50 nm thick CdS shells on ZnO nanowires which
2 Synthesis of type II heterostructures were remarkably associated with time and temperature
variation.50
Due to their wide application in the degradation of pollutants, Our group has recently successfully synthesized a ZnSxSe1
x
energy conversion and water splitting, controllable synthesis of shell on a vertical ZnO nanowire array via the CVD method.44

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Firstly, a single crystalline ZnO nanowire array was obtained on 0.2 M CH4N2S, 10 mL of 1.5 M NH4NO3and 10 mL 0.5 M KOH to
an Au deposited Si substrate using a two-zone furnace tube and deposit the CdS shell at 85  C. Typical SEM and TEM images of
mixed graphite and ZnO powder as sources. In the second step, the TiO2/CdS are shown in the Fig. 5. This facile method was
a homogenous shell of ZnSxSe1
x was deposited on the exposed also used in another example to fabricate heterostructured
surface of ZnO by CVD. In detail, ZnS and ZnSe mixed in a 3 : 7 ZnxCd1
xS/ZnO.47 The morphologies of the ZnO/ZnxCd1
xS
mole ratio were used as the source in the center of a quartz tube heterostructure could be controlled by altering the ratio of the
keeping 8 cm of distance from the pre-grown ZnO nanowire ZnxCd1
xS precursors.
substrate. The source was evaporated at 1100  C and deposited
on the ZnO nanowire array, and the shell thickness was care-
fully controlled by adhering to the optimum deposition time. 2.3 Electrochemical deposition
The synthesized core/shell structure is presented in Fig. 4. Compared with the CVD method, electrochemical deposition
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Fig. 4a represents the ZnO nanowire before coating (inset of allows large-scale nanostructure fabrication at low temperature.
Fig. 4a) and aer ZnSSe coating. X-ray EDS spectra demonstrate This conventional technique is most suitable for production of
that the core and shell have an approximate 1 : 3 atomic ratio highly dense, uniform and ordered type-II heterostructured
(Fig. 4b). Transmission electron microscopy (TEM) investiga- nanomaterials for large scale applications.60–64 The shell thick-
tion conrms that the synthesized material was a typical core/ ness of type-II heterostructures, which directly inuences their
shell structure and with a ne single crystalline structure as performance, can be controlled by temperature, potential and
shown in Fig. 4c and d. time duration. For instance, Yao and co-workers reported that
the thickness of CdS shell on ZnO nanorod can be controlled by
this method via adjustment of deposition time.60 In addition,
2.2 Chemical deposition
Wu and co-workers synthesized Co3O4 nanowires on Ni foil by a
Chemical deposition is a simple and low cost method to fabricate hydrothermal method and then used this material as the
type-II heterostructures. In this technique, the growth of thin working electrode for electrodeposition of an NiO shell. Co3O4
lms results from the bulk precipitation of the solution.55 nanowires can be covered by the NiO nanoake shell when
Chalcogenide layers are usually prepared by this method. The 0.25 mA cm
2 constant anodic current was applied for 1 h.64
temperature, pH, deposition time, and the concentration of the In the electrodeposition system, the pre-grown materials on
precursor play important roles in this method. Based on this indium-doped tin oxide (ITO), uorine-doped tin oxide (FTO) or
method, some type II heterostructures can be easily obtained,56,57 other relevant substrates is used as the working electrode. As a
such as CdS/TiO2,45 CdSe/CdS/ZnO,46 ZnxCd1
xS/ZnO,47 CdS/ representative case, the large scale electrodeposition of a CdTe
ZnS,58 g-C3N4/TiO2.59 shell on a ZnO nanorod array was reported by Wang and co-
For example, TiO2/CdS heterostructure can be obtained by a workers.48 A thermally evaporated ZnO nanorod array on ITO
chemical bath deposition method.45 Firstly, the TiO2 core was was used as the working electrode, Pt foil as the counter elec-
prepared by a hydrothermal method, and then further con- trode and saturated calomel electrode (SCE) as the reference
verted into an ITO substrate, which was vertically immersed in
an aqueous bath containing 10 mL 0.02 M CdCl2$2.5H2O, 10 mL

Fig. 4 (a) SEM image of ZnSxSe1
x/ZnO core/shell nanowires, inset is a side-view

SEM image of ZnO nanowires before coating, (b) an X-ray EDS of ZnSxSe1
x/ZnO
core/shell nanowires. (c) and (d) TEM images of ZnSxSe1
x/ZnO core/shell Fig. 5 SEM images of the as-prepared TiO2 nanorod film before (a) and after (b)
nanowires along inset of enlarged head ends. (e) HRTEM images of a single coating with CdS nanoparticles at high magnification; TEM image of a single CdS/
ZnSxSe1
x/ZnO core/shell nanowire, inset SAED pattern of the core/shell nano- TiO2 core/shell nanorod (c) and high-resolution TEM image of a single CdS/TiO2
wire (reprinted with permission from ref. 44, copyright 2012 American Institute core/shell nanorod (d) (reprinted with permission from ref. 45, copyright
of Physics). 2007 Elsevier).

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electrode. Electrodeposition of the CdTe shell was completed by thus a ZnS shell with similar morphology to the initial ZnO was
applying
1.0 V versus SCE in TeO32
and Cd2+ electrolyte obtained.66 Meanwhile, through the exchange of metal ions in
solution with pH 8.3. The thickness of the CdTe shell was solution, synthesis of columnar and tubular lms of Ag2S, Cu2S,
controlled by maintaining the total charge of the electrodepo- Bi2S3, or Sb2S3 has been achieved from columnar ZnO.66
sition system. Fig. 6a and c display SEM images of the bare ZnO Khanchandani and the co-workers67 have synthesized CdS/ZnO
nanorod array. Fig. 6b and d show the SEM images of ZnO core/shell nanorod arrays through an ion exchange reaction
nanorods aer CdTe electrodeposition. The TEM image in between [Zn2+O2
] ions and [Cd2+S2
] ions. The thickness of the
Fig. 6e reveals the smooth covering of the ZnO core with an 11 shell can be controlled by adjusting the amounts of precursors.
nm CdTe shell, and the HRTEM image in Fig. 6f depicts the The different morphologies of ZnO nanorods and CdS/ZnO are
crystalline structure of CdTe/ZnO nanocable. As demonstrated shown in the Fig. 7. The comparison of photocatalytic proper-
by these examples, electrochemical deposition is a suitable ties, photoluminescence (PL), and absorbance band of ZnO
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technique to fabricate controlled type-II heterostructures. nanorods and CdS/ZnO is shown in Table 1.

2.4 Ion exchange 2.5 Successive ionic layer adsorption and reaction
Ion exchange is a novel technique to prepare core/shell heter- The “successive ionic layer adsorption and reaction” (SILAR)
ostructures by exchanging the ions at the interface of the het- technique is another facile synthetic method to fabricate type-II
erostructure. In this method, the anion or cation is transferred core/shell heterostructures. This method was proposed by Nic-
into the nanostructure, then the shell is formed in gas or olau68 in 1985. It is a heterogeneous chemical reaction at the
solution phase. In the process of cation exchange,65 external solution–solid interface on which the cations and anions are
cations enter the parent crystal at the same time as the original absorbed. This reaction is as follows: m[CLp]n+ + n[AL0 q]m
/
cations diffuse out of the crystal. For example, Konenkamp and CmAnY + mpL + nqL0 . Here, L and L0 stand for different ligands
Dloczik have proved that the oxygen component of highly and [CLp]n+and [AL0 q]m
are cations and anions. Aer each
structured ZnO lms can be replaced by S in the H2S phase and immersion, the substrate with core/shell arrays should be
rinsed by deionized water. The shell synthesized by SILAR can
achieve better photoluminescence properties than those of
shells synthesized by other methods.
For example, Lee and Yong49 fabricated CuS nanoparticle/
ZnO nanowire heterostructures on a mesh substrate. In this
process, uniform CuS NPs were deposited on the pre-grown ZnO
NWs array through SILAR. The synthesized CuS/ZnO hetero-
structured NWs exhibited superior photocatalytic activity under
visible light illumination compared with that of the pure ZnO
NWs. In addition, type-II heterostructured PbS/CdS p–n junc-
tions have also been synthesized by successive cation
exchange.69 Moreover, the photoelectrochemical activity of this
structure could be tuned by changing the size and density of the
PbS nanoparticles on the CdS nanowires. The morphology of
this nanostructure is shown in Fig. 8.

2.6 Solvothermal/hydrothermal method

The methods mentioned above are normally utilized to
synthesize core/shell structures on substrates. For the prepa-
ration of powdery type II heterostructured photocatalysts, these

Fig. 6 ZnO nanorod arrays (a) before and (b) after electrodeposition (160 nm
thick shell) with total charge of 6.7 C; ZnO nanorod arrays (c) before and (d) after
electrodeposition (11 nm thick shell) with total charge of 0.7 C. (e) Low-magni-
fication TEM image showing the uniform morphology of a single CdTe/ZnO
nanocable; (f) typical HRTEM image taken from the same CdTe/ZnO nanocable,
showing the interface and crystalline structure of the nanocable (reprinted with Fig. 7 FESEM images of (a) ZnO nanorods and (b) CdS/ZnO nanorods (reprinted
permission from ref. 48, copyright 2010 American Chemical Society). with permission from ref. 67, copyright 2012 American Chemical Society).

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Table 1 Absorbance band, PL band, current, and photocatalytic efficiency of ZnO and CdS/ZnO core/shell nanorod arrays with varying shell thickness (reprinted with
permission from ref. 57, copyright 2012 American Chemical Society)

Shell thickness Absorbance band Photocatalytic

Sample (nm) (nm) PL band (nm) Current (A) efficiency (%)

ZnO 372 380 9.22  10
7 70.0

ZnO/CdS1 10 425 460 8.09  10
6 85.0
ZnO/CdS2 15 442 473 1.62  10
5 91.5
ZnO/CdS3 30 465 490 1.75  10
5 98.0
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and (NH4)2S (microemulsion C) were successively added in the

mix solution. With simultaneous coprecipitation of Cd(NO3)2
and (NH4)2S in the water nanodroplets, CdS was coupled with
TiO2 colloids.

3 Photocatalysis properties and

applications
During the past decades, various photocatalysts have been
reported, such as TiO2, ZnO, WO3, ZnWO4, Bi2WO6, etc. The
coupling of different semiconductors will result in improved
photocatalytic activity. In type II heterostructure, excited elec-
trons on the sensitizer semiconductor can transfer to the lower
conduction band of the wide bandgap semiconductor, while
holes are conned in sensitizer semiconductor, leading to an
enhanced photocatalytic performance and an extended light
absorption spectrum. Powdery photocatalysts have been a focus
Fig. 8 (a) SEM image of PbS/CdS synthesized by a cation exchange method,
of great attention and development due to the high photo-
inset is EDX of the heterostructure. (b) TEM image showing a section of the
nanowire with islands. (c) HRTEM indicating the presence of CdS and (d) FFT
catalytic activity and relative simplicity of fabrication. However,
(SAED) pattern confirming the formation of PbS (reprinted with permission from powdery photocatalysts dispersed in solution agglomerate
ref. 69, copyright 2012 Royal Society of Chemistry). easily and are hard to separate from water. Recently, one-
dimensional (1D) semiconductor nanostructures with type II
core/shell structure grown on a substrate have made a profound
impact on the application of photocatalysis. In this section, we
methods are not the ideal choices due to the fact that powdery
review the photocatalytic properties of both powdery type II
heterostructures are always dispersed in the solution. Sol-
heterostructure photocatalysts and 1D type II core/shell
vothermal/hydrothermal methods, where the reaction occurs in
structures grown on substrates based on very commonly used
a solvent, are one of the most commonly used preparation
TiO2 and ZnO material systems. Some others photocatalysts
methods of powdery nanostructures.24,70–73 In a typical process,
like ZnWO4, Bi2WO6, a-Fe2O3, which have been intensively
the mixture of a reagent such as amines and a precursor with
studied recently, are also presented. In particular, some type II
appropriate ratio are injected in to a solvent which not only
structures which show high photocatalytic performance are
accelerates the dissolution of precursor but also speeds up the
highlighted.
reaction rate between precursor and reagent with the increase
of pressure and temperature. A pronounced advantage of this
method is that most materials can be dissolved in appropriate 3.1 Powdery photocatalysts
solvent by modulating the temperature and pressure. In the Photocatalysts are widely used in powdery form due to the high
case of the synthesis of AgIn5S8/TiO2 heterojunction nano- photocatalytic activity and relative simplicity of fabrication. A
composites,72 the mixture of TiO2, thioacetamide, AgNO3 and wide bandgap semiconductor is usually coated with a narrow
In(NO3)3$4.5H2O were dissolved in distilled water. Aer bandgap semiconductor to form a type II heterostructure. As a
adjusting the pH value of the mixed solution to 10.2, it was then result, the photoinduced charge separation efficiency and the
sealed in a Teon-lined autoclave. Keeping the temperature at solar energy utilization of semiconductor are greatly improved.
180  C for 24 h, the AgIn5S8/TiO2 heterojunction nanocomposite The morphology and geometry of heterostructure, surface
was precipitated. Interestingly, Yu and co-workers developed a texture, and particle size of the sensitizer play important roles in
microemulsion-mediated solvothermal synthetic method that interface charge transfer and photocatalytic performance.
simplies the formation of CdS/TiO2 nanocomposites.24 In 3.1.1 TiO2-based powdery type II heterostructures. TiO2
detail, titanium isopropoxide was rst added into Millipore photocatalyst is the most widely studied photocatalyst due to its
water (microemulsion A), and then Cd(NO3)2 (microemulsion B) high oxidative efficiency, photochemical stability, nontoxicity

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and low-cost.7–9 However, the high recombination ratios of

photoinduced electron–hole pairs and poor response to visible
light have hindered the application of TiO2 in photo-
catalysis.10,11 Coupling with a narrow bandgap semiconductor to
form a type II heterostructure is an effective way to improve
photocatalytic activity and extend the light adsorption spectrum
of TiO2. There has been much interest in this topic. Powdery
TiO2 type II heterostructures such as CdS/TiO2,24,74–78 CdSe/
TiO213 WS2/TiO2,29 Bi2S3/TiO279 have been reported. A chalco-
genide with narrow bandgap is widely used as a photosensitizer
to fabricate a TiO2 based heterostructure and has received much
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attention. Taking a CdS/TiO2 heterostructure as an example,

CdS, with a bandgap of 2.25 eV, can be excited by visible light to
generate electron–hole pairs, while TiO2 can only function
under the illumination of UV light. Since the CB position of CdS
is higher than that of TiO2, excited electrons on CdS can inject
into TiO2 while the holes remains in CdS as shown in Fig. 9.
Visible light generated electron transfer from CdS to TiO2
can not only enhance the charge separation efficiency but
also extend the spectral response. Liu and co-workers prepared
CdS/TiO2 semiconductor nanoparticles by microemulsion-
mediated solvothermal hydrolyzation followed by acidic pepti-
zation of the precipitate. The photocatalytic activity of the
CdS/TiO2 photocatalyst was conrmed by methylene blue (MB) Fig. 10 (a and b) TEM and HRTEM images of CdS/TiO2; (c) the MB degradation
under visible light irradiation (660 nm) in the prepared photocatalysts (reprinted
degradation under visible light irradiation (l > 420 nm).74 Yu
with permission from ref. 24, copyright 2003 Royal Society of Chemistry).
and co-workers prepared nanosized CdS-sensitized TiO2
nanocrystals via a microemulsion-mediated solvothermal
method.24 The morphologies of CdS/TiO2 are shown in Fig. 10a nanoparticles were synthesized via in situ photoreduction
and b. Compared with pure TiO2, CdS/TiO2 nanocrystals exhibit deposition by the same group.29 The quantum connement
enhanced efficiency for decomposition of methylene blue under effects of MoS2 and WS2 can cause an appropriate alternation in
visible light irradiation (Fig. 10c). Formation of Ti3+ on TiO2 the energy levels of the conduction and valence band edges,
under visible-light irradiation was demonstrated by electron making them suitable for the photosensitization of visible light
paramagnetic resonance spectrum (EPR), indicating the effec- in a coupled semiconductor system. Compared with pure TiO2,
tive photogenerated electron transfer from CB of CdS to that of MoS2/TiO2 and WS2/TiO2 heterostructures show higher photo-
TiO2. They also synthesized a CdSe/TiO2 heterostructured catalytic activity in MB and 4-chlorophenol degradation under
photocatalyst by an ultrasound-driven solution method.13 visible light irradiation (l > 400 nm).29 Besides the chalcogen-
The CdSe/TiO2 heterostructured photocatalyst shows a higher ides, there are various narrow bandgap semiconductors that
photocatalytic activity than that of pure TiO2 in the degradation can be coupled with TiO2 to form a type II heterostructure,
of 4-chlorophenol under visible light irradiation (l > 400 nm). enhancing photocatalytic performance and extending the light
The quantum size effect of CdSe plays an important role in adsorption spectrum of TiO2, such as Ag2O,80,81 CuAlO2,82
enhancing charge separation efficiency and photocatalytic LaVO4,28 AgIn5S8,83 V2O5.84
activity of the CdSe/TiO2 heterostructured photocatalyst.13 In addition, type II heterostructures can combine with
Moreover, MoS2 and WS2 nanocluster sensitized TiO2 another material to form ternary hybrid catalysts. For example,
TiO2 type II heterostructures usually combine with noble metals
to enhance the photocatalytic activity in hydrogen production.85
In the CdS/TiO2/Pt system, the formation of the potential
gradient at the interface between CdS and TiO2 and the Pt
fabrication method play important roles in determining the
hydrogen production efficiency.85
3.1.2 ZnO-based powdery type II heterostructures.
Although TiO2 is the most widely employed photocatalyst, ZnO
appears to be a suitable alternative to TiO2. ZnO is also relatively
inexpensive and its photodegradation mechanism is similar to
that of TiO2.86 Moreover, some reports pointed out that ZnO
exhibits a higher efficiency than TiO2 in the photocatalytic
degradation of some dyes in water.87–89 Coupling with a narrow
Fig. 9 Schematic illustration of charge transfer in CdS/TiO2 heterostructure. bandgap semiconductor is an effective way to enhance the

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charge separation efficiency and improve the utilization of solar

light of ZnO, such as C3N4,25 ZnSe,90 In2O3,91 etc. Lee and co-
workers synthesized three distinct type II ZnSe/ZnO hetero-
structures through simple solution-based surface modication
reactions.90 The morphologies of three distinct type ZnSe/ZnO
heterostructures are shown in Fig. 11a. Compared with pure
ZnO structure, these ZnSe/ZnO heterostructures showed higher
photocatalytic activities in orange-II degradation under visible
light irradiation (Fig. 11b). The group also investigated the
effect of the morphologies and exposed crystal faces of ZnO on
the photocatalytic activity. Yu and co-workers synthesized
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In2O3/ZnO heteronanostructures by a coprecipitation method.91

The photocatalytic activity of In2O3/ZnO heterostructures was
demonstrated to be higher than that of pure ZnO due to the
enhanced charge separation and transport of the type II heter-
Fig. 12 Photocatalytic degradation of MB over ZnO and C3N4/ZnO photo-
ostructure. Different compositions and annealing temperatures
catalysts: (a) under UV light irradiation and (b) under visible light irradiation
affect the photocatalytic activities. The highest photocatalytic (visible light region in the range of 400–800 nm; the main wavelength is about
activity was obtained when annealing at 800  C with a Zn/In 550 nm); schematic drawing illustrating the mechanism of charge separation of
ratio of 1 : 1. It is worth pointing out that ZnO has low stability C3N4/ZnO photocatalyst: (c) under UV light irradiation and (d) under visible light
under long reaction times due to photocorrosion, and some irradiation (reprinted with permission from ref. 25, copyright 2011 Royal Society
effort has been devoted to inhibiting photocorrosion. of Chemistry).

Zhu and co-workers fabricated a type II graphite-like C3N4/

ZnO heterostructure.25 Aer coupling with C3N4, the photocur-
rent and photocatalytic activity of ZnO were both greatly ZnWO4. Our group synthesized ZnWO4 nanorods by a hydro-
enhanced under UV and visible light irradiation (Fig. 12a and thermal method,26 and then prepared a C3N4/ZnWO4 hetero-
b). Moreover, the photocorrosion of ZnO was successfully sup- structure via chemisorptions (Fig. 13a and b). As shown in
pressed in the C3N4/ZnO heterostructure. The photocorrosion Fig. 13c, a loading amount of 5% C3N4 over ZnWO4 leads to an
of ZnO is caused by photoinduced dissolution due to hole 80% increase in the photocatalytic activity under UV light irra-
oxidation. Since the VB position of ZnO is lower than that of the diation. The enhanced UV light photocatalytic activity could be
C3N4, the photogenerated holes on ZnO could directly transfer attributed to the high separation efficiency of the photo-
to C3N4, leading to an effective photocorrosion inhibition generated charge pairs due to the type II heterostructure
(Fig. 12c). As shown in Fig. 12d, the visible photoactivity of between C3N4 and ZnWO4. Visible light activity of C3N4/ZnWO4
C3N4/ZnO heterostructure originates from the injection of was observed, which originated from the injection of excited
excited electrons from CB of C3N4 to the CB of ZnO. electrons from the CB of C3N4 to the CB of ZnWO4 (Fig. 13d).
3.1.3 Other powdery type II heterostructures. Besides TiO2
and ZnO, there are also many other semiconductors with
excellent photocatalytic properties that have been intensively
studied recently, such as Fe2O3,92,93 WO3,94 Bi2WO6,27,95
ZnWO4,26,96 and BiPO4.97,98 ZnWO4 has received considerable
attention as UV light driven photocatalysts due to their relatively
high activities for degradation of organic compounds.26 It is
important to develop novel methods for the improvement of the
photocatalytic activity and solar energy utilization efficiency of

Fig. 13 The morphology of ZnWO4 and C3N4/ZnWO4 photocatalysts: (a)

ZnWO4 (b) C3N4/ZnWO4; pseudo-first-order rates of MB degradation over
Fig. 11 (a) SEM images of ZnO/ZnSe heterostructures; (b) schematic diagram ZnWO4 and C3N4/ZnWO4 photocatalysts: (c) under UV light irradiation (l ¼
showing the energy band structures of a ZnO/ZnSe heterostructure (reprinted 254 nm) (d) under visible light irradiation (l > 420 nm) (reprinted with permission
with permission from ref. 90, copyright 2011 American Chemical Society). from ref. 26, copyright 2012 Royal Society of Chemistry).

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BiPO4 as an oxoacid salt photocatalyst has been reported to have Signicantly, Yang and co-workers synthesized Z-scheme
an excellent photocatalytic activity under UV light irradiation. type CdS/Au/TiO2 hollow nanorod arrays (THNAs) on glass
Zhu and co-workers fabricated a C3N4/BiPO4 core/shell struc- substrates by co-modifying TiO2 nanorods with Au and CdS
ture via an ultrasonic dispersion method.98 Aer coupling with nanoparticles.111 Ultraviolet-visible absorption spectra showed a
C3N4, the UV light photocatalytic activity of BiPO4 was greatly red shi to 585 nm due to the strong electromagnetic coupling
enhanced and visible light photocatalytic activity was generated of Au and CdS compared with the pure TiO2 nanorod arrays and
due to the type II structure. Recently, many new visible-light- single Au or CdS nanoparticles. The CdS/Au/THNAs three-
active photocatalysts have been reported to have good photo- component nanojunction also exhibited enhanced photo-
catalytic performance, such as Bi2WO6,27,95 BiVO4,99 and catalytic activity. Using this kind of three-component nano-
InVO4.100 The formation of type II structure is also an effective junction photocatalyst, the content of MB reduced by 72% aer
way to enhance the photocatalytic activity of visible-light-active 2 h which is much more than that (15%) of pure THNAs under
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photocatalysts. It has been reported that a C3N4/Bi2WO6 pho- the same conditions.
tocatalyst has higher photocatalytic activity than that of Some ternary compounds are also used to modify TiO2 to get
pure Bi2WO6.27 The enhanced photocatalytic activity of the continuously adjustable spectral absorption by controlling the
C3N4/Bi2WO6 photocatalyst could be attributed to the components. Park and co-workers reported that the TiO2
enhanced charge separation efficiency due to the type II struc- nanocable arrays coated by an Se-rich composition (CdS/CdSSe/
ture. A Bi2S3/Bi2WO6 heterostructure was prepared to overcome CdSe multishell structures) showed excellent solar photocur-
the drawback of low photocatalytic efficiency and narrow pho- rents and hydrogen generation rates.112 They also studied the
toresponse range of Bi2WO6.101 The Bi2S3/Bi2WO6 hetero- photoelectric conversion efficiency of samples shelled with
structure possesses a wide photoabsorption until 800 nm and different compositions. It was conrmed that the CdS/CdSSe/
shows a higher photocatalytic activity for phenol degradation CdSe multishell structures gained higher photoelectric conver-
than that of pure Bi2WO6. sion efficiency than that of CdSe and CdS.
In addition to TiO2 nanowire arrays, TiO2 nanotube arrays
have also been used for type II band structures by decorating
with CdS (ref. 113) and SrTiO3.114 Lin and co-workers used free-
3.2 1D type II core/shell photocatalysts standing open-ended TiO2 nanotube membranes to degrade
Compared with powder photocatalysts, one-dimensional (1D) RhB, and then fabricated compound nanocables by stuffing the
semiconductor nanostructures with type II core/shell structures membrane with CdS.113 Fig. 14 shows the setup used for ow-
grown on substrates have made a profound impact on the through photocatalysis experiments and the way in which the
application of photocatalysts because they effectively avoid CdS is loaded. CdS/TiO2 nanocomposites show higher photo-
agglomeration and possess a direct electrical pathway for the catalytic degradation activity compared with that of bare TiO2
rapid transport of photogenerated carriers to the photo- nanotubes. The results suggest that the load of CdS increases
electrode.102–104 The core is usually coated with a uniform shell light absorption of the CdS/TiO2 nanocomposites and, mean-
and consequently a large interfacial area is formed in the while, enhances the carrier separation efficiency. Furthermore,
interlayer, which ensures rapid charge separation. As a result, N and F codoped TiO2 nanotube arrays coupled with PbO
the nonradiative recombination of the electrons with electrolyte nanoparticles showed signicant enhancement on the photo-
is inhibited and corrosion of core nanowires is prevented from catalytic degradation of organic pollutants due to the opto-
electrolyte.105 Sometimes, the shell is substituted by quantum electronic cooperation between TiO2 and PbO.115 Also, based on
dots, which has been conrmed as a promising alternative to the same mechanism, this enhanced photocatalytic degrada-
photosensitive dyes.106 They can produce multiple electron–hole tion has been realized with a CdSe nanoparticle-decorated TiO2
pairs per photon and thus enhance the photoconversion nanotube array.116
efficiency.107
3.2.1 TiO2-based type II core/shell structure nanowire
arrays. Compared with TiO2 lm, TiO2 nanowire arrays have
larger surface area, which improves the light absorption effi-
ciency. Aer decoration with small bandgap semiconductor
quantum dots, the light absorption efficiency is further
enhanced. For example, the formation of CdS quantum dots on
vertically aligned TiO2 nanorods make the photocurrent of the
composite 28.6 times higher than that of a pure TiO2 nanorod
array.108 In addition, Li and co-workers demonstrated that a CdS
quantum dot-decorated TiO2 nanowire array showed an
enhanced photoactivity in the entire wavelength region from
350 to 550 nm.109 Similar improved photoelectrochemical
performance has also been achieved on a CdS nanoparticle-
sensitized TiO2 nanorod array grown by a hydrothermal Fig. 14 Schematic of applications of free-standing open-ended TiO2 nanotube
method.110 membranes (reprinted with permission from ref. 113, copyright 2012 Elsevier).

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Furthermore, compared with single shell nanostructures, a wavelength of 800 nm. A photocurrent density as high as
double-shell TiO2 nanostructures further improve photo- 11 mA cm
2 at
0.5 V (vs. SCE) under 1.5 AM irradiation was
electrochemical (PEC) properties, as reported by Xiao and co- achieved. This kind of enhanced light harvesting is obviously
workers.117 Cu2O could absorb a wide range of visible light due attributed to the synergy between WOx/ZnO and CdSe/CdS as
to its narrow band gap (<2 eV), but it's difficult to use for water well as the formation of type II core/shell structure. Fig. 16b and
splitting due to its weak stability in solution. Xiao and co- c show current density of CdSe/CdS/WOx/ZnO under chopped
workers prepared TiO2/CuO/Cu2O nanowire arrays on Au-coated illumination.
copper substrates through controlled air annealing of the In addition to quantum dots, a more commonly used deco-
electrodeposited Cu nanowires and then dip coating with TiO2. ration is the uniform nanoscale shell. For example, a ZnO
The step-by-step enhancement of charge separation efficiency is nanowire array coated with a CdTe shell demonstrated a
indicated in the electrochemical impedance spectra (EIS) data photocurrent density of 5.9 mA cm
2 under visible light illu-
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in Fig.15a. Fig. 15b shows the energy band diagram of TiO2/ mination of 100 mW cm
2 at zero bias potential. The authors
CuO/Cu2O nanowire arrays and also the charge transfer route in suggested that the favorable absorption of CdTe and the type II
electrolyte solution. band alignment contributed to the excellent performance of
3.2.2 ZnO-based type II core/shell nanowire arrays. this photoelectrode.48 Furthermore, our group recently
Compared with TiO2, ZnO possesses a higher electron mobility successfully fabricated ZnSxSe1
x/ZnO core/shell nanowires via
and longer photoexcited electron lifetime.118 Thus, it is a two-step CVD method. The obtained core/shell structure
considered as a promising alternative to TiO2. Indeed, coupling showed a signicant improvement of visible light absorption
with a small bandgap semiconductor quantum dots, ZnO-based efficiency. It was explicitly demonstrated that the introduction
type II core/shell nanowire array photocatalysts have shown of a ZnSxSe1
x shell to ZnO nanowires profoundly improved the
high-performance photocatalytic properties. For example, photogenerated charge separation process.44
signicant photocurrent and efficiency were obtained on a ZnO Based on the similar mechanism, there are also other 1D
nanowire array sensitized by CdTe quantum dots.32 This is core/shell examples like CdSSe/ZnO.50 However, these works
because a type II core/shell structure was formed by coating the paid more attention to the manipulation of electronic structure.
CdTe quantum dots on the ZnO nanowires. In addition, the One method is to tailor the composition of the shell through
stability of the overall water-splitting reaction was increased controlling the synthetic process, and thus a tunable band gap
because the employment of CdTe avoided anodic decomposi- can be achieved, which results in the continuous absorption of
tion and corrosion. Therefore, the electrochemical reaction the solar spectrum. For example, ZnxCd1
xSe/ZnO core/shell
performance was enhanced. The photoconversion efficiency nanowire arrays which were synthesized by temperature-
(1.83%) was more than 200% higher than that of pristine ZnO gradient CVD yielded a continuous absorption edge from 2.7 to
nanowires. Similarly, a CdS nanoparticle/ZnO nanowire array 1.77 eV across the sample surface by adjusting the Zn compo-
also showed enhanced photocurrent characteristics compared sition.35 This core/shell nanowire array showed photocurrent
with the photoelectrode cell of a bare ZnO nanowire array, density of 5.6 mA cm
2 under 1 sun solar light illumination at
owing to their higher visible-light absorption capability and zero bias versus Ag/AgCl. Another example is the ZnxCd1
xS/ZnO
charge carrier transfer efficiency.30,31 An Al-doped ZnO nanorod core/shell nanorod array whose shell also showed a tunable
array decorated with PbS nanoparticles also showed excellent band gap from 2.52 to 3.11 eV.47 They exhibited a high photo-
photocatalytic properties.119 catalytic activity and good stability in the degradation of the
Recently, highly efficient photoelectrochemical hydrogen methylorange.
generation has been demonstrated on hierarchical WOx/ZnO Another method is to change the element ratio of the inter-
nanowires by cosensitizing CdSe and CdS as shown in mediate layer so that exciton generation and separation were
Fig. 16a.120 The support of the CdSe shell and CdS nanoparticles facilitated. For example, due to the formation of a CdZnSSe
extended the light absorption of the WOx/ZnO nanowire array to intermediate layer, CdSSe/ZnO core/shell nanowire showed

Fig. 15 (a) EIS data of Cu2O, Cu2O/CuO and Cu2O/CuO/TiO2 nanowire array based photocathodes both in the dark and under light; (b) energy band diagram and
charge transfer for Cu2O/CuO/TiO2 (reprinted with permission from ref. 117, copyright 2013 Royal Society of Chemistry).

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Nanoscale Review

pure ZnO nanowires. In addition, aer annealing, the absorp-

tion of UV became weak while visible light absorption was
enhanced due to the low diffusion of Zn atoms into the V2O5
layer. To further improve photoelectrochemical hydrogen
generation, a double-shell structure such as CdSe/CdS has been
used to decorate ZnO nanowire arrays.122 This fabrication
lengthens the absorbance spectra of ZnO NWs array to 700 nm.
The PEC performance of pure ZnO NWs, CdS/ZnO NWs, CdSe/
CdS/ZnO NWs also demonstrated a step by step enhancement.
3.2.3 Other kinds of nanowire array-based type II core/shell
heterostructures. Recently, a-Fe2O3 has been widely explored as
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photocatalyst due to its favorable optical band gap (2.1 eV),

natural abundance, low cost, and good chemical stability.123,124
However, its practical applications are limited because of its
small absorption coefficient and the low carrier mobility. To
solve this problem, Feng and co-workers constructed a type II
heterojunction between a-Fe2O3 and BiV1
xMoxO4. A graphene
sheet, which has excellent charge carrier mobility, was utilized
as the electron mediator. The BiV1
xMoxO4/graphene/a-Fe2O3
core/shell heterojunction array yielded a pronounced photo-
current density of 1.97 mA cm
2 at 1.0 V vs. Ag/AgCl and a
high photoconversion efficiency of 0.53% at
0.04 V vs. Ag/
AgCl under the irradiation of a Xe lamp as shown in Fig. 17c and
d.34 This demonstrated that the graphene sheet behaves as an
electron and hole conductor, which accelerated the electron–
hole separation as shown in Fig. 17b. Fig. 17a is the top view
SEM image of BiV1
xMoxO4/graphene/a-Fe2O3 core/shell.
In visible light driven photocatalytic systems, Si nanowire
was also used as the core owing to its relatively high conduction
band and valence band. Semiconductor materials with wide
bandgap were used as the shell, such as TiO2,125,126 ZnO,127
ZnSe.128 As discussed in Xie's work, p-Si nanowires/TiO2 het-
erojunction arrays as the photocathode could utilize the visible

Fig. 16 (a) Schematic of the photoelectrochemical hydrogen generation system

based on CdSe/CdS/WOx/ZnO; (b) current density as a function of potential
under chopped illumination (100 mW cm
2) of (black) as-prepared WOx nano-
whiskers, (red) WOx/ZnO, (blue) CdS/WOx/ZnO, and (green) CdSe/CdS/WOx/
ZnO; (c) comparison of J–E curves of CdSe/CdS/WOx/ZnO and CdSe/CdS/ZnO
under chopped illumination (reprinted with permission from ref. 120, copyright
2011 American Chemical Society).

higher photocurrent and hydrogen generation rate than that of

CdS/TiO2 under AM 1.5 G conditions.50 The authors believe that
Zn containing alloy layers in the interface region improved the
epitaxial growth of single-crystalline shell layers on the ZnO
nanowire core by the way of reducing the lattice mismatch and
the number of defect sites.
Some other narrow band gap semiconductor materials, such
as V2O5 whose band gap is 2.2 eV covering visible light range,
have also been used to decorate ZnO.121 In the example of a Fig. 17 (a) Top SEM image of BiV1
xMoxO4/graphene/a-Fe2O3 core/shell; (b)
schematic of energy band structure of BiV1
xMoxO4/graphene/a-Fe2O3 core/
V2O5-sensitized ZnO nanowire array, a ZnO nanowire array was
shell; (c) potential-dependent photocurrent density and (d) photoconversion
rst synthesized by a hydrothermal growth process, and then efficiency as a function of applied potential of a-Fe2O3, RGO/a-Fe2O3, BiV1
x-
coated with V2O5 by magnetron sputtering. The absorption edge MoxO4/graphene/a-Fe2O3 (reprinted with permission from ref. 34, copyright
of the V2O5/ZnO core/shell structure was longer than that of 2012 American Chemical Society).

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light including wavelengths longer than 600 nm.125 They used p- nanoscale heterostructured photocatalysts, production by these
Si as the under-layer to construct a p–n heterojunction with n- methods is far from sufficient for industrial applications. In
type TiO2 so that the semiconductors with narrow band gap addition, type II heterostructured nanomaterials still suffer
could capture most of the sunlight photons to generate more from chemical instability, which severely decreases the effi-
photoelectrons for pollutant decomposition. The results show ciency of the photocatalysts. Even the safety and the secondary
that the degradation efficiency of phenol reached 80.7% in 100 pollution to the environment of nanoscale photocatalysts are
min under visible light owing to the synergy between the elec- still ambiguous. All in all, researchers all around the world need
trochemical process and the photocatalytic process. Later, to carry out systematic and careful experimental studies and
Wang and co-workers demonstrated a mace-like core/shell thus establish general and rational design guidelines in fabri-
three-dimensional (3D) nanorod network. In this network, the cating type II heterostructured nanoscale photocatalysts.
core array is composed of Si nanowires and the TiO2 nanorods
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were grown vertically on the frame.126 This unique structure Acknowledgements

gained a PEC efficiency of 2.1% which is three times higher than
that of the TiO2 lm/Si nanowire structure. This work was supported by the 973 Program of Ministry of
Based on a similar principle, Chen and co-workers obtained Science and Technology of China (no. 2012CB934103) and the
ZnO/Si core/shell nanowire arrays with about 8% optical 100-Talents Program of the Chinese Academy of Sciences (no.
reectance in the visible region, which results in good optical Y1172911ZX).
absorption.127 They also studied the water splitting performance
of ZnO/Si nanowire arrays. It was conrmed that the ZnO/Si Notes and references
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