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www.rsc.org/materials | Journal of Materials Chemistry

Solar hydrogen production with nanostructured metal oxides

Roel van de Krol,* Yongqi Liang and Joop Schoonman

Published on 11 March 2008. Downloaded by Chungnam National University on 04/05/2014 19:02:26.

Received 10th December 2007, Accepted 18th February 2008

First published as an Advance Article on the web 11th March 2008
DOI: 10.1039/b718969a
The direct conversion of solar energy into hydrogen represents an attractive but challenging alternative
for photo-voltaic solar cells. Several metal oxide semiconductors are able to split water into hydrogen
and oxygen upon illumination, but the efficiencies are still (too) low. The operating principles of
photo-electrochemical devices for water splitting, their main bottlenecks, and the various device
concepts will be reviewed. Materials properties play a key role, and the advantages and pitfalls of the
use of interfacial layers and dopants will be discussed. Special attention will be given to recent progress
made in the synthesis of nanostructured metal oxides with high aspect ratios, such as nanowire arrays,
which offers new opportunities to develop efficient photo-active materials for solar water splitting.

Introduction
Growing environmental concerns and an increasing energy
demand drive the search for new, sustainable sources of energy.
In 2001, the global energy consumption rate was 13.5 TW, of
which more than 85% originated from fossil fuels.1 To meet
future demands, which are estimated to reach 27 TW in 2050,
new sustainable energy sources have to be found. While no single
source will be able to meet all our energy needs, solar energy may
go a long way to meet this formidable challenge.2 With 120 000
TW of solar energy striking the surface of the earth at any given
moment, it is by far the most abundant clean energy source
available. Most energy sources that are currently being scrutinized (fossil fuels, wind, tide, hydropower, biomass) originate
from solar energy. However, direct use of solar energy by e.g.
solar thermal power or photo-voltaic solar cells is still limited,
and only 0.04% of all energy is generated by photo-voltaics. By
covering 0.16% of the surface of the earth with 10% efficient
solar cells, 20 TWpeak of power could be generated.2 While
0.16% appears to be a small number, it should be realized that
this corresponds to the surface areas of France and Germany
Delft University of Technology, Faculty of Applied Sciences, Department
DelftChemTech / Materials for Energy Conversion and Storage
(MECS), P.O. Box 5045, 2600 GA Delft, The Netherlands. E-mail:
r.vandekrol@tudelft.nl; Fax: +31-15-2788668; Tel: +31-15-2782659
This paper is part of a Journal of Materials Chemistry theme issue on
hydrogen storage and generation. Guest editor: John Irvine.

Dr Roel van de Krol received his PhD

degree at Delft University of Technology
(TUD). After a postdoc fellowship at
MIT, he returned to TUD where he is
currently an assistant professor. His main
interest is in the solid state chemistry of
metal oxides. His current research focuses
on nanostructured photo-electrodes and
photo-catalysts for water splitting and
degradation of pollutants.

combined. Covering such a large area with solar cells presents

a daunting task, even when this is undertaken on a (de-centralized) global scale. Interestingly, the solar cell market is currently
growing by 3540% per year, and is one of todays fastest
growing markets. With a total produced capacity of 1200
MWpeak reported for 2004,2 a sustained 35% annual growth
rate would lead to a total installed capacity of 20 TWpeak in 2036.
One of the challenges with solar cells is that they only generate
electricity during daytime. Hence, large-scale use of solar energy
requires an efficient energy storage solution. So far, the only
practical way to store such large amounts of energy is in the
form of a chemical energy carrier, i.e., a fuel. Hydrogen is one
of the prime candidates as a future energy carrier. It can be
made by electrolysis of water, and upon combustion in a fuel
cell it returns to its original form (water) without generating
any harmful by-products. The future prospect of a so-called
Hydrogen Economy has attracted much interest, and many
research efforts are currently underway to develop new technologies for the production, storage, utilization, and transport of
hydrogen.
The most straightforward method to produce hydrogen from
water and sunlight is by coupling an electrolyzer to a solar cell
array. The current generation of commercially available electrolyzers have electricity-to-hydrogen conversion efficiencies of up
to 85%, which seems to make this an attractive route. However,
to achieve a current density of
1 A cm2 that is normally used in
electrolyzers, a cell voltage of 1.9 V is required. Since the

Dr Yongqi Liang received his PhD degree

on physical chemistry from Peking University (Beijing, China) in 2005. He is
currently a postdoctoral fellow at Delft
University of Technology, where he works
on photo-electrochemical H2 generation
with metal oxides. His main research interests are on the application of nanostructured materials (nanowires, nanotubes)
in energy conversion technologies.

This journal is The Royal Society of Chemistry 2008

Joop Schoonman is a professor of Inorganic Chemistry at Delft University of

Technology. He has several honorary
degrees at universities in Romania and
Poland, and has been a visiting professor
at Stanford University since 2004. His
research interests include gas-phase
synthesis and defect chemistry of nanostructured materials for energy conversion
and storage, and ceramic membranes for
gas separation.
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thermodynamic potential required for splitting water into

hydrogen and oxygen is 1.23 eV, the overall energy conversion
efficiency has an upper limit of 65% (1.23/1.9). When combining
the electrolyzer with a 12% solar cell, the overall conversion
efficiency is limited to
8%.3
A potentially more attractive route is the use of photo-electrochemical cells. Here, the photo-active semiconductor is immersed
in water and the photo-generated electrons and electron-holes are
directly used to reduce and oxidize water, respectively. Since the
photo-active area is the same as the electrochemically active
area, much smaller current densities are allowed (1030 mA
cm2). This results in lower overpotentials and higher overall
energy conversion efficiencies.3 Moreover, the functions of solar
cell and electrolyser are now combined in a single device, which
is favourable in terms of packaging and overall systems costs.
This paper will start by describing the operating principles of
photo-electrochemical devices for water splitting. The requirements on the materials properties will be discussed in detail,
and we will outline how different device concepts, materials
combinations, and purpose-built nano-architectures can be
used to overcome some of the limitations imposed by conventional materials.

Photo-electrochemical water splitting

The principle of operation for a photo-electrochemical cell
(PEC) for water splitting is presented in the energy diagram of
Fig. 1. When the material is illuminated with photons that
have an energy that is equal to or larger than the bandgap,
electrons are excited from the valence band into the conduction
band. In an n-type semiconductor, the electrons travel to the
back contact and are transported to the counter electrode where
they reduce water to form hydrogen gas. The electron-holes that
remain in the valence band migrate to the surface, where they
oxidize water to form oxygen gas.
The recombination of electrons and holes is prevented by the
presence of an electric field close to the surface of the semiconductor. This field, indicated by a bending of the energy bands
in Fig. 1, is formed during the formation of a Schottky-type
contact between the semiconductor and the aqueous electrolyte.4
During the formation of the Schottky contact, free electrons
from the bulk are trapped into surface states at the semiconductor/electrolyte interface. This sheet of negative charge is

Fig. 1 Energy diagram of a PEC cell for the photo-electrolysis of water.

The cell is based on an n-type semiconducting photo-anode.

2312 | J. Mater. Chem., 2008, 18, 23112320

compensated by the remaining positive charges in the bulk,

i.e., the ionized (shallow) donors.
Assuming that all the current that flows through the outer
circuit corresponds to the water splitting reaction (i.e., absence
of any competing side reactions), the overall solar-to-hydrogen
conversion efficiency of the device can be determined from the
following expression:
jVredox  VB
hSTH
(1)
Plight
Here, j is the photo-current density (A m2), Plight is the incident
light intensity in W m2, Vredox is the potential required for water
splitting, and VB is the bias voltage that can be added in series
with the two electrodes in order to assist the water splitting
reaction (Fig. 1). Vredox is usually taken to be 1.23 eV (at room
temperature) based on a Gibbs free energy change for water
splitting of 237 kJ mol1. Alternatively, the enthalpy change
(286 kJ mol1) is sometimes used, which corresponds to a redox
potential of 1.48 eV. There is some debate on which of these
values is the more appropriate one for photo-electrolysis.
Usually, the Gibbs free energy value is used which results in
more conservative efficiency numbers.
Suitable photo-electrode materials for efficient solar hydrogen
generation have to fulfil the following requirements:
1. Strong (visible) light absorption
2. High chemical stability in the dark and under illumination
3. Suitable band edge positions to enable reduction/oxidation
of water
4. Efficient charge transport in the semiconductor
5. Low overpotentials for the reduction/oxidation reactions
6. Low cost
The spectral region in which the semiconductor absorbs light
is determined by the bandgap of the material. The minimum
bandgap is determined by the energy required to split water
(1.23 eV) plus the thermodynamic losses (
0.4 eV)5 and the
overpotentials that are required at various points in the system
to ensure sufficiently fast reaction kinetics (
0.30.4 eV).6,7 As
a result, the bandgap should be at least 1.9 eV, which corresponds to an absorption onset at
650 nm. The maximum value
of the bandgap is determined by the solar spectrum shown in
Fig. 2. Below 400 nm the intensity of sunlight drops rapidly,
imposing an upper limit of
3.1 eV on the bandgap. Hence,
the optimum value of the bandgap should be somewhere
between 1.9 and 3.1 eV, which is within the visible range of the
solar spectrum.
Several authors have made predictions for the maximum
attainable efficiency based on the bandgap of the material, the
solar spectrum, and estimated values for the thermodynamic
losses, overpotentials, optical reflection losses, etc.57 Most
recently, Murphy et al. predicted a maximum efficiency of
16.8% for a hypothetically ideal material with a bandgap of
2.03 eV.7 Higher efficiencies can be obtained by using
a multiple-bandgap system (see section on tandem cells below).
The second requirement, the stability against (photo-)corrosion, is a severe one that limits the usefulness of many
photo-active materials. Most non-oxide semiconductors, such
as Si, GaAs, GaP, CdS, etc. either dissolve or form a thin oxide
film which prevents electron transfer across the semiconductor/
electrolyte interface. Almost all metal oxide photo-anodes are
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Fig. 2 Intensity of sunlight versus wavelength for AM1.5 conditions.

The grey area represents the part of the spectrum that can be absorbed
by a hypothetically ideal bandgap of 2.03 eV.7

thermodynamically unstable, which means that the photo-generated holes are able to oxidize the semiconductor.4 However, if
the kinetics of charge transfer across the interface (oxidation of
water) are faster than the anodic decomposition reaction,
photo-corrosion is avoided. For example, TiO2 and SnO2 show
excellent stability over a wide range of pH values and applied
potentials, while ZnO always decomposes in aqueous environments upon illumination. Fe2O3 represents an intermediate
case, for which the stability appears to depend on the presence
of dopants, pH, and oxygen stoichiometry.8,9 The general trend
is that wide-bandgap metal oxide semiconductors are stable
against photo-corrosion, while small bandgap semiconductors
are not. While this is in obvious conflict with the requirement

of visible-light absorption, it does not represent a fundamental

limitation.
The third requirement implies that the conduction and valence
band edges should straddle the reduction and oxidation potentials of water. Specifically, EC should be above Ered(H2/H+) and
EV should be below Eox(OH/O2). Fig. 3 shows the band-edge
positions of various semiconductors, along with the reduction
and oxidation potentials of water. It should be noted that the
data in Fig. 3 are drawn for a pH of 14, and that the reduction
and oxidation potentials of water vary with 59 mV per pH
unit. Most metal oxides (and even several non-oxide semiconductors) also show a 59 mV pH1 variation in the flatband
potential.17 For these materials, the band positions do not
move with respect to Ered(H2/H+) and Eox(OH/O2) and the
diagram can also be used at different pH values. Fig. 3 indicates
that most non-oxide semiconductors are able to reduce, but not
oxidize water. Conversely, most oxide semiconductors are able
to oxidize, but not reduce water. Since the stability criterion
favors oxide semiconductors, the reduction of water appears to
be challenging. In most cases, an externally applied voltage or
a separate electrode compartment with a different pH is necessary to assist the reduction reaction.18 Indeed, only a few metal
oxides have been demonstrated to be able to evolve both oxygen
and hydrogen, and only SrTiO3 has been shown to photo-cleave
water in a two-electrode system without any assistance.19 The
efficiency was, however, less than 1% due to the large bandgap
of the material (3.2 eV).
The fourth requirement, that of efficient charge transport, is
easily fulfilled by some materials, while in others it is the main
cause of poor overall conversion efficiencies. The intrinsic
electron and hole mobilities are determined by the electronic
structure of the material.20 The conduction and valence band
of most (but not all) metal oxides are primarily composed of

Fig. 3 Energy band positions for various semiconductors at pH 14.4,1016 When no experimental data were available for this pH, the band positions
were extrapolated using 59 mV per pH unit. It should be noted that values reported in the literature show significant scatter, up to a few tenths of
a volt. Most values shown here are for polycrystalline films, obtained using capacitance (MottSchottky) measurements and corrected for the difference
between the flatband potential and the conduction band.

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metal 3d orbitals and oxygen 2 p orbitals, respectively.21 Hence,

extensive overlap of the metal 3d orbitals will lead to high
electron mobilities, while the amount of overlap between the
O-2p orbitals determines the hole mobility. While orbital overlap
arguments may provide some initial guidelines for evaluating the
charge transport properties of a material, extrinsic factors such
as the presence of defects often play a much more important
role. Shallow donors or acceptors enhance the conductivity of
a semiconductor, whereas defects with deeper lying energy levels
usually act as recombination centers.
The fifth requirement implies that hole transfer across the
n-type semiconductor/electrolyte interface should be sufficiently
fast in order to compete with the anodic decomposition reaction.
Furthermore, it should also be fast enough to avoid the accumulation of holes at the surface, as this would lead to a decrease of
the electric field and a concomitant increase in electronhole
recombination. To improve the kinetics of hole transfer, catalytically active surface species can be added. Perhaps the best
known example of an effective oxygen evolution catalyst is
RuO2, whereas Pt is usually employed as a catalyst for hydrogen
evolution.4,22

Photo-anode materials
In the above, we have outlined the basic working principles of
photo-electrochemical cells and identified the main materials
requirements. Despite extensive research efforts, mainly in the
1970s and early 1980s, no photo-active material has yet been
found that fulfils all these requirements. However, the exciting
progress made in the field of nanostructured materials during
the last decade offers new opportunities for solar water splitting.
We will illustrate this by discussing recent developments for two
widely studied photo-anode materials, TiO2 and Fe2O3.
TiO2 has been the most extensively investigated material for
photo-electrochemical and photo-catalytic applications. The
main reason for its popularity is its excellent chemical stability,
its low cost, and the fact that it is widely available. It is by far
the most popular material for photo-catalytic oxidation of
organic compounds in e.g. water purification. Efforts to use
this material in a photo-electrochemical device date back to
1972, with the publication of Fujishima and Hondas landmark
paper in which they first demonstrated the possibility to split
water by shining light on a semiconducting photo-anode.18 Since
TiO2 only absorbs UV light due to its bandgap of 3.2 eV, most
research efforts were aimed at shifting the optical absorption
towards the visible part of the spectrum. Some success has
been achieved by doping the material with various transition
metal ions, such as Fe and Cr.23,24 These dopants introduce
additional energy levels in the bandgap, and excitation from
these levels to the conduction band requires less energy than
excitation of valence band electrons.
Although cation doping indeed results in a visible-light
response, the absorption coefficient is usually very small due to
low dopant concentrations (limited solubility) and small absorption cross-sections. To address this, work in our laboratory has
focused on developing highly structured TiO2 photo-electrodes.25 The SEM image in Fig. 4a shows an example of a Cr
and Fe co-doped TiO2 film made by chemical vapor deposition
(CVD). Extensive light scattering in such a morphology
2314 | J. Mater. Chem., 2008, 18, 23112320

Fig. 4 Scanning electron micrographs of: A) fractal-shaped TiO2

deposited by chemical vapour deposition; B) Fe2O3 nanobelts obtained
by oxidizing Fe foil at 800  C in air; C) and D) Fe2O3 nanoflakes
obtained by oxidizing Fe foil at 450  C in air; E) 100 nm Fe2O3 film
obtained by thermal oxidation of an electrodeposited Fe film at 450  C
in air; F) same as E) but for a film with twice the thickness.

enhances the absorption coefficient, while the high aspect ratio

of these fractal-like structures ensures that the photo-generated
holes have to travel only short distances before reaching the
surface. This minimizes the chance for charge trapping and
recombination. The first fractal-shaped TiO2 electrodes did not
generate any photo-current under visible light, although sensitisation with Ru-based dye molecules resulted in a solar cell with
an efficiency of 2.7%.25 Recently, however, we showed that
fractal-shaped TiO2 can also generate photo-currents under
visible light illumination by co-doping with Fe and Cr.26 Fig. 5
reveals that fractal-shaped TiO2 films have a remarkably
enhanced visible light response compared to undoped, dense
TiO2. This enhancement is many times higher than observed
for dense, smooth TiO2 films doped with Fe and Cr, indicating
that the nanostructured morphology plays a crucial role. Fig. 5
also shows that the enhanced absorption of visible light comes
at the cost of lower absorption at wavelengths below 350 nm.
This is attributed to the shorter penetration depth of the light
at these wavelengths, which leads to longer distances that the
electrons have to travel before reaching the back contact and
a higher chance of recombination at defect sites. An interesting
(though unfavourable) phenomenon observed for these fractalshaped films is that extensive degradation occurs during simultaneous exposure to light and to H2O or O2. Under these
conditions the color changes from the original cinnamon-brown
to white, and the optical absorption reverts back to that of
undoped TiO2. While these films are of limited use for
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Fig. 5 Incident photon-to-current conversion efficiency (IPCE) of

a fractal-shaped TiO2 photo-anode doped with Cr and Fe and deposited
by CVD, compared to an undoped dense TiO2 film. The data for dense
TiO2 were recorded at 0 V vs. Ag/AgCl in an aqueous 0.1 M KOH
electrolyte (pH 13). Since the fractal-shaped TiO2 was unstable in water,
its (short-circuit) photo-current was measured in a two-electrode cell
using 0.5 M KI + 0.05 M I2 in propylene carbonate as the electrolyte.
The optical absorption of the nano-TiO2 film shows a similar spectral
shape as its IPCE.

photo-electrochemical water splitting, it does illustrate that one

can tune the materials properties by adopting suitable
nanostructured morphologies.
Although substitutional doping with metal ions can indeed be
used to sensitize wide-bandgap semiconductors to visible light, it
does not significantly improve the overall efficiency of
photo-electrodes. This is because the dopants introduce defect
states deep in the bandgap which act as recombination centers.
In 2001, research interest in the sensitization of wide-bandgap
metal oxides by doping returned after a paper by Asahi et al.
on anion-doped TiO2.27 Quantum-chemical calculations
indicated that the wave functions of anion dopants, such as
nitrogen and carbon, show significant overlap with the valence
band wavefunctions. The sub-bandgap defect levels are,
therefore, less localized than for cation dopants, and recombination should be less severe. Nitrogen- and carbon-doping of TiO2
particles have indeed been shown to result in higher photocatalytic activities.2830
Attempts to incorporate carbon or nitrogen into thin film
TiO2 photo-anodes have met with limited success. Spray
pyrolysis of TiO2 under a CO2 atmosphere31 or a high-temperature treatment of TiO2 in a hexane-containing environment32
result in carbon concentrations that are too low for a significant
change in the absorption spectrum. Interestingly, even a low
concentration of carbon shifts the anatase-to-rutile phase
transformation temperature from 600  C to beyond 800  C.
This can be useful in the synthesis of TiO2-based photo-catalysts,
since the anatase phase is the more active one. To increase the
concentration of carbon in TiO2, the oxidative annealing of
TiC films may be a more promising route.33 Sputter-deposition
in a CO2 containing atmosphere may also lead to enhanced
carbon concentrations. Lindgren et al. published some interesting work on nitrogen-doped TiO2 films deposited by reactive
DC magnetron sputtering.34,35 An optimal concentration of
This journal is The Royal Society of Chemistry 2008

nitrogen improved the white-light response by a factor of 200

compared to undoped TiO2. However, nitrogen doping also
decreases the UV response,34 in a similar manner as observed
for the metal-doped TiO2 films in Fig. 5. This suggests that
recombination centers are difficult (if not impossible) to avoid
when doping wide-bandgap semiconductors, regardless of
whether anion or cation dopants are used.
An alternative approach is to start with a material that has an
intrinsically small bandgap, such as a-Fe2O3 (hematite). This
material has an orange-brown color and with a bandgap of
2.12.2 eV it readily absorbs light with wavelengths below

600 nm. Moreover, it is stable against photo-corrosion in
aqueous solutions. Older work on Fe2O3 has already shown
high photo-conversion efficiencies for polycrystalline Fe2O3
pellets9 and single crystalline Fe2O3 samples.36 For practical
applications, however, thin films are preferred in order to avoid
electrical conductivity limitations and to reduce the cost for
fabrication. Several authors have reported the beneficial
effects of dopants, especially Ti and Si, on the photo-electrochemical properties of a-Fe2O3.3740 Recently, an exceptionally
high photo-current of 2.7 mA cm2 was reported at a bias
of 1.23 V vs. reversible hydrogen (RHE) under simulated
AM1.5 sunlight for Si-doped porous films synthesized using
atmospheric pressure chemical vapor deposition (APCVD).41,42
The key ingredients for the high performance of these films
seem to be i) Si doping, which is thought to induce a favorable
morphology during film growth, ii) the presence of an ultrathin (
1 nm) SiO2 interfacial layer between the Fe2O3 and the
transparent conducting substrate, and iii) the addition of a cobalt
catalyst.
To investigate the effects of Si doping in more detail, we have
deposited Si-doped Fe2O3 films by spray pyrolysis of an
ethanolic solution of Fe(AcAc)3.43 First, the effect of a 5 nm
SnO2 interfacial layer between the transparent conducting
substrate and the Fe2O3 was investigated. Although this layer
is significantly thicker than the 1 nm SiO2 interfacial film
mentioned above42 (and non-insulating), a similar beneficial
effect was observed. The currentvoltage characteristics shown
in Fig. 6 (left) reveal that the SnO2 layer shifts the photo-current
onset potential to
0.2 V more negative values. This results in
a photo-current increase from 0.04 to 0.33 mA cm2 at a potential
of 0.2 V vs. Ag/AgCl. The right-hand side of Fig. 6 shows that the
optimal Si concentration in the spray solution is
0.2% and
1%
for films with and without the interfacial layer, respectively.
Another effect of the interfacial layer is a significant improvement
of the reproducibility of the photo-response, especially for
undoped samples. Without the interfacial layer, photo-current
variations of up to a factor of
5 or more are observed between
samples made under the same conditions. With the interfacial
layer, these variations are within a factor of 2.
The fact that these films were dense (i.e., non-porous) allowed
us to study the electrical properties by quantitative impedance
spectroscopy. A donor density of 1  1020 cm3 was found for
films deposited from a spray solution containing 0.9% of Si,
which is three orders of magnitude higher than for undoped
Fe2O3 films (
1  1017 cm3).43 This shows that in addition to
the structure-directing effect reported by Cesar et al.,41 Si also
acts as a donor-type dopant in Fe2O3. This is consistent with
front- and back-side illumination experiments, which reveal
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Fig. 6 Left: IV curves in the dark and under simulated 80 mW cm2 AM1.5 sunlight for Fe2O3 doped with 0.2% Si with (A) and without (B) a 5 nm
SnO2 interfacial layer. Right: dependence of the photo-current on the Si doping concentration at 0.23 VAg/AgCl for Fe2O3 films with and without the
interfacial layer. In both cases, an aqueous solution of 1 M KOH (pH 14) was used as an electrolyte.

that electron transport is rate limiting for undoped Fe2O3 films,

whereas hole transport limits the photo-current in Si-doped
films.43
Poor hole transport is one of the main factors that limit the
photo-response of Fe2O3 photo-anodes. An elegant solution
for this is to use high aspect-ratio nanowire electrodes, as
illustrated in Fig. 7. By ensuring that the wires have a radius
that is less than the hole diffusion length of Fe2O3 (24 nm38
or 20 nm),44 hole transport limitations can be avoided. The large
specific surface area of a nanowire electrode addresses the
intrinsically slow water oxidation kinetics by valence band
holes.44 Since recombination at grain boundaries was found to
limit the photo-response in particle-based photo-anodes,45 each
wire should consist of a single crystallite.46 When the nanowires
are sufficiently narrow, one-dimensional quantum confinement
can occur. Vayssieres et al. have reported a significant blue-shift
for a-Fe2O3 nanorod arrays with a primary rod diameter of
45 nm.47 If the blue-shift manifests itself in an upward shift
of the conduction band, direct reduction of water may
become feasible without the need for an additional bias (cf.
Fig. 3).47 Thus far, however, no one has succeeded to split

water using a-Fe2O3 photo-anodes without assistance of a bias

voltage.
In addition to hydrothermal methods for Fe2O3 nanowire
growth on conducting substrates,47,48 thermal oxidation of
metallic Fe can also result in high aspect-ratio morphologies.4954
Oxidation of iron foil in air at 800  C leads to the nanowires
with a diameter of 50100 nm, as shown in Fig. 4B. At 450  C,
a similar treatment results in the formation of high aspect-ratio
nanoflakes (Fig. 4C and D). These features have been observed
at different labs, and can be readily reproduced. Photo-electrochemical measurements on thermally oxidized Fe foil show very
high background currents and a photo-response of a few tens of
mA cm2 under AM1.5 illumination.55 This is due to exposure of
the underlying metallic Fe/Fe3O4 substrate to the electrolyte,
and can be avoided by using thin films of Fe that can be fully
oxidized. However, for such films the thermal growth of nanowires
seems to be less straightforward than for Fe foil. While
sputter-deposited films have been reported to form nanowires
upon oxidation,50,54 we have found different morphologies after
oxidation of electrodeposited metallic Fe films, as can be seen in
Fig. 4E and F.55 The 100 nm Fe2O3 film in Fig. 4E shows porous
micron-sized features. When the thickness is doubled (Fig. 4F),
the feature size becomes significantly smaller and some high
aspect-ratio outcroppings are observed. The latter may be
interpreted as the onset of nanoflake growth, and suggests
a required minimum film thickness for nanowire growth by
thermal oxidation. Clearly, further progress in this area requires
a more detailed understanding of the growth mechanism during
thermal oxidation.

Tandem cells

Fig. 7 Optimized morphology for an a-Fe2O3 photo-anode for water

splitting. The small diameter of the nanowires ensures short hole
diffusion path lengths.

2316 | J. Mater. Chem., 2008, 18, 23112320

A closer look at Fig. 2 and 3 reveals that metal oxide semiconductors absorb only a small portion of the solar spectrum. By
using a tandem cell approach, the remaining part of the spectrum
can be used to provide the additional bias voltage required for
the reduction reaction (i.e., to satisfy the criterion of suitable
band edge positions). Augustynski and Gratzel used a dye-sensitized solar cell (DSSC) to provide a bias voltage to a WO3 or
Fe2O3 photo-anode. An efficiency of 4.5% has been published
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for the WO3-based photo-anodes,56 which is close to the

theoretical efficiency that has been reported for this material.7
By using highly efficient dendritic a-Fe2O3 photo-anodes, overall
solar-to-hydrogen efficiencies of 2.2% are within reach.42
Although biasing with a separate solar cell is attractive from an
efficiency point of view, the fact that it involves two separate
devices, each with its own electrodes and electrolyte (in the case
of a DSSC), complicates the system and increases the cost. Several
efforts have been made to design and fabricate a monolithic
tandem cell, where multiple functional layers are combined into
a single plate. When this plate is immersed in a solution and illuminated, hydrogen should evolve from one side while oxygen is
formed on the other side. Turner et al. have successfully fabricated
a monolithic tandem cell based on a p-type GaInP2 photo-cathode
biased by a GaAs pn junction solar cell.57 The solar-to-chemical
conversion efficiency is 12.4% (based on the Gibbs free energy
change of water splitting) under an illumination intensity of
11
suns. As pointed out by the authors, the use of concentrated
sunlight is necessary due to the high cost of the device. The main
problem, however, is that the lifetime of the tandem device is
measured in hours instead of years due to severe photo-corrosion.
Licht et al. addressed the photo-corrosion problem by using
efficient co-catalysts for H2 and O2 evolution (Pt and RuO2,
respectively).22,58 They used a complex multiple bandgap system
based on AlxGa1xAs and Si pn junctions to achieve a record
18.3% efficiency for water splitting. However, it should be noted
that this system is composed of a small area tandem cell coupled
to a large-area electrode for electrolysis. As this state-of-the-art
device is composed of about 10 layers of high-quality thin film
semiconductors, the main challenges for this approach are
scale-up and cost reduction.56 It is not a priori clear whether
such a system will be cost effective in a solar concentrator
system. Practical design issues and light scattering by evolving
gas bubbles limit the illumination intensity to an estimated
1020 suns.57 For comparison, photo-voltaic concentrator
systems based on these materials usually operate at light intensities exceeding 100 suns.59
Miller et al. used a triple-junction amorphous silicon photovoltaic cell in combination with efficient hydrogen and oxygen
evolution catalysts.60 Amorphous silicon (a-Si) is much cheaper
than GaAs-based materials and requires less energy to process.
Sputter-deposited NiMo and Fe:NiOx were used as hydrogen
and oxygen evolution catalysts, respectively. These materials
are pure electrocatalysts, i.e., they are not photo-active. A
solar-to-hydrogen conversion efficiency of 7.8% was achieved
for a small-area prototype device (<1 cm2). Both catalysts
showed excellent resistance against (photo-)corrosion. It should
be noted that the photo-active area is not the same as the electrochemically active area, since the catalysts are not transparent for
visible light. To address this, one of the a-Si junctions is replaced
by Fe2O3 or WO3.61 So far, the a-Si/WO3 hybrid photo-electrodes show solar-to-hydrogen conversion efficiencies of 1% in
outdoor tests.62 A particular challenge for these systems is to
deposit the metal oxides at sufficiently low temperatures
(<300  C) in order to avoid degradation of the underlying a-Si
junctions. Aerosol spray pyrolysis requires a temperature of

400  C and cannot be used. With reactive sputtering the
substrate temperature could be kept below 200  C at the cost
of being a more expensive technique.
This journal is The Royal Society of Chemistry 2008

Photo-catalyst particles in suspensions

From the previous sections it becomes clear that the search for
suitable photo-anodes for water splitting is severely hampered
by the many requirements that the materials have to fulfil. An
alternative approach is to simply disperse a photo-catalyst
powder in water. This eliminates the need for a conducting
substrate so that conventional high-temperature solid-state
synthesis routes can be used, allowing complex, single-phase
compounds to be made with relative ease. Co-catalysts (see
below) can be easily added in the desired quantities by simple
mixing and firing. Scale-up is readily accomplished and allows
accurate chemical analysis of the evolved gasses, even at very
low efficiencies. As such, these systems also provide a convenient
screening method for selecting suitable photo-anode materials.
For particulate systems, the reduction and oxidation reactions
both have to take place at the surface of a single particle, as illustrated in Fig. 8. To enhance the kinetics and to avoid chemical
recombination of H2 and O2, small amounts of co-catalysts,
such as Pt, NiOx or RuO2 are deposited onto the photo-catalysts
surface to ensure that H2 and O2 evolve at spatially separated
sites. Typical loadings are 13 g of catalyst powder per 1000
ml H2O, and co-catalyst loadings of 0.51% vs. the amount of
photo-catalyst. The aqueous slurry is contained in a closed pyrex
glass cell which is illuminated using fluorescent tubes (blacklight), or high-power xenon or high-pressure mercury lamps.
By connecting the cell to a closed gas circulation system, the
amounts of evolved hydrogen and oxygen can be determined
on-line with gas chromatography.
In many cases, the photo-catalyst is only able to evolve either
hydrogen or oxygen gas, not both at the same time. If only
hydrogen (oxygen) evolves, a sacrificial electron donor
(acceptor) must be present to ensure the stoichiometric consumption of electrons and holes. While sacrificial systems are of
considerable technical interest as they permit the study of
electrode reactions, they cannot be used as a commercial
hydrogen source due to the consumption of high-value (in terms
of energy and cost) compounds, such as methanol, EDTA,
formic acid, etc. Examples of oxygen evolution photo-catalysts

Fig. 8 Left: one-pot system containing a suspension of photo-catalyst

particles in water. Illumination occurs either from the side or from the
top of the reaction vessel. The hydrogen and oxygen need to be separated
to avoid explosive mixtures. Right: energy diagram for a particle-based
photo-catalyst for water splitting. For very small particles (<100 nm),
the electric field inside the particles is negligible. To avoid electron
hole recombination, co-catalysts (here shown only for the reduction
reaction) are added to enhance the surface reaction rates.

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Table 1 Overview of particle-based photo-catalyst systems reported in the literature that are able to split water in stoichiometric ratios
Photo-catalyst

Co-catalyst

Lamp, electrolytea

Efficiency (solar-to-hydrogen)

Stability

Absorption

Ref.

Single particle systems:

M2Sb2O7 M]Ca, Sr
NaTaO3
BaIn0.5Nb0.5O3
In0.9Ni0.1TaO4
(Ga1xZnx)(N1xOx)
TiSi2

RuO2
NiO
NiOx
NiOx
CrRh oxide
TiO2/SiO2

L1
L2, 103 M NaOH
L3
L3
L2/L3, pH 4.5 (H2SO4)
350 or 540 nm lamps, spectral
width 60 nm

20% @ 270 nm
0.66% @ >420 nm
2.5% @ 420 nm
3.9% @ 540 nm

>4 h
>14 h
>40 h
>120 h
>35 h
>1000 h

UV
UV
UV/VIS
UV/VIS
UV/VIS
UV/VIS

72
73
74
75
71
76

L2, >12 mM NaOH

L3

50% in UV
12% @ 270 nm

>20 h

UV
UV

77
78

L2
L2

4.2% @320 nm

>220 h
>400 h

UV
UV

79
80

L3, 100 mM NaI

L2, 0.1 M NaI, pH 11

0.1% @ 420 nm

>250 h
>100 h

UV/VIS
UV

70
81

Layered materials:
NiO
Ba:La2TiO7
NiO
Sr2Ta2O7
Composite particles:
NiO
Zn:Lu2O3/Ga2O3
NiOx
Cr:Ba2In2O5:In2O3
Particle mixtures, Z-scheme:
Pt/Pt
WO3/(Ca,Ta):SrTiO3
Pt/Pt
an-TiO2/ru-TiO2
a

L1 200 W Hg-Xe; L2 400500 W high pressure Hg; L3 300 W Xe.

are BiVO463,64 and WO3.65 AgNO3 or Ce4+(aq) are often used as

electron acceptors (or electron scavengers) in these systems.
Oxygen gas is sometimes used as an electron scavenger in other
photo-oxidation reactions. Hydrogen evolution photo-catalysts
appear to be more common, examples include InVO4,66
Bi2RNbO7 (R Y, rare earth),67 and BaCr2O4.68 Methanol is
almost always used as a sacrificial electron donor (hole
scavenger), but other hole scavengers such as EDTA and formic
acid may also work.
Table 1 presents an overview of recently reported suspensionbased photo-catalyst systems that are able to split water in a H2
: O2 ratio of 2 : 1 without the need for any sacrificial agents.
Co-catalysts are required in all cases and the reported efficiencies
are low, especially in the visible-light region. In addition to the
straightforward single component systems, several other systems
have been studied. In all cases, the main goals are to i) spatially
separate hydrogen from oxygen to prevent chemical recombination and ii) provide different surfaces with different catalytic
activities for hydrogen and oxygen evolution. In the layered
perovskite compounds (Table 1), water molecules are able to
diffuse spontaneously into the crystal structure of the material
where photo-oxidation takes place. The oxygen diffuses back to
the surface through the interlayers, while photo-reduction takes
place at the surface of the co-catalyst.69 In the composite particles,
an nn heterojunction forms between two different particles. Due
to the different energetic positions of the conduction and valence
band edges, the electrons are transported to one particle, while the
holes move to the other particle. In the mixed-particle system, this
concept is taken a step further by performing the oxidation and
reduction of water on two different particles that are not in direct
contact with each other. To ensure a complete redox reaction at
each individual particle, an I/IO3 redox mediator is used to
transport electrons from the oxygen evolving particles to their
hydrogen evolving counterparts.70
There are also some disadvantages of using powder photocatalysts. It is often difficult to determine the actual number of
photons that is absorbed by the suspension, which prohibits
accurate efficiency measurements. When reactivation of the
2318 | J. Mater. Chem., 2008, 18, 23112320

catalyst is necessary, the filtration process needed to separate

the catalyst from the water is not very convenient. Furthermore,
hydrogen and oxygen are produced in the same reactor volume,
forming an explosive mixture, and need to be separated immediately afterwards. This not only represents a safety issue, the
separation also costs energy and lowers the overall efficiency of
the process. Ritterskamp et al.76 recently published some
interesting work on TiSi2 photo-catalysts for which the mixing
of H2 and O2 is no longer a problem. Upon irradiation only
hydrogen evolves, while oxygen remains adsorbed at the TiSi2
surface. It can be released by heating the catalyst to 100  C,
allowing easy separation. A conversion efficiency of
4% has
been reported for this system, which does not take into account
the amount of energy needed to heat the suspension.
Finally, it should be realized that the efficiencies for powder
photo-catalysts are significantly lower than for photo-anodes
in a photo-electrochemical cell. A very good powder photo-catalyst for visible light water splitting generates perhaps 200 mmol
H2 per gram of catalyst per hour,71 although much smaller values
are also considered promising.66 In contrast, a 1 mm thick Fe2O3
film that shows a photo-current of 2 mA cm2 (ref. 42) produces
hydrogen at a rate of
70 mmol g1 h1, i.e. 350 times more.

Conclusions
The operating principles of photo-electrochemical cells for solar
water splitting have been described. The severe requirement of
stability against (photo-)corrosion in an aqueous environment
limits the choice of the photo-anode material to metal oxides.
TiO2 photo-anodes show excellent chemical stability and charge
transport properties, but the large bandgap limits the efficiency.
Doping may enhance the optical absorption, but not the photoelectrochemical performance since it appears impossible to avoid
the presence of deep defects that act as recombination centers.
a-Fe2O3 has a nearly ideal bandgap, absorbs visible light and
shows good chemical stability under the right conditions. Its
performance can be enhanced by moderate use of (shallow)
dopants to improve the electronic conductivity, and by
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introducing a thin interfacial layer that presumably improves the

alignment of the band edges. High aspect-ratio morphologies,
such as nanowires, can be used to overcome the poor hole transport properties and the slow surface reaction kinetics. A growing
interest in complex oxides is expected to lead to a much broader
choice in photo-active materials, and current research efforts on
powder photo-catalysts offer a convenient route towards the
selection of suitable photo-anode materials. Further improvements in the field of solar hydrogen production can be expected
as new, low-cost and low-temperature techniques for the
controlled synthesis of metal oxides are developed.

Acknowledgements
The authors gratefully acknowledge the contributions of the
following postdocs, students, and other co-workers to this
work: Dr J.C. van t Spijker, E.L. Maloney (Everest Coatings),
C.S. Enache, and T.J. Olthof. Financial support for this work
was provided by the Delft Institute for Sustainable Energy,
SenterNovem, and the NWO/ACTS Sustainable Hydrogen
program (project nr. 053.61.009). RvdK also acknowledges the
Netherlands Organization for Scientific Research (NWO) for
a VENI grant which made part of these investigations possible.

References
1 N. S. Lewis and D. G. Nocera, Proc. Natl. Acad. Sci. U. S. A., 2006,
103, 15729.
2 Basic research needs for solar energy utilization (report), US
Department of Energy, Office of Basic Energy Sciences, 2005.
3 O. Khaselev, A. Bansal and J. A. Turner, Int. J. Hydrogen Energy,
2001, 26, 127.
4 R. Memming, Semiconductor Electrochemistry, Wiley, Weinheim,
2000.
5 M. F. Weber and M. J. Dignam, Int. J. Hydrogen Energy, 1986, 11,
225.
6 J. R. Bolton, S. J. Strickler and J. S. Connolly, Nature, 1985, 316, 495.
7 A. B. Murphy, P. R. F. Barnes, L. K. Randeniya, I. C. Plumb,
I. E. Grey, M. D. Horne and J. A. Glasscock, Int. J. Hydrogen
Energy, 2006, 31, 1999.
8 R. Shinar and J. H. Kennedy, J. Electrochem. Soc., 1983, 130, 860.
9 R. Shinar and J. H. Kennedy, Sol. Energy Mater., 1982, 6, 323.
10 S. U. M. Khan and J. Akikusa, J. Phys. Chem. B, 1999, 103, 7184.
11 D. E. Scaife, Sol. Energy, 1980, 25, 41.
12 J. M. Bolts and M. S. Wrighton, J. Phys. Chem., 1976, 80, 2641.
13 R. Van de Krol, A. Goossens and J. Schoonman, J. Electrochem.
Soc., 1997, 144, 1723.
14 P. E. de Jongh, D. Vanmaekelbergh and J. J. Kelly, J. Electrochem.
Soc., 2000, 147, 486.
15 M. F. Finlayson, B. L. Wheeler, N. Kakuta, K. H. Park, A. J. Bard,
A. Campion, M. A. Fox, S. E. Webber and J. M. White, J. Phys.
Chem., 1985, 89, 5676.
16 M. Nanu, J. Schoonman and A. Goossens, Adv. Mater., 2004, 16,
453.
17 S. R. Morrison, Electrochemistry of Semiconductor and Oxidized
Metal Electrodes, Plenum Press, New York, 1980.
18 A. Fujishima and K. Honda, Nature, 1972, 238, 37.
19 J. G. Mavroides, J. A. Kafalas and D. F. Kolesar, Appl. Phys. Lett.,
1976, 28, 241.
20 S. M. Sze, Physics of Semiconductor Devices, John Wiley & Sons, New
York, 1981.
21 R. Hoffmann, Solids and surfaces a chemists view of bonding in
extended structures, Wiley-VCH, New York, 1988.
22 S. Licht, B. Wang, S. Mukerji, T. Soga, M. Umeno and H. Tributsch,
J. Phys. Chem. B, 2000, 104, 8920.
23 H. Kato and A. Kudo, J. Phys. Chem. B, 2002, 106, 5029.
24 H. P. Maruska and A. K. Ghosh, Sol. Energy Mater., 1979, 1, 237.

This journal is The Royal Society of Chemistry 2008

25 A. Goossens, E. L. Maloney and J. Schoonman, Chem. Vap.

Deposition, 1998, 4, 109.
26 J. C. vant Spijker, E. L. Maloney, J. Schoonman and R. Van de Krol,
Unusually high photocurrents in anatase TiO2 thin films with fractal
morphologies, presented at the 16th International Conference on
Photochemical Conversion and Storage of Solar Energy (IPS-16),
Uppsala, Sweden, 2006.
27 R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki and Y. Taga, Science,
2001, 293, 269.
28 S. Sakthivel and H. Kisch, Angew. Chem., Int. Ed., 2003, 42, 4908.
29 S. Sakthivel and H. Kisch, ChemPhysChem, 2003, 4, 487.
30 X. B. Chen, Y. B. Lou, A. C. S. Samia, C. Burda and J. L. Gole, Adv.
Funct. Mater., 2005, 15, 41.
31 C. S. Enache, J. Schoonman and R. Van de Krol, J. Electroceram.,
2004, 13, 177.
32 C. S. Enache, J. Schoonman and R. Van de Krol, Appl. Surf. Sci.,
2006, 252, 6342.
33 H. Irie, Y. Watanabe and K. Hashimoto, Chem. Lett., 2003, 32, 772.
34 T. Lindgren, J. M. Mwabora, E. Avendano, J. Jonsson, A. Hoel,
C. G. Granqvist and S. E. Lindquist, J. Phys. Chem. B, 2003, 107,
5709.
35 T. Lindgren, J. Lu, A. Hoel, C. G. Granqvist, G. R. Torres and
S. E. Lindquist, Sol. Energy Mater. Sol. Cells, 2004, 84, 145.
36 C. Sanchez, M. Hendewerk, K. D. Sieber and G. A. Somorjai, J. Solid
State Chem., 1986, 61, 47.
37 J. H. Kennedy, M. Anderman and R. Shinar, J. Electrochem. Soc.,
1981, 128, 2371.
38 J. H. Kennedy and K. W. Frese, Jr., J. Electrochem. Soc., 1978, 125,
709.
39 C. J. Sartoretti, B. D. Alexander, R. Solarska, W. A. Rutkowska,
J. Augustynski and R. Cerny, J. Phys. Chem. B, 2005, 109, 13685.
40 J. A. Glasscock, P. R. F. Barnes, I. C. Plumb and N. Savvides,
J. Phys. Chem. C, 2007, 111, 16477.
41 I. Cesar, A. Kay, J. A. G. Martinez and M. Gratzel, J. Am. Chem.
Soc., 2006, 128, 4582.
42 A. Kay, I. Cesar and M. Gratzel, J. Am. Chem. Soc., 2006, 128,
15714.
43 Y. Liang, C. S. Enache and R. Van de Krol, Int. J. Photoenergy, 2008,
in press.
44 M. P. Dare Edwards, J. B. Goodenough, A. Hamnett and
P. R. Trevellick, J. Chem. Soc., Faraday Trans. 1, 1983, 79, 2027.
45 U. Bjorksten, J. Moser and M. Gratzel, Chem. Mater., 1994, 6, 858.
46 N. Beermann, L. Vayssieres, S. E. Lindquist and A. Hagfeldt,
J. Electrochem. Soc., 2000, 147, 2456.
47 L. Vayssieres, C. Sathe, S. M. Butorin, D. K. Shuh, J. Nordgren and
J. H. Guo, Adv. Mater., 2005, 17, 2320.
48 L. Vayssieres, N. Beermann, S. E. Lindquist and A. Hagfeldt,
Chem. Mater., 2001, 13, 233.
49 Y. Y. Fu, R. M. Wang, J. Xu, J. Chen, Y. Yan, A. Narlikar and
H. Zhang, Chem. Phys. Lett., 2003, 379, 373.
50 T. Yu, Y. W. Zhu, X. J. Xu, K. S. Yeong, Z. X. Shen, P. Chen,
C. T. Lim, J. T. L. Thong and C. H. Sow, Small, 2006, 2, 80.
51 C. H. Kim, H. J. Chun, D. S. Kim, S. Y. Kim, J. Park, J. Y. Moon,
G. Lee, J. Yoon, Y. Jo, M. H. Jung, S. I. Jung and C. J. Lee, Appl.
Phys. Lett., 2006, 89.
52 R. M. Wang, Y. F. Chen, Y. Y. Fu, H. Zhang and C. Kisielowski,
J. Phys. Chem. B, 2005, 109, 12245.
53 X. G. Wen, S. H. Wang, Y. Ding, Z. L. Wang and S. H. Yang,
J. Phys. Chem. B, 2005, 109, 215.
54 Y. L. Chueh, M. W. Lai, J. Q. Liang, L. J. Chou and Z. L. Wang,
Adv. Funct. Mater., 2006, 16, 2243.
55 T. J. Olthof, BSc thesis, Delft University of Technology, 2007.
56 M. Gratzel, Nature, 2001, 414, 338.
57 O. Khaselev and J. A. Turner, Science, 1998, 280, 425.
58 S. Licht, J. Phys. Chem. B, 2001, 105, 6281.
59 C. Algora, E. Ortiz, I. Rey-Stolle, V. Diaz, R. Pena, V. M. Andreev,
V. P. Khvostikov and V. D. Rumyantsev, IEEE Trans. Electron
Devices, 2001, 48, 840.
60 R. E. Rocheleau, E. L. Miller and A. Misra, Energy Fuels, 1998, 12, 3.
61 E. L. Miller, R. E. Rocheleau and X. M. Deng, Int. J. Hydrogen
Energy, 2003, 28, 615.
62 E. L. Miller, D. Paluselli, B. Marsen and R. E. Rocheleau, Sol.
Energy Mater. Sol. Cells, 2005, 88, 131.
63 A. Kudo, K. Omori and H. Kato, J. Am. Chem. Soc., 1999, 121,
11459.

J. Mater. Chem., 2008, 18, 23112320 | 2319

Published on 11 March 2008. Downloaded by Chungnam National University on 04/05/2014 19:02:26.

View Article Online

64 K. Sayama, A. Nomura, T. Arai, T. Sugita, R. Abe, M. Yanagida,

T. Oi, Y. Iwasaki, Y. Abe and H. Sugihara, J. Phys. Chem. B,
2006, 110, 11352.
65 G. R. Bamwenda and H. Arakawa, Sol. Energy Mater. Sol. Cells,
2001, 70, 1.
66 J. H. Ye, Z. G. Zou, M. Oshikiri, A. Matsushita, M. Shimoda,
M. Imai and T. Shishido, Chem. Phys. Lett., 2002, 356, 221.
67 Z. G. Zou, J. H. Ye and H. Arakawa, Top. Catal., 2003, 22, 107.
68 D. Wang, Z. Zhigang and Y. Jinhua, Chem. Phys. Lett., 2003, 373, 191.
69 T. Takata, Y. Furumi, K. Shinohara, A. Tanaka, M. Hara,
J. N. Kondo and K. Domen, Chem. Mater., 1997, 9, 1063.
70 K. Sayama, K. Mukasa, R. Abe, Y. Abe and H. Arakawa,
Chem. Commun., 2001, 23, 2416.
71 K. Maeda, K. Teramura, D. L. Lu, T. Takata, N. Saito, Y. Inoue and
K. Domen, Nature, 2006, 440, 295.
72 J. Sato, N. Saito, H. Nishiyama and Y. Inoue, J. Photochem.
Photobiol., A, 2002, 148, 85.

2320 | J. Mater. Chem., 2008, 18, 23112320

73 H. Kato and A. Kudo, J. Phys. Chem. B, 2001, 105, 4285.

74 J. Yin, Z. G. Zou and J. H. Ye, J. Phys. Chem. B, 2003, 107, 61.
75 Z. G. Zou, J. H. Ye, K. Sayama and H. Arakawa, Nature, 2001, 414,
625.
76 P. Ritterskamp, A. Kuklya, M. A. Wustkamp, K. Kerpen,
C. Weidenthaler and M. Demuth, Angew. Chem., Int. Ed., 2007, 46,
7770.
77 J. Kim, D. W. Hwang, H. G. Kim, S. W. Bae, J. S. Lee, W. Li and
S. H. Oh, Top. Catal., 2005, 35, 295.
78 A. Kudo, H. Kato and S. Nakagawa, J. Phys. Chem. B, 2000, 104,
571.
79 D. F. Wang, Z. G. Zou and J. H. Ye, Chem. Phys. Lett., 2004, 384,
139.
80 D. F. Wang, Z. G. Zou and J. H. Ye, Chem. Mater., 2005, 17,
3255.
81 R. Abe, K. Sayama, K. Domen and H. Arakawa, Chem. Phys. Lett.,
2001, 344, 339.

This journal is The Royal Society of Chemistry 2008