Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268

Contents lists available at ScienceDirect

Journal of Photochemistry and Photobiology C:

Photochemistry Reviews
journal homepage: www.elsevier.com/locate/jphotochemrev

Invited review

Photocatalytic water splitting using semiconductor particles: History and

recent developments
Kazuhiko Maeda a,b,∗
a
Department of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
b
Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), 4-1-8 Honcho Kawaguchi, Saitama 332-0012, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Overall water splitting to produce H2 and O2 over a semiconductor photocatalyst using solar energy is a
Received 31 May 2011 promising process for the large-scale production of clean, recyclable H2 . Numerous attempts have been
Received in revised form 7 July 2011 made to develop photocatalysts that function under visible-light irradiation to efficiently utilize solar
Accepted 11 July 2011
energy. In general, overall water splitting over a photocatalyst particle can be achieved by modifying
Available online 20 July 2011
the photocatalyst with a suitable cocatalyst to provide an active redox site. Therefore, the development
of active photocatalytic materials has relied on both photocatalysts and cocatalysts. This review article
Keywords:
describes the historical development of water-splitting photocatalysts.
Artificial photosynthesis
Hydrogen production © 2011 Elsevier B.V. All rights reserved.
Photocatalysis
Solar energy conversion
Visible light
Water splitting

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
1.1. Research background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
1.2. Basic principles of water splitting on a semiconductor particle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
1.3. Half-reactions using sacrificial electron donors and acceptors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
1.4. Principal elemental components of photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
1.5. Scope of this review article . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
2. Development history of water-splitting photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
2.1. d0 -Type metal oxides for UV water splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
2.1.1. TiO2 and SrTiO3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
2.1.2. Metal oxides with structural regularities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
2.1.3. Tantalates as highly efficient photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
2.1.4. Other d0 metal oxides (titanates, niobates, etc.) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
2.2. Effect of electronic band structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
2.2.1. d10 -Type metal oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
2.2.2. Mixed-configuration metal oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
2.3. Development of photocatalysts that can utilize visible photons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
2.3.1. Difficulty in developing a water-splitting photocatalyst that operates under visible light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
2.3.2. Doped metal oxide photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
2.3.3. Valence band-controlled metal oxide photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
2.3.4. Non-oxide photocatalysts with a d0 electronic configuration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
2.3.5. d10 -Type (oxy)nitrides and oxysulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249

∗ Correpondance address: The University of Tokyo, Department of Chemical System Engineering, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
Tel.: +81 3 5841 1652; fax: +81 3 5841 8838.
E-mail address: kmaeda@chemsys.t.u-tokyo.ac.jp

1389-5567/$20.00 © 2011 Elsevier B.V. All rights reserved.

doi:10.1016/j.jphotochemrev.2011.07.001
238 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268

2.3.6. Metal-free photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251

2.3.7. Spectral sensitization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
2.4. Water splitting through two-step photoexcitation (Z-scheme) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
2.4.1. Basic principle and difficulties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
2.4.2. Metal oxide-based systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
2.4.3. (Oxy)nitride-based systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
3. Strategy to improve the photocatalytic activity of a given material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
3.1. General strategy to improve the quality of a photocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
3.2. Controlling the shape or form of a photocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
3.2.1. Mesoporous transition-metal oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
3.2.2. Transition-metal oxide nanosheets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
3.2.3. Composite-type photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
3.2.4. Doping with foreign elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
3.2.5. Surface modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
3.3. Cocatalysts for the promotion of surface reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
3.3.1. General role of cocatalysts in photocatalytic water splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
3.3.2. A general strategy to improve activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
3.3.3. Traditional cocatalysts for water splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
3.3.4. Mixed oxide cocatalysts containing chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
3.3.5. Core/shell-structured noble-metal/Cr2 O3 nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
3.3.6. Loading both H2 - and O2 -evolution cocatalysts onto the same photocatalyst particle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
3.4. Effect of reaction conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
3.4.1. Reaction pH and electrolyte in the reactant solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
3.4.2. Pressure and temperature in the reaction system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
4. Summary and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265

Kazuhiko Maeda received his B.Sc. from the Tokyo Uni- anode, an n-type semiconductor, is illuminated by light with energy
versity of Science (2003), his MSc. from the Tokyo Institute greater than the band gap of TiO2 , electrons and holes are generated
of Technology (2005), and his Ph.D. from The University in the conduction band and valence band, respectively. When an
of Tokyo (2007). From 2008 to 2009, he was a postdoc-
toral fellow at Pennsylvania State University where he
anodic potential is applied through an external circuit, these elec-
worked with Professor Thomas E. Mallouk. He is cur- trons migrate through the bulk to reach the Pt counter electrode,
rently an Assistant Professor at The University of Tokyo thereby reducing H+ into H2 . Meanwhile, the holes that were left
and a research fellow of the PRESTO/JST program (Chemi-
behind on the surface of the TiO2 oxidize water, forming O2 . The
cal Conversion of Light Energy). His research interests are
photocatalytic and photoelectrochemical water splitting overall reaction process is illustrated in Fig. 1A. Recently, numer-
using semiconductor particles of (oxy)nitrides, inorganic ous PEC cells have been developed, many of which were designed
metal oxide nanosheets, and polymeric carbon nitride,
specifically for the efficient utilization of solar energy. However,
combining nanotechnology and materials chemistry.
due to a lack of suitable photoelectrode materials with appropri-
ate band-gap structures and stability, the systems proposed to date
1. Introduction
have been rather complicated, such as integrated multi-layer and
tandem systems [2–4].
1.1. Research background
If the anode and cathode materials of a water-splitting
PEC cell are directly coupled without an electric circuit, a
To effectively address the depletion of fossil fuels and the serious
metal–semiconductor composite is formed (e.g., Pt/TiO2 ) and
environmental problems accompanying their combustion, mod-
one might expect that a water-splitting reaction is achiev-
ern society has been searching for a new form of energy that is
able on the material, as shown in Fig. 1B. This composite
a clean, renewable, cheap, safe, and viable alternative to fossil fuels
(metal/semiconductor) structure appears advantageous to macro-
and nuclear energy. Recently, hydrogen has received considerable
sized PEC cells, as it is scalable, especially in a powder form. Here,
attention as a next-generation energy carrier. Over the past three
the metal component is generally called the “cocatalyst”, and the
decades, photocatalytic overall water splitting using inexhaustible
semiconductor is called the “photocatalyst”.
sunlight has been studied as a potential method of hydrogen pro-
Overall water splitting for the production of H2 using a semi-
duction from renewable resources.
conductor particle is similar in many ways to the photosynthetic
Catalytic splitting of pure water into H2 and O2 (Eq. (1)) is a
reaction. The reaction has been under investigation since 1980, and
typical “uphill reaction”, involving a large positive change in the
has been extensively studied by many researchers, as will be dis-
Gibbs free energy (G◦ = 238 kJ mol−1 ).
cussed in a later section. For practical future applications, Domen
2H2 O → 2H2 + O2 (1) et al. suggested that an area of 250,000 km2 , corresponding to 1%
of the earth’s desert area, would be required to provide one-third
The half-reactions are described as follows:
of the projected energy needs of human society in 2050 from solar
2H+ + 2e− → H2 (2) energy, assuming a conversion efficiency of 10% and an integrated
solar energy of AM1.5G (1 sun = 0.1 W cm−2 ) irradiation for a day
2H2 O + 4h+ → O2 + 4H+ (3)
including a sunlight-angle correction [5]. One possible scheme for
Research in this field was initiated by the demonstration of pho- large-scale H2 production via solar water splitting is depicted in
toelectrochemical (PEC) water splitting using a single-crystal TiO2 Fig. 2. From the viewpoint of such large-scale hydrogen production,
(rutile) photoanode and a Pt cathode with an external bias [1]. particulate photocatalyst systems have a wider range of potential
This is well-known as the Honda-Fujishima effect. When a TiO2
 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 1. (A) PEC water splitting using a TiO2 photoanode, and (B) a short-circuit model of a PEC cell.
applications, although a method for separating the simultaneously
produced H2 and O2 remains to be developed.
1.2. Basic principles of water splitting on a semiconductor particle
Fig. 3 shows a schematic illustration of the basic principles of
overall water splitting on a semiconductor particle, which is essen-
tially identical to a water-splitting PEC cell. Under irradiation with
an energy equivalent to or greater than the band gap of the semi-
conductor photocatalyst, electrons in the valence band are excited
into the conduction band, leaving holes in the valence band. These
photogenerated electrons and holes cause reduction and oxida-
tion reactions, respectively. To achieve overall water splitting, the
bottom of the conduction band must be more negative than the
reduction potential of H+ to H2 (0 V vs. NHE at pH 0), while the top of
the valence band must be more positive than the oxidation poten-
tial of H2 O to O2 (1.23 V vs. NHE). Therefore, the minimum photon
energy thermodynamically required to drive the reaction is 1.23 eV,
which corresponds to a wavelength of ca. 1000 nm, in the near-
infrared region. Accordingly, it would appear possible to utilize the
entire spectral range of visible light (400 <  < 800 nm). However,
there is an activation barrier in the charge transfer process between
the photocatalyst and water molecules as will be mentioned in the
later section, necessitating a photon energy greater than the band
gap of the photocatalyst to drive the overall water-splitting reac-
Fig. 2. Possible scheme for large-scale H2 production via solar water splitting.
10,000 of the solar plant (25 km2 ) would be required to provide one-third of the
projected energy needs of human society in 2050 from solar energy.
Reprinted with permission from Ref. [5]. Copyright 2010 American Chemical Society.
239
tion at a reasonable rate. In addition, the backward reaction; that is,
water formation from H2 and O2 , must be strictly inhibited, and the
photocatalysts themselves must be stable in the reaction. Further-
more, although there are a large number of materials that possess
suitable band-gap potentials, there are very few that function as a
photocatalyst for overall water splitting, due to other factors that
will be discussed below.
As shown in Fig. 4, overall water splitting on a semiconductor
photocatalyst (typically of submicron size) occurs in three steps: (1)
the photocatalyst absorbs photon energy greater than the band-gap
energy of the material and generates photoexcited electron–hole
pairs in the bulk, (2) the photoexcited carriers separate and migrate
to the surface without recombination, and (3) adsorbed species
are reduced and oxidized by the photogenerated electrons and
holes to produce H2 and O2 , respectively. The first two steps are
strongly dependent on the structural and electronic properties of
the photocatalyst. In general, high crystallinity has a positive effect
on activity, since the density of defects, which act as recombi-
nation centers between photogenerated carriers, decreases with
increasing crystallinity. Higher photocatalytic activity can also be
obtained by reducing the particle size of a photocatalyst, because
the diffusion length for photogenerated electron–hole pairs can be
shortened. The third step, on the other hand, is promoted by the
presence of a solid cocatalyst. The cocatalyst is typically a noble
metal (e.g., Pt, Rh) or transition-metal oxide (e.g., NiOx , RuO2 ) and
is loaded onto the photocatalyst surface as a dispersion of nanopar-
ticles (typically <50 nm in size) to produce active sites and reduce
Fig. 3. Basic principle of overall water splitting on a semiconductor particle.
Reprinted with permission from Ref. [7]. Copyright 2007 American Chemical Society.
240 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 4. Processes involved in photocatalytic overall water splitting on a semicon-
ductor particle.
Reprinted with permission from Ref. [7]. Copyright 2007 American Chemical Society.
the activation energy for gas evolution. In most cases, cocatalysts
are loaded for the promotion of H2 evolution, presumably because
most photocatalysts are unable to activate hydrogen on the surface.
It is thus important to design both the bulk and surface proper-
ties of the material carefully so as to obtain a high activity for this
photocatalytic reaction.
The performance of a given photocatalytic material should ide-
ally be evaluated on the basis of quantum yield. However, it is
almost impossible to measure the real quantum yield of a photocat-
alytic system for water splitting. The main obstacle is the lack of a
suitable method of evaluating the loss of incident photons by scat-
tering and reflection in a particulate suspension. In other words,
there is no reliable means of determining the number of photons
absorbed by the photocatalyst particles. Therefore, a quantum yield
of a given photocatalyst for water splitting is evaluated, without
exception, as an apparent (or external) quantum yield (AQY), in
which all of the incident photons are assumed to be absorbed in a
given photocatalyst suspension. AQY can be estimated as:
A × R
AQY(%) = × 100
I instead of H+ , thereby promoting water oxidation by valence band
where A, R, and I represent coefficients based on the reactions (H2
evolution, 2; O2 evolution, 4), the H2 or O2 evolution rate, and the
rate of incident photons, respectively. The flux of incident photons
is typically measured using a calibrated photodiode or chemical
actinometry.
As the main component of the solar spectrum (approximately
50%) consists of visible photons (400 <  < 800 nm), a primary goal
in photocatalytic water splitting is to efficiently utilize visible light
to achieve the reaction. Fig. 5 shows that the solar energy conver-
sion efficiency () increases for overall water splitting under longer
wavelength irradiation, because the number of available photons
in the solar spectrum increases with increasing wavelength. Here,
 can be calculated according to the following equation:
 Output energy as H2

(%) = × 100
Energy of incident sunlight
More concretely, one can describe Eq. (5) as follows:
 
(RH [mol s−1 ] × G0 (H2 O) [J mol−1 ])
(%) = × 100
(Isun [W cm−2 ] × S [cm2 ])
where RH , G◦ (H2 O), Isun, and S represent the rate of H2 evolution
during water splitting, the standard Gibbs free energy of water, the
density of incident sunlight, and the irradiated area, respectively.
Fig. 5. Calculated solar energy conversion efficiency as a function of wavelength for
overall water splitting using photocatalysts with various quantum efficiencies. Solar
irradiance used for the calculation was taken from AM 1.5G data.
Reprinted with permission from Ref. [5]. Copyright 2010 American Chemical Society.
1.3. Half-reactions using sacrificial electron donors and acceptors
As overall water splitting is generally difficult to achieve due
to the uphill nature of the reaction, photocatalytic activities of a
given compound for water reduction or oxidation are usually exam-
ined in the presence of methanol or silver nitrate as a sacrificial
reagent. Reactions using sacrificial reagents are not “overall” water-
splitting reactions, but are often carried out as test reactions for
overall water splitting. The basic principle of photocatalytic reac-
tions using sacrificial reagents is depicted schematically in Fig. 6.
When the photocatalytic reaction is conducted in the presence of
an electron donor such as methanol, photogenerated holes in the
valence band irreversibly oxidize methanol instead of H2 O, thus
facilitating water reduction by conduction band electrons if the bot-
tom of the conduction band of the photocatalyst is located above
the water reduction potential. On the other hand, in the presence of
an electron acceptor such as a silver cation, photogenerated elec-
(4) trons in the conduction band irreversibly reduce electron acceptors
holes if the top of the valence band of the photocatalyst is more
positive than the water oxidation potential. However, it should be
noted that the ability of a photocatalyst to both reduce and oxi-
dize water separately does not guarantee the capability to achieve
overall water splitting without sacrificial reagents.
(5)
(6)
Fig. 6. Basic principle of photocatalytic reactions in the presence of sacrificial
reagents.
Reprinted with permission from Ref. [9]. Copyright 2009 The Royal Society of Chem-
istry.
 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
1.4. Principal elemental components of photocatalysts
There are two main groups of elements that can act as active
cation components in a water-splitting photocatalyst. Fig. 7 shows
the groups of metallic elements that can form suitable band-gap
structures of the corresponding oxide materials, and which have
been successfully applied as photocatalysts for overall water split-
ting. In all cases, the oxidation states of the metallic elements in
such photocatalysts are the highest, that is, Ti4+ , Zr4+ , Nb5+ , Ta5+ ,
W6+ , and Ce4+ in the red group and Ga3+ , In3+ , Ge4+ , Sn4+ , and
Sb5+ in the green group (as indicated in the figure). Photocatalysts
based on transition-metal cations with empty d orbitals are defined
as having a d0 electronic configuration (red group), while those
based on typical metal cations with filled d orbitals are defined as
having a d10 electronic configuration (green group). The introduc-
tion of transition-metal cations with partly filled d electrons (i.e.,
dn electronic configuration: 0 < n < 10) into photocatalytic mate-
rials generally contributes to an inefficient photoresponse. Other
metal oxides with d0 or d10 electronic configurations, such as Mo6+
and Zn2+ , are also expected to be active photocatalysts for overall
water splitting, although there have been no reports of such pho-
tocatalysts with good reproducibility. In the first half of this article,
various d0 - and d10 -type photocatalysts will be discussed.
1.5. Scope of this review article
Owing to recent rising interest in photocatalytic water splitting,
many review papers have been published [6–14]. Kudo and Miseki
published an excellent review paper on water splitting using par-
ticulate photocatalysts, which covers fundamental concepts and
experimental methods for water splitting [9]. There have also been
several reviews focusing on specific aspects of water-splitting pho-
tocatalysts [6,7,10,12]. Furthermore, detailed reviews that enable
the comparison of the performance of a given photocatalytic system
with that of others are also available [8,9,14].
In order to avoid redundant discussion in the present review
article, the author will discuss how water-splitting photocatalysts
and the related chemistry were developed. In recent years, the
number of papers describing photocatalytic H2 evolution from
water using sophisticated materials has increased, with AQYs
reaching several tens of percent. Nevertheless, this review deals
only with research that aimed to achieve overall water splitting. In
the next section, the history of the development of photocatalysts
for water splitting is introduced. Then, the discussion moves to a
description of how photocatalytic activity can be improved, focus-
ing on the structure of a photocatalyst and cocatalysts that function
as reaction sites. Finally, the future outlook for research in this field
is discussed.
Fig. 7. Principal cation components of semiconductor photocatalysts for water splitting.
241
2. Development history of water-splitting photocatalysts
2.1. d0 -Type metal oxides for UV water splitting
2.1.1. TiO2 and SrTiO3
Overall water splitting using particulate photocatalytic sys-
tems, with particle sizes of a few micrometers to several
hundred nanometers, was first demonstrated unequivocally in
1980 [15–17]. Although there were several reports claiming to
have achieved water splitting using particulate systems prior to
this time and afterwards [18,19], the studies lacked clear evidence
of simultaneous catalytic evolution of H2 and O2 from water. The
three systems, reported in 1980, using TiO2 [15] and SrTiO3 [16,17],
were developed for the splitting of water vapor. The results indi-
cated that suppressing the reverse reaction (water formation from
H2 and O2 ) on the loaded cocatalysts is essential, and that adsorbed
water molecules are necessary for the evolution of H2 and O2 . For
example, Pt-loaded TiO2 exhibits little water-splitting activity due
to rapid water formation from H2 and O2 . Coating of Pt/TiO2 with
NaOH, however, results in appreciable stoichiometric H2 and O2
evolution (H2 /O2 = 2) [15,20]. The NaOH coating is believed to sup-
press H2 –O2 recombination on Pt and to hold water molecules near
the catalyst surface. Subsequent to this work, however, most photo-
catalytic water-splitting reactions have been designed for aqueous
solutions, since the reaction rate in an aqueous solution is generally
faster than in the gaseous phase [21].
2.1.2. Metal oxides with structural regularities
In 1986, K4 Nb6 O17 was reported to be an active water-splitting
photocatalyst that has a layered structure with two different inter-
layers, called (I) and (II) [22–24]. K4 Nb6 O17 can be readily prepared
by solid state reaction of K2 CO3 and Nb2 O5 at temperatures higher
than 1273 K, and is obtained as a well-grown lamellar particle. Even
without the aid of a cocatalyst, K4 Nb6 O17 alone produces H2 and O2
from water under band-gap irradiation (>ca. 3.3 eV). Modification
of K4 Nb6 O17 with nanoparticulate Ni, which is intercalated in the
interlayer (I), results in a marked increase in the water-splitting
rate. Interestingly, the photocatalytic activity of K4 Nb6 O17 for
overall water splitting is almost insensitive to gaseous oxygen, indi-
cating that the photoreduction of oxygen, which sometimes takes
place during photocatalytic water splitting, scarcely occurs. Based
on a variety of analyses including X-ray diffraction (XRD), transmis-
sion electron microscopy (TEM), X-ray photoelectron spectroscopy
(XPS), and X-ray absorption fine-structure spectroscopy (XAFS),
a mechanism for overall water splitting over Ni/K4 Nb6 O17 was
proposed, as shown in Fig. 8. According to this mechanism, both
interlayer spaces are hydrated, and photoexcited electrons migrate
to the Ni metal nanoparticles in interlayer (I), where H+ and/or H2 O
242 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 8. Schematic structure of Ni/K4 Nb6 O17 , and the reaction mechanism of overall
water splitting.
Reproduced from Ref. [24] with permission.
are reduced to H2 . Photoexcited holes react with water molecules
in interlayer (II) to form O2 . The sites of H2 and O2 evolution are thus
physically separated by niobate sheets, which results in reducing
the probability of H2 –O2 recombination, thereby contributing to a
relatively high AQY of ∼20%.
Since the discovery of K4 Nb6 O17 , which has a layered struc-
ture and exhibits a high photocatalytic activity, photocatalysts with
unique structures such as layered and tunnel structures have also
been reported. Inoue et al. reported that tunnel-structured BaTi4 O9
and Na2 Ti6 O9 , which have a built-in polarization field in the crys-
tal, become active for overall water splitting when modified with
RuO2 as a cocatalyst [25,26]. It has been suggested that the inter-
nally generated field due to dipole moments in the lattice of metal
oxides is responsible for promoting photogenerated charge trans-
fer, resulting in high photocatalytic performance [27]. Inoue et al.
have also pointed out by means of electron spin resonance (ESR)
spectroscopy at 77 K under UV irradiation that without excep-
tion, the photocatalytically active titanates they examined were
able to generate O− radicals that were derived from lattice oxygen
O2 − [27–30]. The pentagonal prism tunnel structure of BaTi4 O9 is
shown in Fig. 9, with a dipole moment inside the TiO6 octahedra. A
more detailed explanation is available in the review paper by Inoue
[12].
Ruddlesden–Popper type layered perovskites of A2 La2 Ti3 O10
(A = K, Cs, Rb) showed a fairly high activity for overall water split-
ting [31,32]. These compounds consist of [La2 Ti3 O10 ]2− perovskite
layers with A+ cations hosted in the interlayer space, which can
be hydrated to form A2 La2 Ti3 O10 ·nH2 O under ambient conditions.
Modification of the external surface of the Rb2 La2 Ti3 O10 particles
(ca. 1 ␮m in size) with nanoparticulate NiOx resulted in an appre-
ciable enhancement of the activity for overall water splitting. As
with Ni/K4 Nb6 O17 , the active sites for H2 and O2 evolution on
NiOx /Rb2 La2 Ti3 O10 are separate, and water reduction occurs on
NiOx nanoparticles loaded on the external surface of Rb2 La2 Ti3 O10 ,
while intercalated water molecules are oxidized to form O2 in the
interlayer nanospace. This idea was supported by the observation
that partial replacement of Ti4+ cations in Rb2 La2 Ti3 O10 with Nb5+
to reduce the layer charge density resulted in a loss of ability to
undergo hydration of the interlayer space, and a significant drop in
photocatalytic activity.
Lee et al. reported that a series of layered perovskites, expressed
as Am Bm O3m+2 (m = 4, 5; A = Ca, Sr, La; B = Nb, Ti), act as highly effi-
cient photocatalysts for water splitting, with AQYs higher than 20%
under UV irradiation ( < 320 nm) [33,34]. Lee et al. concluded that
these high activities are due to the layered structure and the high
Fig. 9. A pentagonal prism tunnel structure of BaTi4 O9 , and the dipole moments
inside the TiO6 octahedral units.
Reprinted with permission from Ref. [12]. Copyright 2009 The Royal Society of
Chemistry.
donor concentration compared to bulk-type perovskite photocata-
lysts.
2.1.3. Tantalates as highly efficient photocatalysts
Since the mid-1990s, many tantalates have been reported to be
highly active photocatalysts [35–53]. Many tantalates with band
gaps of 4.0–4.5 eV generally have relatively high activity for over-
all water splitting under UV irradiation, compared to titanates and
niobates. NiO-loaded NaTaO3 with a distorted perovskite struc-
ture shows the highest activity among the tantalates [40]. As will
be mentioned later, the activity of a NiO/NaTaO3 photocatalyst is
remarkably improved by doping with lanthanoid or alkaline earth
metal ions. One of the beneficial aspects of tantalate photocata-
lysts is their relatively high conduction band potential, compared to
titanates and niobates. Sr2 Nb2 O7 and Sr2 Ta2 O5 , for example, have
band gaps of 3.9 and 4.6 eV, respectively [39]. Because their valence
bands are composed of the same (O2p) orbitals [54], the difference
in the band gap is attributed to their conduction bands, as shown
in Fig. 10. In this situation, the conduction band electrons should
have a higher ability to reduce water. This is considered to be the
main reason that tantalates have a relatively high water-splitting
activity.
Machida et al. examined the photocatalytic properties of tanta-
lates containing lanthanoid metal ions [47–51] and Dion–Jacobson
phase layered perovskite [52,53] for overall water splitting. Because
the lanthanoid metal ions have unique properties that can modu-
late the electronic band structure, surface morphology, and other
properties, tantalates containing lanthanoid metal ions exhibit
interesting photocatalytic behavior. Taking LnTaO4 (Ln = La, Ce, Pr,
 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 10. Band structures of Sr2 M2 O7 (M = Nb and Ta) photocatalysts.
Reproduced with permission from Ref. [39]. Copyright 2000 American Chemical
Society.
Nd, and Sm) as an example, only the La-derivative is active for over-
all water splitting. That LaTaO4 has the highest activity among the
LnTaO4 series has been mainly attributed to the overlap between
the Ta5d and O2p orbitals, which produces a wide density-of-states
distribution in the conduction band. On the other hand, tanta-
lates containing from one (Ce3+ ) to five (Sm3+ ) 4f electrons are
largely inactive, because unoccupied 4f levels lying on or below
the conduction band-edge are expected to act as trapping centers
for photoexcited electrons. A schematic band diagram is shown in
Fig. 11.
2.1.4. Other d0 metal oxides (titanates, niobates, etc.)
ZrO2 has a band gap of 5.0 eV, can operate under UV irradia-
tion ( < 250 nm), and is a unique photocatalyst that exhibits a high
activity even without a cocatalyst [55]. The rates of both H2 and O2
evolution increase upon the addition of Na2 CO3 and NaHCO3 into
the reactant suspension. This also enables the production of CO as
a reduction product, while maintaining the overall stoichiometry
of the reaction. It has been reported that the special characteristics
of ZrO2 arise from its highly negative flat-band potential and wide
band gap.
Since 2000, research on d0 metal oxides, in addition to tan-
talates, has been conducted, and several interesting reports are
available [56–64]. Abe et al. reported that metal oxides, expressed
as R3 MO7 and R2 Ti2 O7 (R = Y, Gd, La; M = Nb, Ta), that have dif-
Fig. 11. Band structure models of LnTaO4 (Ln = La, Pr, and Nd).
Reprinted with permission from Ref. [51]. Copyright 2001 American Chemical Soci-
ety.
243
Fig. 12. Schematic drawing of (a) weberite La3 TaO7 , (b) pyrochlore Y2 Ti2 O7 , and (c)
perovskite La2 Ti2 O7 .
Reprinted with permission from Ref. [57]. Copyright 2006 American Chemical Soci-
ety.
ferent crystal structures exhibit different photocatalytic activities
[56,57]. Stoichiometric decomposition of pure water proceeds over
La3 TaO7 and La3 NbO7 (orthorhombic weberite structure), Y2 Ti2 O7
and Gd2 Ti2 O7 (cubic pyrochlore structure), and La2 Ti2 O7 (mono-
clinic perovskite structure). All of these photocatalysts consist of
crystal structures that contain a network of corner-shared octahe-
dral units of metal cations (TaO6 , NbO6 , or TiO6 ). Compounds that
lack such a network, such as Y3 TaO7 and Y3 NbO7 (fluorite-cubic
structure), Gd3 TaO7 and Gd3 NbO7 (cubic pyrochlore structure),
and La3 TaO7 and La3 NbO7 (cubic pyrochlore structure), were inac-
tive for the water-splitting reaction. Therefore, the network of
octahedral units of metal cations significantly affects the photo-
catalytic activity of oxide semiconductor materials. The crystal
structures of these compounds are shown in Figs. 12 and 13.
Titnates and niobates with activities comparable to those of tan-
talates have also been reported, as exemplified by Y2 Ti2 O7 [59],
Fig. 13. Schematic drawing of (a) fluorite Y3 TaO7 and (b) pyrochlore Gd3 TaO7 .
Reprinted with permission from Ref. [57]. Copyright 2006 American Chemical Soci-
ety.
244 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 14. A correlation between photocatalytic activity and dipole moment of octahe-
dral GaO6 and tetrahedral GaO4 in MGa2 O4 (M = Mg, Sr, Ba). Photocatalyst: powder,
photocatalyst amount 0.25 g; Ar gas pressure, 13.3 kPa; light source, Hg–Xe lamp
without filter; light intensity, 200 W.
Reprinted with permission from Ref. [12]. Copyright 2009 The Royal Society of
Chemistry.
BaLa4 Ti4 O15 , and Ba5 Nb4 O15 [61,62] when modified with NiOx
as a cocatalyst. Ikeda et al. reported that tungsten-based metal
oxides, AMWO6 (A = Rb, Cs; M = Nb, Ta), loaded with NiOx cocatalyst
are active under UV irradiation for the stoichiometric cleavage of
water [64].
2.2. Effect of electronic band structure
2.2.1. d10 -Type metal oxides
Inoue pointed out that the high activity of metal oxides with
an empty d orbital (d0 configuration) for photocatalysis sug-
gests that metal oxides with a completely occupied d orbital (d10
configuration) should also be useful, because the d0 and d10 con-
figurations behave similarly from a quantum chemistry viewpoint
[12]. Inspired by this idea, Inoue et al. have developed, since
2001, typical metal oxides with d10 electronic configurations as
a new group of efficient photocatalysts for overall water splitting
under UV irradiation when combined with RuO2 as a cocatalyst
[65–73].
The photocatalytic water-splitting activity of d10 metal oxides
is strongly dependent on their geometric structure. For example,
distorted MGa2 O4 (M = Sr, Ba) with dipole moments are photocat-
alytically active, while distortion-free MgGa2 O4 exhibits negligible
activity, as shown in Fig. 14. This tendency has been observed
not only in gallates but also in indates (AInO2 (A = Li, Na), MIn2 O4
(M = Ca, Sr)), stannates, (M2 SnO4 (M = Ca, Sr, Ba)), and antimonates
(M2 Sb2 O7 (M = Ca, Sr), CaSb2 O6 and NaSbO3 ). Inoue et al. proposed
that the metal–oxygen bond length affects photoexcitation, and
that the poor symmetry of octahedral and tetrahedral coordina-
tion tends to lead to the formation of isolated orbitals, affecting
the photoexcitation efficiency. It has also been suggested that local
internal fields due to the dipole moment inside the distorted units
contribute to electron–hole separation upon photoexcitation.
The electronic structure is also an important factor, because the
behavior of photoexcited charge carriers is determined by the band
level and dispersion. From the viewpoint of the electronic band
structure, d10 -based semiconducting materials offer advantages
over the d0 configurations as photocatalysts, because although the
top of the valence band consists of O2p orbitals, the bottom of the
conduction band is composed of hybridized s,p orbitals of typical
metals. The hybridized s,p orbitals have a large dispersion, leading
to increase mobility of photogenerated electrons in the conduc-
tion band and thus a high photocatalytic activity, as schematically
depicted in Fig. 15.
␤-Ga2 O3 , a photocatalyst with a d10 electronic configuration and
a band gap of ca. 4.5 eV, has also been reported to produce H2 or
O2 from aqueous solutions containing methanol or silver nitrate,
Fig. 15. Schematic band structures of a d0 - and d10 -photocatalyst.
respectively [74]. Subsequently, Sakata et al. reported in 2004 that
photocatalytic decomposition of water over NiO-loaded ␤-Ga2 O3
can be achieved [75]. As will be mentioned later, Sakata et al.
have further modified the ␤-Ga2 O3 photocatalyst to improve its
activity.
2.2.2. Mixed-configuration metal oxides
Inoue et al. examined complex metal oxides containing two
kinds of metal ions with d10 –d10 [76], d10 s2 –d0 [77–79], and
d10 s2 –d10 [12] electronic configurations, because the resultant geo-
metric and electronic structures, which can affect photocatalytic
activity, vary considerably. In the local structures, the presence
of two different metal ions in the unit cell causes distortion of
the tetrahedral and octahedral coordination of the metal oxides.
This is exemplified by LiInGeO4 , which consists of InO6 octahe-
drons and GeO4 tetrahedrons with dipole moments of 3.0 and
3.4 Debye, respectively, and shows a much higher activity than
LiInO2 [76]. For a metal oxide that contains two different elec-
tronic configurations, it is expected that hybridization of the atomic
orbitals of the two metal ions occurs, resulting in a significant
effect on the density of states and energy dispersion in the con-
duction bands. For example, RuO2 -loaded PbWO4 with a d10 s2 –d0
electronic configuration functions as a photocatalyst, stoichiomet-
rically producing H2 and O2 from pure water under UV irradiation.
On the other hand, an analogous sample of CaWO4 , which has a
crystal structure (viz., scheelite) close to that of PbWO4 , evolves
only a small amount of H2 and no O2 . As shown in Fig. 16, density
functional theory (DFT) calculations for PbWO4 with a d10 s2 –d0
electronic configuration indicated that the top of the valence band
(HOMO) is composed of hybridized O2p + Pb6s orbitals, while the
bottom of the conduction band (LUMO) consists of hybridized
W5d + O2p + Pb6p orbitals. Considerable dispersion was observed
for both the conduction and valence bands, which was different
from the low dispersion observed for the photocatalytically inac-
tive CaWO4 . The mobility of photoexcited electrons and holes in
such highly dispersed conduction and valence bands should be
high, contributing to the higher photocatalytic performance of
PbWO4 .
Another example of a water-splitting photocatalyst with an
interesting electronic structure was reported by Inoue et al. They
reported that Ce(IV) oxide (CeO2 ) with an [Xe] f0 d0 s0 electronic
structure, which is a kind of closed-shell structure of the d0 elec-
tronic configuration, functions as a photocatalyst for water splitting
[80]. Although it has been reported that CeO2 has the ability to
produce oxygen from an aqueous solution containing Ce4+ ions
as an electron acceptor [81], RuO2 -loaded undoped CeO2 exhibits
negligible photocatalytic activity under UV irradiation without an
electron acceptor. Interestingly, doping CeO2 with Sr2+ enables
 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 16. Band dispersion and DOS for PbWO4 and CaWO4 .
Reprinted with permission from Ref. [78]. Copyright 2007 American Chemical Society.
functionality as a water-splitting photocatalyst in the presence of
an RuO2 cocatalyst, demonstrating the first example of a photo-
catalytically active lanthanide oxide for water splitting. Due to the
deviation from the ideal ratio of ions in the fluorite structure, some
of the Ce4+ ions are converted to Ce3+ ions to maintain the fluo-
rite structure. Since Sr2+ is slightly larger in ionic raduis and less
positively charged than Ce4+ , the Sr-doping suppresses the gener-
ation of Ce3+ ions, which can act as charge recombination centers,
in the CeO2 . According to DFT calculations for Sr2+ -doped CeO2 , the
valence band is composed of the O2p orbital, while the unoccu-
pied band consists of the Ce4f orbital band and the Ce5d orbital
hybridized with Sr5s5p orbitals, which appear at an upper energy
level. Although undoped and Sr2+ -doped CeO2 both have an absorp-
tion threshold at ca. 400 nm, no photocatalytic reaction occurs
under irradiation by light with a wavelength longer than 300 nm.
The threshold of absorption around 400 nm is due to electron trans-
fer from the O2p orbital (HOMO) to the unoccupied Ce4f orbital, but
the excited electrons do not participate in the water-splitting reac-
tion. This indicates that the electrons transferred to the Ce5d orbital
do contribute to the reaction. A proposed band model is shown in
Fig. 17.
Fig. 17. A model of the band structure and photocatalysis of Sr-doped CeO2 .
Reprinted with permission from Ref. [80]. Copyright 2007 The Chemical Society of
Japan.
245
2.3. Development of photocatalysts that can utilize visible
photons
2.3.1. Difficulty in developing a water-splitting photocatalyst that
operates under visible light
As discussed earlier, metal oxide photocatalysts that exhibit
water-splitting activity under UV irradiation ( < 400 nm) are well
established. However, achieving water splitting on a metal oxide
under visible light ( > 400 nm) remains a challenge. In general,
the conduction band of a metal oxide photocatalyst is formed by
empty d orbitals of a transition metal or s,p orbitals of a typical
metal, which lie above the water reduction potential of H2 O (0 V vs.
NHE at pH 0). On the other hand, the potential of the valence band,
which consists of O2p orbitals (ca. +3 V), is considerably more posi-
tive than the water oxidation potential (1.23 V). Therefore, the band
gaps of metal oxide photocatalysts inevitably become wider than
3 eV, if they meet the thermodynamic requirement for water split-
ting. Scaife visualized this situation by examining the relationship
between the flat-band potentials (VFB ) and the band gaps (Eg ) of
various metal oxides [54], giving the following empirical equation:
VFB (NHE) ≈ 2.94 − Eg (7)
From the viewpoint of solar energy conversion, however, the
development of a photocatalyst that splits water efficiently under
visible light ( > 400 nm) is indispensable. Until the early 1990s,
only a few chalcogenides and metal oxides (e.g., CdS [82,83]
and WO3 [84–86]) were known to be photocatalytically active
under visible light. Certain metal chalcogenides, including CdS
and CdSe, appeared to be suitable photocatalysts for overall water
splitting, exhibiting band-gap energies sufficiently small to allow
absorption of visible light and having conduction and valence
bands at potentials appropriate for water reduction and oxidation.
These metal chalcogenides, however, are not stable in the water
oxidation reaction to form O2 because the S2− and Se2− anions are
more susceptible to oxidation than water, causing the CdS or CdSe
catalyst itself to be oxidized and degraded [87,88]. Although WO3
functions as a stable photocatalyst for O2 evolution under visible
light in the presence of an appropriate electron acceptor, the
bottom of the conduction band of the material is higher than the
246 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 18. Schematic illustration of the band structures of several semiconductor pho-
tocatalysts.
Reprinted with permission from Ref. [7]. Copyright 2007 American Chemical Society.
potential for water reduction. As a result, WO3 cannot reduce H+ to
H2 . Fig. 18 shows a schematic illustration of the band structures of
some photocatalysts, highlighting the abovementioned dilemma.
Until very recently, reproducible photocatalytic systems for
visible-light-driven overall water splitting had not been realized,
although there are several reports that claimed to demonstrate
the decomposition of water under visible light.
The difficulty in developing a suitable photocatalyst can thus
be attributed to the lack of known materials that meet these three
requirements:
(1) band-edge potentials suitable for overall water splitting
(2) band-gap energy lower than 3 eV
(3) stability in the photocatalytic reaction
To date, numerous attempts have been made to prepare a pho-
tocatalytic material that efficiently functions under visible light.
In UV-active metal oxide photocatalysts, as mentioned, the bot-
toms of the conduction bands are slightly below 0 V (vs. NHE) at
pH 0, and the tops of the valence bands are above 3 V. This makes
the band gap of the material too large to harvest visible light, but
suggests that metal oxide photocatalysts have sufficient potential
to oxidize water because of the difference between the oxidation
potential of H2 O into O2 (1.23 V vs. NHE) and the valence band-edge
potential (ca. 3 V vs. NHE). It is therefore very important to design
the band structure of a metal oxide while keeping the conduc-
tion band potential. The primary approaches to making a wide-gap
metal oxide sensitive to visible light are schematically illustrated
in Fig. 19, and can be classified as follows.
Fig. 19. Conceptual drawing of strategies to develop a visible-light-driven photocatalyst through modification of a metal oxide.
(1) Doping with transition-metal ions having a dn (0 < n < 10) elec-
tronic configuration
(2) Valence band control using an anion’s p orbitals or the s orbitals
of p-block metal ions
(3) Spectral sensitization
In the following sections, each strategy will be introduced in
more detail.
2.3.2. Doped metal oxide photocatalysts
Doping a wide-gap metal oxide with foreign elements is one
of the most well-known approaches for modification of the metal
oxide crystal, and in most cases a crystal lattice point of the
host material is replaced with the dopant. When the dopant is a
transition-metal cation that has a partially filled d orbital (i.e., dn
(0 < n < 10) configuration) or is an anion such as C4− , N3− , or S2− ,
a donor or acceptor level is formed in the forbidden band of the
material as a center for absorption at visible wavelengths. However,
doping also hinders the rapid migration of photogenerated elec-
trons or holes in the material, since the dopant frequently provides
a discreet energy level rather than an energy band [89]. Moreover,
in most cases, it is difficult to maintain charge balance when a
dopant is introduced into the host metal oxide, generating vacan-
cies that act as recombination centers for photogenerated electrons
and holes. The doping method is therefore somewhat disadvanta-
geous in the development of an efficient visible-light-responsive
oxide-based photocatalyst.
The negative effects of doping can be partially addressed by
codoping with another suitable dopant [90–93]. Kato and Kudo
have demonstrated the validity of this idea; rutile TiO2 codoped
with Cr3+ and Sb5+ is an effective photocatalyst for water oxidation
in the presence of silver nitrate as a sacrificial electron acceptor
under visible light ( > 420 nm), and can achieve a substantially
higher activity than doping with Cr3+ alone [90]. Codoping with
Rh3+ and Sb5+ also activates rutile TiO2 to exhibit visible-light pho-
tocatalytic O2 evolution activity [92]. The activity of this doped
TiO2 was found to be strongly dependent on the amount of Sb5+
codapant, as shown in Fig. 20. When TiO2 was doped with only
Cr, no activity was observed, and the color of the photocatalyst
remained black. When the ratio of Sb/Cr was equal to or larger than
unity, O2 evolution was observable, and the photocatalyst color
changed from black to orange. TiO2 :Cr without Sb codopant con-
tains Cr6+ and oxygen defects as a result of charge compensation. As
the ratio of Sb codopant increases, the formation of Cr6+ and oxy-
gen defects is suppressed. Thus, codoping with Sb5+ stabilizes the
Cr3+ state, forming an electron donor level to maintain charge bal-
 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268 247

Fig. 21. Diffuse reflectance spectra of valence band-controlled photocatalysts.

Reprinted from Ref. [13] with permission.

atomic orbitals of the constituent elements would be more desir-

Fig. 20. Dependence of photocatalytic activity of TiO2 :Sb (X%)/Cr (2.3%) on the able.
ratio of antimony to chromium. Catalyst: 0.5 g, an aqueous silver nitrate solution: Such “valence band-controlled photocatalysts” have been
0.05 mol L−1 , 320 mL, 300 W Xe lamp ( > 420 nm), side irradiation cell. reported by many groups. Domen et al. reported that a
Reprinted with permission from Ref. [90]. Copyright 2002 American Chemical Soci-
Dion–Jacobson phase layered perovskite, RbPb2 Nb3 O10 , and its
ety.
proton-exchanged derivatives act as photocatalysts capable of pro-
ducing H2 or O2 from aqueous solutions containing methanol or
silver nitrate, respectively, under visible light [98]. The band gap
ance, resulting in an appreciable increase in photocatalytic activity.
of RbPb2 Nb3 O10 is ca. 2.6 eV, smaller than that of KCa2 Nb3 O10 (ca.
Onishi et al. conducted time-resolved infrared (IR) absorption spec-
3.5 eV), a perovskite material with an identical crystal structure.
troscopy to observe photo-induced carrier dynamics in TiO2 :Cr/Sb
Although it has been claimed that the mechanism by which the
photocatalysts, revealing that Sb5+ codoping prolonged the lifetime
visible-light response of RbPb2 Nb3 O10 is realized remains unclear
of photogenerated electrons, and that TiO2 :Cr/Sb with an optimum
[98], it appears to be attributed to the contribution of Pb6s orbitals,
ratio of 1.0–2.0 gives the slowest decay when excited by 532 nm
which lie below the O2p orbitals, to the valence band formation.
light pulses [93]. Similarly, SrTiO3 doped with Cr3+ and either Ta5+
Undoped metal oxides that exhibit activity for the H2 and/or O2
or Sb5+ exhibits activity for H2 evolution from an aqueous methanol
evolution half-reactions were reported by Kudo et al. [99–109], who
solution under visible light ( > 420 nm), when modified with a
demonstrated that certain metal oxides containing Bi3+ [100–104],
Pt cocatalyst [92]. Among doped metal oxides, Rh-doped SrTiO3
Ag+ [105–107], and Sn2+ [108–110] cations are capable of harvest-
exhibits the highest water reduction performance, with an AQY
ing visible photons to cause photocatalytic reactions. Both AgNbO3
of 5.2% at 420 nm from an aqueous methanol solution [94]. It has
and SnNb2 O6 are rare oxide photocatalysts that have the ability
been claimed that the visible-light response of this material can be
to reduce and oxidize water in the presence of sacrificial reagents
attributed to electron transitions from the donor level formed by
under visible light. Fig. 21 shows the diffuse reflectance spectra for
Rh ions to the conduction band composed of Ti 3d orbitals of SrTiO3 ,
these oxide photocatalysts. Lee et al. reported the photocatalytic
and that the reversible Rh species contributes to the formation of a
properties of PbBi2 Nb2 O9 , an Aurivillius phase perovskite that has a
visible-light absorption band and the surface reaction sites.
band gap of 2.88 eV [111]. Under visible light ( > 420 nm), the oxide
Although TiO2 and SrTiO3 have been extensively used as host
material exhibits a relatively high activity for both water reduc-
semiconductors to prepare doped photocatalysts, it has been
tion and oxidation in the presence of methanol and silver nitrate,
reported that other semiconductors are also applicable. A simi-
respectively. According to band structure calculations using the
lar material based on CaTiO3 perovskite was reported by Miyake
Wien97 program, they concluded that the bottom of the conduc-
et al. to be active for visible-light-driven H2 evolution [95]. Lee et al.
tion band of PbBi2 Nb2 O9 consists mostly of empty Nb4d orbitals,
reported that Cr or Fe-doped La2 Ti2 O7 is capable of producing H2
while the top of the valence band is formed by hybridized Bi6s and
from an aqueous methanol solution under visible light [96]. Codop-
Pb6s orbitals. The hybridized orbitals are likely to raise the posi-
ing with Ir and either Sr, Ba, or La into NaMO3 (M = Nb and Ta) makes
tion of the valence band, giving a smaller band gap than that of
the host material active for visible-light-driven H2 or O2 evolution
compounds that do not contain Pb and Bi in their structure.
in the presence of sacrificial reagents, and the activity is strongly
Although BiVO4 , which has a band gap of 2.4 eV, is unable to
dependent on the concentration and type of codopant(s) employed
reduce water due to the conduction band potential being more pos-
[97].
itive than the water reduction potential, it is one of the most active
photocatalysts for visible-light-driven water oxidation [101–104].
2.3.3. Valence band-controlled metal oxide photocatalysts BiVO4 is a polymorphic compound, exhibiting tetragonal zircon,
The conventional doping strategy introduced above has resulted monoclinic scheelite, and tetragonal scheelite phases with different
in several successful examples of visible-light photocatalysis. How- crystal structures [112,113]. Among these, the monoclinic scheelite
ever, the generation of recombination centers such as oxygen phase shows the highest performance as a photocatalyst for water
defects is an unwanted side effect of doping with foreign ele- oxidation using AgNO3 as an electron acceptor, and exceeds the
ments. Furthermore, the impurity levels created by dopants in performance of WO3 , a representative photocatalyst for water oxi-
the forbidden band of the material are usually discrete, which is dation [102]. Furthermore, photoelectrochemical water splitting
disadvantageous for the migration of photogenerated holes. In con- can be achieved using a porous BiVO4 electrode under visible light
trast, semiconductors having a continuous valence band formed by in the presence of an externally applied potential [114,115].
248 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 22. Schematic band structures of a metal oxide (NaTaO3 ) and metal (oxy)nitride
(BaTaO2 N).
Reprinted with permission from Ref. [7]. Copyright 2007 American Chemical Society.
In addition to WO3 , many other metal oxides with a visible-light
response have been reported to use the s electrons of the con-
stituent elements (Pb2+ , Bi3+ , Ag+ , and Sn2+ ). Some have achieved
both H2 and O2 evolution individually in the presence of suitable
sacrificial reagents. Although overall water splitting using these
metal oxides has yet to be achieved, some have been successfully
applied to Z-scheme water-splitting systems mimicking natural
photosynthesis in green plants, which involves two-step photoex-
citation, as will be introduced in a later section.
2.3.4. Non-oxide photocatalysts with a d0 electronic
configuration
Since 2000, Domen et al. have studied non-oxide compounds
such as (oxy)nitrides and oxysulfides having a d0 electronic config-
uration as photocatalysts for overall water splitting under visible
light [116–130]. Some metal (oxy)nitrides have attracted atten-
tion as non-toxic inorganic pigment alternatives to chalcogenides.
For example, a series of LaTaON2 –CaTaO2 N solid solutions was
reported to vary in color from yellow to red [131]. In addition,
these materials were chemically stable except in very strong acids,
e.g., aqua regia and hot concentrated sulfuric acid. It has also been
claimed that this type of material differs from materials doped with
nitrogen or sulfur [132], as the constituent anion component in such
non-oxides does not form a discreet (or isolated) impurity level, but
forms valence bands. Therefore, these non-oxide materials can be
regarded as valence band-controlled photocatalysts.
Fig. 22 shows the schematic band structures of the metal oxide
NaTaO3 and (oxy)nitride BaTaO2 N, both of which have the same
perovskite structure [7]. The top of the valence band (i.e., the high-
est occupied molecular orbital, HOMO) of the metal oxide consists
of O2p orbitals. When N atoms are partially or fully substituted for
O atoms in a metal oxide, the HOMO of the material is expected to
shift above that of the corresponding metal oxide without affect-
ing the level of the bottom of the conduction band (i.e., the lowest
unoccupied molecular orbital, LUMO). DFT band structure calcula-
tions for BaTaO2 N indicated that the HOMO consists of hybridized
N2p and O2p orbitals, whereas the LUMO is mainly composed of
empty Ta5d orbitals. The HOMO for the (oxy)nitride is at a higher
potential energy than that of the corresponding oxide due to the
contribution of N2p orbitals, making the band gap small enough
to respond to visible light (<3 eV). Similar results were obtained in
calculations for other (oxy)nitrides and oxysulfides.
Some particulate (oxy)nitrides containing d0 transition-metal
cations can be readily obtained by heating a corresponding metal
oxide powder under a flow of ammonia, typically at 1073–1273 K
[116–127,133]. Fig. 23 shows UV-visible diffuse reflectance spec-
tra for certain (oxy)nitrides containing transition-metal cations of
Ti4+ , Nb5+ , and Ta5+ with a d0 electronic configuration. It is clear
Fig. 23. UV-visible diffuse reflectance spectra for (oxy)nitrides containing Ti4+ , Nb5+ ,
and Ta5+ .
Reprinted with permission from Ref. [7]. Copyright 2007 American Chemical Society.
that these (oxy)nitrides have absorption bands at 500–750 nm,
corresponding to band-gap energies of 1.7–2.5 eV. Most of these
(oxy)nitrides are capable of reducing and oxidizing water in
the presence of a sacrificial electron donor or acceptor, respec-
tively, and exhibit relatively high photocatalytic activity for water
oxidation to form molecular oxygen under visible irradiation
( > 420 nm). Among them, TaON has achieved the highest AQY of
34%. (Oxy)nitrides also produce H2 from an aqueous methanol solu-
tion upon visible irradiation when loaded with nanoparticulate Pt
as a cocatalyst for H2 evolution. However, the activities for H2 pro-
duction are about an order of magnitude lower than those for O2
evolution, although the photocatalytic performance for H2 evolu-
tion is stable. In this context, several new modifications to enhance
the H2 evolution rate of (oxy)nitrides have been pursued, and will
be introduced in a later section.
It is important to note that in most cases, a low level of N2 evolu-
tion accompanies the initial stage of photocatalytic reactions over
these (oxy)nitrides, indicating that they are partially decomposed
by the photogenerated holes (instead of water oxidation) according
to the reaction:
2N3− + 6h+ → N2 (8)
However, the production of N2 is completely suppressed as
the reaction progresses, as shown in Fig. 24, which shows a typ-
ical time course of H2 evolution over Pt-loaded TaON from an
aqueous methanol solution under visible light ( > 420 nm). Fur-
thermore, no change in the XRD pattern of the (oxy)nitrides as a
result of the reaction has been detected. It therefore appears that
(oxy)nitride photocatalysts are essentially stable in the individ-
ual water reduction and oxidation reactions. It remains to extend
this performance to overall water splitting, which has yet to be
achieved. The main obstacle appears to be the low activity of H2
evolution on (oxy)nitrides. Nevertheless, PEC water splitting under
visible light can be achieved using some d0 -type (oxy)nitrides as
anode materials [134–139]. Among these, a modified TaON elec-
trode exhibits the highest performance, with a 76% incident photon
to electron conversion efficiency (IPCE) at 400 nm under an exter-
nally applied bias of 0.6 V vs. Ag/AgCl [138].
Oxysulfide Ln2 Ti2 S2 O5 (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Ho and Er)
is also a stable photocatalyst, with a wide absorption band in the
visible region ( < 600 nm) and band-edge potentials suitable for
overall water splitting [128–130]. DFT calculations for Sm2 Ti2 S2 O5
 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 24. Time course of H2 evolution over Pt-loaded TaON under visible-light irradi-
ation ( > 420 nm). Reaction conditions: 0.4 g of catalyst and 200 mL of an aqueous
methanol solution (10 vol.%); xenon lamp fitted (300 W) fitted with a cutoff filter;
top irradiation-type reaction vessel.
Reprinted with permission from Ref. [116]. Copyright 2002 The Royal Society of
Chemistry.
(Ln = Sm) indicate that the S3p atomic orbitals constitute the upper
part of the valence band and make an essential contribution to low-
ering the band-gap energy from that of the corresponding metal
oxide (Sm2 Ti2 O7 ). Metal sulfides such as CdS are not suitable for use
as a photocatalyst for water oxidation due to the inherent instability
of these materials in the reaction because of the photogeneration
of holes. Interestingly, Sm2 Ti2 S2 O5 functions as a stable photocat-
alyst for water oxidation to produce O2 . It has also been confirmed
by XRD and XPS that decomposition of Sm2 Ti2 S2 O5 in the bulk and
at the surface, in particular the oxidation of S2− species, does not
occur during water photooxidation, even though the valence band
consists partially of S3p atomic orbitals. H2 evolution from an aque-
ous solution containing S2− and SO3 2− also proceeds steadily on
Sm2 Ti2 S2 O5 when modified with nanoparticulate Pt as H2 evolu-
tion sites. Therefore, the oxysulfide Sm2 Ti2 S2 O5 has functionality
as a stable photocatalyst for water reduction or oxidation under vis-
ible irradiation. Other Ln2 Ti2 S2 O5 (Ln = Pr, Nd, Gd, Tb, Dy, Ho and
Er) oxysulfides with the same layered perovskite structure are also
active, stable photocatalysts for H2 or O2 evolution from an aqueous
solution containing a sacrificial electron donor or acceptor under
visible irradiation. The photocatalytic activities of Ln2 Ti2 S2 O5 are
strongly dependent on the kind of lanthanoid (Ln) used, which
affects the electronic band structure.
2.3.5. d10 -Type (oxy)nitrides and oxysulfides
As mentioned in Section 2.2.1, d10 -semiconductors containing
typical metal cations have an advantage as photocatalysts, com-
Fig. 25. (A) Powder XRD patterns and (B) UV-visible diffuse reflectance spectra for various (Ga1 − x Znx )(N1 − x Ox ) solid solutions.
Reprinted with permission from Ref. [7]. Copyright 2007 American Chemical Society.
249
pared to materials with a d0 electronic configuration, because of
their electronic band structure. (Oxy)nitrides and oxysulfides with
a d10 electronic configuration are therefore of interest as potentially
efficient photocatalysts for overall water splitting. In evaluating
such d10 -compounds based on this hypothesis, it was found in
2005 that ␤-Ge3 N4 loaded with RuO2 nanoparticles functions as
a photocatalyst for overall water splitting [140–143]. This was the
first case involving a non-oxide photocatalyst for the cleavage of
pure water. Since this discovery, the photocatalytic properties and
effects of post-treatment to enhance the activity of Ge3 N4 have
been examined in detail [141,142]. The relationship between the
structural characteristics and the photocatalytic performance of
Ge3 N4 has also been investigated [143]. Unfortunately, the band
gap of ␤-Ge3 N4 is about 3.8 eV, so it is responsive only to UV light
[140,142].
Domen et al. reported in 2005 that a solid solution of GaN and
ZnO, represented as (Ga1 − x Znx )(N1 − x Ox ), is a stable photocata-
lyst, able to split water into H2 and O2 under visible light when
modified with RuO2 as a cocatalyst [144,145]. Because both GaN
and ZnO have wurtzite structures with similar lattice parameters,
a solid solution can be formed between the two. The solid solution,
(Ga1 − x Znx )(N1 − x Ox ) with x = 0.05–0.42, can be readily prepared by
heating a mixture of Ga2 O3 and ZnO under a flow of ammonia at
∼1223 K. Elemental analysis by inductive coupled plasma optical
emission spectroscopy (ICP-OES) revealed that the ratios of Ga to N
and Zn to O in the products were close to 1, and that the nitrogen and
oxygen concentrations increased with increasing gallium and zinc
concentrations. The atomic composition of (Ga1 − x Znx )(N1 − x Ox ) is
controllable by changing the nitridation conditions. As shown in
Fig. 25A, X-ray diffraction (XRD) analysis showed that the prepared
material had a wurtzite structure similar to GaN and ZnO, and the
diffraction peaks were at positions intermediate between those of
GaN and ZnO. In addition, neutron powder diffraction analysis con-
firmed that oxygen atoms were substituted for nitrogen atoms in
(Ga1 − x Znx )(N1 − x Ox ) with no interstitial sites being formed and no
significant disorder to the material [146]. Based on these results,
it was concluded that the obtained material was indeed a solid
solution of GaN and ZnO.
Taking into account the large band-gap energies of GaN and
ZnO (>3 eV), it was believed that the band gap of the solid solu-
tion should exceed 3 eV, despite the formation of the solid solution.
Interestingly, however, the (Ga1 − x Znx )(N1 − x Ox ) solid solution has
absorption edges in the visible region. Fig. 25B shows the UV-visible
diffuse reflectance spectra of several samples. The absorption edge
shifted to longer wavelengths with increasing Zn and O concen-
tration (x) in (Ga1 − x Znx )(N1 − x Ox ). The band-gap energies of the
solid solutions were estimated to be 2.4–2.8 eV based on diffuse
250 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 26. Expected energy level diagram for impurity levels in undoped GaN, Zn-
doped GaN, and GaN-rich (Ga1 − x Znx )(N1 − x Ox ) solid solutions. Arrows denote
photoabsorbtion, photoluminescence, and thermal relaxation.
Reprinted with permission from Ref. [148]. Copyright 2010 American Chemical Soci-
ety.
reflectance spectra. Initially, the origin of the visible-light absorp-
tion was thought to be band-gap narrowing of GaN due to p–d
repulsion between Zn 3d and N 2p electrons in the upper part of the
valence band [144,145]. Follow-up studies on the electronic struc-
ture of GaN-rich (Ga1 − x Znx )(N1 − x Ox ) using photoluminescence
spectroscopy and DFT calculations suggested that this material
absorbs visible light via electron transitions from the Zn acceptor
level to the conduction band while maintaining the band-gap struc-
ture of the host GaN, as illustrated in Fig. 26 [147,148]. Because the
concentration of Zn in (Ga1 − x Znx )(N1 − x Ox ) is relatively high, the
acceptor level, which is filled with electrons derived from O donor
levels (or thermal excitation), is likely to behave as an impurity
band with a high density of states. Electrons can thus be transferred
from the Zn acceptor level to the conduction band by visible-light
absorption.
Fig. 27 shows a typical time course of overall water splitting on
(Ga1 − x Znx )(N1 − x Ox ) (x = 0.12) loaded with 5 wt% RuO2 under visi-
ble irradiation ( > 400 nm). No reaction took place in the absence
of irradiation, whereas both H2 and O2 evolved steadily and stoi-
chiometrically upon visible-light irradiation. It has been reported
that O2 evolution occurs on a ZnO electrode as a result of degrada-
Fig. 27. Typical time course of overall water splitting on 5 wt% RuO2 -loaded
(Ga1 − x Znx )(N1 − x Ox ) (x = 0.12) under visible light ( > 400 nm). Reaction conditions:
0.3 g of catalyst and 390 mL of distilled water; high-pressure mercury lamp light
source (450 W); Pyrex inner irradiation-type reaction vessel with aqueous NaNO2
filter.
Reprinted with permission from Ref. [7]. Copyright 2007 American Chemical Society.
Fig. 28. Band structures of (A) Ge3 N4 , (B) ZnGeN2 , and (C) (Zn1 + x Ge)(N2 Ox ).
Reprinted with permission from Ref. [152]. Copyright 2007 American Chemical Soci-
ety.
tion when employed as a photoanode for water oxidation in a PEC
cell [149]. Interestingly, it was confirmed through 18 O-isotopic H2 O
cleavage experiments that the O2 evolution on the solid solution
was due to water oxidation, and the XRD pattern of the sam-
ple remained unchanged after the reaction. Control experiments
showed no gas evolution in the absence of either a photocatalyst
or a light source. These results indicate that a (Ga1 − x Znx )(N1 − x Ox )
solid solution functions as a stable photocatalyst for overall water
splitting under visible light. More information on the preparation
and performance of (Ga1 − x Znx )(N1 − x Ox ) is available in a review
paper [150].
A solid solution of ZnGeN2 and ZnO, (Zn1 + x Ge)(N2 Ox ), which is
a similar material to (Ga1 − x Znx )(N1 − x Ox ), is another stable pho-
tocatalyst for overall water splitting under visible light [151–153].
(Zn1 + x Ge)(N2 Ox ) solid solutions can be prepared in a method sim-
ilar to that for (Ga1 − x Znx )(N1 − x Ox ), but with a mixture of ZnO and
GeO2 starting materials. The crystal structure of the synthesized
sample was confirmed by Rietveld analysis and neutron powder
diffraction to be wurtzite, with space group P63 mc. On the basis of
the absorption edges, the band gap of the material was estimated
to be 2.5–2.7 eV, which was smaller than the band gaps of ␤-Ge3 N4
(ca. 3.8 eV), ZnGeN2 (ca. 3.3 eV), and ZnO (ca. 3.2 eV). The visible-
light-response of the material originates from the wide valence
bands, which consist of N2p, O2p, and Zn3d atomic orbitals, and
p–d repulsion between Zn3d and N2p + O2p electrons in the upper
part of the valence bands, as schematically illustrated in Fig. 28.
Therefore, the absorption edge of (Zn1 + x Ge)(N2 Ox ) tends to shift to
longer wavelengths with increasing ZnO concentration.
Neither ZnGeN2 nor ZnO alone exhibited photocatalytic activ-
ity for overall water splitting under UV irradiation ( > 300 nm).
However, (Zn1 + x Ge)(N2 Ox ) became photocatalytically active under
visible irradiation ( > 400 nm) when loaded with an appropriate
cocatalyst. Overall water splitting on (Zn1 + x Ge)(N2 Ox ) modified
with a cocatalyst proceeds by band-gap photoexcitation from the
valence band formed by N2p, O2p, and Zn3d atomic orbitals to the
conduction band consisting of Ge4s,4p hybridized atomic orbitals.
As mentioned above, both (Ga1 − x Znx )(N1 − x Ox ) and
(Zn1 + x Ge)(N2 Ox ) function as stable water-splitting photocat-
alysts under irradiation by light with wavelengths shorter than
500 nm. For more efficient utilization of the solar spectrum,
Domen et al. have attempted to extend the absorption band of
(Ga1 − x Znx )(N1 − x Ox ) further into the red region by incorporating
InN, which has a much narrower band gap (∼1 eV). The resulting
material (referred to as Ga–Zn–In–O–N) is a brown powder, which
can be prepared by nitriding an oxide precursor containing gallium,
zinc, and indium, which can be prepared by a low-temperature
precursor route, under a flow of NH3 at 873 K for 15 h [154].
Fig. 29 shows that Ga–Zn–In–O–N has a wider absorption band
 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 29. UV-visible diffuse reflectance spectra for (a) Ga–Zn–In–O,
Ga–Zn–In–O–N, and (c) (Ga1 − x Znx )(N1 − x Ox ) with x = 0.42.
Reproduced from Ref. [154] with permission.
than (Ga1 − x Znx )(N1 − x Ox ), which can be attributed to the indium
content in the material. Structural characterization by XRD and
TEM revealed that Ga–Zn–In–O–N is incompletely crystallized
into aggregated nanoparticles of ∼10 nm in size. XAFS analysis
also indicated that the valence states of Ga, Zn, and In were
somewhat close to those of the corresponding metal oxides, but
were not completely consistent. This can be attributed to the
lower nitrogen concentration than that expected from an ideal
solid solution of GaN, ZnO, and InN. When Rh metal and CoOx were
loaded separately as cocatalysts for water reduction and oxidation
onto Ga–Zn–In–O–N, both H2 and O2 evolution were achieved
individually upon visible-light irradiation ( > 400 nm). In the case
of O2 evolution, the CoOx acted as a cocatalyst to improve the O2
evolution rate while suppressing N2 production.
Oxysulfide-containing d10 typical metal cations have also been
reported by Domen et al. [155,156]. Some oxysulfides containing
La and either In or Ga show photocatalytic activity for individual H2
and O2 evolution from aqueous solutions containing an appropriate
electron donor and acceptor, respectively, under visible light. The
Fig. 30. (A) Schematic diagram of a perfect graphitic carbon nitride sheet constructed from melem units. (B) Ultraviolet–visible diffuse reflectance spectrum of the polymeric
carbon nitride. Inset: photograph of the photocatalyst.
Reprinted by permission from Macmillan Publishers Ltd: [Nature Materials] (Ref. [158]), copyright (2009).
251
activities of these d10 oxysulfides for water reduction are higher
than those for water oxidation. It appears that a major challenge
in d10 oxysulfide photocatalysts for overall water splitting is the
improvement of water oxidation activity.
2.3.6. Metal-free photocatalysts
Until 2009, all visible-light-responsive photocatalysts that were
observed to exhibit water reduction and oxidation capability
were metal-based inorganic solids, including metal oxides, metal-
(oxy)nitrides, and metal-oxysulfides, primarily due to the lack of a
material with appropriate band-edge positions and adequate sta-
bility during photocatalysis, as discussed earlier. Synthetic polymer
semiconductors such as polyparaphenylene have also been used for
hydrogen production, but these are active only in the ultraviolet
region and have only moderate performance [157].
In 2009, Wang et al. found that graphitic carbon nitride (g-
C3 N4 ) with a band gap of 2.7 eV is a promising photocatalyst
for water-splitting applications [158]. This organic semiconductor
can be prepared by thermal polycondensation of common organic
(b) monomers (e.g., cyanamide). As shown in Fig. 30A, the graphitic
planes are constructed from tri-s-triazine units connected by pla-
nar amino groups. The in-plane organization of tri-s-triazine units
and the compression of aromatic planes were found to follow
the perfection of condensation, enabling the generation of car-
bon nitride polymers with adjustable electronic properties, while
maintaining the shapeability of a polymer made from liquid pre-
cursors. The as-prepared g-C3 N4 powder achieved functionality
as a stable photocatalyst for H2 evolution from water contain-
ing an appropriate electron donor under visible-light irradiation
( > 420 nm), even without using a cocatalyst. In addition, with
modification by RuO2 as a cocatalyst, g-C3 N4 becomes active
for O2 evolution from an aqueous silver nitrate solution under
visible light, although unloaded g-C3 N4 undergoes oxidative self-
decomposition to release N2 , resulting in a slower rate of O2
evolution [159]. This is a successful example of visible-light-driven
H2 and O2 evolution using a non-metallic semiconductor photocat-
alyst with adequate stability.
A UV-visible diffuse reflectance spectrum of g-C3 N4 is shown in
Fig. 30B, along with a photograph of the powder. DFT calculations
suggest that the visible-light response of the photocatalyst origi-
nates from electron transitions from the valence band populated
by N2p orbitals to the conduction band formed by C2p orbitals,
252 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 31. Schematic energy diagram of water splitting based on spectral sensitization.
which contributes to the visible-light photocatalytic activity. The
absorption capability of C3 N4 can be extended by copolymeriza-
tion from dicyandiamide and barbituric acid, in which the extent
of copolymerization can be used to tune the electronic and optical
properties of the product. The obtained hybrid semiconductors are
capable of harvesting photons with wavelengths of up to 750 nm
[160].
The discovery of a non-metallic material achieving the same
functionality as conventional metal-based photocatalysts under
visible light is expected to offer new opportunities for progress in
the field of artificial photosynthesis. Teng et al. recently reported
that reduced graphene oxide functions as a photocatalyst to pro-
duce H2 from a water–methanol mixture, even without loading a
cocatalyst [161].
2.3.7. Spectral sensitization
Spectral sensitization of wide-gap semiconductor particles,
which was demonstrated by Gerischer in 1972 [162], has since been
extensively studied as a potential means of H2 evolution via visible-
light water splitting [163–189]. Fig. 31 illustrates the basic principle
of water splitting based on spectral sensitization. Here, sensitiz-
ers may be organic dyes or inorganic narrow-gap semiconductors,
which must have both an energy gap sufficiently small to harvest
visible photons and an excited-state potential that is more nega-
tive than the conduction band of the metal oxide for efficient charge
injection. When sensitizers absorb photon energy, they inject elec-
trons into the conduction band of a metal oxide. These electrons
are consumed by the reduction of water at a catalytic particle such
as Pt to form H2 , while the oxidized sensitizers are regenerated by
accepting electrons from a donor molecule. In non-sacrificial sys-
tems, the ultimate electron donor is water, but usually a sacrificial
reagent such as ethylenediaminetetraacetic acid (EDTA) is used to
allow one to study the system without the complications of H2 –O2
recombination and O2 evolution catalysis. In this reaction scheme,
semiconductor particles mediate the transfer of electrons from
photoexcited dye molecules to catalytic species such as Pt nanopar-
ticles, where the reduction of water to H2 competes kinetically
with back electron transfer to the oxidized sensitizer. The effi-
ciency of sensitized H2 evolution is therefore strongly dependent on
the semiconductor employed, as well as on the sensitizer and cat-
alyst used [163–165,167,169,171,174,177–180,182,183]. Several
photosystems that operate under visible light to produce H2 from
water containing a suitable electron donor with AQYs of several
tens of percent have been established [170,173,179,182,183,187].
Although non-sacrificial H2 evolution under visible light has been
achieved using Pt-intercalated lamellar solids sensitized by Ru(II)
dyes [166–168], overall water splitting according to the sensitiza-
tion principle had not been achieved until very recently.
Fig. 32. Schematic diagram of a water-splitting dye-sensitized solar cell. The inset
illustrates a sensitizer-capped IrO2 ·nH2 O catalyst particle in the mesopores of the
TiO2 electrode film.
Reprinted with permission from Ref. [10]. Copyright 2009 American Chemical Soci-
ety.
Mallouk et al. recently demonstrated water splitting using
dye-sensitized metal oxide semiconductor particles [188]. When
sensitizer molecules adsorbed on the surface of TiO2 are linked to
IrO2 nanoparticles, a dye-sensitized TiO2 electrode functions as a
photoanode for water splitting under visible light, with a maximum
internal quantum yield of ca. 1% at 450 nm under an applied bias.
This system is schematically illustrated in Fig. 32. Laser flash pho-
tolysis experiments revealed that the relatively low performance
of this system can be attributed to slow electron transfer from
the nanoparticulate IrO2 catalyst to the oxidized dye, which does
not compete effectively with back electron transfer from the con-
duction band of TiO2 to the dye. Abe et al. succeeded in splitting
water into H2 and O2 using Pt-intercalated K4 Nb6 O17 sensitized by
a coumarin dye for H2 evolution, a WO3 -based photocatalyst for O2
evolution, and an I3 − /I− redox couple [189]. This system is based
on two-step photoexcitation mechanism, and will be discussed in
more detail in the next section. It has been shown that the oxidized
states of coumarin dyes having an oligo-thiophene moiety in their
structure are sufficiently kinetically stable, even in water, to allow
for their regeneration by I− ions. This robustness of the coumarin
dye contributes to the sustained water-splitting capability.
2.4. Water splitting through two-step photoexcitation (Z-scheme)
2.4.1. Basic principle and difficulties
As mentioned above, overall water splitting using a single
photocatalyst (through one-step photoexcitation) has remained
a significant challenge. In the development of visible-light-driven
photocatalysts for one-step water splitting, another approach to
achieve water splitting with visible light was originally introduced
by Bard in 1979 [190]. This system was inspired by natural photo-
synthesis in green plants, and called the Z-scheme. In this system,
two different photocatalysts (or photosystems) are combined
using an appropriate shuttle redox mediator. Visible light can
be utilized more efficiently than in conventional water-splitting
systems because the energy required to drive each photocatalyst
is reduced. It is also possible to apply a photocatalyst that has
either water reduction or oxidation potential to one side of the
system. For example, the potential of the conduction band of
WO3 , which has a band gap of ca. 2.7 eV, is more positive than
that of water reduction, preventing its use as an H2 evolution
photocatalyst, even in the presence of methanol. However, WO3
is capable of producing O2 from an aqueous solution containing
appropriate electron acceptors under visible light, and acts as
 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 33. Schematic energy diagrams of photocatalytic water splitting for a two-step photoexcitation system. D and A indicate electron donating and accepting species,
respectively.
Reprinted with permission from Ref. [216]. Copyright 2011 American Chemical Society.
an effective building block for O2 evolution in Z-scheme water
splitting.
A schematic illustration of Z-scheme water splitting is shown
in Fig. 33. In an H2 evolution system, the forward reactions that
should occur on the photocatalyst surface are the reduction of pro-
tons by conduction band electrons and the oxidation of an electron
donor (D) by valence band holes to yield the corresponding electron
acceptor (A), as follows:
2H+ + 2e− → H2 (photoreduction of H+ to H2 )
+
D + nh → A (photooxidation of D to A)
On the other hand, the forward reactions on an O2 evolution
photocatalyst are as follows:
A + ne− → D (photoreduction of A to D)
− +
4OH + 4h → O2 + 2H2 O (photooxidation of H2 O to O2 )
where the electron acceptor generated by the paired H2 evolution
photocatalyst is converted to its reduced form (D), and water oxi-
dation occurs with the valence band holes. Thus, a cycle of redox
pairs (D and A) occurs, and the water-splitting reaction is achieved.
In addition to efficient utilization of visible light, it is important
to control the selectivity of chemical reactions that occur during Z-
scheme water splitting. As shown in Fig. 33, the reduction of A and
oxidation of D are, respectively, more likely to occur on H2 and O2
evolution photocatalysts than water reduction and oxidation. For
this reason, the number of Z-scheme water-splitting systems show-
ing a reasonable level of activity under visible light is limited, even
though a large number of visible-light-responsive photocatalysts
have been developed. Thus, controlling the selectivity for the for-
ward reactions on each photocatalyst is important in establishing
a highly efficient Z-scheme system.
2.4.2. Metal oxide-based systems
Many efforts have been made to construct metal oxide-based
systems, focusing on the development of both new materials and
effective electron relays [189,191–216]. Sayama et al. demon-
strated in 1997 that stoichiometric water splitting can be achieved
in a two-step photoexcitation system based on WO3 powder
suspended in an aqueous FeSO4 solution under UV irradiation
( > 200 nm) [197]. In this system, H2 evolution occurs photo-
chemically through excitation of Fe2+ by UV light followed by
253
photochemical reduction of water and the generation of Fe3+ , while
the WO3 photocatalyzes water oxidation using this Fe3+ as an elec-
tron acceptor. In 2001, Abe et al. succeeded in two-step water
splitting, using a system consisting of Pt/TiO2 (anatase) as an H2
evolution photocatalyst and TiO2 (rutile) as an O2 evolution pho-
tocatalyst under UV irradiation ( > 200 nm) in the presence of an
IO3 − /I− redox mediator [199]. They also reported in the same year
that visible-light water splitting ( > 420 nm) was achieved using
suspended particles of Pt-loaded SrTiO3 doped with Cr and Ta (H2
(9)
evolution photocatalyst) and Pt-loaded WO3 (O2 evolution photo-
(10) catalyst) with an IO3 − /I− redox pair [200–202]. In these systems,
the intrinsic properties of rutile TiO2 and WO3 allow for selective
water oxidation. Because of their unique surface properties, water
oxidation occurs on these photocatalysts even in the presence of
(11) electron donors such as Fe2+ and I− , which are thermodynamically
more susceptible to oxidation than water.
(12) Kudo et al. succeeded in extending the available wavelength for
O2 evolution, resulting in visible-light water splitting with up to
520 nm photons [204,205]. Their system consisted of Pt- or Ru-
loaded SrTiO3 doped with Rh (H2 evolution photocatalyst) and
BiVO4 (O2 evolution photocatalyst), in which electron transport
between the two photocatalysts was mediated by an Fe3+ /Fe2+
redox mediator. Kudo et al. also reported Z-scheme water split-
ting using Ru/SrTiO3 :Rh and BiVO4 without redox mediators [207].
In this system, inter-particle electron transfer occurs from BiVO4 to
Ru/SrTiO3 :Rh, and many different O2 evolution photocatalysts can
be applied. It has been proposed that the donor level formed by the
Rh dopant in the band-gap structure of SrTiO3 plays an important
role in interfacial electron transfer. This system can also operate
under simulated sunlight, with a solar energy conversion efficiency
of 0.12% under optimal conditions.
2.4.3. (Oxy)nitride-based systems
Compared to metal oxide photocatalysts, (oxy)nitrides are more
interesting compounds for application to Z-scheme water split-
ting because of their available absorption wavelengths. Abe et al.
applied Pt/TaON as an H2 evolution photocatalyst to a two-step
water-splitting system in combination with Pt/WO3 as an O2 evo-
lution photocatalyst and an IO3 − /I− redox mediator [208,209].
Further screening of (oxy)nitrides for application in H2 evolution
systems allowed us to increase the absorption wavelength avail-
able for H2 evolution to 660 nm using BaTaO2 N [210,211]. For more
254 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 34. A schematic illustration of a two-step water-splitting system driven by visible light in the presence of an Fe3+ /Fe2+ or IO3 − /I− redox mediator. Water reduction occurs
on an H2 evolution photocatalyst, while an O2 evolution photocatalyst plays a role in oxidizing water. Electron transfer between the two photocatalysts is mediated by an
IO3 − /I− shuttle redox mediator.
efficient utilization of visible photons in O2 evolution, the replace-
ment of WO3 by an (oxy)nitride with a longer absorption edge
has been undertaken. So far, it has been reported that RuO2 /TaON
[212,216] and Ir/TiO2 (rutile)/Ta3 N5 [215] photocatalysts that have
absorption edges of 520 and 600 nm, respectively, achieve function-
ality as O2 evolution photocatalysts in the presence of an IO3 − /I−
redox mediator. The combination of photocatalysts for Z-scheme
water splitting under visible light is illustrated in Fig. 34.
3. Strategy to improve the photocatalytic activity of a given
material
As explained in Section 2.1 and shown in Fig. 4, the water-
splitting rate over a photocatalyst can be enhanced by (1) improving
the physicochemical properties of the photocatalyst, (2) refining
cocatalysts, and (3) controlling the reaction conditions. To maxi-
mize the performance of a photocatalyst, numerous attempts have
been made so far and there have been several benchmarks. This
section introduces methodologies that can enhance photocatalytic
activity using the above three approaches.
3.1. General strategy to improve the quality of a photocatalyst
With particulate semiconductors under band-gap irradiation,
electrons and holes are created in the conduction and valence
bands, respectively. The particle size of a given photocatalyst affects
the number of surface reaction sites that are present. While a
smaller particle size increases the density of surface catalytic sites,
it usually results in a lower degree of crystallinity, which can
increase the probability of recombination between photogenerated
electrons and holes, as illustrated in Fig. 35. That is, there is a trade-
off between particle size and crystallinity for a given photocatalyst
[217]. It has been reported that the activity of many metal oxide
Fig. 35. Trade-off between particle size of a photocatalyst and charge migration in
the bulk.
photocatalysts for overall water splitting is strongly dependent on
the particle size (surface area and crystallinity) of the photocatalyst
[60,63,68,69,71,72,76,78]. For (Ga1 − x Znx )(N1 − x Ox ), on the other
hand, the water-splitting activity depends not on surface area, but
on the crystallinity and composition [145,218]. Although the gen-
eral trend, in which a material with a higher crystallinity and a
higher surface area is more active, applies to many photocatalysts,
one must be careful of these exceptional cases.
In general, metal oxide photocatalysts are synthesized by a con-
ventional ceramic route, in which appropriate amounts of metal
oxides or carbonates are mixed mechanically, followed by heating
for a long period at high temperatures to allow inter-diffusion of
the metal cations. One of the serious problems with this method is
the great difficulty in preparing the compounds in their pure form
at relatively low temperatures. The rapid grain growth that occurs
during high-temperature synthesis is a major obstacle to improving
the photocatalytic activity of metal oxides.
The polymerized complex (PC) method, originally developed
by Pechini [219], is a powerful and convenient technique that
allows for the synthesis of complex crystalline metal oxides, even at
reduced temperatures [220–225]. As shown in Fig. 36, this method
consists of two essential steps: (1) incorporation of inorganic pre-
cursors in a polymer resin with molecular-level dispersion, and
(2) subsequent calcination to eliminate the polymer and produce a
crystalline metal oxide. The PC method has been applied to the syn-
thesis of a number of mixed metal oxides, including Sr2 Nbx Ta2 − x O7
[222], K2 La2 Ti3 O10 [223,224], KTiNbO5 [225], Ba5 Nb4 O15 [61], and
Fig. 36. Polymerized complex method for preparation of a metal oxide photocata-
lyst. Shown is an example of the synthesis of Sr2 Ta2 O7 .
Reprinted with permission from Ref. [9]. Copyright 2009 The Royal Society of Chem-
istry.
 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268 255

KCa2 Nb3 O10 [180,226]. With this method, the particle size can be
controlled by changing the final calcination temperature (step 2),
and one can obtain a relatively high activity compared with mate-
rials obtained by a solid state reaction.
Other precursor routes can also be used to effectively prepare
photocatalysts with enhanced activity. For example, hydrother-
mally synthesized NaTaO3 particles exhibit a higher rate of water
splitting than an analog prepared by a conventional solid state
reaction [227]. A colloidal array of NaTaO3 nanoparticles 20 nm in
size, which exhibits an enhanced water-splitting rate, can be pre-
pared through the confined space method using three-dimensional
mesoporous carbon and the hydrothermal reaction of NaOH and
Ta2 O5 [228]. Saito and Kudo have reported that under UV irradia- Fig. 37. Schematic illustration of overall water splitting on a mesoporous metal
tion, nanowires of Nb2 O5 and NaNbO3 show a higher photocatalytic oxide.
activity than the bulk-type analogs, due to the favorable structural
anisotropy of the nanowires for photocatalytic reaction [229,230].
Employing “the nanosizing strategy” is also successful for aspect of mesoporous Ta2 O5 is that excited electrons in the con-
Ta3 N5 , a visible-light-driven photocatalyst that has a band gap duction band of Ta2 O5 have higher potentials than those in TiO2 , as
of 2.0 eV. Nanoparticulate Ta3 N5 can be readily prepared from a mentioned earlier.
nanoparticulate Ta2 O5 precursor produced using a precipitation It would be natural to expect that a much higher water-splitting
method [231]. Compared to conventional bulk-type Ta3 N5 parti- activity would be attained if the wall of mesoporous tanta-
cles (300–500 nm), nanoparticulate Ta3 N5 with a particle size of lum oxide were crystallized, which would suppress undesirable
30–50 nm was shown to exhibit enhanced photocatalytic activity electron–hole recombination while maintaining the mesoporos-
for H2 evolution from an aqueous solution containing methanol as ity. The crystallization of an amorphous Ta2 O5 framework was
an electron donor under visible light, when loaded with a Pt cocat- achieved upon prior treatment of the mesoporous Ta2 O5 with
alyst. Diffuse reflectance spectroscopy and photoelectrochemical 1,1,1,3,5,5,5-heptamethyltrisiloxane ([(CH3 )3 SiO]2 -SiHCH3 ), fol-
measurements suggested that the enhancement was due to a pro- lowed by calcination to form an SiO2 -protected structure and
motion of the water reduction process because of the lower defect subsequent alkaline treatment to remove the SiO2 layer. The prepa-
density of the material. It is also possible to prepare nanosized ration scheme is displayed in Fig. 38. The resulting material has a
Ta3 N5 particles through a template approach using mesoporous crystallized framework and exhibits nearly an order of magnitude
carbon nitride (mpg-C3 N4 ) [232]. In this case, the final particle size higher activity than the amorphous analog [237].
of Ta3 N5 can be adjusted by changing the pore size of the mpg- The photocatalytic activity of Ta3 N5 for H2 evolution from an
C3 N4 . Ta3 N5 with a very small particle size, which was prepared aqueous methanol solution under visible light ( > 420 nm) can
from mpg-C3 N4 with a pore size of 7 nm, showed approximately be also improved by applying a similar strategy [238]. Ordered
one order of magnitude higher activity than bulk Ta3 N5 . In addi- mesoporous Ta3 N5 having crystallized thin-wall structures with
tion to the small particle size and high surface area, the low density 2 nm thick and 4 nm pores was successfully obtained by nitrid-
of defect sites should also improve the activity, since fewer defect ing an amorphous silica-coated mesoporous Ta2 O5 , followed by an
sites would be favorable for electron migration from the Ta3 N5 bulk alkaline treatment. The photocatalytic activity of the as-prepared
to the surface and/or electron transfer from the conduction band of mesoporous Ta3 N5 was three times that of conventional bulk Ta3 N5
Ta3 N5 to the loaded Pt. under the same reaction conditions, because the thin crystallized
pore wall enabled efficient charge transfer of photoexcited elec-
3.2. Controlling the shape or form of a photocatalyst trons and holes to surface active sites. Similarly, the activity of
g-C3 N4 for H2 evolution was improved by introducing mesopores
3.2.1. Mesoporous transition-metal oxides [239] or a 2D accessible framework using colloidal silica or SBA-15
Nomura and Domen et al., reported that a mesoporous tantalum silica, respectively, as a template in g-C3 N4 [240].
oxide, prepared by a ligand-assisted templating method, functions
as a photocatalyst capable of splitting water into H2 and O2 under
UV irradiation ( > 200 nm), when modified with an NiOx cocata-
lyst [233]. Even though the wall of this material in the mesoporous
structure was amorphous, it exhibited a higher water-splitting rate
than crystallized bulk particles. Similarly, the activity of a 2D hexag-
onal mesoporous Mg–Ta oxide for water splitting was much higher
than that of a crystallized bulk-type analog [234]. This high activity
appears to be due to the thin walls of the mesopores, which provide
a short distance for the excited electrons and holes to travel to the
surface, reducing the probability of electron–hole recombination,
as schematically illustrated in Fig. 37. Nevertheless, amorphous
materials in general show considerably lower photocatalytic activ-
ity [217,235], and hence these results may appear unusual. The
photocatalytic activity of amorphous mesoporous TiO2 for the
decomposition of 2-propanol into acetone was actually lower than
that of anatase TiO2 [236], while mesoporous Ta2 O5 is considerably
photoactive despite its amorphous nature, as mentioned above.
It has been claimed that photoexcited electrons in mesoporous
Ta2 O5 would migrate in the ∼1.8-nm-thick amorphous wall, which Fig. 38. Crystallization of a mesoporous metal oxide via SiO2 -coating, followed by
consists of 9 Ta–O bonds, to reach the surface. Another beneficial calcination and subsequent removal of the SiO2 layer by NaOH.
256 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
3.2.2. Transition-metal oxide nanosheets
Metal oxide nanosheets are another interesting class of mate-
rials because of their morphological characteristics. As introduced
earlier, certain ion-exchangeable layered metal oxides photocat-
alyze overall water splitting into H2 and O2 under band-gap
irradiation [22–24,31,32,44–46,52,53,223–225]. These compounds
consist of negatively charged corner- and/or edge-shared MO6
(M = Ti, Nb, Ta) octahedral units that stack to form a two-
dimensional layered structure interleaved with alkaline cations
to compensate for the negative charge of the sheets. Upon pho-
toexcitation, electrons and holes are generated in the sheets,
causing redox reactions with reactant molecules adjacent to the
layers. Therefore, the primary requirement to achieve a high
efficiency using a layered photocatalyst is the intercalation of reac-
tant molecules (e.g., H2 O) into the interlayer galleries, because of
enhanced access of photogenerated carriers to the reactants, as
discussed earlier [31,46,53].
One of the most convenient ways to utilize the inter-
layer nanospace for reactions is a technique called “exfoliation–
restacking” [241–245]. Certain layered metal oxides can be exfo-
liated by reaction with bulky base molecules, yielding unilamellar
nanosheet colloids with a thickness of ≈1 nm [246–248]. The col-
loidal nanosheets are readily restacked by changing the ionic
strength or pH of the colloidal suspension to give aggregates of
nanosheets that have much higher specific surface area than the
parent layered material. The resulting nanoscale thickness and
high surface area are both favorable for photocatalytic applications.
With the exfoliation–restacking technique, it is possible to incor-
porate catalytic nanoparticles or light-harvesting metal complexes
into the galley space of nanosheets to produce a multicomponent
photoassembly, as illustrated in Fig. 39.
For application to photocatalytic water splitting, Ebina et al.
reported that Pt nanoparticles or RuOx clusters can be loaded
onto sheets of the layered perovskite KCa2 Nb3 O10 by the
exfoliation–restacking technique [243,244]. This KCa2 Nb3 O10 ,
internally decorated with nanoparticulate Pt, had a higher activ-
ity for UV-photolysis of methanol than Pt-loaded P25, which
is a benchmark photocatalyst [243]. Although neither lamellar
KCa2 Nb3 O10 nor the RuOx -loaded derivative obtained via a con-
ventional impregnation procedure photocatalyzes overall water
splitting, restacked KCa2 Nb3 O10 nanosheets that accommodate
RuOx clusters in the galley space exhibited activity for the stoichio-
metric decomposition of pure water under band-gap irradiation
[244]. Mallouk et al. reported the modification of the interlayer gal-
leries of restacked KCa2 Nb3 O10 nanosheets with highly dispersed
Rh(OH)3 or Rh2 O3 nanoparticles through the direct deposition
of nanoparticulate Rh species onto exfoliated Ca2 Nb3 O10 − sheets
Fig. 39. Schematic illustration of an exfoliation–restacking route to prepare a multi
component photoassembly based on nanosheets.
[245]. These materials efficiently catalyze H2 evolution from aque-
ous methanol solution under UV irradiation ( > 300 nm). The
loaded Rh(OH)3 or Rh2 O3 nanoparticles collect photogenerated
electrons from the photoactive Ca2 Nb3 O10 − layers and provide
catalytic sites for H2 evolution, resulting in a higher rate of H2
evolution than that of analogous Pt-loaded materials.
Maeda and Mallouk examined the structural effects of restacked
niobate nanosheets, which were prepared by exfoliation of the cor-
responding Dion–Jacobson-type layered perovskites (HCa2 Nb3 O10 ,
HSr2 Nb3 O10 and HLaNb2 O7 ), on H2 evolution from water con-
taining 2-propanol as an electron donor under UV irradiation
( > 300 nm) [249]. Physicochemical analysis suggested that in
triple-layered perovskite nanosheets, photocatalytic activity is
influenced by several factors, including the conduction band
potential and the band-gap energy (the number of avail-
able photons), which are derived from distortion of perovskite
blocks consisting of NbO6 octahedra. Interestingly, the activ-
ity of a triple-layered nanosheet (HSr2 Nb3 O10 ) was an order of
magnitude higher than that of an HLaNb2 O7 nanosheet with
double perovskite layers, despite their physicochemical similar-
ity, as shown in Fig. 40. The considerable difference in activity
between double- and triple-perovskites was also observed in
lamellar RbLaTa2 O7 (double-perovskite) and RbCa2 Ta3 O10 (triple-
perovskite), as reported by Machida et al. [52]. Their computational
studies suggested that the reactivity of holes in the valence band
(populated by O2p orbitals) with intercalated molecules varied
with respect to the number of perovskite layers, and that the termi-
nal oxygen atoms facing the interlayer galleries in the three-layer
perovskite made a strong contribution to the formation of the
valence band maximum, whereas those in the two-layer perovskite
did not. As a result, the three-layer perovskite exhibited a higher
reactivity than the two-layer analog.
Niobate nanosheets and nanoscrolls have recently been
reported as building blocks for dye-sensitized H2 production from
water [178–180] – a half-reaction of an artificial photosynthetic
assembly that was intended to be coupled with an O2 evolu-
tion system [10,188]. Using Ru(bpy)3 2+ (bpy = 2,2 -bipyridine) as
a sensitizer, the negatively charged nanoscrolls bound the cationic
complex. H2 was photocatalytically generated, even without any
chemical bonds linking the sensitizer to the nanoscroll surface,
when EDTA and Pt nanoparticles were employed as an electron
Fig. 40. Comparison of photocatalytic H2 evolution using HSr2 Nb3 O10 (three-layer
perovskite) and HLaNb2 O7 (two-layer perovskite).
Reprinted with permission from Ref. [249]. Copyright 2009 The Royal Society of
Chemistry.
 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
donor and catalyst, respectively. The rate of visible light H2 evolu-
tion in the nanoscroll-based system was 10 times higher than that
of similarly sensitized P25 titania and the parent layered mate-
rial [178]. It appears that the intrinsic properties of nanoscrolls
(negatively charged surface and single-crystalline texture) have
a positive effect on the dye-sensitized H2 evolution. Restacked
calcium niobate nanosheets, HCa2 Nb3 O10 , photocatalytically pro-
duced H2 from water in a similar way [179].
To further explore the relationship between catalyst structure
and activity, restacked HCa2 Nb3 O10 nanosheets with different lat-
eral dimensions (controlled by the PC synthesis) were tested as
photocatalysts for H2 evolution from aqueous methanol solutions
under band-gap irradiation ( > 300 nm), and as building blocks for
Ru(bpy)2 (4,4 -(PO3 H2 )2 bpy)2+ -sensitized H2 evolution from aque-
ous EDTA solutions irradiated with visible light ( = 450 ± 20 nm)
[180]. Reducing the structural imperfections and increasing the
specific surface area of the nanosheets both enhanced the activ-
ity under band-gap irradiation. In contrast, the rate of sensitized
H2 production was not significantly affected by these structural
properties. This study suggests that it is possible to improve pho-
tocatalytic activity of other nanosheet materials by refining the
preparation conditions of the parent layered solids.
Osterloh et al. evaluated the photocatalytic activity for H2
evolution from water over individually dispersed Ca2 Nb3 O10 −
nanosheets stabilized by tetra(n-butyl)ammonium hydroxide
(TBAOH) [250–252]. With modification by Pt nanoparticle cocata-
lysts, the nanosheets produced H2 from pure water, but no O2 . Prod-
uct analysis indicated that the oxidation product was hydrogen per-
oxide [252]. Photogenerated charge carriers relaxed with second-
order kinetics on a sub-nanosecond time scale that depended on
the nanosheet size. Exfoliated Ca2 Nb3 O10 − nanosheets are also
amenable to layer-by-layer stacking on submicron order silica
spheres with cationic poly(diallyldimethylammonium) chloride
(PDDA) to form core/shell-structured functional composites, which
show H2 evolution activity from an aqueous methanol solution
under band-gap irradiation [253].
3.2.3. Composite-type photocatalysts
As introduced in the previous section (Section 2.1.2), crystal
structures that provide local polarization fields play a significant
role in promoting photocatalytic water splitting [27]. Similarly, a
built-in electric field formed at the interface between two differ-
ent semiconductors is believed to inhibit charge recombination,
thereby increasing the photocatalytic efficiency [254–256]. Build-
ing upon the basic concept of a photochemical diode proposed
by Nozik in 1976 [257], Lee et al. extended the idea to pre-
pare a particulate p/n junctioned composite photocatalyst [254].
Its working principle is schematically shown in Fig. 41, with an
energy band model for one p/n junction. The energy scale in
the figure was drawn according to the flat-band potential mea-
Fig. 41. a) Schematic drawing of a photocatalytic diode (PCD). b) Schematic drawing
of the energy band model of a PCD showing the formation of the p–n junction and
the process of water oxidation.
Reprinted with permission from Ref. [254]. Copyright 2005 Wiley–VCH Verlag
GmbH & Co. KGaA.
257
surements. At thermal equilibrium, the Fermi levels of the two
semiconductors were aligned. When the device was immersed in
an electrolyte, the conduction and valence band edges became bent.
Photocatalytic reactions were initiated by absorption of band-gap
photons in both the n- and p-type semiconductors. Photogener-
ated holes and electrons were separated by the built-in electric
field; holes moved to the p-CaFe2 O4 , while electrons entered the
n-PbBi2 Nb1.9 W0.1 O9 counterpart. The net effect of the p–n diode
formation was therefore the efficient separation of electron–hole
pairs, which minimized charge recombination. This nanodiode
material showed enhanced photocatalytic performance for indi-
vidual H2 and O2 evolution from aqueous solutions containing
methanol and silver nitrate, respectively, as well as for the degrada-
tion of toxic organic substrates under visible light ( > 420 nm). The
introduction of an Ohmic junction between the n- and p-type semi-
conductors also increases the photocatalytic activity for producing
H2 or O2 , as exemplified by the n-WO3 /W/p-PbBi2 Nb1.9 Ti0.1 O9
photocatalyst [255]. In this system, the photogenerated majority
carriers in each semiconductor region migrate towards the Ohmic
layer (metallic W) between the two semiconductors, where the
carriers undergo non-radiative recombination. Thus, an optimal
population of photogenerated electrons and holes in each semi-
conductor can promote the redox reactions that occur on the
semiconductor surface.
3.2.4. Doping with foreign elements
Doping a photocatalyst with foreign elements can change its
physicochemical properties such as particle size, surface morphol-
ogy, and band structure, depending on the dopant. As introduced
earlier, doping may seem an unsuitable approach, because dopants
in a photocatalyst can often act as electron–hole recombination
centers, decreasing the photocatalytic efficiency even though addi-
tional visible-light absorption bands are created. Nevertheless,
there have been exceptions in which doping resulted in a marked
improvement in photocatalytic activity.
As discussed earlier, NiO-loaded NaTaO3 is highly active for pho-
tocatalytic water splitting under UV irradiation [36,37,40]. Kato
and Kudo successfully enhanced the water splitting rate by 2–3
times by doping with lanthanides (viz., La, Pr, Nd, Sm, Gd, Tb and
Dy) [258,259]. La-doped NaTaO3 with a NiO cocatalyst showed the
highest activity, with an apparent quantum yield of 56% at 270 nm
under optimal conditions [259]. The doping reduced the NaTaO3
particle size from 2–3 to 0.1–0.7 ␮m. A similar particle size reduc-
tion could be also achieved by doping with Ca, Sr, or Ba [260,261].
In addition to the reduced particle size, NaTaO3 doped with La, Ca,
Sr, or Ba has a surface nanostructure with steps of 3–15 nm. Kudo
et al. explained that this effect was due to the difference in ionic
radii between the dopants and the Na cations. Considering the ionic
radii of La3+ , Ca2+ , Sr2+ , and Ba2+ in 6- and 12-coordinated envi-
ronments, it is natural to presume that in NaTaO3 , the A sites in
the perovskite structure become occupied by the dopants. The fine
crystalline particles and the surface nanostep structure are believed
to be formed due to a suppression of crystal growth by distortion of
the local structure. It has been reported that the formation of highly
crystalline fine particles with a surface nanostep structure effec-
tively separates H2 and O2 evolution sites from each other, thereby
enhancing photocatalytic activity [259]. The reaction mechanism
for overall water splitting over NiO/NaTaO3 :La is shown in Fig. 42.
The dynamics of photoexcited electrons in NaTaO3 -based
catalysts have been examined by time-resolved IR absorption
spectroscopy [262]. Electrons generated by 266 nm pump pulse
excitation exhibit a monotonic absorption of mid-IR light. The num-
ber of electrons in La-doped catalysts showed a correlation with
their activity in the steady-state water-splitting reaction, which
suggested that these electrons participated in the reaction. When
NiO was deposited as a cocatalyst, the electrons excited in the La-
258 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 42. Mechanism of highly efficient water splitting over an NiO/NaTaO3 :La photocatalyst.
Reprinted with permission from Ref. [259]. Copyright 2002 American Chemical Society.
doped NaTaO3 were transferred to the cocatalyst within 1 ␮s after
the pulse excitation. Electron dynamics calculations in water vapor
indicated that the cocatalyst mediated efficient electron transfer to
water.
Sakata et al. examined the effects on photocatalytic performance
of metal ion addition into ␤-Ga2 O3 , which was previously reported
by the same group to be an active photocatalyst for overall water
splitting under UV irradiation ( > 200 nm) [263,264]. The addition
of Ca, Cr, Zn, Sr, Ba, or Ta ions resulted in enhanced activity by 2–7
times [263]. Among these, Zn-added ␤-Ga2 O3 exhibited the highest
activity. Although the reason for the activity improvement has yet
to be fully elucidated, Zn-added ␤-Ga2 O3 modified further with
nanoparticulate Rh2 − y Cry O3 cocatalyst exhibited a water-splitting
rate comparable to the most active NiO/NaTaO3 :La under similar
reaction conditions.
For non-oxide type materials, there are interesting cases in
which the photocatalytic activity can be enhanced by doping. GaN
becomes an active water-splitting photocatalyst when modified
with Rh2 − y Cry O3 nanoparticles as cocatalysts for H2 evolution
under band-gap irradiation [265]. Inoue et al. reported that the pho-
tocatalytic activity of GaN for overall water splitting is significantly
improved by doping with divalent ions (viz., Be2+ , Mg2+ , and Zn2+ )
[266,267]. The activation was attributed to the formation of p-type
GaN with acceptor levels above the valence bands, which improves
the mobility of holes.
Domen et al. reported that Mn or Cu-doped (Zn1 + x Ge)(N2 Ox )
functions as a photocatalyst for visible-light-driven water splitting
more efficiently than undoped analogs [268]. It was speculated that
the enhanced performance may have resulted from a reduced den-
sity of defects in (Zn1 + x Ge)(N2 Ox ). Very recently, Domen et al. also
reported metal ion addition into Sm2 Ti2 S2 O5 to achieve enhanced
photocatalytic activity for H2 production from an aqueous Na2 S-
Na2 SO3 solution under visible light [269,270]. Among the dopants
examined, Ag and Mg resulted in activity improvement. In this case,
a promotion of photocatalytic oxidation and a reduction of defect
density were the main effects of Ag and Mg doping, respectively,
and H2 evolution was accelerated. The photocatalytic activity of
Sm2 Ti2 S2 O5 was enhanced by seven times by adding a combination
of 1% Ag and 5% Mg.
3.2.5. Surface modification
Surface modification is sometimes done in an attempt to
improve the quality of the photocatalyst surface. Because the sur-
face of a photocatalyst hosts active sites for redox reactions and is
where charge transport occurs, modification of the surface to bring
about a desired property or specific function is important. The most
commonly known method is to load a cocatalyst that promotes sur-
face redox reactions, as will be introduced in the next section. In
this section, surface modification techniques that improve photo-
catalytic activity are reviewed.
For Z-scheme water splitting in the presence of a given redox
couple, controlling the adsorption of redox species onto the pho-
tocatalyst is of particular importance in order to facilitate the
desirable forward reaction(s) and suppress the undesirable side
reaction(s), as mentioned in Section 2.4 and depicted in Fig. 43.
Ohno et al. demonstrated that visible-light-driven water oxida-
tion on WO3 in an aqueous solution containing Fe3+ as an electron
acceptor can be improved by coating the WO3 particles with
a thin TiO2 layer [195]. It was shown that the TiO2 layer pro-
vides adsorption sites for Fe3+ rather than Fe2+ , allowing one to
make O2 more efficiently in the presence of Fe2+ ions, which
complete with water oxidation. Similarly, Domen et al. recently
applied rutile TiO2 nanoparticles as a modifier on Ta3 N5 to achieve
functionality as an O2 evolution photocatalyst in a two-step water-
splitting system with an IO3 − /I− shuttle redox mediator under
visible light ( > 420 nm) in combination with a Pt/ZrO2 /TaON H2
evolution photocatalyst [215]. The rutile TiO2 modifier suppresses
the adsorption of I− on Ta3 N5 , allowing Ta3 N5 to evolve O2 in a
two-step water-splitting system, with further modification by Ir
nanoparticles that function as reduction sites for IO3 − ions. It was
also noted that the reproducibility of O2 evolution was poor when
Ir/Ta3 N5 (without rutile TiO2 ) was used. Thus, it became possible to
utilize visible photons up to 600 nm (corresponding to the absorp-
tion edge of Ta3 N5 ) for an O2 evolution system in Z-scheme water
splitting.
It has been reported that modification of TaON with nanopartic-
ulate ZrO2 results in a reduced density of defects in TaON [214,271].
Because TaON is an intermediate phase between Ta2 O5 and Ta3 N5 ,
it seems difficult to control the crystallinity of TaON by adjustment
of the preparation parameters alone. Furthermore, due to its low
thermal stability, post-calcination to reduce the density of defects
appears to be disadvantageous for TaON. In fact, post-calcination
of TaON under O2 or N2 results in a decrease in activity [135].
Fig. 43. Schematic drawing of the controlled adsorption of reactants through surface
modification.
 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268 259

Fig. 44. Nitridation of ZrO2 /Ta2 O5 composite to produce ZrO2 /TaON while suppressing the production of reduced tantalum species (defect sites) near the surface of the
material.
Reprinted with permission from Ref. [271]. Copyright 2008 The Chemical Society of Japan.

When ZrO2 is used as a “protector” in the preparation of TaON, on nanoparticulate cocatalysts loaded on a photocatalyst, and
one can reduce the density of defects in TaON, as schematically reviewed the history of the development of these photocatalysts.
illustrated in Fig. 44. Specifically, monoclinic ZrO2 nanoparticles
are dispersed on the surface of Ta2 O5 precursor before nitrida- 3.3.1. General role of cocatalysts in photocatalytic water splitting
tion, thereby protecting Ta5+ cations in the TaON surface from Fig. 45 shows a schematic illustration of a photocatalyst loaded
being reduced by H2 (derived from disassociation of NH3 at high with a cocatalyst during a water-splitting reaction, where an H2
temperatures) during nitridation. As has been observed for other evolution process was assumed. It is believed that the loaded
(oxy)nitrides such as LaTiO2 N [119,120], TiNx Oy Fz [122–124], and cocatalysts extract photogenerated electrons and holes from the
Ta3 N5 [231,232], the reduction of Ta5+ cations in TaON dur- photocatalyst (process I) and host active sites for gas evolution
ing nitridation generates reduced tantalum species, which can (process II). Therefore, the overall efficiency of a given photocat-
act as recombination centers between photogenerated electrons alytic system is dependent on the loaded cocatalyst. In particular,
and holes. On the other hand, when ZrO2 is loaded on the sur- the structural characteristics and intrinsic catalytic properties of
face of Ta2 O5 , tantalum cations at the interface between Ta2 O5 a cocatalyst for H2 (or O2 ) evolution are important. For example,
(and/or TaON) and the loaded ZrO2 should interact with ZrO2 Pt is well-known as an excellent catalyst for the reduction of pro-
and thereby become more cationic. As a result, the formation of tons to give H2 molecules. However, a photocatalyst loaded with
reduced tantalum species on the TaON surface is effectively sup- a Pt cocatalyst does not always exhibit the highest activity among
pressed by prior loading with nanoparticulate ZrO2 . As expected,
the as-prepared ZrO2 -modified TaON (represented as ZrO2 /TaON)
exhibited enhanced water reduction behavior compared to unmod-
ified TaON. In particular, combining Pt-loaded ZrO2 /TaON with
Pt/WO3 and an IO3 − /I− shuttle redox mediator achieved stoichio-
metric water splitting into H2 and O2 under visible light, yielding
an AQY of 6.3% under irradiation by 420.5 nm monochromatic light
under optimal conditions, six times greater than the yield achieved
using a TaON analog [214]. To the best of the author’s knowl-
edge, this is the highest reported value to date for a non-sacrificial
visible-light-driven water-splitting system. This enhancement of
activity can be attributed to the reduce density of defects in
ZrO2 /TaON, which contributes to a lower probability of undesirable
electron–hole recombination in ZrO2 /TaON than in TaON.

3.3. Cocatalysts for the promotion of surface reactions

As mentioned earlier, photocatalytic water splitting with a

measurable reaction rate can be realized, in most cases, by mod-
ifying a photocatalyst with a proper cocatalyst that hosts active Fig. 45. A schematic illustration of electron transfer from a photocatalyst to a loaded
sites for gas evolution. The development of these new cocatalysts cocatalyst (Process I) and H2 evolution (Process II) in overall water splitting.
has brought about numerous breakthroughs. This section focused Reproduced from Ref. [291] with permission.
260 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 46. Trade-off between cocatalyst loading and activity.
analogs loaded with other metals (e.g., Ru and Rh). This suggests
that the contribution of process (I) to the overall efficiency can be
more important than that of process (II). For example, Ru-loaded
TaON exhibits a much higher activity for H2 evolution from aqueous
alcohol solution than Pt-loaded TaON [272]. Although it has been
reported that various factors (e.g., band-edge potential [39,41] and
work function [273] of the photocatalyst and the loaded species)
affect the efficiency of process (I), no report has yielded a system-
atic understanding. Regardless, one must consider both processes
(I) and (II) when designing an efficient photocatalytic system.
3.3.2. A general strategy to improve activity
There are two representative methods of introducing cocata-
lysts onto a semiconductor photocatalyst. One is an impregnation
method, where proper precursor species are impregnated with a
photocatalyst, followed by thermal annealing to produce a desired
form of cocatalyst. In this method, there are many choices of
precursors and solvents for the impregnation procedure and con-
ditions for the final treatment. This type of loading method is
well-known in the field of heterogeneous catalysis. The other
method is in situ photochemical deposition, which was originally
developed by Kraeutler and Bard, who demonstrated that nanopar-
ticles of metals (e.g., Pt, Pd) can be prepared by irradiation of an
aqueous solution containing a semiconductor powder (e.g., TiO2 ,
WO3 ), metal ions, and an electron donor [274]. Metal cations with
appropriate redox potentials can be reduced by electrons gener-
ated through the photoexcitation of a semiconductor powder. Such
photochemical deposition has been studied extensively over the
past 30 years for applications in photocatalysis [275–277], cataly-
sis [278–280], the recovery of noble metals [281], and the removal
of heavy metals from waste water [282].
In general, the photocatalytic activity of a given material (cocat-
alyst/photocatalyst composite) for water splitting is dependent on
the loading method of the cocatalyst, as this determines the physic-
ochemical characteristics of the loaded cocatalyst (e.g., valence
state and dispersion). Generally, in heterogeneous (photo)catalysis,
highly dispersed nanoparticles contribute to faster catalytic reac-
tions, and excess loading leads to lower catalytic activity. In
photocatalysis, excessively loaded cocatalysts hinder light absorp-
tion by the base photocatalyst, and also can act as recombination
centers for photogenerated electrons and holes. Accordingly, as
shown in Fig. 46, there is a volcano-type trend between the loading
amount of a given cocatalyst and the activity in most cases (regard-
less of the preparation method, base photocatalyst, and loaded
cocatalyst). Therefore, refinement of the preparation conditions to
Fig. 47. Schematic view of the structures of a NiO-SrTiO3 catalyst after various
treatments.
Reprinted with permission from Ref. [284]. Copyright 1986 American Chemical
Society.
allow for an optimal distribution of cocatalyst on a photocatalyst
is important when constructing a highly efficient photocatalytic
system for overall water splitting.
3.3.3. Traditional cocatalysts for water splitting
Although some of the photocatalysts developed to date (e.g.
tantalates and zirconia) can decompose water without a cocata-
lyst [35–42,55], most require the loading of a suitable cocatalyst to
obtain a high activity and reasonable reaction rates. Noble metals
such as Pt and Rh are excellent promoters for H2 evolution, but can
also catalyze a backward reaction, forming water from H2 and O2 ,
limiting their usefulness as cocatalysts for photocatalytic overall
water splitting. To avoid the backward reaction, transition-metal
oxides that do not exhibit activity for water formation from H2 and
O2 are usually applied as cocatalysts for overall water splitting. Of
course, there are some exceptional cases in which noble metals
have been effectively employed as cocatalysts for photocatalytic
water splitting, as exemplified by NaOH-coated Pt/TiO2 [15].
In 1980, NiOx was successfully applied as an H2 evolution
cocatalyst when loaded on the surface of SrTiO3 [16]. The photo-
catalytic activity of NiOx /SrTiO3 for the decomposition of water
vapor depends strongly on the state of the loaded cocatalyst
[283,284]. Without modification, SrTiO3 does not catalyze the
reaction. When Ni-metal-loaded SrTiO3 is oxidized with O2 at
a relatively moderate temperature (473 K), the surface of the
loaded Ni particles is oxidized to give an Ni/NiO (core/shell)
structure (denoted as NiOx ). The as-prepared NiOx /SrTiO3 catalyst
is capable of splitting pure water. On the other hand, Ni/SrTiO3
shows little activity. The positive effect of the NiO layer on
Ni is to suppress water formation on Ni and the oxidation of
Ni by water. The structural change in each preparation step is
schematically depicted in Fig. 47. This strategy has long been
acknowledged as one of the most effective modification meth-
ods to achieve water splitting with a particulate photocatalyst,
although the optimal modification conditions are to some extent
dependent upon the photocatalyst used. NiO-based cocatalysts
can function as effective cocatalysts with many photocatalysts
[16,21–24,31–41,43–53,56–64,222–225,227,228,233,234,237,259].
Another representative metal oxide cocatalyst for photocat-
alytic water splitting is ruthenium (IV) oxide. Inoue et al. have
applied RuO2 for overall water splitting as a cocatalyst with
A2 Ti6 O13 (A = Na, K, Rb) [25,285], Na2 Ti3 O7 [286], K2 Ti4 O9 [287],
and BaTi4 O9 [26,287,288]. The use of RuCl3 -derived RuO2 with
these metal oxides resulted in a high activity for overall water
splitting, despite the metallic Ru species themselves being poor
cocatalysts [288]. In a study on BaTi4 O9 , XPS and TEM analysis
revealed that the active Ru species in these catalysts are well-
dispersed as RuO2 species fixed in BaTi4 O9 “nests” (1.4–3.0 nm)
[286,287]. It was suggested that the pentagonal prism tunnel struc-
 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268 261

Table 1
Photocatalytic activities of (Ga1 − x Znx )(N1 − x Ox ) loaded with a transition-metal oxide and Cr oxide for overall water splitting under UV irradiation ( > 300 nm)a .

Entry Cocatalyst Activity/␮mol h−1 Coloading amount of Cr/wt% Activity of coloaded

catalysts/␮mol h−1

Elementb Loading amount/wt% H2 O2 H2 O2

1 None 0 0
2 Cr 1.0 0 0
3 Fe 1.0 0 0 1.0 73 36
4 Co 1.0 2.0 0 1.0 48 24
5 Ni 1.25 126 57 0.125 685 336
6 Cu 1.0 2.0 0 1.0 585 292
7 Ru 1.0 71 27 0.1 181 84
8 Rh 1.0 50 1.6 1.5 3835 1988
9 Pd 1.0 1.0 0 0.1 205 96
10 Ag 1.0 0 0 1.0 11 2.3
11 Ir 1.5 9.3 3.1 0.1 41 17
12 Pt 1.0 0.9 0.4 1.0 775 357

Reproduced from Ref. [291].

a
Catalyst (0.3 g); distilled water (370–400 mL); light source, high-pressure mercury lamp (450 W); inner irradiation-type reaction vessel made of Pyrex.
b
Transition-metal species are expressed as metallic form for simplicity.

ture of BaTi4 O9 prevents mobilization of the RuO2 particles from
these aggregates. Ru3 (CO)12 was found to be a superior precursor to
RuCl3 , as it achieved a better dispersion of RuO2 [286]. Accordingly,
it appears important to achieve a good dispersion of Ru species on
a photocatalyst in order to obtain a high activity. RuO2 is also an
essential component as a cocatalyst with various metal oxides of
d10 [65–73], d10 –d10 [76], d10 s2 –d0 [77–79], and d10 s2 –d10 [12]
electronic configuration, as well as (oxy)nitrides [140–145,151] for
overall water splitting.
3.3.4. Mixed oxide cocatalysts containing chromium
NiOx and RuO2 have been applied to many photocatalysts as
cocatalysts. However, no cocatalyst more effective than NiOx or
RuO2 was found, until recently. Domen et al. reported in 2000
that the photocatalytic activity of Ni-loaded K2 La2 Ti3 O10 for over-
all water splitting can be improved by coloading with Cr, while
modification with Cr alone does not result in appreciable evolu-
tion of H2 or O2 [289]. Recently, they re-examined the effect of
Cr-coloading to prepare new metal oxide cocatalysts containing Cr
and one other metal component for photocatalytic overall water
splitting using (Ga1 − x Znx )(N1 − x Ox ) [290,291]. As listed in Table 1,
it was reported in 2006 that the photocatalytic activity of vari-
ous transition metal loaded catalysts was markedly improved by
coloading with Cr. The cocatalyst, a combination of Cr and one other
metal component, was loaded onto (Ga1 − x Znx )(N1 − x Ox ) by a co-
impregnation method. All of the examples except for the Ag–Cr
system achieved stoichiometric evolution of H2 and O2 from pure
water. The photocatalytic activity of (Ga1 − x Znx )(N1 − x Ox ) loaded
with Cr and a transition metal was strongly dependent on the
amount of loaded Cr. In Ni–Cr and Rh–Cr systems, for exam-
ple, the activities increased with Cr content to a maximum at a
certain loading amount, above which the activity decreased. The
highest activities were obtained at 0.125 wt% Cr with 1.25 wt%
Ni, and 1.5 wt% Cr with 1 wt% Rh. These results suggest that the
optimal Cr loading depends upon the coloaded transition metal.
The improvement in activity was attributed to the formation of
suitable reaction sites by intimate interaction between Cr and
the paired metal component. The largest improvement in activ-
ity was obtained by loading the base catalysts with a combination
of 1 wt% Rh and 1.5 wt% Cr. The activity of this catalyst system
was two orders of magnitude higher than for catalysts loaded
with 1 wt% Rh under the same reaction conditions. Scanning elec-
tron microcopy (SEM), high-resolution TEM, energy dispersive
X-ray spectroscopy (EDS), XPS, and XAFS results indicated that the
activity of Rh2 − y Cry O3 /(Ga1 − x Znx )(N1 − x Ox ) is strongly dependent
on the generation of trivalent Rh–Cr mixed oxide nanoparticles
(10–30 nm in size) with optimal composition and distribution
[292]. It should be noted that even though loading with Fe, Co, Cu,
Pd, or Ag alone did not activate the (Ga1 − x Znx )(N1 − x Ox ) catalyst
for overall water splitting (see Table 1), coloading with Cr and one
of these inactive metal components resulted in measurable photo-
catalytic activity. Coloading Cr probably facilitates charge transfer
from the (Ga1 − x Znx )(N1 − x Ox ) bulk to the cocatalyst, and/or pro-
motes the creation of catalytic gas evolution sites on the cocatalyst
surface. Optimized Rh2 − y Cry O3 /(Ga1 − x Znx )(N1 − x Ox ) achieved an
AQY of ca. 5.1% at 410 nm for overall water splitting [5], at
least an order of magnitude greater than that achieved using
RuO2 /(Ga1 − x Znx )(N1 − x Ox ). The higher activity of Rh2 − y Cry O3 -
loaded photocatalyst is a result of both the superior ability of
Rh2 − y Cry O3 nanoparticles to host H2 evolution sites and the inac-
tivity for O2 photoreduction and H2 –O2 recombination, which
are undesirable backward reactions that can occur during pho-
tocatalytic water splitting [293]. Furthermore, this Rh2 − y Cry O3
cocatalyst is also applicable to other photocatalytic systems, such
as TiO2 , (Zn1 + x Ge)(N2 Ox ) and GaN, to significantly enhance their
photocatalytic water-splitting rates, regardless of electronic con-
figuration or the type of photocatalyst [152,237,264,265,291].
Similarly, Cu(II)–Cr(III) mixed-oxide nanoparticles on
(Ga1 − x Znx )(N1 − x Ox ) act as cocatalysts for water splitting,
and are resistant to both the photoreduction of O2 and water
formation from H2 and O2 [294]. While the optimized activity
of (Ga1 − x Znx )(N1 − x Ox ) loaded with a Cu(II)–Cr(III) mixed-oxide
for overall water splitting was at most 25–30% of that obtained
using a similarly optimized catalyst loaded with Rh2 − y Cry O3 , the
price of Cu is approximately three orders of magnitude lower than
that of Rh, and a cheaper catalyst component is advantageous in
large-scale applications.
It is also possible to prepare nanoparticulate Rh2 − y Cry O3
cocatalysts by in situ photodeposition using (NH4 )3 RhCl6 and
K2 CrO4 as precursors under O2 -free conditions, not only
onto (Ga1 − x Znx )(N1 − x Ox ) but also onto various semiconductors
[295,296]. This demonstrates the first example of the photodeposi-
tion of a mixed metal oxide using photoactive semiconductors. The
photodeposition was conducted in an aqueous suspension contain-
ing semiconductor powder, (NH4 )3 RhCl6 , K2 CrO4 , and H2 O as an
electron donor. With increasing K2 CrO4 concentrations, the valence
state of the co-deposited Rh species varied from metallic to triva-
lent, while that of Cr remained trivalent. At intermediate concentra-
tions of K2 CrO4 , the photodeposits were core/shell-like crystalline
nanoparticles consisting of a metallic Rh core and an Rh(III)–Cr(III)
mixed-oxide shell. Typical TEM images of the co-deposited
nanoparticles at different concentrations of K2 CrO4 are shown in
262 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268

Fig. 48. HR-TEM images of samples with various additions of Cr and a common amount of Rh (0.75 ± 0.15 wt% Rh): (a) 0, (b) 0.175, and (c) 1.5 wt%.
Reprinted with permission from Ref. [296]. Copyright 2010 The Royal Society of Chemistry.

Fig. 48. The photocatalytic activity for visible-light-driven over-
all water splitting ( > 400 nm) was strongly dependent on the
structure of the photodeposits. Comparative experiments using an
analog modified with core/shell-structured Rh/Cr2 O3 nanoparti-
cles, revealed that core/shell-structured nanoparticles consisting
of a metallic Rh core were more effective than Rh–Cr trivalent
mixed oxides at enhancing the photocatalytic activity. However,
the absolute activity of these photodeposited catalysts was rela-
tively moderate compared to the optimally impregnated catalyst.
dispersion of Rh, and further Cr2 O3 shell deposition resulted in
3 times the activity of an analog containing poorly dispersed Rh
nanoparticles [299,300]. This follows a general trend in heteroge-
neous (photo)catalysis, in which highly dispersed catalytic species
generally provide higher reaction rates.
The mechanism of H2 evolution on core/shell-structured
nanoparticles was investigated using electrochemical and in situ
spectroscopic measurements of model electrodes that consisted

3.3.5. Core/shell-structured noble-metal/Cr2 O3 nanoparticles

In 2006, a new type of H2 -evolution cocatalyst, a noble-
metal/Cr2 O3 (core/shell) nanoparticle, was developed [297,298].
Preparation of the core/shell nanoparticles was conducted through
stepwise photodeposition on (Ga1 − x Znx )(N1 − x Ox ) under O2 -
free conditions, as schematically depicted in Fig. 49A. Fig. 49B
shows high-resolution transmission electron microscope (HR-
TEM) images of metallic Rh-loaded (Ga1 − x Znx )(N1 − x Ox ), before
and after the photoreduction of Cr(VI) ions. The figure shows that a
shell of approximately 2 nm thick was deposited on the Rh metal,
forming a core/shell structure. XPS and XAFS analysis revealed that
the shell consisted of Cr2 O3 . As shown in Fig. 49C (left panel), Rh-
loaded (Ga1−x Znx )(N1−x Ox ) exhibited little photocatalytic activity
for overall water splitting, most likely due to rapid water forma-
tion on the Rh nanoparticles. However, (Ga1−x Znx )(N1−x Ox ) loaded
with a Rh core/Cr2 O3 shell cocatalyst exhibited stoichiometric H2
and O2 evolution from pure water (Fig. 49C, right panel). Therefore,
significant water formation from H2 and O2 occurs on uncovered Rh
nanoparticles during overall water splitting, and the suppression of
water formation is essential for achieving efficient evolution of H2
and O2 in this system. The use of Cr2 O3 shells on other noble metal
cores, such as Pd and Pt, produced similar results. This modifica-
tion method is also applicable to metal oxide cocatalysts, which
can sometimes catalyze photoreduction of O2 and undergo degra-
dation due to a change in the cocatalyst state by exposure to a
reactant solution [299]; that is, the photocatalytic activity of metal
oxide-loaded (Ga1 − x Znx )(N1 − x Ox ) for overall water splitting was
improved by forming a core/shell-like configuration with a Cr2 O3
shell.
Among the noble metals and metal oxides examined as nanopar-
ticulate cores, Rh was the most effective at enhancing activity.
One of the most serious drawbacks of the original prepara-
tion method was that the Rh-based nanoparticles tended to
aggregate on (Ga1 − x Znx )(N1 − x Ox ). To address this drawback,
highly dispersed Rh nanoparticles (1.9 ± 0.6 nm in size) were Fig. 49. (A) Schematic illustration of Cr2 O3 deposition through the reduction of
introduced onto (Ga1 − x Znx )(N1 − x Ox ) without aggregation by Cr(VI) ions (D and A indicate electron donor and acceptor, respectively.). (B) HR-TEM
images of (Ga1 − x Znx )(N1 − x Ox ) with photodeposited Rh (left) before and (right) after
adsorbing Rh nanoparticles that were stabilized by 3-mercapto-
photodeposition of a Cr2 O3 shell. (C) Time course of overall water splitting under vis-
1-propanesulfuric acid (prepared by a liquid-phase reduction ible light ( > 400 nm) using (Ga1 − x Znx )(N1 − x Ox ) modified with (left) Rh and (right)
method) onto (Ga1 − x Znx )(N1 − x Ox ), followed by calcination under core/shell-structured Rh/Cr2 O3 .
vacuum at 673 K for 30 min. The resulting sample had a better Reprinted with permission from Ref. [5]. Copyright 2010 American Chemical Society.
 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 50. Schematic illustration of H2 evolution on core/shell-structured nanoparti-
cles (with a noble metal or metal oxide core and a Cr2 O3 shell) as a cocatalyst for
photocatalytic overall water splitting.
Reprinted with permission from Ref. [301]. Copyright 2008 American Chemical Soci-
ety.
of Rh and Pt plates with electrochemically deposited 1.8–3.5-nm-
thick Cr2 O3 [301]. For both Cr2 O3 -coated and bare electrodes,
proton adsorption/desorption and H2 evolution currents were
observed, and an infrared absorption band assigned to Pt–H stretch-
ing was apparent. Therefore, the Cr2 O3 layer did not interfere with
proton reduction or H2 evolution, and proton reduction took place
at the Cr2 O3 /Pt interface. However, the reduction of O2 to water
was suppressed only in the Cr2 O3 -coated samples. It was con-
cluded that the Cr2 O3 layer is permeable to protons and evolved
H2 molecules, but not to O2 . The reaction mechanism of H2 evolu-
tion on core/shell-structured nanoparticles (with a noble metal or
metal oxide core and a Cr2 O3 shell) in photocatalytic overall water
splitting is illustrated in Fig. 50.
3.3.6. Loading both H2 - and O2 -evolution cocatalysts onto the
same photocatalyst particle
As discussed earlier, significant efforts have been devoted to the
development of an efficient water reduction cocatalyst. However,
it would be natural to expect that loading both H2 and O2 evolution
cocatalysts onto the same photocatalyst would improve water-
splitting activity, compared to that of photocatalysts modified with
either an H2 or O2 evolution cocatalyst. Very recently, Domen
et al. demonstrated a proof of concept using (Ga1 − x Znx )(N1 − x Ox )
loaded with Rh/Cr2 O3 (core/shell) and Mn3 O4 nanoparticles as
H2 and O2 evolution promoters, respectively, under visible-light
irradiation ( > 420 nm) [302]. The proposed reaction scheme is
illustrated in Fig. 51. The loaded nanoparticles of Mn3 O4 func-
tioned as O2 evolution sites, as indicated by photoelectrochemical
measurements, while Rh/Cr2 O3 (core/shell) nanoparticles hosted
H2 evolution sites. With assistance from Mn3 O4 nanoparticles in
O2 evolution, the photocatalytic activity for overall water split-
ting of (Ga1 − x Znx )(N1 − x Ox ) modified with core/shell-structured
Rh/Cr2 O3 nanoparticles was improved, compared to analogs mod-
ified with either H2 or O2 evolution cocatalysts.
263
Fig. 51. A proposed reaction mechanism for visible-light-driven overall water
splitting on (Ga1 − x Znx )(N1 − x Ox ) modified with Mn3 O4 and Rh/Cr2 O3 (core/shell)
nanoparticles.
Reprinted with permission from Ref. [302]. Copyright 2010 Wiley–VCH Verlag
GmbH & Co. KGaA.
3.4. Effect of reaction conditions
As discussed in the previous section (Section 2.1.1), the rate
of photocatalytic water splitting in a liquid-phase is generally
faster than in a gas phase. In most cases, therefore, photocatalytic
water splitting has been conducted in a liquid-phase. This section
describes reaction parameters that can affect water-splitting activ-
ity.
3.4.1. Reaction pH and electrolyte in the reactant solution
The pH of the reactant solution is one of the most impor-
tant factors in a liquid-phase water-splitting system, because it
can directly affect the stability of a given photocatalytic material
and the redox processes of both water reduction and oxida-
tion. For example, NiOx -loaded d0 -metal oxide photocatalysts,
e.g., NiOx /SrTiO3 [21], Ni/K4 Nb6 O17 [23], NiOx /K2 La2 Ti3 O10 [32],
NiOx /Sr2 Nb2 O7 [34], NiO/NaTaO3 [40], and NiO/NaTaO3 :La [259],
in general favor alkaline solutions for overall water splitting.
In contrast, the rates of water splitting over RuO2 -loaded d10 -
(oxy)nitrides, ␤-Ge3 N4 [140,142] and (Ga1 − x Znx )(N1 − x Ox ) [144],
are higher in acidic pH conditions than in neutral conditions. How-
ever, even using the same photocatalyst, the optimal reaction pH
may differ with respect to the cocatalyst employed, as exempli-
fied by (Ga1 − x Znx )(N1 − x Ox ) loaded with RuO2 and Rh2 − y Cry O3 ;
the former exhibits the highest performance at pH 3 [144] while
the latter at pH 4.5 [293]. In particular, as shown in Fig. 52,
Rh2 − y Cry O3 /(Ga1 − x Znx )(N1 − x Ox ) exhibited a stable, high photo-
catalytic activity in an aqueous solution of pH 4.5 for 72 h, but
the performance was much lower at pH 3.0 and pH 6.2 because
of corrosion of the cocatalyst and hydrolysis of the catalyst.
Electrolytes in the reactant solution also have a significant effect
on photocatalytic water splitting, even though they do not undergo
reduction or oxidation by conduction band electrons and valence
band holes like a sacrificial reagent would. Sayama and Arakawa
found that the addition of carbonate ions (CO3 2− ) into a pho-
tocatalyst suspension resulted in a marked enhancement in the
water-splitting rate [303–305]. Interestingly, Pt-loaded photocat-
alysts, which did not show any appreciable activity in water at
the same reaction pH, became active for stoichiometric H2 and
O2 evolution from an aqueous solution containing CO3 2− . They
proposed that surface-adsorbed carbonate species on a photo-
catalyst facilitate the desorption of O2 gas produced during the
water-splitting reaction, which would otherwise easily undergo
photoreduction in an undesirable catalytic cycle, thereby allow-
ing for the stoichiometric evolution of H2 and O2 . According to the
264 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
Fig. 52. Overall water splitting on Rh2 − y Cry O3 /(Ga1 − x Znx )(N1 − x Ox ) under visible-light irradiation ( > 400 nm) at (A) pH 3.0, (B) pH 4.5, and (C) pH 6.2. Catalyst (0.3 g); an
aqueous H2 SO4 solution or distilled water (370 mL); light source, high-pressure mercury lamp (450 W); inner irradiation-type reaction vessel made of Pyrex with an aqueous
NaNO2 solution filter.
Reprinted with permission from Ref. [293]. Copyright 2006 American Chemical Society.
propose mechanism, carbonate addition is effective only when light
with a wavelength shorter than 300 nm is irradiated.
It was also reported by the same group that the addition of
a small amount of iodide anion (I− ) into an aqueous suspen-
sion containing a Pt-loaded metal oxide photocatalyst significantly
improved the water-splitting rate, producing H2 and O2 stoichio-
metrically [306]. However, overall water splitting did not occur
when excessive I− was added, due to the oxidation of I− by valence
band holes that competed with water oxidation. They concluded
that the iodide anions were adsorbed preferentially onto the sur-
face of Pt as iodine atoms, forming an iodine layer that effectively
suppressed the backward reaction of water formation from H2 and
O2 on Pt.
The effects of electrolyte addition on water-splitting activ-
ity have recently been reported, with the practical application
of splitting seawater as a goal. Lee et al. reported that overall
water splitting using NiOx -loaded La2 Ti2 O7 under UV irradiation
( > 200 nm) can be achieved in seawater, although at half the activ-
ity of that in pure water [307]. It was concluded that the suppression
of activity in seawater is mainly attributable to the presence of Mg2+
in the reactant solution. Domen et al. demonstrated the direct split-
ting of seawater to produce H2 and O2 using Rh2 − y Cry O3 -loaded
(Ga1 − x Znx )(N1 − x Ox ) under visible light ( > 400 nm) [308]. In that
case, however, the water-splitting rate was approximately half that
achieved from pure water, even with a substantial deviation from
the stoichiometric evolution ratio (H2 /O2 > 2). This low activity of
seawater splitting was primarily due to the presence of Cl− , which
undergoes oxidation by photogenerated holes in the valence band
of (Ga1 − x Znx )(N1 − x Ox ).
3.4.2. Pressure and temperature in the reaction system
Pressure and temperature are both important parameters that
influence the rate of a given chemical reaction. This is also the
case in photocatalytic water splitting. As described in a review
paper by Kudo and Miseki [9], photocatalytic water-splitting reac-
tions are in most cases performed in a glass closed gas circulation
system after evacuation using a vacuum pump to remove the air,
although a flow-type reaction system has recently been reported
as an alternative [206,309]. In a closed system, gases produced dur-
ing the water-splitting reaction are accumulated, increasing the
pressure in the system, which can hinder the release of evolved
gases from the solution phase into the gas phase. It is known that
the gaseous pressure, particularly of O2 , in the reaction system
affects the photocatalytic activity for overall water splitting. For
example, the photocatalytic activities of Pt-loaded TiO2 [305], NiO-
loaded SrTiO3 [310], RuO2 -loaded ␤-Ge3 N4 [142], and RuO2 -loaded
(Ga1 − x Znx )(N1 − x Ox ) [293] are reportedly suppressed in the pres-
ence of gaseous O2 , although all of these are active for water
splitting under the proper reaction conditions. As described earlier,
photoreduction of O2 on a metal oxide cocatalyst can be suppressed
by introducing a Cr2 O3 shell onto the metal oxide, even though
the reaction is performed in a closed system [299]. Another prob-
lem that can occur in a closed system is the acceleration of water
formation from the H2 and O2 gases produced during water split-
ting, especially on noble-metal cocatalysts. Although this can be
addressed by applying the same Cr2 O3 shell strategy, it is also
possible to minimize the negative impact by using a flow system,
because evolved H2 and O2 do not accumulate in the system [206]. It
should be stressed here that a photocatalyst modified with a Cr(III)-
containing mixed oxide (e.g., Rh2 − y Cry O3 ) cocatalyst is resistant to
these two undesirable reverse reactions [293,294], and gas evo-
lution by water splitting on Rh2 − y Cry O3 /(Ga1 − x Znx )(N1 − x Ox ) is
observable as continuous bubbles, even at atmospheric pressure
[290]. This property would be useful for practical applications.
Kinetic studies on photocatalytic water splitting can provide
rational strategies for improving efficiency. During the develop-
ment of photocatalytic systems for overall water splitting under
visible light, a number of photocatalyst materials and preparation
methods have been reported, as discussed earlier. Many studies
have focused on the development of materials that are suitable
for visible-light-driven overall water splitting by addressing light
absorption properties, band-edge position, crystallographic qual-
ity, particle morphology, and phase purity. However, it is difficult to
understand what factor or factors dominate the net photocatalytic
activity based on the above physical properties, because the pho-
tocatalytic reactions proceed through a complicated sequence of
competing multistep processes. This demonstrates the importance
of understanding the kinetics and dynamics of a photocat-
alytic reaction to establish rational strategies for the immediate
development of photocatalytic systems and for future practical
applications.
Domen et al. recently examined mechanistic aspects of pho-
tocatalytic water splitting on Rh2 − y Cry O3 /(Ga1 − x Znx )(N1 − x Ox )
with respect to the effects of cocatalyst loading, light intensity,
hydrogen/deuterium isotopes, and reaction temperature on photo-
catalytic activity [311]. The water-splitting rate with an optimally
modified photocatalyst was proportional to light intensity under
solar-equivalent or weaker irradiation, indicating that accumula-
tion of photoexcited electrons and holes was negligible. Excess
loading of the cocatalyst did not improve the water-splitting rate.
The H-D isotope effect on overall water splitting was signifi-
cantly lower than previously reported values for photocatalytic
 K. Maeda / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 12 (2011) 237–268
and electrochemical H2 evolution reactions. The apparent activa-
tion energy for overall water splitting was 7.6 ± 2.4 kJ mol−1 , and
was unchanged by the addition of electron donors or acceptors.
These results reflect a shortage of photoexcited carriers available
for surface redox reactions under steady light irradiation. To sum-
marize, the experimental results indicate that the balance between
the rates of redox reactions on the photocatalyst surface and carrier
generation/recombination in the photocatalyst bulk determines
the steady-state charge concentration in the photocatalyst.
Their work also indicated that the water-splitting rate could
be enhanced by increasing the reaction temperature from 275
to 321 K, although the degree of enhancement was moderate. A
similar result was obtained using Rh2 − y Cry O3 - or Ni-loaded ␤-
Ga2 O3 doped with Zn [309]. The apparent activation energies for
the photocatalytic reaction were 8 or 15 kJ mol−1 for photocat-
alysts loaded with Rh2 − y Cry O3 or Ni, respectively. These were
comparable to the apparent activation energy of overall water split-
ting on Rh2 − y Cry O3 /(Ga1 − x Znx )(N1 − x Ox ) [311], but were smaller
than those of electrochemical H2 evolution on metal electrodes
(31 kJ mol−1 for Rh and 56 kJ mol−1 for Ni) [312,313]. This is because
surface redox reactions proceed after a sequence of photoexcitation
and charge migration in photocatalytic water splitting, as shown in
Fig. 4. It is suggested that there exists a potential barrier for electron
injection to a cocatalyst at the interface of an n-type semiconduc-
tor and a deposited cocatalyst [314]. It appears that this barrier
significantly affects the overall efficiency of photocatalytic water
splitting.
4. Summary and outlook
The research on photocatalytic water splitting was reviewed,
with a focus on the historical development of new photocat-
alysts and strategies to improve the activity of photocatalytic
water-splitting systems. As described above, in the search for
visible-light-responsive photocatalysts, significant effort has been
devoted to the development of new photocatalysts and active
sites (cocatalysts) on photocatalysts, as well as elucidating reac-
tion mechanisms. This has led to significant progress in the field
of heterogeneous photocatalysis for water splitting, especially in
the last 10 years. Although overall water splitting by visible light
had once been described as one of the “Holy Grails” of chemistry
[315], it became relatively easy for one to achieve overall water
splitting with visible photons around 400–450 nm using certain
photocatalytic systems. However, the development of a photocat-
alyst with a wider absorption band is still needed. While there is
an activation barrier for surface chemical reactions that evolve H2
and O2 , a photocatalyst with a 600 nm absorption edge would be
optimal. Several candidates, such as LaTiO2 N, CaNbO2 N, Ta3 N5 , and
Sm2 Ti2 S2 O5 , which have band gaps of ∼2 eV (an absorption edge
near 600 nm), have already been developed. Although the photo-
catalytic activities of these 600 nm class materials are insufficient
to achieve overall water splitting at present, recent progress in
materials chemistry towards reducing the density of defects should
enable their use. Fortunately, in a two-step water-splitting sys-
tem, the absorption wavelengths available for H2 and O2 evolution
have been increased to 660 nm (using BaTaO2 N) and 600 nm (using
Ta3 N5 ), respectively.
In future research on photocatalytic water splitting, it is
expected that not only searching for new photocatalyst and cocat-
alyst materials and improving their preparation methods, but also
elucidating the reaction mechanisms and interactions between
loaded cocatalysts and their base photocatalysts will become
more important. Several attempts to investigate the mechanistic
aspects of water splitting and the cocatalyst/photocatalyst inter-
face by kinetic analysis, spectroscopic and (photo)electrochemical
265
measurements, and computational approaches have already been
reported. Specifically, understanding the properties of the inter-
face between a photocatalyst and a loaded cocatalyst is a major
challenge in this research field.
A tentative goal for research on H2 production via solar-driven
overall water splitting using a particulate photocatalyst is to
develop a stable photocatalytic system that can achieve a quan-
tum efficiency of 30% at 600 nm [7]. The state of the art in this
field is, at most, an AQY of a few percent at wavelengths as long
as 500 nm, with a solar energy conversion efficiency on the order
of 0.1%. Therefore, more efficient photocatalytic materials with a
band gap as narrow as 2 eV (corresponding to 600 nm) must be
developed.
Acknowledgements
The author thanks a PRESTO/JST program and a Grant-in-Aid for
Young Scientists (Start-up) (No. 21850009) from the Japan Soci-
ety for the Promotion of Science (JSPS) for their funding support.
Acknowledgement is also extended to Nippon Sheet Glass Founda-
tion for Materials Science and Engineering.
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