International Journal of Hydrogen Energy 31 (2006) 197 – 202

www.elsevier.com/locate/ijhydene

Development of photocatalyst materials for water splitting

Akihiko Kudoa, b,∗
a Department of Applied Chemistry, Faculty of Science, Science University of Tokyo, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
b Core Research for Evolutional Science and Technology, Japan Science and Technology Agency (CREST, JST), 4-1-8 Honcho,
Kawaguchi-shi, Saitama 332-0012, Japan

Available online 13 June 2005

Abstract
Various photocatalyst materials developed by the group of the author are described. Alkali and alkaline earth tantalates
have arisen as a new group of photocatalyst materials for water splitting into H2 and O2 under ultraviolet light irradiation.
They showed the activities even without co-catalysts such as Pt, being different from titanate photocatalysts. When NiO
co-catalysts were loaded on the tantalate photocatalysts, the photocatalytic activities were drastically increased. Among the
tantalates, NiO/NaTaO3 doped with La showed the highest activity. Some metal sulfide photocatalysts such as AgGaS2 and
AgInZn7 S9 showed high activities for H2 evolution from aqueous solutions containing S2− and SO2− 3 as electron donors
under visible light irradiation (wavelength > 420 nm). The H2 evolution was observed even under irradiation using a solar
simulator. Pt/SrTiO3 doped with Rh has also arisen as a novel oxide photocatalyst for H2 evolution from aqueous solutions
containing reducing reagents under visible light irradiation. On the other hand, BiVO4 and AgNbO3 showed high activities
for O2 evolution in the presence of sacrificial reagent (Ag+ ) under visible light irradiation.
䉷 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Photocatalyst materials; Water splitting; Ultraviolet light irradiation

1. Introduction inorganic chemistry, etc. for about 30 years since the

The importance of hydrogen energy has recently been rec-
ognized again, especially by the spread of a fuel cell from
the viewpoint of an environmental issue. However, hydro-
gen is industrially produced by steam reforming of hydro-
carbons such as methane. Dihydrogen has to be produced
from water using a natural energy if one thinks of the en-
vironmental issue. Therefore, water splitting using a pho-
tocatalyst is a challenging reaction because it is one of the
ultimate reactions to solve energy and environmental issues.
Water splitting using photocatalysts is not a new theme.
Water splitting has been studied in the research fields of
catalysis, electrochemistry, photochemistry, organic and
∗ Department of Applied Chemistry, Faculty of Science, Science
University of Tokyo, 1-3 Kagurazaka, Shinjuku-ku, Tokyo
162-8601, Japan. Fax: +81 3 3235 2214.
E-mail address: a-kudo@rs.kagu.tus.ac.jp.
Honda–Fujishima effect was reported using a TiO2 semi-
conductor electrode [1]. However, the number of reported
photocatalysts which were able to decompose water into
H2 and O2 in a stoichiometric amount with a reasonable
activity had been much limited. The active photocatalysts
are only oxide materials at the present stage. In such a
background, various types of new photocatalysts for water
splitting have been developed [2–4] and this research field
is taking a new turn. In the present paper, new photocat-
alyst materials, developed by the author, aiming at water
splitting of an artificial photosynthesis, are reviewed.
2. Tantalate photocatalysts for water splitting [5–14]
Most of reported photocatalysts for water splitting had
been titanates [4]. So, it is important to develop new types
of photocatalyst materials. On the other hand, it has been

0360-3199/$30.00 䉷 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2005.04.050
198 A. Kudo / International Journal of Hydrogen Energy 31 (2006) 197 – 202

Table 1 250
Water splitting over alkali and alkaline earth tantalate photocatalysts

Catalyst Band gap NiO loaded Activity (
mol/h) 200

Volume of evolved gas

(eV) (mass%)

H2 O2 150

K3 Ta3 Si2 O13 4.1 None 53 23

K3 Ta3 Si2 O13 4.1 1.3 390 200 100
LiTaO3 4.7 None 430 220
LiTaO3 4.7 0.10 98 52 50
NaTaO3 4.0 None 160 86
NaTaO3 4.0 0.05 2180 1100
KTaO3 3.6 None 29 13 0
KTaO3 3.6 0.10 7.4 2.9 0 100 200 300 400
CaTa2 O6 4.0 None 21 8.3 Time / h
CaTa2 O6 4.0 0.10 72 32
Fig. 1. Photocatalytic water splitting into H2 and O2 on
SrTa2 O6 4.4 None 140 66
NiO(0.2 wt%)/NaTaO3 : La(1.5 mol%). Catalyst: 1 g, 1 mM NaOH:
SrTa2 O6 4.4 0.10 960 490
390 ml, 400 W high-pressure Hg lamp, inner irradiation cell made
BaTa2 O6 4.1 None 33 15
of quartz.
BaTa2 O6 4.1 0.30 629 303
Sr 2 Ta2 O7 4.6 None 57 18
in the development of a highly active photocatalyst,
Sr 2 Ta2 O7 4.6 0.15 1000 480
NiO/NaTaO3 doped with La [13,14]. H2 evolved with a
K2 PrTa5 O15 3.8 None 10 3
K2 PrTa5 O15 3.8 0.1 1550 830 rate of 20 mmol/h (500 ml/h) using a 400 W high-pressure
mercury lamp as shown in Fig. 1. Although the photocat-
Alkali tantalates were prepared in the presence of excess amounts alyst cannot be used practically because of the wide band
(5%) of alkali. Photocatalyst: 1.0 g, water: 390 ml, reaction cell: gap (4.1 eV), it is noteworthy that such a high activity was
inner irradiation-type reaction cell made of quartz, light source: obtained using a powdered photocatalyst system without
400 W high-pressure mercury lamp.
any sacrificial reagents. Observation by a scanning electron
microscopy revealed that the La-doped NaTaO3 possessed
reported that some oxides with structural regularities such a small particle size (0.1.0.7
m), high crystallinity, and
as layered and tunneling structures are active [3,4]. Then, characteristic surface step structure as shown in Fig. 2. The
new photocatalyst materials, except for titanates, have been decrease in the particle size and the creation of the step
surveyed by the author’s group. structure by the La-doping probably cause a decrease in the
Table 1 shows tantalate photocatalysts which are active migration distance of photogenerated electrons and holes
for water splitting. These materials were synthesized by to reach the reaction site on the surface, and the creation
solid-state reactions or a flux method. These tantalate pho- of active sites, respectively. These factors contribute to the
tocatalysts are active even without co-catalysts. Moreover, highly photocatalytic activities.
loading a NiO co-catalyst which works as a H2 evolution
site drastically improves the photocatalytic activity. LiTaO3
3. Visible light driven photocatalysts working under
was most active among the naked alkali and alkaline earth
visible light irradiation for H2 or O2 evolution
tantalates. Among tantalates loaded with a NiO co-catalyst,
NiO/NaTaO3 was most active. Therefore, the authors tried Water splitting into H2 and O2 in stoichiometric amounts
to improve the activity by some modifications. This resulted is a tough reaction because of an up-hill reaction. Sacrificial

Fig. 2. SEM images of (a) NaTaO3 and (b) NaTaO3 : La.

 A. Kudo / International Journal of Hydrogen Energy 31 (2006) 197 – 202 199

-
e- e-
H+/H2
Band gap Redox
potential of
Potential hν Redox potential oxidizing
of reducing reagent reagent
O2/H2O
h+ h+

+ H2 formation in the presence O2 formation in the presence

(a) of reducing reagents (b) of oxidizing reagent

Fig. 3. Scheme of photocatalytic H2 or O2 evolution in the presence of sacrificial reagents.

reagents are often used as half reactions of the water split- 30

ting in order to evaluate photocatalytic abilities. The role

Apparent quantum yield / %

of sacrificial reagents in photocatalytic reactions is shown 25

Absorbance / arb. units

in Fig. 3. When the photocatalytic reaction is carried out
in aqueous solutions including easily oxidizable reducing
reagents such as alcohol, S2− , and SO2− 3 , photogenerated
holes irreversibly oxidize the reducing reagents instead of
water. It makes the electrons in the photocatalyst rich and a
H2 evolution reaction is enhanced as shown in Fig. 3(a). On
the other hand, in the presence of electron acceptors such
as Ag+ and Fe3+ , the photogenerated electrons in the con-
duction band are consumed by them and an O2 evolution
reaction is enhanced as shown in Fig. 3(b). These reactions
using sacrificial reagents are regarded as half reactions and
often employed for test reactions of photocatalytic H2 or
O2 evolution. However, one should know that the results do
not guarantee a photocatalyst to be active for overall wa-
ter splitting into H2 and O2 in the absence of sacrificial
reagents.
Photocatalytic reactions mentioned below were carried
out in the presence of sacrificial reagents.
3.1. Metal sulfide photocatalysts working under visible
light irradiation for H2 evolution from aqueous solutions
containing sacrificial reagents [15]
Although metal sulfides usually have a problem of pho-
tocorrosion, they are attractive as photocatalysts with visi-
ble light response. The representative photocatalyst is CdS
which is active for H2 evolution under visible light irradia-
tion. The photocorrosion is considerably suppressed in the
presence of sacrificial reagents.
On our surveying metal sulfides, AgGaS2 and
AgInZnX SX+2 showed activities for photocatalytic H2 evo-
lution from aqueous solution containing sacrificial reagents
of Na2 S and K2 SO3 under visible light irradiation without
Pt co-catalysts.
Calcopylite-type material AgGaS2 with a 2.6 eV band
gaps showed the photocatalytic activity for H2 evolution
from an aqueous Na2 S and K2 SO3 solution under visible
light irradiation. Loading noble metal co-catalysts to the
20
15
10
5
0
300 350 400 450 500 550 600
Wavelength / nm
Fig. 4. Diffuse reflection and action spectra of Rh/AgGaS2 pho-
tocatalyst. Catalyst: 0.3 g, an aqueous sulfite and sulfide solution:
Na2 S (0.1 mol dm−3 ) and K2 SO3 (0.5 mol dm−3 ), 150 ml, light
source: 300 W Xe lamp with band-pass filter and cut-off filter.
AgGaS2 dramatically improved the photocatalytic activity.
The onset of the action spectrum agreed with that of the
diffuse reflection spectrum indicating that the H2 evolution
proceeded with the band gap excitation as shown in Fig. 4.
The Rh (1 wt%)-loaded AgGaS2 photocatalyst gave ca.
25% of the quantum yield at 440 nm. The electronic band
structure study using a plane-wave-based density functional
method revealed that the valence band consisted of a hy-
brid orbital of S 3p and Ag 4d, and the conduction band is
composed of a hybrid orbital of S 3p + Ga 4s4p.
AgInZnX SX+2 of Wurtzite-type solid solutions between
ZnS and AgInS2 showed activities for photocatalytic H2
evolution from aqueous solutions containing sacrificial
reagents of K2 SO3 under visible light irradiation without
Pt co-catalysts [15].
The diffuse reflectance spectra of the AgInZnX SX+2
solid solution photocatalysts successively shifted with the
change in the composition X (X = 2.10) as shown in
Fig. 5. The band gaps of the catalysts estimated from the
onsets of the visible light absorption bands were 2–2.4 eV
(X = 2.10). The photocatalytic H2 evolution depended on
200 A. Kudo / International Journal of Hydrogen Energy 31 (2006) 197 – 202

Evacuation of a gas phase

X=0.17 (2.40eV) 1000
X=0.22 (2.33eV)

Amount of H2 evolved / µmol

Absorbance / arb. units

X=0.29 (2.24eV) 800

X=0.33 (2.17eV)
600
X=0.40 (2.10eV)
X=0.50 (1.95eV) 400

AgInS2
ZnS 200
(1.80eV)
(3.45eV)
0
300 400 500 600 700 800 900 0 5 10 15 20 25
Wavelength / nm Time / h

Fig. 5. Diffuse reflectance spectra of (Agln)X Zn2(1−X) S2 photo- Fig. 7. H2 evolution from an aqueous methanol (10 vol%) solu-
catalysts. tion under visible light irradiation (wavelength > 440 nm) over a
Pt(0.1 wt%)/SrTiO3 : Rh(1%) photocatalyst. Catalyst: 0.3 g, reac-
tant solution: 150 ml, light source: 300 W Xe lamp with cut-off
500 filters (L42 + Y44).
Rate of H2 evolution / µmol h-1

400
300
200
100
0
0 0.2 0.4
ZnS X in (AgIn)XZn2(1-X)S2
Fig. 6. Dependence of photocatalytic activities for H2 evolution
from an aqueous K2 SO3 solution over Pt(3 wt%)/(Agln)X
Zn2(1−X) S2 solid solutions upon the value of X.
the composition as shown in Fig. 6. Pt-loaded AgInZn7 S9
(2.3 eV) showed the highest activity for the H2 evolution.
The rate of H2 evolution was 944
mol/h and the quantum
yield at 420 nm was 20%. Scanning electron microscope
observation revealed that the AgInZnX SX+2 solid solution
photocatalyst possessed the surface nano-step structure and
a Pt co-catalyst was selectively photodeposited on the edge
of the step structure. This unique surface nano-structure
seems to contribute to the high photocatalytic ability.
3.2. Metal oxide photocatalysts working under visible
light irradiation for H2 evolution from aqueous solutions
containing sacrificial reagents [16]
The creation of visible light response by doping some
transition metal ions into photocatalysts working under ul-
traviolet irradiation has been studied for a long time. The
Catalyst:0.3g
0.5 M K2SO3aq.

> 420nm base photocatalyst was mainly TiO2 [17]. The doping of
transition metal ions with partially filled d-orbitals colors
TiO2 photocatalysts. However, in most of the cases, the
dopant worked as a recombination center between photogen-
erated electrons and holes resulting in the drastic decrease
in the photocatalytic activity even under the ultraviolet
irradiation.
The author’s group has paid attention to SrTiO3 as a host
0.6 0.8 1 photocatalyst besides TiO2 . Rh-doped SrTiO3 possessed an
AgInS2 intense absorption band in the visible light. The Rh-doped
SrTiO3 loaded with Pt co-catalysts produced H2 from an
aqueous methanol solution under visible light irradiation as
shown in Fig. 7 [16]. The Rh (1%)-doped SrTiO3 photocat-
alyst loaded with a Pt co-catalyst (0.1 wt%) gave 5.2% of
the quantum yield at 420 nm for the H2 evolution reaction.
The visible light response was due to the transition from the
electron donor level formed by the Rh ions to the conduc-
tion band composed of Ti3d orbitals of SrTiO3 .
3.3. BiVO4 and AgNbO3 working under visible light
irradiation for O2 evolution from aqueous solutions
containing sacrificial reagents [18–21]
The formation of recombination centers is not completely
suppressed in the doping system mentioned above. An ab-
sorption coefficient should depend on the amount of dopants.
Moreover, the impurity levels formed by the doping are
usually discrete and are inconvenient for the migration of
photogenerated holes in that level. Therefore, a continuous
valence band should be formed with some orbitals besides
O2p . Here, Bi3+ with 6s2 configuration and Ag+ with 4d10
configuration attracted our attention as candidates which can
form such valence bands.
 A. Kudo / International Journal of Hydrogen Energy 31 (2006) 197 – 202 201

700 the band–band transition. The valence bands of BiVO4 and

Amount of O2 evolved / µmol

BiVO4
AgNbO3 consist of Bi6s and Ag4d orbitals mixed with O2p
600
resulting in the rise of the valence band potentials and the
500 decrease in the band gaps. The information obtained in the
present study is important for the control of a valence band
400
in order to develop new visible light-response photocata-
300 lysts. Although BiVO4 did not have a potential for H2 evo-
WO3 lution, it is worthwhile that it was active for O2 evolution
200
accompanied with 4-electron oxidation. The valence band
100 consisting of Bi6s and O2p actually possesses not only the
thermodynamical but also the kinetic potential for the O2
0
evolution.
0 1 2 3 4
Time / h
4. Conclusions
Fig. 8. Photocatalytic O2 evolution from aqueous AgNO3 solutions
under visible light irradiation (wavelength > 420 nm) on BiVO4
prepared by an aqueous process.
NiO/NaTaO3 : La was found to be a highly active pho-
tocatalyst for water splitting, a very tough reaction, under
UV light irradiation. This result has proven that highly effi-
cient water splitting is actually possible using a photocatalyst
powder system. Moreover, although a sacrificial reagent is
CB Nb4d,V3d needed, various oxide and sulfide photocatalysts, AgGaS2 ,
Absorbance / arb. units

AgInZnX SX+2 , Rh-doped SrTiO3 , BiVO4 , and AgNbO3 ,

for H2 or O2 evolution under visible light irradiation have
VB Ag4d,Bi6s been developed. The results make us expect to find highly
O2p active photocatalysts for H2 production from water using a
solar light energy.

Acknowledgements
AgNbO3 BiVO4
This work was supported by Core Research for Evolu-
tional Science and Technology (CREST), and a Grant-in-
300 400 500 600 700 800
Aid (no. 11640601) from the Ministry of Education, Sci-
Wavelength / nm
ence, Sports, and Culture, Japan.
Fig. 9. Diffuse reflection spectra of BiVO4 and AgNbO3 photo-
catalysts for O2 evolution.
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