Chemistry TOC

Proceeding of ISEC 2003

2003 International Solar Energy Conference
Hawaii, USA, 15-18 March 2003
ISEC2003-44301

SOLAR HYDROGEN PRODUCTION –

DIRECT WATER SPLITTING INTO HYDROGEN AND OXYGEN BY NEW PHOTOCATALYSTS
UNDER VISIBLE LIGHT IRRADIATION

Hironori Arakawa* Zhigang Zou

Photoreaction Control Research Center (PCRC)
National Institute of Advanced Industrial Science and Technology (AIST)
AIST Tsukuba Central-5, 1-1-1, Higashi, Tsukuba, Ibaraki 305-8565, Japan
E-mail:h.arakawa@aist.go.jp

Kazuhiro Sayama Ryu Abe

Photoreaction Control Research Center (PCRC)
National Institute of Advanced Industrial Science and Technology (AIST)
AIST Tsukuba Central-5, 1-1-1, Higashi, Tsukuba, Ibaraki 305-8565, Japan

ABSTRACT developed yet. We have been investigating such a new

The photocatalytic splitting of water into hydrogen and
oxygen using solar energy is one of the most attractive
renewable sources of hydrogen fuel. Therefore, considerable
efforts have been paid in developing photocatalysts capable of
using visible light, which accounts for about 43% of the solar
energy. However such a photocatalyst has not been developed
so far. We have developed a new Ni-doped indium-tantalum
oxide photocatalyst, In1-xNixTaO4 (x=0.0~0.2), which induced
direct splitting of water into stoichiometric amount of oxygen
and hydrogen under visible light irradiation with a quantum
yield of about 0.66% at 420.7 nm. We have also developed a
new two-step water splitting system using two different
semiconductor photocatalysts, Pt/WO3 photocatalyst for oxygen
evolution and Pt/SrTiO3(Cr-Ta-doped) photocatalyst for
hydrogen evolution, and a redox mediator, I-/IO3-, mimicking
the Z-scheme mechanism of the natural photosynthesis. The
quantum yield of this system was about 0.1% at 420.7nm. Both
photocatalytic methods are the first examples for visible light
water splitting system in the world.
Keywords: Solar hydrogen production, Water splitting, Visible
light, Powder photocatalysts, Oxide semiconductor, Pt/WO3,
SrTiO3 (Cr-Ta-doped), I-/IO3- redox mediator
INTRODUCTION
Hydrogen production by direct splitting of water using
photocatalysts under solar light is one of the most attractive
research subjects in terms of a clean energy supply in this
century. Therefore, a number of researches on photocatalytic
splitting of water have been conducted so far. As a result,
several oxide semiconductor photocatalysts, such as Na2CO3-
Pt/TiO2,1) NiOx/K4Nb6O17,2) NiOx/Ta2O53), and NiOx/NaTaO34),
which were able to split water under UV light irradiation, were
reported. However, photocatalysts, which can utilize visible
light for stoichiometric splitting of water, have not been
photocatalytic system by two different approaches. The one is
to design and synthesize narrow band gap oxide semiconductor
photocatalysts which are able to split water under visible light
irradiation. The other is to design the two-step water splitting
system which is composed of the combination of two different
oxide semiconductor photocatalysts for H2 and O2 production,
respectively, and a shuttle redox mediator working in between
two photocatalysts. This system mimics the Z-scheme
mechanism in natural photosynthetic process. These new
approaches are introduced and discussed.
NOMENCLATURE
λ: wave length of irradiated light, TEM: transmission electron
micrograph, EDAX: energy dispersion analysis of x-ray, PSI:
photosynthesis step I, PSII: photosynthesis step II.
ONE STEP WATER SPLITTING BY NEW OXIDE
SEMICONDUCTOR PHOTOCATALYSTS WITH A
NARROW BAND GAP
We have synthesized various kinds of new mixed oxide
semiconductor materials which could absorb visible light. The
first group is Bi2MNbO7 (M= Al3+, Ga3+, In3+, Y3+, Rare Earth3+) 5)
of A2B2O7 pyrochlore structure. The second group is BiMO4
(M=Nb5+, Ta5+)6) of stibotantalite structure and the third group is
InMO4 (M=Nb5+, Ta5+)7) of wolframite-type structure with space
group P2/a. Figure 1 shows the structure of InTaO4. The
structure contains TaO6 and InO6 octahedra in a unit cell. The
InO6 octahedra share edges to form zigzag chains along the
[100] direction, with individual [InO6]∞ octahedral chains linked
by TaO6 octahedra into a three dimensional network. The
volume of the InO6 and TaO6 octahedra in InTaO4 are 13.051
and 10.648 A3, respectively. Because the ionic radius of Ni2+
(0.78 A) is much smaller than that of In3+ (0.92 A), substituting
In3+ by Ni2+ should reduce the volume of the InO6 octahedra, and

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 hence the cell volume of InTaO4. This should in turn affect the
direct metal-metal bonding in the crystal, with the In-In
distance shortened, resulting in significant alternations of the
electronic properties of the compounds.

Abs. (arb.units)
x=0.1

x=0.0

200 400 600 800

Wavelength/nm
Fig. 2 UV-visible diffuse reflectance spectra of
In1-xNixTaO4 (X=0 and 0.1) at room temperature

Fig. 1 The unit cell structure of InTaO4 photocatalyst

Table 1. Rates of gas evolution properties of the
The band structure of these materials is estimated that the newly synthesized photocatalysts
conduction band is composed of Ta/Nb d-level mainly and the ---------------------------------------------------------------------------
valence band is composed of O 2p-level mainly. The band gaps Photocatalyst Rate of evolution (µ mol h-1)b)
of these materials determined by UV-visible reflectance spectra NiOx/ RuO2/
as shown in Figure 2 were between 2.7 and 2.4 eV. Among H2 O2 H2 O2
these materials, NiOx (surface oxidized Ni) or RuO2 promoted ---------------------------------------------------------------------------
a)
InTaO4 and InNbO4 photocatalysts, such as NiOx/InTaO4, SiO2 0.0 0.0 0.0 0.0
RuO2/InTaO4 and NiOx/InNbO4, showed photocatalytic InTaO4 3.2 1.1 0.75 0.35
activities for pure water splitting under visible light irradiation In0.95Ni0.05TaO4 4.2 2.1 2.0 1.0
(λ > 420 nm, 300W Xe-lamp). However, the activities were In0.90Ni0.10TaO4 16.6 8.3 8.7 4.3
very low. In0.85Ni0.15TaO4 8.3 4.1 4.8 2.3
In order to improve water splitting activity, transition metal In0.80Ni0.20TaO4 4.3 0.9 0.83 0.4
doped InTaO4 and InNbO4 were synthesized.8) Among these ---------------------------------------------------------------------------
doped materials, Ni-doped InTaO4 and Ni-doped InNbO4 a): In order to investigate the effect of NiOx on
photocatalytic activity onto the surface of photocatalysts,
photocatalysts such as NiOx/In0.9Ni0.1TaO4, RuO2/ In0.9Ni0.1TaO4,
the 1.0wt%NiOx/SiO2 sample was prepared because SiO2
NiOx/In0.9Ni0.1TaO4 and RuO2/In0.9Ni0.1TaO4 showed the highest does not have photocatalytic activity under visible light
activities. Table 1 shows the result of photocatalytic water irradiation.
splitting using various kinds of Ni-doped InTaO4 photocatalysts. b): NiO / is 1.0wt% NiOx loading on the surface of
The rate of H2 and O2 evolution were 16.6 and 8.3 µmol/h, photocatalyst; RuO2/ is 1.0wt% RuO2 loading on the surface
respectively, and the quantum efficiency at 402 nm was 0.66% of photocatalyst. The rate of gas evolution was calculated
in the case of 1wt%NiOx/ In0.9Ni0.1TaO4 photocatalyst.9) The for 24 h using catalyst 0.5 g under visible light irradiation λ
absorption band due to Ni-doping was observed at 420-520nm > 420 nm.
in addition to that of In0.9Ni0.1TaO4. This is one of reasons of
activity increase. The stability of this photocatalyst and Figure 3 shows the evolution of H2 and O2 from pure water
reproducibility of photocatalytic water splitting reaction were containing aqueous suspension of NiOx/In0.9Ni0.1TaO4 under
fairly good. TEM photographs of In0.9Ni0.1TaO4 photocatalyst visible light irradiation ( λ > 420 nm ). The gas evolution
showed the particles size were 300 to 500 nm and NiOx stopped when the light was turned off, showing that the
particles on In0.9Ni0.1TaO4, were 15 to 30 nm. A clear formation reaction is induced by the absorption of visible light and not by
of stepped- structure was also observed in In0.9Ni0.1TaO4 tribological processes, such as the so-called mechano-catalysis.
particles and TEM-EDAX analysis showed In0.9Ni0.1TaO4 has a After evacuating the reaction system and re-running the
homogeneous atomic distribution.10) experiment, almost identical gas production rates were

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 achieved in the second run. More than 7,200 µmol gases
evolved (H2: about 4,800µmol; and O2: about 2,400µmol)
during the course of a 400-hours experiment. The catalysts
samples remained unchanged during the course of reaction,
suggesting that the photocatalytic activity is stable under visible
light irradiation. The turnover number ( the ratio of total
amount of gas evolved to photocatalyst (1,412µmol ) exceeded
5 after 400-hours reaction time. The turnover number in terms
of reacted electrons relative to the amount of Ni loaded on the
surface of the sample and Ni doped InTaO4 reached 39 at 400-
hours reaction time, indicating that the reaction occurs
catalytically.
400
Light Dark
Amount of evolved gases /µ mol
300
H2
O2
200
100
0
0 10 20 30 40
Irradiation time/h
Fig. 3 The reaction time course of photocatalytic H2
and O2 evolution
Experiment were conducted using 0.5g photocatalysts
powder suspended in 250 ml pure water in a pyrex glass
cell under visible light irradiation (λ > 420 nm). Light
source: 300-W Xe lamp. The gases evolved were measured
by a pressure gas sensor and determined by TCD
gaschromatograph.
The first principle calculations were conducted to
determine of the band structure of In0.9Ni0.1TaO4 using of
In14Ni2Ta16O64 model. The electrons from the Ni-3d8 dopant
seem to be somewhat delocalized, thus contributing to the
formation of the new band with the O-2p electrons. Based on a
comparison with the light absorption and photocatalytic activity,
we think the eg state of the Ni-3d8 plays a significant role in the
photocatalytic splitting of pure water under visible light
irradiation.
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TWO STEP WATER SPLITTING BY TWO DIFFERENT
OXIDE SEMICONDUCTOR PHOTOCATALYSTS AND A
REDOX MEDIATOR, MIMICKING A Z-SCHEME
MECHANISM IN NATURAL PHOTOSYNTHESIS
It is not easy to design efficient photocatalysts using a
conventional reaction mechanism for one-step water splitting
under visible light irradiation as shown in Fig.1 (a). On the
other hand, in natural photosynthesis, carbohydrate and O2 are
formed from CO2 and water using visible light under solar light
irradiation. This system utilizes so-called Z-scheme reaction
which is composed of two photo-excitation centers, PSI and
PSII, and many redox mediators. In order to develop the
photocatalytic water splitting into H2 and O2 stoiciometrically
under visible light irradiation, the mimicking system of the Z-
scheme mechanism using reversible redox mediators (Ox/Red)
as shown in Fig. 1 (b) was investigated.
Light
(a)
H2O
+
H /H2 H2
O2 / H2O
H2O
O2
(b)
PSII[O2] PSI[H2]
50 60 70 H2O
Ox
+ H2
H /H2 Red
Ox/Red
O2 / H2O Red
H2O Ox
O2
Fig. 4 Reaction mechanisms of photocatalytic water
splitting into H2 and O2
(a): the conventional mechanism of photocatalytic water
splitting ( one-step photo-excitation system)
(b): the new mechanism mimicking the Z-scheme system
( two-step photoexcitation system)
To look for both a stable shuttle redox mediator and its
appropriate reaction condition is very important. We found IO3-
/I- redox system could work for water splitting using the
mixture of Pt/TiO2 (anatase) and TiO2 (rutile) photocatalysts as
PSI[H2] and PSII[O2], respectively. The H2 evolution took place
over Pt/TiO2 (anatase) with the oxidation of I- to IO3-, and O2
evolution took place over TiO2 (rutile) with the reduction of
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 IO3- to I- in the one reactor under UV light irradiation.11) Various neutralize the total charge. WO3 for O2 evolution could absorb
kinds of visible light responding oxide semiconductor visible light up to 460 nm as shown in Figure 6..
photocatalysts, such as Fe2O3, Bi2WO6, In2O3(ZnO)9, CrTaO4,
InTaO4, SrTiO3 and so on, were screened for H2 evolution from

absorbance / arb.units
water including I- ion as a reversible electron donor. On the
other hand, O2 evolution from water including IO3- as a
reversible electron acceptor was also tested using various kinds
of oxide semiconductor photocatalysts such as WO3, In2O3, (c)
Bi2O3, BiVO4, CuWO4, NiWO4 and so on.
Finally, we found both H2 and O2 evolution with a (a) (b)
stoichiometric ratio of H2/O2=2/1 occurred stably for more than
250 hours under visible light irradiation using a mixture of 300 400 500 600 700 800
Pt/WO3 photocatalysts for O2 evolution and Pt/StTiO3(Cr, Ta- wavelength / nm
doped) photocatalyst for H2 evolution in NaI aqueous solution,
as shown in Fig. 5.
Fig. 6 UV-visible diffuse reflectance spectra of (a)
SrTiO3, (b) SrTiO3 (Cr-Ta-doped), and (c) WO3
µ m ol

photocatalysts
100 dark
light light dark light
80 We have established a new visible light water splitting
am ou nt o f gas e vo lution /

system with a two-step photo-excitation mechanism using a

pair of I-/IO3- shuttle redox mediator. The quantum efficiency at
We 60
H 2 a new visible light water splitting system
established 420 nm was about 0.1%.12,13) A proposed reaction mechanism
40 for two-step water splitting by the combination of two different
photocatalysts, Pt/WO3 for O2 evolution and Pt/SrTiO3 (Cr-Ta-
20 doped) for H2 evolution, and a shuttle redox mediator, I-/IO3-, is
O2
shown in Fig. 7
0
0 50 100 150 200 250 PSII[O2] PS1[H2]
Tim e / h H2O
- Pt
e H2
-0.41 Pt +
e - H /H2
Fig. 5 Photocatalytic splitting of water into H2 and O2 IO3
0.09
under visible light ( λ > 420 nm ) I
- h
visible - -
PSI photocatalyst: 0.2g of 0.3wt%Pt/SrTiO3 doped with Cr
0.6 IO3 /I
and Ta (1 mol% of Ti was doped respectively) 0.8 h - O2/H2O
PSII photocatalysts: 0.2g of 1wt%Pt/WO3 IO3
O2 visible h+
Initial reaction solution: NaI aqueous solution (100 ml/l, -
pH=7.0) I
The magnetic stirring was continued under both light h+
H2O Pt-WO3 Pt-SrTiO3(Cr-Ta doped)
irradiation and dark reaction condition..

Fig. 6 shows the UV-visible diffuse reflectance spectra of

(a) SrTiO3 and (b) SrTiO3(Cr-Ta-doped). The non-doped
SrTiO3 absorbed UV light up to 395 nm, and the band gap was
estimated to be 3.1 eV. The absorption band of the doped Fig. 7 A proposed reaction mechanism for two-step
semiconductor was very broad and extended to more than 700 water splitting system
nm. The H2 evolution was observed on the Pt-loaded SrTiO3
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