PAPER www.rsc.

org/ees | Energy & Environmental Science

Water splitting into H2 and O2 over niobate and titanate

photocatalysts with (111) plane-type layered perovskite structure
Yugo Miseki, Hideki Kato† and Akihiko Kudo*
Received 24th October 2008, Accepted 26th November 2008
First published as an Advance Article on the web 13th January 2009
DOI: 10.1039/b818922f

Photophysical and photocatalytic properties of A5Nb4O15 (A ¼ Sr and Ba), Ba3LaNb3O12,

ALa4Ti4O15 (A ¼ Ca, Sr, and Ba), and La4Ti3O12 with layered perovskite structures, in which a plane in
parallel with (111) of a simple perovskite structure was exposed at interlayer, were investigated. These
oxides were obtained by a polymerizable complex method at 973–1473 K though only A5Nb4O15 (A ¼
Sr and Ba) were prepared by a solid state reaction even at 1673 K. The shapes of these complex metal
oxides were plate-like derived from the perovskite layered structure. These band gaps were estimated to
be 3.7–4.1 eV from the onsets of diffuse reflection spectra. These oxides showed photoluminescence
at 77 K. These oxides loaded with NiO cocatalysts showed activities for water splitting under UV
irradiation. NiOx/BaLa4Ti4O15 and NiOx/Ba5Nb4O15 showed the highest activities among the titanates
and niobates tested in the present study. NiOx/BaLa4Ti4O15 and NiOx/Ba5Nb4O15 gave 15% and 17%
of quantum yields at 270 nm, respectively. Photocatalytic activities of ALa4Ti4O15 (A ¼ Ca, Sr, and Ba)
strongly depended on the alkaline earth metal ion. Pt, Au, Ni, and PbO2 were selectively
photodeposited on basal or edge plane of the BaLa4Ti4O15 plate-like powder while these were randomly
loaded on CaLa4Ti4O15. It was suggested that this difference in the surface property was the one of the
important factors affecting photocatalytic ability for ALa4Ti4O15 (A ¼ Ca, Sr, and Ba).

1. Introduction ingful. Recently, metal oxynitride and nitride photocatalysts,36,37

Photocatalytic water splitting using a heterogeneous semi-
conductor powder has been studied as an ideal H2 production
method which does not give any burdens to the environment.
Many oxide photocatalysts consisting of d0 and d10 metal ions
show photocatalytic activities for water splitting under UV
irradiation.1–35 Each material possesses unique character even if
they seem similar to each other. So, finding a new material for the
attractive and tough reaction, and studying its science is mean-
Department of Applied Chemistry, Faculty of Science, Tokyo University of
Science, 1-3 Kagurazaka, Shinjyuku-ku, Tokyo, 162-8601, Japan. E-mail:
a-kudo@rs.kagu.tus.ac.jp; Fax: +81-35261-4631; Tel: +81-35228-8267
† Current address: Materials and Structures Laboratory, Tokyo Institute
of Technology, 4259 Nagatsuda, Midori-ku, Tokohama, 226-8503,
Japan.
and Z-scheme-type photocatalysts accompanied with two-
photon process38–42 have been reported for water splitting under
visible light irradiation. The final target of this research is
efficient solar hydrogen production from water. The present
efficiency is not satisfying for practical use. Photocatalytic water
splitting is an attractive and challenging reaction. Therefore,
basic research is still important in this research field. The
construction of a photocatalyst library and clarification of
factors affecting photocatalytic abilities are important in order
to establish a guiding principle for design of a photocatalyst.4
NiO/NaTaO3 photocatalyst shows high activity for water
splitting under UV irradiation.5 Moreover, the activity of NiO/
NaTaO3 is remarkably improved by La doping (1–2%).6 La-
doping gives nano-sized NaTaO3 particles and characteristic
surface step structure. Active sites for H2 evolution are separated

Broader context
There is no doubt that solar hydrogen production from water is highly desirable. Water splitting using a particulate photocatalyst is
one of the candidates for the solar hydrogen production. The photocatalyst system is not at the stage of practical use. Therefore,
basic research is still important in this research field. The construction of a photocatalyst library and clarification of factors
dominating photocatalytic activities are important in order to establish a guiding principle of photocatalyst design. In the present
study, A5Nb4O15 (A ¼ Sr, Ba), Ba3LaNb3O12, ALa4Ti4O15 (A ¼ Ca, Sr, Ba), and La4Ti3O12 with a (111) plane-type layered
perovskite structure in which alkaline earth metal and lanthanum cations are ordered or not at interlayer and A-site were found to be
new niobate and titanate photocatalyst materials for water splitting. 15% of the quantum yield was obtained. The ordering caused
anisotropic characters of photocatalytic properties that were revealed by DRS, SEM, photodeposition of metals, and photo-
luminescence. The relationship between photocatalytic activities, and crystal and energy structures are systematically discussed in
detail. These results and discussion will be valuable in this research field of not only water splitting but also photocatalytic
degradation of hazardous organic compounds.

306 | Energy Environ. Sci., 2009, 2, 306–314 This journal is ª The Royal Society of Chemistry 2009
from those for O2 evolution by the surface nano-step structure.
So, the surface morphology is important. On the other hand, the
metal oxides with layered structures, such as K4Nb6O17,7
K2La2Ti3O10,8 A2A0 2O7 (A ¼ Ca and Sr, A0 ¼ Nb and Ta),12,14,30
RbNdTa2O7,15 La2Ti2O7,19 H2La2/3Ta2O7,23 K2Sr1.5Ta3O10,32
H1.8Sr0.81Bi0.19Ta2O7,33 and LiCa2Ta3O1034 show high activities
for water splitting under UV irradiation. The interlayer can
function as reaction sites and separate oxidation reaction sites
from reduction reaction sites in hydrated layered compounds.
The anisotropy derived from the layered structure may also
affect the photocatalytic ability. Therefore, it is important to
examine photocatalytic properties of various compounds with
surface morphology and characteristic crystal structure like
a layered structure in order to obtain further information on
photocatalytic water splitting.
There are many kinds of compounds with layered perovskite
structure consisting of various elements, and perovskite frame-
work and interlayer structures. Layered perovskite compounds
are attractive materials as photocatalysts. Layered perovskite
structure can be classified into (100) and (110) plane structures
due to the plane directions of interlayer. The (110) plane struc-
ture can be classified further into (110) and (111) plane-type
structures due to the plane defect structure of perovskite crystal
structure. In the present paper, layered perovskite structures are
classified into (100), (110), and (111) plane-type structures due to
the plane defect structure (Fig. 1). Here, (100), (110), and (111)
plane-types mean that the interlayer is in parallel with (100),
(110), and (111) planes of a bulk type perovskite structure,
respectively. These structures can also be distinguished from each
other by the exposed part of MO6 octahedra in interlayer, corner,
edge, and face of the octahedra. It has been reported that
K2La2Ti3O10,8 Sr4Ti3O10,16 A2A0 Ta2O7 (A ¼ H and K, A0 ¼ La2/
18,23
3 and Sr), La2Ti3O9,19 Sr3Ti2O7,29 and LiCa2Ta3O1034 with the
(100) plane-type layered perovskite structure and La4CaTi5O17,12
A2A0 2O7 (A ¼ Ca and Sr, A0 ¼ Nb and Ta),12,14,30 La2Ti2O7,19
and H1.81Sr0.81Bi0.19Ta2O733 with the (110) plane-type layered
perovskite structure show photocatalytic activities for water
splitting under UV irradiation. In addition, the modified pho-
tocatalysts of these layered perovskite compounds have been also
reported.22,35 On the other hand, there are few reports of oxide
photocatalysts with the (111) plane-type layered perovskite
structure.21,24 Moreover, a titanate photocatalyst with the (111)
plane-type layered perovskite structure is not reported.
A polymerizable complex method (PC method) is one of the
preparation methods of functional material powders.43 Various
Fig. 1 Layered perovskite structures with different face defects.
This journal is ª The Royal Society of Chemistry 2009
complex metal oxides can be prepared under mild condition by
the PC method. We can prepare complex oxides with different
crystallinity, particle size, and morphology by changing calci-
nation temperature in a wide range. Investigation using these
samples with a series of different conditions is meaningful for
clarification of the factors affecting photocatalytic activities. It
has been reported that the particles of K2La2Ti3O108 and
KTiNbO513 prepared by a PC method have higher crystallinity
and finer crystal size than those prepared by a solid-state reac-
tion, resulting in that these photocatalytic activities remarkably
increase. We have preliminary reports that the particles of
Ba5Nb4O15 with (111) plane-type layered perovskite structure
prepared by the PC method were plate-like crystals, and showed
high activity for water splitting under UV irradiation.26 On the
other hand, A5Ta4O15 (A ¼ Sr and Ba) with (111) plane-type
layered perovskite structure prepared by a PC method also shows
high activity for water splitting under UV irradiation.21,24 Thus,
(111) plane-type layered perovskite oxides with high crystallinity
and fine particle size can be prepared by a PC method.
In the present paper, we investigated photophysical properties
and photocatalytic activities for water splitting of (111) plane–
type A5Nb4O15 (A ¼ Sr and Ba), Ba3LaNb3O12, ALa4Ti4O15 (A
¼ Ca, Sr, and Ba), and La4Ti3O12 prepared by a PC method. The
main characteristic point of the materials reported in the present
study is the new-type layered perovskite structure in which
alkaline earth metal and lanthanum cations are ordered or not
at interlayer and A-site. Diffuse reflectance spectroscopy
(DRS), photoluminescence, scanning electron microscope
(SEM) measurements, and photodeposition of some metal and
metal oxides were carried out as characterizations in order to
investigate the properties based on the anisotropy of the layered
structure. The relationship between photocatalytic activities, and
crystal and energy structures are discussed based on the different
ordering of alkaline earth metal and lanthanum cations.
2. Experimental
CaCO3 (Kanto Chemical; 99%), SrCO3 (Kanto Chemical;
99.9%), BaCO3 (Kanto Chemical; 99%), La(NO3)3$6H2O (Wako
Pure Chemical; 99.9%), Ti(OC4H9)4 (Kanto Chemical; 97%),
Nb(OC2H5)5 (Kojundo Chemical; 99.99%), PrCl3$6H2O (Rare
Metallic; 99.99%), citric acid (Sigma Aldrich Japan; 99.5%),
ethylene glycol (Kanto Chemical; 99.5%), and propylene glycol
(Kanto Chemical; 99.0%) were employed as starting materials for
PC method according to a previous report.43 Metal compounds
and a citric acid were dissolved in a mixed solvent of methanol
and ethylene glycol or propylene glycol. The mixed solution was
aged at 353 K for 2 h. At this stage, a solution containing citric
complexes was formed. The solution was dehydrated to form gel
by polymerization at 393 K for 12 h. A precursor was obtained
by calcination of the gel containing a citric acid using a mantle
heater. Various titanates and niobates were prepared by calci-
nation of these precursors at 1073–1473 K for 10 h. Phase purity
of the obtained powders was confirmed by X-ray diffraction
(Rigaku; MiniFlex). Diffuse reflection spectra were measured
using a UV-vis-NIR spectrometer (Jasco; UbestV-570) and were
converted from reflectance to absorbance by the Kubellka-Munk
method. Photoluminescence spectra of these complex metal
oxides with and without Pr-doping as a luminescent probe were
Energy Environ. Sci., 2009, 2, 306–314 | 307
measured using a fluorospectrometer (HORIBA JOBIN YVON;
SPEX Fluorolog-3). Temperature control of the photo-
luminescence measurement was carried out using a cryostat
(Oxford; ITC 503S). The photocatalyst particles were observed
by a scanning electron microscope (SEM, JEOL JSM-6700F). In
order to investigate the surface reactivity of photocatalysts, Au,
Pt, Ni, and PbO2 particles photodeposited on photocatalysts
from aqueous HAuCl4, K2PtCl6, [Pt(NH3)4]Cl2, Ni(NO3)2, and
Pb(NO3)2 solutions were observed by SEM.
NiO and RuO2 cocatalysts were loaded by an impregnation
method from aqueous Ni(NO3)2 and RuCl3 solutions. The
powder impregnated with Ni(NO3)2 was calcined at 543 K for 1 h
in air. Pretreatment of reduction with 200 torr of H2 at 773 K for
2 h followed by oxidation with 100 torr of O2 at 373–573 K for 1 h
was carried out for NiO-loaded photocatalysts, if necessary.44 The
powder impregnated with RuCl3 was calcined at 673 K for 2 h in
air. Water splitting reactions were carried out in a gas-closed
circulation system. The photocatalyst powder (0.5 g) was
dispersed in pure water (380 mL) by a magnetic stirrer in an inner
irradiation reaction cell made of quartz equipped with a 400 W
high-pressure mercury lamp (SEN: HL400EH-5). The amounts
of evolved H2 and O2 were determined using on-line gas
chromatography (Shimadzu; MS-5A column, TCD, Ar carrier).
Apparent quantum yields at 270 nm were measured using a reac-
tion cell with a top window made of quartz and a 300 W Xe
illuminator (ILC technology; CERMAX-LX300) attached with
a band-pass filter (Kenko; BPUV-270, WHM: 16 nm). The
number of incident photon was determined using a photodiode
(OPHIRA: PD300-UV of a head and NOVA of a power monitor).
Fig. 2 XRD patterns of (I) Ba5Nb4O15 and (II) BaLa4Ti4O15 prepared
The photocatalyst powder (0.05–0.3 g) was dispersed in pure by a PC method. (a) and (b) precursor, powders calcined at (c) 873 K, (d)
water (300 mL) for the measurement of the apparent quantum 973 K, (e) 1073 K, (f) 1273 K, (g) 1173 K, (h) 1273 K, and (i) 1323 K.
yield. The apparent quantum yields were determined by eqn (1). Calcination time was 10 h.
Apparent quantum yield ð%Þ
The number of reacted electrons Almost pure phases of Ba5Nb4O15 and BaLa4Ti4O15 were
¼ 100
The number of incident photons (1) successfully obtained by calcination at 973 and 1323 K, respec-
2ðthe number of evolved H2 moleculesÞ tively. The diffraction peaks of (103) and (203) of BaLa4Ti4O15
¼ 100
The number of incident photons and Ba5Nb4O15 became larger than that of (110), as the calci-
nation temperature became high. Fig. 3 shows SEM images of
Ba5Nb4O15 prepared at different calcination temperatures. The
shape of particles was plate-like derived from the layered
3. Results and discussion perovskite structure. As the calcination temperature was high,
the aspect ratio of particles was decreased by crystal growth to
3-1. Synthesis and characterization
the direction in a plane parallel to the (
110) plane. This is the
A single phase of A5Nb4O15 (A ¼ Sr and Ba) was obtained by reason why the (110) diffraction peak became relatively small
a solid-state reaction (SSR method) at 1373 K. In construct, with increasing the calcination temperature. La4Ti3O12, Ba3L-
single phases of Ba3LaNb3O12, ALa4Ti4O15 (A ¼ Ca, Sr, and aNb3O12, Sr5Nb4O15, and ALa4Ti4O15 (A ¼ Sr and Ca) were also
Ba), and La4Ti3O12 were not obtained even at 1673 K of the obtained as plate-like particles.
calcination temperature. It is probably caused by low reactivity
of lanthanum oxide with alkali earth metal oxides. Therefore,
3-2. Crystal and energy structures
synthesis of these compounds was attempted by a polymerizable
complex method (PC method). These pure complex metal oxides Factors affecting the band gaps of layered perovskite oxides are
were successfully prepared by calcination of the precursors at considered as follows.
973–1473 K. The synthetic processes by the PC method for Factor (i): the bond angle between metal and oxygen ions of
Ba5Nb4O15 and BaLa4Ti4O15 that showed high photocatalytic octahedra units (M–O–M). As the bond angle is apart from 180 ,
activities as mentioned later were examined in detail. the band gap becomes wide and the excited energy state is
Fig. 2 shows XRD patterns of Ba5Nb4O15 and BaLa4Ti4O15 localized.5,14,45,46
prepared by a PC method. Broad diffraction patterns of both Factor (ii): the thickness of the perovskite layer. As the thick-
precursors were assigned to a simple perovskite structure. ness of the perovskite layer decreases, the two dimensionality of

308 | Energy Environ. Sci., 2009, 2, 306–314 This journal is ª The Royal Society of Chemistry 2009
 Table 1 The relationships between band gaps and the factors affecting
the band gaps

Niobate Titanate

Factors Sr5Nb4O15 Ba5Nb4O15 CaLa4Ti4O15 BaLa4Ti4O15

Cation of Sr2+ Ba2+ La3+, Ca2+ La3+, Ba2+

interlayer
Ionic 1.44 1.61 1.36, 1.34 1.36, 1.61
radius/Å
Cation of Sr2+ Ba2+ La3+, Ca2+ La3+
perovskite slab
Ionic 1.44 1.61 1.36, 1.34 1.36
radius/Å
Bond angle 168 180 Similar
between metal
and oxygen ions
Effect on Wider Narrower Similar
band gap
Thickness Four Four Four Four
of perovskite
layer
Effect on Similar Similar
band gap
Interaction Large Small Large Small
between
perovskite
layers
Effect on Narrower Wider Narrower Wider
band gap
Polarization Large Small Large Small
ability of
cation
Effect on Narrower Wider Narrower Wider
band gap
Band gaps/eV 4.04 3.91 3.79 3.85

factor (i). The difference between bond angles of Ba5Nb4O15 and

Fig. 3 SEM images of Ba5Nb4O15 powders synthesized at (a) 1073 K
and (b) 1273 K.
crystal structure becomes high, resulting in the band gap
becoming wide and the excited energy state more localized.
Factor (iii): the interaction between perovskite layers. As the
ionic radius of cations at the interlayer becomes large, the
distance between perovskite layers becomes long, accordingly an
excited energy state becomes localized by decreasing interaction
between the layers.
Factor (iv): the polarization ability of cations at the interlayer
towards the oxygen ions of octahedra faced at the interlayer. For
example, H+-exchange of layered oxides sometimes causes red
shift in absorption spectra due to high polarization ability of
proton showing band gap narrowing.47,48 The relationships
between these factors and band gaps are summarized in Table 1.
Fig. 4 shows diffuse reflection spectra of A5Nb4O15 (A ¼ Sr
and Ba), Ba3LaNb3O12, ALa4Ti4O15 (A ¼ Ca, Sr, and Ba), and
La4Ti3O12. The band gaps of Sr5Nb4O15 and Ba5Nb4O15 with
four-octahedra thickness of perovskite layer were estimated to be
4.0 eV and 3.9 eV from the onsets of absorption, respectively
(Fig. 4(I)). The bond angles of Nb–O–Nb in the frameworks of
perovskite structures of Ba5Nb4O15 and Sr5Nb4O15 are 180 and
168 , respectively.49,50 Because the bond angle of Ba5Nb4O15 is
closer to 180 than that of Sr5Nb4O15, the band gap of
Ba5Nb4O15 is narrower than that of Sr5Nb4O15 according to the
Sr5Nb4O15 is almost the same as those of KTaO3 and NaTaO3
with bulk-type perovskite structures, respectively. However, the
difference in the band gap between Ba5Nb4O15 and Sr5Nb4O15
(0.1 eV) was smaller than that between KTaO3 and NaTaO3
(0.4 eV).5 This result implies that the factors (iii) and (iv) also
affect the band gaps. The interaction between perovskite layers
of Ba5Nb4O15 would be smaller than that of Sr5Nb4O15 because
Ba2+ at the interlayer is larger than Sr2+. In addition, the energy
structures of the perovskite layers are changed by different
polarization abilities between Sr2+ and Ba2+ at the interlayer. The
balance of these factors seems to cause the small difference in
band gaps between Ba5Nb4O15 and Sr5Nb4O15.
The band gaps of CaLa4Ti4O15, SrLa4Ti4O15, and BaLa4-
Ti4O15 were 3.78 eV, 3.82 eV, and 3.85 eV, respectively. This
order in the band gap was reverse to that for ATiO3 (A ¼ Ca, Sr,
and Ba) with bulk-type perovskite structure. The positions of
La3+, Ca2+, and Ba2+ in crystal structures of ALa4Ti4O15 (A ¼ Ca
and Ba) give some information to consider this difference in the
order of band gaps. The ratio of Ba2+ to La3+ at the interlayer is
1 : 1 in BaLa4Ti4O15 while only La3+ exists in the perovskite layer
as shown in Fig. 5.51 On the other hand, Ca2+ and La3+ randomly
exist at the interlayer and perovskite layer in CaLa4Ti4O15. The
distortion of the perovskite framework structure of BaLa4Ti4O15
would be close to that of CaLa4Ti4O15 because the ionic radius of
La3+ (1.36 Å) is nearly equal to that of Ca2+ (1.34 Å). Therefore,
the factor (i) would be negligible. The band gap of BaLa4Ti4O15
is wider than that of CaLa4Ti4O15 due to an increase in the

This journal is ª The Royal Society of Chemistry 2009 Energy Environ. Sci., 2009, 2, 306–314 | 309

Fig. 4 Diffuse reflection spectra of (I) niobates and (II) titanates; (a)
Ba3LaNb3O12, (b) Sr5Nb4O15, (c) Ba5Nb4O15, (d) CaLa4Ti4O15, (e)
SrLa4Ti4O15, (f) BaLa4Ti4O15, and (g) La4Ti3O12.
distance between layers (factor (iii)) and the different polariza-
tion ability of Ca2+ and Ba2+ (factor (iv)) because the ionic radius
of Ba2+ is larger than that of Ca2+. The band gap of Ba3LaNb3O12
with layered perovskite structure with three-octahedra thickness
was estimated to be 4.1 eV. The perovskite layer of Ba3LaNb3O12
is thinner than that of Ba5Nb4O15. Therefore, the band gap
of Ba3LaNb3O12 was wider than that of Ba5Nb4O15 according to
Fig. 5 Crystal structures of ALa4Ti4O15 (A ¼ Ca and Ba) with layered
perovskite structure.50
310 | Energy Environ. Sci., 2009, 2, 306–314
the factor (ii). The band gap of La4Ti3O12 with layered perovskite
structure with three-octahedra thickness was also wider than
that of ALa4Ti4O15 with layered perovskite structure with four-
octahedra thickness.
Ba5Nb4O15 shows a broad yellow emission with maximum at
580 nm.52 The photoluminescent properties of A5Nb4O15 (A ¼ Sr
and Ba), Ba3LaNb3O12, ALa4Ti4O15 (A ¼ Ca, Sr, and Ba), and
La4Ti3O12 were measured as shown in Fig. 6. These materials did
not show any emission at room temperature, but did so at 77 K.
The onsets of excitation spectra of these materials agreed with
those of absorption spectra, indicating that these emissions were
due to the band gap excitation.
Information on the migration of excited energy in the layered
oxide photocatalysts can be obtained by monitoring the emission
of some doped lanthanide cations as guests.53–55 Photo-
luminescent properties of ALa4Ti4O15 (A ¼ Ca and Ba) doped
with 1% of Pr3+ were examined as shown in Fig. 7. Pr3+ would be
doped in the site of La3+ at an A-site of the perovskite layer and
interlayer, judging from the ionic radius and electric charge of
Pr3+. Luminescence of the doped Pr3+ was observed for ALa4-
Ti4O15:Pr(1%) (A ¼ Ca and Ba) by the host excitation at room
temperature. This result indicates that the photo-generated
carrier or excited energy in the host material can migrate to the
Pr3+ guest. The ratio of an excitation band of a host around 280
nm to that of a Pr3+ guest at 449.7 nm for BaLa4Ti4O15 was larger
than that for CaLa4Ti4O15. It suggests that excited energy in the
perovskite framework migrates to the Pr3+ guest more easily for
BaLa4Ti4O15 than CaLa4Ti4O15. It may also be due to the
amount of Pr3+ in the perovskite framework of BaLa4Ti4O15
being greater than that in CaLa4Ti4O15. Reported niobate
and titanate photocatalysts for water splitting show
Fig. 6 Excitation and emission spectra of (I) niobates and (II) titanates;
(a) Sr5Nb4O15, (b) Ba5Nb4O15, (c) CaLa4Ti4O15, (d) SrLa4Ti4O15, and (e)
BaLa4Ti4O15 at 77 K.
This journal is ª The Royal Society of Chemistry 2009
 3-3. Photocatalytic water splitting

Table 2 shows photocatalytic activities of A5Nb4O15 (A ¼ Sr and

Fig. 7 Diffuse reflection spectra and photoluminescence spectra of (I)
BaLa4Ti4O15:Pr(0.1%) and (II) CaLa4Ti4O15:Pr(0.1%) at room temper-
ature. (a) and (b): the diffuse reflection spectra, (c) and (d): the excitation
spectra were obtained by monitoring luminescence of Pr3+ at 606 nm, (e)
and (f): the emission spectra were obtained by host excitation at 280 nm.
photoluminescence at 77 K.20,53–55 Moreover, the photo-gener-
ated carrier or excited energy can migrate in the perovskite layer.
Therefore, A5Nb4O15 (A ¼ Sr and Ba), Ba3LaNb3O12, ALa4-
Ti4O15 (A ¼ Ca, Sr, and Ba), and La4Ti3O12 were expected to
work as photocatalysts for water splitting.
Ba), Ba3LaNb3O12, ALa4Ti4O15(A ¼ Ca, Sr and Ba), and
La4Ti3O12. The amounts of NiO-loaded and pretreatment
conditions were optimized for the photocatalytic water splitting
over these photocatalysts. The activities of these photocatalysts
without cocatalysts were low. However, when NiO cocatalysts
were loaded, the activities were improved more than two orders
of magnitude.
Fig. 8 shows the band structures of these titanate photo-
catalysts and a NiO cocatalyst.56 The band positions were
estimated by the band gaps and the valance band maxima that
were supposed to be +3.0 eV.57 Photogenerated electrons in
a conduction band of a host material must transfer to a NiO
cocatalyst that is a hydrogen evolution site. Therefore, it is
required that the conduction band level of a photocatalyst is
higher than that of a NiO cocatalyst. If the band level of pho-
tocatalyst does not satisfy the requirement, the activation
pretreatment of H2 reduction and subsequent O2 oxidation
is usually needed.44 The activation pretreatment for the
NiO cocatalyst was effective for all photocatalysts as well
as previously reported titanate and niobate photo-
catalysts.7,8,12,14,16,20,29,44,58 On the other hand, La4Ti3O12 showed
high activity without the activation pretreatment because of the
high conduction band level. NiOx(0.5 wt%)/BaLa4Ti4O15 and
NiOx(0.5 wt%)/Ba5Nb4O15 showed the highest activities for
water splitting among titanates and niobates, respectively. The
photocatalytic activity of Ba5Nb4O15 calcined at 1073 K was
higher than that at 1273 K. The SEM images indicated that
Ba5Nb4O15 calcined at 1073 K had higher aspect ratio and
smaller particle size than that at 1273 K as shown in Fig. 3. In the
case of layered perovskite photocatalyst of which the interlayer
space is not hydrated, the photogenerated e
and h+ have to
reach the surface to react with water molecules. Therefore, the

Table 2 Water splitting over various metal oxides with layered perovskite structuresa

Activity/mmol h
1
Surface area Band gap NiO loaded
Photocatalyst Preparation condition /m2 g
1 /eV (wt%) Pretreatmentb H2 O2

La4Ti3O12 1473 K, 10 h 3.4 3.95 None No 9 0

La4Ti3O12 1473 K, 10 h 3.4 3.95 0.6 No 357 179
La4Ti3O12 1473 K, 10 h 3.4 3.95 0.6 R673–O373 330 150
CaLa4Ti4O15 1373 K, 10 h 6.2 3.79 None No 3 0
CaLa4Ti4O15 1373 K, 10 h 6.2 3.79 0.2 No 11 4
CaLa4Ti4O15 1373 K, 10 h 6.2 3.79 0.2 R673–O373 593 276
SrLa4Ti4O15 1373 K, 10 h 6.2 3.82 None No 2 0
SrLa4Ti4O15 1373 K, 10 h 6.2 3.82 0.7 No 23 11
SrLa4Ti4O15 1373 K, 10 h 6.2 3.82 0.7 R673–O373 1171 546
BaLa4Ti4O15 1323 K, 10 h 6.1 3.85 None No 5 2
BaLa4Ti4O15 1323 K, 10 h 6.1 3.85 0.5 No 118 62
BaLa4Ti4O15 1323 K, 10 h 6.1 3.85 0.5 R673–O373 2300 1154
Ba3LaNb3O12 1073 K, 10 h 5.8 4.07 None No 2 0
Ba3LaNb3O12 1073 K, 10 h 5.8 4.07 0.5 R773–O473 1185 588
Sr5Nb4O15 1073 K, 10 h 7.9 4.04 None No 3 0
Sr5Nb4O15 1073 K, 10 h 7.9 4.04 0.7 R773–O473 2200 1100
Ba5Nb4O15 1073 K, 10 h 7.2 3.91 None No 3 0
Ba5Nb4O15 1073 K, 10 h 7.2 3.91 0.5 R773–O473 4021 1972
Ba5Nb4O15 1273 K, 5h 1.9 3.87 0.1 R773–O473 939 453
a
Catalyst: 0.5 g, pure water: 380 mL, inner irradiation cell made of quartz, 400 W high-pressure mercury lamp. b R and O indicate temperatures in K for
H2 reduction for 2 h and O2 oxidation for 1 h, respectively.

This journal is ª The Royal Society of Chemistry 2009 Energy Environ. Sci., 2009, 2, 306–314 | 311
 Table 3 Water splitting over BaLa4Ti4O15 photocatalyst loaded with
various metals and oxidesa

Activity/mmol h
1
Cocatalyst Loading
(wt%) method Pretreatmentb H2 O2

None — — 5 2
Ni (0.5) Photo-deposition None 10 0.5
NiO (0.5) Impregnation O543 118 62
NiOx (0.5) Impregnation R773–O473 1333 673
NiOx (0.5) Photo-deposition R773–O473 432 203
RuO2 (1.0) Impregnation O673 575 265
Au (1.0) Photo-deposition None 36 10
IrO2 (1.0) Photo-deposition None 3 0
Pt (1.0) Photo-deposition None 35 1
Fig. 8 Band structures of various titanate photocatalysts.
PbO2 (1.0) Photo-deposition None 5 0
a
Catalyst: 0.5 g, pure water: 380 mL, inner irradiation cell made of
photocatalytic activity is improved by the preparation giving quartz, 400 W high-pressure mercury lamp. b R and O indicate
temperatures in K for H2 reduction for 2 h and O2 oxidation for 1 h,
high crystallinity and fine particle. Charge separation of photo- respectively.
generated e
and h+ might be enhanced by high anisotropy of the
crystal structure.14 These factors mean that the photocatalytic
activity of Ba5Nb4O15 that had been calcined at 1073 K was
higher than that treated at 1273 K.
Table 3 shows the photocatalytic activities of BaLa4Ti4O15
loaded with various metals and oxides. NiOx/BaLa4Ti4O15
obtained by the impregnation method followed by the activation
pretreatment showed the highest activity for water splitting. The
activities of Ni/BaLa4Ti4O15 obtained by photo-deposition
method and NiOx/BaLa4Ti4O15 prepared by photo-deposition
method followed by oxidation pretreatment were low compared
with that of NiOx/BaLa4Ti4O15 prepared by the impregnation
method. Metallic Au and RuO2 cocatalysts were also effective
for BaLa4Ti4O15.
The time course for water splitting on optimized NiOx(0.5
wt%)/BaLa4Ti4O15 photocatalyst is shown in Fig. 9. At the initial
stage, NiOx(0.5 wt%)/BaLa4Ti4O15 produced H2 and O2 at the
rates of 2.3 and 1.14 mmol h
1 using a 400 W high-pressure
mercury lamp, respectively. The turnover number of the amount Fig. 9 Photocatalytic water splitting over optimized NiOx (0.5 wt%)/
BaLa4Ti4O15. (a): H2 and (b): O2. Catalyst: 0.5 g, pure water: 380 mL,
of reacted electrons/holes to the molar quantity of BaLa4Ti4O15
inner irradiation cell made of quartz, 400 W high-pressure mercury lamp.
was 30 at 4 h of the reaction time. It clearly indicated that the
reaction proceeded photocatalytically. The apparent quantum
yield was 15% at 270 nm.
Table 4 summarizes metal oxide photocatalysts with layered (A ¼ Ca, Sr, and Ba) is due to the conduction band level and the
perovskite structures for water splitting. Although the detailed anisotropy that are caused by A-site cations as shown in Fig. 5. It
experimental condition was not the same for each other, the (111) has been reported that the reactivity of e
and h+ on a TiO2
plane-type layered perovskite oxide photocatalysts found in the surface can be examined by observing on which plane Pt and
present paper showed relatively high activities compared with PbO2 are photodeposited reductively and oxidatively, respec-
layered titanate and niobate photocatalysts previously reported. tively.58 Therefore, the features of photodeposited metals and
PbO2 were examined to see the effect of the anisotropy as shown
in Fig. 10. Metallic Au was selectively deposited from AuCl4
not
3-4. Difference in photophysical and photocatalytic properties
on a basal plane but on an edge plane. In contrast, PbO2 was
between CaLa4Ti4O15 and BaLa4Ti4O15
oxidatively photodeposited from Pb2+ on the basal plane.
The order of photocatalytic activities of ALa4Ti4O15 (A ¼ Ca, Sr, Metallic Ni was reductively photodeposited from Ni2+ only on
and Ba) was Ba > Sr > Ca. This order seems to depend on the the basal plane with the characteristic whisker-like shape.
ionic radii of cations at interlayer. Photocatalytic properties Metallic Pt was non-selectively photodeposited from [PtCl6]2
on
would depend on the anisotropy of layered perovskite structure. the whole surface. When metallic Pt was photodeposited from
The difference in the framework distortion of perovskite struc- [Pt(NH3)4]2+, the particle size on the basal plane was smaller than
ture between ALa4Ti4O15 (A ¼ Ca, Sr, and Ba) photocatalysts is that on the edge plane. In contrast, the plane-selective photo-
not significant for the activity as discussed in section 3-2. The deposition was not observed for CaLa4Ti4O15. Moreover,
shapes of these particles are similar to each other. Therefore, A5Nb4O15 (A ¼ Sr and Ba) in which A-site cations is the same as
the difference in photocatalytic activities between ALa4Ti4O15 interlayer cations did not show the selective deposition neither.

312 | Energy Environ. Sci., 2009, 2, 306–314 This journal is ª The Royal Society of Chemistry 2009
Table 4 Comparison in photocatalytic activity for water splitting among various metal oxides with layered perovskite type structuresa

Activity/mmol h
1
Band gap Apparent quantum yield
Photocatalyst Interlayer structure type Cocatalyst /eV H2 O2 (%) Ref.

K2La2Ti3O10 (100) NiOx 3.4 2186 1131 — 8

Sr3Ti2O7 (100) NiOx 3.2 144 72 — 29
Sr4Ti3O10 (100) NiOx 3.3 170 4.5 16
La2Ti3O9 (100) NiOx 386 — 20
La2Ti2O7 (110) NiOx 3.8 441 220 12 20
La2Ti2O7:Ba (110) NiOx 3.8 5000 50 20
La4CaTi5O17 (110) NiOx 3.8 499 20 12
BaLa4Ti4O15 (111) NiOx 3.85 2300 1154 15 This work
KCa2Nb3O10 (100) RuO2 96 47 — 22
Ca2Nb2O7 (110) NiOx 4.3 101 7 13
Sr2Nb2O7 (110) NiOx 4.0 110 36 — 14
Ba5Nb4O15 (111) NiOx 3.91 4021 1982 17 This work
a
Light source: 400–450 W high-pressure mercury lamp, reaction cell: inner irradiation cell made of quartz, reactant: pure water. NiOx indicates
a pretreated NiO cocatalyst.

Fig. 10 SEM images of various metals and PbO2 loaded on BaLa4Ti4O15 photocatalysts by a photo-deposition method; (a) Au, (b) Ni, (c) PbO2, (d) Pt
from [PtCl6]2
, (e) Pt from [Pt(NH3)4]2+, and (f) magnification of (e).

This unique selective photodeposition is due to the difference in
adsorption property for ions between edge and basal planes, and
the charge separation promoted by the structural anisotropy due
to the different distribution of alkali earth metal cations. This
character resulted in that BaLa4Ti4O15 showed higher activity
than CaLa4Ti4O15.
The reduction with H2 at 773 K for 2 h followed by oxidation
with O2 at 473 K for 1 h was carried out for the Ni/BaLa4Ti4O15
prepared by the photodeposition. The pretreatment gave NiOx
loaded only on the basal plane of BaLa4Ti4O15. The shape of this
NiOx was similar to the NiOx loaded by an impregnation
method. The activity of this NiOx/BaLa4Ti4O15 photocatalyst
was lower than that of NiOx/BaLa4Ti4O15 prepared by the
impregnation method. It suggests that the NiO cocatalyst loaded
on the edge plane was more effective than that on the basal plane.
4. Conclusions
A5Nb4O15 (A ¼ Sr and Ba), Ba3LaNb3O12, ALa4Ti4O15 (A ¼
Ca, Sr, and Ba), and La4Ti3O12 with a (111) plane-type layered
perovskite structure were found to be new niobate and titanate
photocatalyst materials for water splitting. A PC method was
advantageous for the preparation of these photocatalysts at
wide-range temperature. These photocatalysts showed photo-
luminescence at 77 K. Moreover, energy migration in the layered
perovskite structure was confirmed by probing luminescence of

This journal is ª The Royal Society of Chemistry 2009 Energy Environ. Sci., 2009, 2, 306–314 | 313
doped Pr3+. This energy structure revealed by photoluminescent
properties is preferable for photocatalysts. BaLa4Ti4O15 showed
the highest activity for water splitting among ALa4Ti4O15 (A ¼
Ca, Sr, and Ba) photocatalysts. Ba2+ and La3+ exist at interlayers
of BaLa4Ti4O15 while only La3+ exists at an A-site of the
perovskite layers. In contrast, Ca2+ and La3+ randomly exist at
the interlayers and the perovskite layers of CaLa4Ti4O15. The
anisotropic surface reactivity was confirmed by selective photo-
deposition of Pt, Ni, Au, and PbO2 for BaLa4Ti4O15 but no for
CaLa4Ti4O15. These results indicated that the structural anisot-
ropy due to the ordered positions of Ba2+ and La3+ in BaLa4-
Ti4O15 was one of the major factors for the high activity. The
application of plate-like BaLa4Ti4O15 particles prepared by a PC
method to other photocatalytic reactions besides water splitting
is expected.
Acknowledgements
This work was supported by Core Research for Evolutional
Science and Technology (CREST) of Japan Science and Tech-
nology Agency (JST) and a Grant-in-Aid (No. 14 050 090) for
the Priority Area Research (No. 417) from the Ministry of
Education, Culture, Sports, Science and Technology, Japan.
References
1 K. Domen, J. N. Kondo, M. Hara and T. Takata, Bull. Chem. Soc.
Jpn., 2000, 73, 1307, and references therein.
2 H. Kato and A. Kudo, Catal. Today, 2003, 78, 561, and references
therein.
3 J. Sato, H. Kobayashi, K. Ikarashi, N. Saito, H. Nishiyama and
Y. Inoue, J. Phys. Chem. B, 2004, 108, 4369, and references therein.
4 A. Kudo and Y. Miseki, Chem. Soc. Rev., 2009, 38, 253, and
references therein.
5 H. Kato and A. Kudo, J. Phys. Chem. B, 2001, 105, 4285.
6 H. Kato, K. Asakura and A. Kudo, J. Am. Chem. Soc., 2003, 125,
3082.
7 S. Ikeda, A. Tanaka, K. Shinohara, M. Hara, J. N. Kondo,
K. Maruya and K. Domen, Microporous Mesoporous Mater., 1997,
9, 253.
8 S. Ikeda, M. Hara, J. N. Kondo, K. Domen, H. Takahashi, T. Okubo
and M. Kakihana, Chem. Mater., 1998, 10, 72.
9 H. Kato and A. Kudo, Catal. Lett., 1999, 58, 153.
10 A. Kudo, S. Nakagawa and H. Kato, Chem. Lett., 1999, 28, 1197.
11 C. Mitsui, H. Nishiguchi, K. Fukamachi, T. Ishihara and Y. Takita,
Chem. Lett., 1999, 28, 1327.
12 H. G. Kim, D. W. Hwang, J. Kim, Y. G. Kim and J. S. Lee, Chem.
Commun., 1999, 1077.
13 H. Takahashi, M. Kakihana, Y. Yamashita, K. Yoshida, S. Ikeda,
M. Hara and K. Domen, J. Alloys Compd., 1999, 285, 77.
14 A. Kudo, H. Kato and S. Nakagawa, J. Phys. Chem. B, 2000, 104,
571.
15 M. Machida, J. Yabunaka and T. Kijima, Chem. Mater., 2000, 12,
812.
16 Y. G. Ko and W. Y. Lee, Catal. Lett., 2002, 83, 157.
17 N. Sato, H. Kadowaki, H. Kobayashi, K. Ikarashi, H. Nishiyama and
Y. Inoue, Chem. Lett., 2004, 33, 1452.
18 K. Shimizu, Y. Tsuji, T. Hatamachi, K. Toda, T. Kodama, M. Sato
and Y. Kitayama, Phys. Chem. Chem. Phys., 2004, 6, 1064.
19 J. Kim, D. W. Hwang, H. G. Kim, S. W. Bae, J. S. Lee, W. Li and
S. H. Oh, Top. Catal., 2005, 35, 295.
20 Y. Miseki, H. Kato and A. Kudo, Chem. Lett., 2005, 34, 54.
314 | Energy Environ. Sci., 2009, 2, 306–314
21 K. Yoshioka, V. Petrykin, M. Kakihana, H. Kato and A. Kudo,
J. Catal., 2005, 232, 102.
22 Y. Ebina, N. Sakai and T. Sasaki, J. Phys. Chem. B, 2005, 109,
17212.
23 K. Shimizu, S. Itoh, T. Hatamachi, T. Kodama, M. Sato and
K. Toda, Chem. Mater., 2005, 17, 5161.
24 H. Otsuka, K. Kim, A. Kouzu, I. Takimoto, H. Fujimori, Y. Sakata,
H. Imamura, T. Matsumoto and K. Toda, Chem. Lett., 2005, 34,
822.
25 M. Machida, T. Mitsuyama and K. Ikeue, J. Phys. Chem. B, 2005,
109, 7801.
26 Y. Miseki, H. Kato and A. Kudo, Chem. Lett., 2006, 35, 1052.
27 T. Kurihara, H. Okutomi, Y. Miseki, H. Kato and A. Kudo, Chem.
Lett., 2006, 35, 274.
28 R. Abe, M. Higashi, K. Sayama, Y. Abe and H. Sugihara, J. Phys.
Chem. B, 2006, 110, 2219.
29 H. Jeong, T. Kim, D. Kim and K. Kim, Int. J. Hydrogen Energy,
2006, 31, 1142.
30 S. Ikeda, M. Fubuki, Y. K. Takahara and M. Matsumura, Appl.
Catal., A, 2006, 300, 186.
31 H. Kadowaki, N. Saito, H. Nishiyama and Y. Inoue, Chem. Lett.,
2007, 36, 440.
32 W. Yao and J. Ye, Chem. Phys. Lett., 2007, 435, 96.
33 Y. Li, G. Chen, C. Zhou and Z. Li, Catal. Lett., 2008, 123, 80.
34 T. Mitsuyama, A. Tsutsui, T. Hara, K. Ikeue and M. Machida, Bull.
Chem. Soc. Jpn., 2008, 81, 401.
35 O. C. Compton, C. H. Mullet, S. Chiang and F. E. Osterloh, J. Phys.
Chem. C, 2008, 112, 6202.
36 Y. Lee, H. Terashita, Y. Shimodaira, K. Teramura, M. Hara,
H. Kobayashi, K. Domen and M. Yashima, J. Phys. Chem. C,
2007, 111, 1042.
37 K. Maeda, K. Teramura, D. Lu, T. Takata, N. Saito, Y. Inoue and
K. Domen, Nature, 2006, 440, 295.
38 K. Sayama, K. Mukasa, R. Abe, Y. Abe and H. Arakawa, Chem.
Commun., 2001, 2416.
39 R. Abe, K. Sayama, K. Domen and H. Arakawa, Chem. Phys. Lett.,
2001, 344, 339.
40 H. Kato, M. Hori, R. Konta, Y. Shimodaira and A. Kudo, Chem.
Lett., 2004, 33, 1348.
41 R. Abe, T. Takata, H. Sugihara and K. Domen, Chem. Commun.,
2005, 3829.
42 M. Higashi, R. Abe, K. Teramura, T. Takata, B. Ohtani and
K. Domen, Chem. Phys. Lett., 2008, 452, 120.
43 M. Kakihana and K. Domen, MRS Bull., 2000, 25, 27.
44 K. Domen, A. Kudo, T. Onishi, N. Kosugi and H. Kuroda, J. Phys.
Chem., 1986, 90, 292.
45 M. Wiegel, M. H. J. Emond, E. R. Stobbe and G. J. Blasse, J. Phys.
Solids, 1994, 55, 773.
46 Z. Zou, J. Ye and H. Arakawa, Chem. Phys. Lett., 2000, 332, 271.
47 A. Kudo and T. Sakata, J. Phys. Chem., 1996, 100, 17323.
48 A. Kudo and E. Kaneko, Microporous Mesoporous Mater., 1998, 21,
615.
49 M. Weiden, A. Grauel, J. Norwig and S. Horn, J. Alloys Compd.,
1995, 218, 13.
50 T. A. Vanderah, T. R. Collins, W. Won-Ng, R. S. Roth and
L. Farber, J. Alloys Compd., 2002, 346, 116.
51 Y. Tohdo, K. Kakimoto, H. Ohsato, H. Yamada and T. Okawa,
J. Eur. Ceram. Soc., 2006, 26, 2039.
52 A. M. Srivastava, J. F. Ackerman and W. W. Beers, J. Solid State
Chem., 1997, 134, 187.
53 A. Kudo and T. Sakata, J. Phys. Chem. B, 1995, 99, 15963.
54 A. Kudo, Chem. Mater., 1997, 9, 664.
55 A. Kudo and E. Kaneko, Microporous Mesoporous Mater., 1998, 21,
615.
56 M. P. Dare-Edwards, J. B. Goodenough, A. Hamnett and
N. D. Nicholson, J. Chem. Soc., Faraday Trans. 2, 1981, 77, 643.
57 D. E. Scaife, Sol. Energy, 1980, 25, 41.
58 T. Ohno, K. Sarukawa and M. Matsumura, New J. Chem., 2002, 26,
1167.
This journal is ª The Royal Society of Chemistry 2009