J. Phys. Chem.

B 2005, 109, 7801-7806 7801

Photocatalytic Property and Electronic Structure of Triple-Layered Perovskite Tantalates,

MCa2Ta3O10 (M ) Cs, Na, H, and C6H13NH3)

Masato Machida,* Tomohiro Mitsuyama, and Keita Ikeue

Department of Applied Chemistry and Biochemistry, Faculty of Engineering, Kumamoto UniVersity,
Kumamoto 860-8555, Japan

Shigenori Matsushima
Kitakyushu National College of Technology, Kitakyushu 802-0985, Japan

Masao Arai
National Institute for Research in Inorganic Materials, Tsukuba 305-0044, Japan
ReceiVed: NoVember 10, 2004; In Final Form: February 2, 2005

The Dion-Jacobson series of triple-layered perovskite tantalates (MCa2Ta3O10, M ) Cs, Na, H, and C6H13-
NH3) were synthesized to evaluate their photocatalytic activity for overall water splitting to evolve H2/O2
under UV irradiation. The photocatalytic activity was susceptible to the hydration of interlayer space. The
hydrous Na phase exhibited much higher activity (H2: 308 µmol‚h-1) compared to the anhydrous Cs phase
(24 µmol‚h-1) and the hydrous H phase (22 µmol‚h-1) in the presence of 0.5 wt % Ni impregnated. H2O/D2O
isotopic experiment suggested that the hydrated interlayer plays as an active site for water splitting, where
the high mobility of water molecule in the interlayer should correlate with the total photocatalytic activity.
The FLAPW electronic structure calculation demonstrated that the terminating oxygen site, O(4), which faces
to the interlayer space, contributes largely to the top of the valence band. Judging from comparison with the
double-layered tantalates, MLaTa2O7, in our previous study, the contribution of terminating oxygen site to
the band structure is supposed to depend on the number of perovskite layers.

Introduction because a series of the same structural unit with hydrous and
anhydrous interlayer is available. The present work has been
Ion-exchangeable layered perovskites are composed of al-
directed to study the effect of ion exchange of interlayer cations
ternative stacking of a two-dimensional perovskite slab with
(M) on the photocatalytic property of triple-layered perovskite
different numbers of layers and monovalent cations. There are
tantalates (MCa2Ta3O10) in relation to their electronic and crystal
two different typical structures, the Dion-Jacobson series
structures. The materials with four different monovalent cations
(A′[An-1BnO3n+1]) and the Ruddlesden-Popper series (A′2
(M ) Cs, Na, H, and C6H13NH3) were synthesized to use them
[An-2BnO3n+1]).1-5 A wide variety of compounds in these
as photocatalysts for water splitting. The results were compared
structural families include titanates, niobates, and tantalates with
with those for double-layered tantalates (MLaTa2O7) in our
the d0 electronic configuration, which can be used as photo-
previous study.14,15
catalysts.6-15 In the applications of such layered ion-exchangers
to photocatalytic water splitting, the role of interlayer is of Experimental Section
general interest because of the hydrated structure. It is already
reported that several layered perovskites, such as K4Nb6O1710 Sample Preparation and Characterization. The synthesis
or K2La2Ti3O10,11 are highly active for overall water splitting, of CsCa2Ta3O10 was conducted by a conventional solid-state
because their interlayer space is easily hydrated to produce active procedure according to that reported by Toda et al.16,17 Powder
sites responsible for photocatalytic water splitting. However, a mixtures of carbonates (Cs2CO3, CaCO3, 99%) and oxide
different situation was observed for hydrated NaLaTa2O7, the (Ta2O5, 99.99%) were calcined at 1000 °C for 10 h in air. As-
activity of which is less than that of the anhydrous RbLaTa2O7.15 prepared Cs phase was ion-exchanged in molten NaNO3 at 400
Thus, the effect of interlayer hydration is not always the °C to convert into a Na phase, which was subsequently washed
predominant factor. The combination of experimental and with distilled water. Since the resultant tantalate was a hydrated
theoretical approaches is strongly requested to gain an under- phase, which contains water in the interlayer, heat treatment at
standing of the chemistry of interlayer in photocatalytic 500 °C was conducted in vacuo to obtain a dehydrated phase.
processes from material viewpoints. A protonated compound (a H phase) was obtained by leaching
The purpose of our study is to elucidate the relationship the hydrated Na phase in 1 M HCl at room temperature for 1
between photocatalytic property and hydrated layered structure. week. The acid solution was refreshed every 2 days. The
In this regard, Dion-Jacobson-type tantalates are very useful resultant solid was washed with distilled water and dried at 60
°C in air. The H phase thus obtained was then stirred in an
* Corresponding author. Fax/tel: +81-96-342-3651; e-mail: machida@ aqueous solution of 5 M C6H13NH2 at room temperature for a
chem.kumamoto-u.ac.jp. week to prepare a C6H13NH3-exchanged phase.
10.1021/jp044833d CCC: $30.25 © 2005 American Chemical Society
Published on Web 03/25/2005
7802 J. Phys. Chem. B, Vol. 109, No. 16, 2005 Machida et al.

Thermogravimetric analysis (TG, Rigaku 8120) and X-ray

analysis (EDX, Horiba MESA-500W) were conducted to
determine water content and chemical composition, respectively.
The crystal structure was identified by use of a powder XRD
(Rigaku Multiflex) with monochromated CuKR radiation (30
kV, 20 mA). Diffuse reflectance spectra were recorded with a
Jasco V-550 UV-vis spectrometer. The optical band gap energy
was calculated from the onset of absorption edge. The micro-
structure was observed by FE-SEM (Hitachi 4100). The BET
surface area was determined by measuring N2 adsorption
isotherm at -196 °C.
The Ni-loaded catalyst was prepared by impregnation of as-
prepared MCa2Ta3O10 (M ) Cs, Na, and H) with an aqueous
solution of Ni(NO3)2 (reagent grade). The impregnated sample
was then submitted to reduction in a stream of H2 at 500 °C
and subsequent reoxidation in a stream of O2 at 200 °C to
Figure 1. Powder XRD patterns of MCa2Ta3O10 with (a) M ) Cs, (b)
prepare partially oxidized nickel (NiOx) catalysts.18,19 The Na, (c) H, and (d) C6H13NH3.
loading amount of Ni metal was from 0.1 to 2.0 wt %.
Characterization of Ni species was done by XPS (VG Sig- TABLE 1: Chemical Composition of Layered Tantalatesa
maprobe spectrometer using Al KR radiation, 15 kV, 7 mA) Cs phase Cs0.97Ca2.00Ta3O10
and TEM (JEOL 2000FX). Na phase Cs0.03Na0.91Ca1.97Ta3O10‚1.86H2O
Electronic Structure Calculation. The first-principle ap- H phase Cs0.03Na0.10 H0.87Ca2.11Ta3O10‚0.38H2O
proach in the present study is based on the FLAPW method a Oxygen nonstoichiometry is not considered.
within the local density approximation (LDA)20 to the density
function theory. The calculation of the electronic structure was
conducted by the use of the WIEN2k package,21 the results of
which include a fully optimized ground-state structure obtained
with total energy and atomic forces, band structure, and densities
of states, as described in our previous papers.22,23 The crystal-
lographic parameters for the calculation, including lattice
parameters and atomic positions, were those reported by Toda
et al.16,17 The parameters of individual atoms were optimized
prior to the calculation using the MS Castep package (Accelrys).
Photocatalytic Reaction. The photocatalytic H2 evolution
from water was conducted in an inner irradiation quartz cell,
which was connected to a closed gas-circulating system (dead
volume: 250 cm3) consisting of a circulation pump, a pressure
sensor, gas sampling valves, and stainless steel tubing. A powder
sample of the tantalate (0.2 g) was suspended in distilled water
(200 cm3) in the cell by use of a magnetic stirrer. Prior to the
reaction, the mixture was deaerated by evacuation and then Figure 2. Crystal structure of RbCa2Ta3O10 with layered perovskite
structure.
flushed with Ar gas (20 kPa) repeatedly to remove O2 and CO2
dissolving in water. The reaction was carried out by irradiating
the mixture with light from a 400 W high-pressure Hg lamp. from Figure 1b, the Na phase shows a significant shift of
Gas evolution was observed only under photoirradiation, being diffraction peaks in accord with the transformation from P4/
analyzed by an online gas chromatograph (Shimadzu, TCD, Ar mmm to I4/mmm, which is consistent with the result reported
carrier, MS-5A and Porapak-Q columns). Any contamination by Toda et al.16,17 This was accompanied by expansion of the
from air was confirmed negligible during at least 50 h of interlayer distance from 1.51 to 1.72 nm, because 1.86 mol-
photoreactions. The rate of photocatalytic gas evolution was H2O‚mol-1 was incorporated into the interlayer during washing
determined for an initial 8-h period. in water. The formation of the hydrated Na phase is very similar
to the double-layered compound, MLaTa2O7.15 Furthermore, Na
Results and Discussion ions in the interlayer could be replaced by H (>98%) during
repeated treatment in 1 M HCl. This resulted in a shift of the
Crystal Phases of MCa2Ta3O10. The XRD patterns and (00l) peaks to the higher 2θ because of the difference of ionic
chemical compositions of MCa2Ta3O10 (M ) Cs, Na, H, and radius between Na+ and H+ (Figure 1c). The H phases possess
C6H13NH3) are shown in Figure 1 and Table 1, respectively. the hydrous interlayer with 0.38 mol-H2O‚mol-1 (Table 1). The
As-calcined compounds, CsCa2Ta3O10 (Figure 1a), consisted of interlayer distance was then significantly expanded to 2.85 nm
a single phase of layered perovskite, the diffraction peaks of by following intercalation of C6H13NH3+ (ca. 0.6 mol‚mol-1,
which were indexed on the basis of the tetragonal cell with the Figure 1d). The corresponding interlayer spacing of ca. 1.7 nm
P4/mmm space group. The value of d001, 1.51 nm, corresponds is much larger than the chain length of n-hexylammonium ion
to the stacking periodicity of a triple-layer perovskite slab (see (ca. 1.0 nm), suggesting the tilting bilayer configuration of alkyl
Figure 2). The Na phase, NaCa2Ta3O10, was not obtained chains in the interlayer.
directly by the solid-state reaction of carbonate/oxide mixtures The microstructure of exchanged tantalates (M ) Cs, Na and
but was produced successfully by ion exchange of CsCa2Ta3O10 H) was observed by SEM, which is included in the Supporting
in molten sodium nitrate at 400 °C (Table 1). As can be judged Information (Figure S1). Well-crystallized submicron particles
Triple-Layered Perovskite Tantalates, MCa2Ta3O10 J. Phys. Chem. B, Vol. 109, No. 16, 2005 7803

TABLE 2: Interatomic Distance of RbCa2Ta3O10a

Ta(1)-O(1) 0.1929 nm
Ta(1)-O(2) 0.1835 nm
Ta(2)-O(2) 0.2430 nm
Ta(2)-O(3) 0.1951 nm
Ta(2)-O(4) 0.1813 nm
a References 16 and 17.

TABLE 3: Properties and Photocatalytic Activity of

MCa2Ta3O10
M Cs+ Na+ H+ C6H13NH3+
da/nm 1.51 1.72 1.44 2.85
nb/mol‚mol-1 0 1.86 0.38
Eg/eV 4.1 4.3 4.2 4.0
ratec H2 7.6 12.2 2.6 110.3
/µmol‚h-1 O2 2.2 7.6 0.7 0
rated H2 23.9 308.4 22.2
/µmol‚h-1 O2 10.3 157.7 5.2
a Interlayer distance. b Interlayer H O. c Ni-unloaded. d 0.5 wt % Ni
2
loaded. Rate was determined from H2/O2 evolution during initial 8-h
photoirradiation.

to as valence band edge. The states in the valence band region

from ca. -6 to 0 eV are mainly composed of the O2p orbital,
which is hybridized with Ta5d, whereas the contributions of
Rb and Ca orbitals appear to be negligible. The partial DOS of
four types of oxygen sites distribute very differently depending
on their coordination environment and interatomic distances.
The similar distributions of the O(1), O(3), and Ta partial DOS
curves in this energy region suggest a considerable hybridization
between O2p and Ta5d orbitals in a two-dimensional Ta-O
network along the layer (//ab). This is contrast to the discrete
Ta(2)-O(4) bond, which is partitioned by every interlayer. The
O(2) DOS is less intense relative to others because of the greatest
Ta(2)-O(2) distances (Table 2).
The conduction band (CB) in the energy range above 3 eV
mainly consists of Tad. The Ta partial DOS is largely ascribable
to 5d orbitals, which are divided into two distribution peaks at
3-7 eV and 8-10 eV as a result of the crystal field splitting in
the octahedral TaO6 environment. The similar double-peak
distributions in the four O partial DOS in this energy region
Figure 3. Total and partial density of states (DOS) for RbCa2Ta3O10
calculated by FLAPW method. support the large hybridization between O2p and Ta5d. Above
the main weight of the Ta5d band, a strong and narrow peak
with planar morphology showed no obvious change after ion due to the Ca orbital was observed, but the contribution to the
exchange. Their BET surface areas were in the range of 2-4 band gap transition should be negligible.
m2‚g-1. Thus, difference in photocatalytic activity arising from Band Gap Energy and Photocatalytic Activity. Table 3
the crystal size and morphology can be neglected. compares the optical band gap energy, Eg, photocatalytic activity
Calculated Electronic Structure. The electronic structure for water splitting of MCa2Ta3O10 (M ) Cs, Na, H, and C6H13-
was studied by using a Rb-type isomorph of Dion-Jacobson NH3). The constant Eg about 4 eV irrespective of different M
series RbCa2Ta3O10 (P4/mmm, a ) 0.387 nm, b ) 1.504 nm)16,17 can be explained on the basis of the electronic structure, where
as shown in Figure 2. This is constructed by alternative stacking the valence band and the conduction band consist primarily of
of a triple-corner-shared TaO6 octahedra and a monatomic Rb O2p and Ta5d, respectively (Figure 3). Therefore, the Eg
layer along the c axis. Each Rb ion is coordinated by eight corresponds to the gap between Ta5d and O2p. On the other
oxygens, O(4), of TaO6 octahedra in adjacent two perovskite hand, the interlayer cation is negligibly associated with the
slabs. There are four different oxygen sites: O(2) bridging Ta(1) values of Eg, because the Cs s and p orbitals form a high-lying
and Ta(2) with different distances (Ta(1)-O(2) 0.1835 nm, antibonding band and a bonding band far below the O2p VB,
Ta(2)-O(2) 0.2430 nm), O(1) and O(3) forming an infinite two- respectively. This is also the case for other monovalent cations,
dimensional TaO2 network, and O(4) facing to the interlayer M ) Cs, Na, and H, atomic orbitals of which take part in neither
space. The different Ta-O distances cause a large distortion in the VB nor the CB.
the TaO6 octahedra, which is characteristic of the layered As-prepared four tantalates, MCa2Ta3O10, were applied to
structure. photocatalytic decomposition of water under UV irradiation
On the basis of the crystal structure, the electronic structure (Figure 4a). For unloaded samples, the rates of evolved H2 as
of RbCa2Ta3O10 was studied by the first-principle calculation well as O2 were low, depending upon M in the sequence of Na
using the FLAPW method. Figure 3 shows calculated partial > Cs > H, but the ratio of H2/O2 evolved was close to the
and total density of states (DOS) of RbCa2Ta3O10. The top of stoichiometry. For a C6H13NH3-intercalated phase, much larger
valence band (VB) is set at zero on the abscissa and is referred H2 evolution (110 µmol‚h-1) occurred in an initial 8-h period,
7804 J. Phys. Chem. B, Vol. 109, No. 16, 2005 Machida et al.

Figure 5. Effect of Ni loading on the rate of photocatalytic H2 evolution

from distilled water over NaCa2Ta3O10. The reaction was carried out
in an inner irradiation quartz cell under UV irradiation from a 400 W
high-pressure Hg lamp.

Figure 4. Gas evolution from water over (a) unloaded and (b) NiOx-
loaded MCa2Ta3O10 (0.5 wt % Ni) under irradiation of UV light from
a 400 W high-pressure Hg lamp. 0 H2, 9 O2.

but after this, the evolution leveled off. The negligible evolution
of O2 implies that the C6H13NH3 accommodated in the interlayer
would be oxidized sacrificially. This was supported by the fact
that the H2 evolution was accompanied by the collapse of
intercalated galley. The photocatalytic activity of these hydrated Figure 6. Change of XRD pattern of MCa2Ta3O10 (M ) Cs, Na, and
tantalates was also measured after loading partially oxidized H). (a) As-prepared, (b) heated at 500 °C in vacuo, and then (c)
nickel catalyst, NiOx (0.5 wt % Ni), which is well-known as an immersed in water at room temperature.
active component for water splitting.18,19 The oxidation state Na, and H) were studied by measuring the X-ray basal reflection
of Ni was confirmed to be 2+ by means of XPS. TEM due to the layer structure (Figure 6). As-prepared MCa2Ta3O10
observation suggested that NiOx particles less than 10 nm in (a) was first heated at 500 °C in vacuo for 5 h (b) and
diameter were highly dispersed on the surface of planar subsequently immersed in deionized distilled water with stirring
crystallites of Cs, Na, and H phases (Figure S2, Supporting at room temperature for 24 h (c). For M ) Cs, negligible change
Information). As shown in Figure 4b, the effect of loading is of basal reflection at 2θ ) ca. 6° is indicative of the totally
obvious, but the rate of gas evolution was more strongly anhydrous nature. By contrast, the basal reflection for the Na
dependent on M, that is, the NiOx-loaded Na phase exhibited phase shifted to higher angles upon heating because of decreased
the highest activity (>300 µmol-H2‚h-1), whereas the NiOx- interlayer spacing from 1.72 to 1.50 nm caused by elimination
loaded Cs and H phase was less active (<30 µmol-H2‚h-1). of water molecule from the interlayer (b). Because the anhydrous
The stoichiometric evolution of H2 and O2 from NiOx supported interlayer thus formed could be easily swelled by the subsequent
on the Na phase increased monotonically with irradiation time, immersion into water, reversible hydration/dehydration of the
giving rise to the rates 308 and 158 µmol‚h-1, respectively. This Na phase occurs very smoothly (c). Although the dehydration
corresponds to the apparent quantum yield of ca. 5%. The rate of interlayer was also observed for the H phase after heating
of photocatalytic gas evolution was measured for the Na phase (b), the rehydration could not be completed by subsequent
as a function of Ni loading in Figure 5. The activity increased immersion in water (c). This is indicative of the irreversible
drastically with increasing the Ni loading up to 0.3 wt %, but nature of a hydrated H phase.
further increase to 1.5 wt % led to almost the same activity. Isotopic Exchange of Interlayer Water. Hydration behavior
The cumulative amounts of H2 and O2 evolved over Ni-loaded of interlayer water was next studied by measuring infrared
samples during 8-h photoirradiation were more than the amount absorption spectra after treatment with D2O (Figure 7). As-
of tantalates, supporting that the reaction proceeded catalytically. prepared Na phase with hydrated interlayer (a) exhibits broad
Reactivity of Hydrated Interlayer. As described above, the bands due to OH stretching mode (νOH) at ca. 3450 cm-1 and
photocatalytic activity of hydrated Na phase for water splitting two sharp bands due to HOH bending mode (δHOH) at 1700
showed significant increase in the presence of Ni catalyst. This and 1640 cm-1. These bands disappeared after evacuation at
is in contrast to a low activity of the Ni-loaded H phase, which 500 °C (c), but subsequent immersion into D2O immediately
exhibits a hydrated structure as well as a band gap similar to yielded νOD (2500 cm-1) and δDOD (1200 cm-1), which is
those of the Na phase. No visible difference of NiOx particle consistent with the accommodation of D2O into the interlayer
size, dispersion, and oxidation state was detected by TEM/XPS space (d). Peaks ascribable to νOH, δHOH, and δHOD (1400 cm-1)
experiment. It is therefore suggested that the hydrous interlayer are due to impurity H2O originated from atmospheric water
in these two phases is different from a viewpoint of reactivity. vapor. The result was in complete contrast to the fact that the
The hydration/dehydration behaviors of MCa2Ta3O10 (M ) Cs, immersion of H2O-hydrated Na phase into D2O showed
Triple-Layered Perovskite Tantalates, MCa2Ta3O10 J. Phys. Chem. B, Vol. 109, No. 16, 2005 7805

Figure 7. Change of FT-IR spectra of NaCa2Ta3O10. (a) As-prepared

H2O-hydrated phase, (b) immersed in D2O at room temperature, and
(c) (a) heated at 500 °C in vacuo, and then (d) immersed in D2O at
room temperature, (e) as-prepared H2O-hydrated phase immersed in
D2O under UV-irradiation.

negligible change in the spectra (b). This means that the

exchange between interlayer H2O and exterior D2O is very slow. Figure 8. Isotopic distribution of photocatalytic gas evolution from
D2O could be accommodated more rapidly when the as-prepared D2O over anhydrous Cs phase and H2O-hydrated Na phase-loaded with
Na phase was immersed in D2O under UV irradiation for 2 h 0.5 wt % Ni.
(e). This may be explained by assuming that the interlayer active
in the interlayer was reacted with holes as a sacrifice for H2
site can decompose H2O to H2/O2 under UV irradiation and
evolution. Hydrogen evolution from H2O-hydrated Na phase
vacant sites thus formed accommodate D2O from an exterior
dispersed in D2O also proves that H2O molecule in the interlayer
liquid phase.
is decomposed to evolve H2/O2 even in the absence of sacrificial
To discriminate between photocatalytic reactions in the agents. This result is consistent with highest photocatalytic
interlayer space and on the outer surface, we measured the activity of hydrated Na phase for water splitting, which
isotopic ratios of gas evolved from MCa2Ta3O10 (M ) Cs and possesses the active site not only on the crystalline surface but
Na), which was dispersed in D2O under UV irradiation from a also in the interlayer. On the contrary, this is not the case for
500 W Xe lamp (Figure 8). When the anhydrous Cs phase (0.5 the H phase, the hydration of which is not reversible as shown
wt % Ni loaded) was dispersed in D2O, the gas evolved in Figure 6; that is, the low mobility of water molecules may
contained almost a constant amount of hydrogen (HD/D2e 0.1, not allow successive photooxidation reactions inside the inter-
H2/D2e 0.02), which should be originated from impurity H2O. layer. Therefore, the different effect of hydration may be
Because of the difference in the dissociation energy, photo- associated with the mobility of water molecule inside the
catalytic H2O splitting proceeded ca. 3.5 times faster than that interlayer space. A negative effect of interlayer hydration may
of D2O. By contrast, the gas evolved in the first stage from also be explained by deformation of H phase perovskite as
H2O-hydrous Na phase contained more hydrogen, and then, HD/ evident from the XRD peaks (Figure 1), which exhibited
D2 and H2/D2 ratios decreased gradually to constant values, 0.28 broadening as compared to the parent Cs phase. Such deforma-
and 0.03, respectively, which were ca. 2 times larger than those tion would yield structural defects, which would give rise to
for the Cs phase. recombination centers of photogenerated carriers. Unlike the
These results represent that H2O molecules between the layers hydrated phase with M ) Na and H, the Cs phase is very stable
of the Na phase take part in the photocatalytic gas evolution. against hydration when suspended in water. The photocatalytic
With a progress of the consumption of H2O in the interlayer gas evolution over the Cs phase should therefore take place on
close to the surface, D2O molecules should be accommodated the outer surface of the crystallites.
from an exterior liquid phase to interlayer to compensate the The present system is an n ) three member of the Dion-
loss of water. In this way, the decrease of the isotopic ratios is Jacobson series layered structure, A′[An-1TanO3n+1]. The effect
in accord with decreased concentration of H2O in the hydrated of hydration on the photocatalytic activity is different from that
interlayer space. Because the interlayer photocatalytic reaction for double-layered tantalates (n ) 2), MLaTa2O7 (M ) Rb, Na,
should take place in only a limited depth from the surface, where and H), in our previous work.22,24 As in the present case, the
the UV light can reach, H2O molecules would be therefore Rb phase for n ) 2 shows totally anhydrous nature, whereas
supplied from the bulk of tantalates. This is a possible reason the Na phase shows smooth and reversible hydration/dehydra-
the isotopic ratios became almost constant after several hours tion. Nevertheless, the photocatalytic activity of hydrous
from the beginning of the reaction (Figure 8). NaLaTa2O7 for water splitting did not exceed that of anhydrous
Role of Interlayer in Photocatalysis. The present study RbLaTa2O7 both in the absence and presence of NiOx. As a
clearly demonstrated that the interlayer of the present layered possible reason for such a different feature between double- and
tantalate plays a role of the active site for photocatalytic water triple-layered tantalates, we notice the dependence of electronic
splitting. An accelerated H2 evolution from a C6H13NH3- structure on the number of layers. As shown in Figure 3, four
intercalated phase (Table 3) suggests that the organic moiety types of oxygen sites, O(1), O(2), O(3), and O(4), in the present
7806 J. Phys. Chem. B, Vol. 109, No. 16, 2005 Machida et al.

triple-layered perovskite (n ) 3) contribute very differently to O(4), which faces to the interlayer and contributes mostly to
the total DOS. The O(1), O(2), and O(3) orbitals exhibit a the valence band top, may lead to preferentially distributed holes
considerable hybridization with Ta5d in the Ta-O network. By on this site under photoirradiation.
contrast, the terminating oxygen, O(4), which faces to the
interlayer space, is less hybridized with Ta5d and contributes Acknowledgment. The present study was financially sup-
primary to the VB edge. Supposing the partial DOS of each ported by CREST and Grant-in aid for Scientific Research from
oxygen reflects the spatial distribution of photogenerated holes the Ministry of Education, Science, Sports, and Culture.
in the hydrated phase, the O(4) site would contribute to the
conversion of interlayer water to O2. This is not the case for Supporting Information Available: SEM photographs of
the double-layered perovskite (n ) 2),22,24 where the DOS peak MCa2Ta3O10 (M ) Cs, Na, and H) and TEM photograph of
due to terminating oxygen situates at ca. 1 eV below the VB CsCa2Ta3O10 loaded with 0.5 wt % Ni. This material is available
edge. No remarkable interaction is expected between water free of charge via the Internet at http://pubs.acs.org.
molecules and holes in the interlayer of hydrated Na phase. References and Notes
These preliminary calculations may suggest that the number of
perovskite layers, n in A′[An-1TanO3n+1], is a key affecting the (1) Schaak, R. E.; Mallouk, T. E. Chem. Mater. 2002, 14, 1455.
(2) Dion, M.; Ganne, M.; Tournoux, N. Mater. Res. Bull. 1981, 16,
contribution of terminating oxygen to the total DOS profile, 1429.
and thus the photocatalytic behavior of interlayer. To evidence (3) Dion, M.; Ganne, M.; Tournoux, N.; Revez, J. Chim. Miner. 1984,
this speculation, the electronic calculation is required to estimate 21, 92.
(4) Ruddlesden, S. N.; Popper, P. Acta Crystallogr. 1957, 10, 538.
the interaction between water molecules and perovskite slab in (5) Gopalakrishnan, J.; Bhat, V. Inorg. Chem. 1987, 26, 4301.
the hydrated interlayer, which would lead to a considerable (6) Domen, K.; Naito, S.; Ohnishi, T.; Tamaru, K. Chem. Phys. Lett.
modification of the VB structure. Further studies concerning 1982, 92, 433.
the relationship between the band structure and the number of (7) Inoue, Y.; Kubokawa, T.; Sato, K. J. Chem. Soc., Chem. Commun.
1990, 1298.
perovskite layers is now under investigation both from theoreti- (8) Inoue, Y.; Niiyama, T.; Asai, Y.; Sato, Y. J. Chem. Soc., Chem.
cal and experimental points of view. Commun. 1992, 579.
(9) Uchida, S.; Yamamoto, Y.; Fujishiro, Y.; Watanabe, A.; Ito, O.;
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Conclusion (10) Kudo, A.; Tanaka, A.; Domen, K.; Maruya, K.; Aika, K.; Ohnishi,
In the present study, we have studied the electronic structure T. J. Catal. 1988, 111, 67.
(11) Takata, T.; Shinohara, K.; Tanaka, A.; Hara, M.; Kondo, J. N.;
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