11352 J. Phys. Chem.

B 2006, 110, 11352-11360

Photoelectrochemical Decomposition of Water into H2 and O2 on Porous BiVO4 Thin-Film

Electrodes under Visible Light and Significant Effect of Ag Ion Treatment

Kazuhiro Sayama,*,† Atsushi Nomura,‡ Takeo Arai,† Tsuyoshi Sugita,‡ Ryu Abe,†
Masatoshi Yanagida,† Takashi Oi,§ Yasukazu Iwasaki,§ Yoshimoto Abe,‡ and Hideki Sugihara†
Energy Technology Research Institute, National Institute of AdVanced Industrial Science and Technology
(AIST), Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan, Faculty of Science and Technology,
Science UniVersity of Tokyo, Yamazaki 2641, Noda, Chiba 278-8514, Japan, and Nissan Research Center,
Nissan Motor Co., Ltd., 1 Natsushima, Yokosuka, Kanagawa 237-8523, Japan
ReceiVed: December 28, 2005; In Final Form: April 1, 2006

The photoelectrochemical properties of porous BiVO4 thin-film electrodes on conducting glass for H2 production
from water under visible light were investigated. BiVO4 films were prepared by the metal-organic
decomposition method, and particles were 90-150 nm in diameter. Under visible-light irradiation, H2 and O2
evolved in a stoichiometric ratio (H2/O2 ) 2) from an aqueous solution of Na2SO4 with an external bias. The
photocurrent increased with addition of methanol. The band structure of BiVO4 was investigated by open-
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circuit potential, flat-band potential, X-ray photoelectron spectroscopy, and calculations based on density
functional theory. The top of the valence-band potential of BiVO4 was shifted negatively compared to the
potentials of the conventional oxide semiconductors without Bi. We surmise that hybridization between the
O-2p and Bi-6s orbitals might contribute to the negative shift of the BiVO4 valence band. Treatment with an
from https://pubs.acs.org/doi/10.1021/jp057539+.

aqueous solution of AgNO3 improved the photocurrent of the BiVO4 electrode significantly. The maximum
incident photon-to-current conversion efficiency at 420 nm was 44%. This value was the highest among
mixed-oxide semiconductor electrodes under visible light irradiation. AgNO3 treatment also improved the
stability of the photocurrent. The Ag+ ion in/on the BiVO4 catalyzed the intrinsic photogeneration of oxygen
with the holes.

1. Introduction
Since the publication of the Honda-Fujishima effect on TiO2
electrodes under UV light,1 photoelectrochemical water splitting
with semiconductor photoelectrodes has been regarded as an
ideal means of converting solar energy directly into clean fuel,
namely, hydrogen energy.2-22 The energy density of solar light
is relatively low; therefore, many featuresssuch as high energy-
conversion efficiency, high stability, low-cost production, and
simple structure for large-area utilizationsare required for
semiconductor photoelectrodes. To increase the solar energy
conversion efficiency, effective utilization of visible light over
a wide wavelength region is indispensable. It should be noted
that oxide semiconductors have many advantages, for example,
they are generally stable, are suitable for O2 evolution, and are
produced easily compared to non-oxide semiconductors. How-
ever, the efficiencies of various oxide semiconductor electrodes
with conventional types, such as single crystal or sintered pellet,
are low in the visible-light region, even when a high external
bias was applied.
It was recently reported that a nanocrystalline WO3 thin film
on a conducting glass electrode showed an excellent incident
photon-to-current conversion efficiency (IPCE > 75%) for water
decomposition under visible light.5,6 The nanocrystalline WO3
film was prepared by spreading a colloidal solution of WO3 on
* Address correspondence to this author. Phone: +81-(0)298-61-6234.
Fax: +81-(0)298-61-4760. E-mail: k.sayama@aist.go.jp.
† National Institute of Advanced Industrial Science and Technology
(AIST).
‡ Science University of Tokyo.
§ Nissan Motor Co., Ltd.
10.1021/jp057539+ CCC: $33.50 © 2006 American Chemical Society
Published on Web 05/19/2006
the conducting glass and then firing it. Moreover, relatively high
IPCEs (ca. 25%) were also reported for porous Fe2O3 thin-film
electrodes on conducting glass prepared by spraying the glass
with a solution containing iron salts.10,15,16 It is worth mentioning
that high IPCEs were obtained with this simple wet process,
although many defects in the porous film electrodes may have
been present.
To effectively absorb visible light from solar light, utilization
of semiconductors having a narrower band gap is essential. In
studies of multijunction hybrid photoelectrodes, which were
designed to decompose water directly with no external bias,20-22
development of effective oxide semiconductors for O2 evolution
has been important. However, oxide semiconductor materials
that have efficient O2 evolution ability and a band gap that is
narrower than that of WO3 are limited. Some porous thin-film
electrodes of various oxide semiconductorsssuch as metal-ion-
doped oxides and mixed oxides on conducting glassshave been
investigated;7-10,13-17 however, their IPCEs are not satisfactory.
We have studied new oxide semiconductors for their water-
splitting ability under visible light. In the field of photocatalysis,
BiVO4 semiconductor powder was reported to show high O2
evolution when Ag+ or Fe3+ ions were used as electron
acceptors under visible light, but this semiconductor had no H2
evolution ability.19,23,24 The band gap of BiVO4 (2.4 eV) was
smaller than that of WO3 (2.7 eV). It is speculated that the top
of the valence band consists of Bi-6s and O-2p orbitals;23
therefore, such physical properties as mobility of charge and
band potentials of BiVO4 are probably different from those of
simple oxide semiconductors. In an earlier work, we reported
Photoelectrochemical Decomposition of Water
briefly that a nanocrystalline BiVO4 film electrode on conduct-
ing glass showed an excellent IPCE for the decomposition of
water.12
In this study, the physical and photoelectrochemical properties
of BiVO4 films, the effect of sacrificial reagent addition, and
the band structure of BiVO4 were investigated in detail.
Moreover, surface modifications of the semiconductor photo-
electrodes,18,25 as well as semiconductor photocatalysts, were
important for improving efficiency and stability. We report
herein that surface modification of a BiVO4 electrode by
treatment with an aqueous solution of AgNO3 substantially
improved both efficiency and stability under visible-light
irradiation.
2. Experimental Section
2.1. Preparation of BiVO4 Electrode. The BiVO4 films were
prepared by a modified metal-organic decomposition (MOD)
method.12,26 Bi(NO3)3‚5H2O (Kanto Chemical Co.) in acetic acid
(0.2 mol/L) and vanadium(IV) (oxy)acetylacetonate (Azmax
Co.) in acetylacetone (0.03 mol/L) were mixed with a 1:1
stoichiometric ratio of Bi to V. The solution was coated by
means of a spin coater (Mikasa Co., 1H-D7, 1000 rpm, 10 s)
on a conducting glass (FTO glass, Nippon Sheet Glass Co.,
F-doped SnO2, 10 Ω/sq) and fired at 500 °C in air for 30 min.
The spin coatings and the calcinations were repeated 6 times.
The average thickness of the rough film, as measured by a step
meter (Tencor, Alpha step), was ca. 0.5 µm for 6 layers.
In the case of the surface modifications, the BiVO4/FTO
electrode was immersed in various aqueous solutions (0.01 mol/
L) in the dark for 12 h and was then thoroughly washed with
distilled water.
2.2. Photoelectrochemical Measurement and Character-
ization. The photoelectrochemical and capacitance measure-
ments were conducted with a potentiostat (BAS, 612A) and a
Pyrex glass cell. A Pt wire and a Ag/AgCl electrode (0.21 V vs
NHE, pH 0) were used as the counter and reference electrodes,
respectively. For stability testing (the photocurrent-time mea-
surement), the photocurrent was measured by a two-electrode
system without a reference electrode. An aqueous solution of
0.5 mol/L of Na2SO4 (pH 5.8) was used most often as the
electrolyte solution because the stability of the BiVO4 film in
Na2SO4 (aq sol) was good compared to that in other solutions.
It should be noted, however, that because the Na2SO4 solution
was unbuffered, the applied potential was probably overesti-
mated owing to the pH change around the electrode surface
during the photoreaction. The light source was a Xe lamp (500
W, Ushio Denki Co.) with/without UV cutoff (HOYA, L-42)
or band-pass filters. The unfiltered light intensity was measured
by a spectroradiometer (Yamashita Denso Co., YSR-1100M)
between 350 and 500 nm, corresponding to the active wave-
length of BiVO4, to be 450 W/m2. The light intensity of AM-
1.5G (Japan Industrial Standard, JIS-C8911) between 350 and
500 nm was 175 W/m2; therefore, the unfiltered Xe light
intensity was nearly equivalent to a condition of 2.6 Sun. The
semiconductor electrodes were irradiated through the FTO
conducting glass. The masked-off irradiated area was 0.28 cm2.
The light-harvesting efficiency (LHE) of the electrode was
calculated from the transmittance (T) and reflectance (R) with
use of an integrating sphere (Jasco, V-570):
LHE ) 1 - R - T (1)
The IPCE was then calculated from the following equation:
J. Phys. Chem. B, Vol. 110, No. 23, 2006 11353
1240 × photocurrent density [µA/cm2]
IPCE ) (2)
wavelength [nm] × photon flux [W/m2]
The monochromatic photon flux through the band-pass filter
(Nihon Shinku Kogaku Co.) was measured by an optical
photodiode power meter (Advantest Co., TQ8210), and it was
corrected for the reflection loss at the Pyrex glass cell and the
FTO glass. The electrodes were characterized by X-ray diffrac-
tometry (XRD, Mac Science, MX-Labo), using Cu KR radiation
at 40 mA, 40 kV, and by Raman spectroscopy (Jasco, NRS-
1000, 532 nm). Scanning electron microscopy (SEM) was
performed on a Hitachi S-800 instrument. The composition of
the semiconductors was measured with an X-ray fluorescence
analyzer (XRF, Rigaku Co., ZSX-mini, 40 kV, 1.2 mA). In the
case of X-ray photoelectron spectroscopy (XPS) (Ulvac-Phi,
XPS-1800), an Al anode with a monochromator was used to
significantly reduce the background signal. To completely
prevent the charge-up effect, many techniques were used. Both
a low-energy electron (<2 eV) and a low-energy Ar+ ion (<10
eV) were emitted to neutralize the charges at the same time to
the BiVO4/FTO electrode, which was grounded to the sample
holder by a Cu wire. The measurement area was relatively large
(2.0-0.8 mm2). The binding energy was referenced to the C-1s
peak taken at 284.8 eV or the O-1s peak at 531.0 eV. The band
structure and the partial density of states of BiVO4 were
calculated based on density functional theory (DFT), using
CASTEP package software (Accelrys Co.). The generalized
gradient approximation (GGA-PBE) was applied.
Measurement of H2 and O2 evolution was performed in a
Pyrex glass cell connected to a closed gas-circulating system.
The BiVO4/FTO electrode was connected with Cu wire by
indium solder, and the connecting part was covered with an
epoxy resin. The light source was a Xe lamp (300 W, Cermax
lamp), and the BiVO4 electrode area was ca. 2 cm2. A Pt wire
was used as the counter electrode, and a reference electrode
was not used. The electrode wires were connected tightly to
the Pyrex glass cell with silicone rubber to prevent any air
leakage. An aqueous solution of Na2SO4 (0.5 mol/L, 80 mL)
was introduced into the cell and was degassed completely, and
then argon gas (100 Torr) was introduced into the system. The
cell was preirradiated for few hours to prevent contamination.
Evolved H2 and O2 gases were detected by on-line gas
chromatography (Shimadzu Co., TCD, 5 Å molecular sieves,
argon carrier gas).
3. Results and Discussion
3.1. Structure of BiVO4 Film and Photoelectrochemical
Properties. Figure 1 shows the SEM photographs of the BiVO4
electrodes prepared by the MOD method. A porous structure
was observed; therefore, the electrolyte solution will penetrate
into the pores of the BiVO4 film. The BiVO4 particles were
90-150 nm in diameter. The BiVO4 electrodes prepared by the
MOD method were strong mechanically, and the film was not
removed by a hard scratch with a Teflon plate and a nail,
suggesting good adhesion properties of the film due to the strong
connection between particles and between particles and the
conducting glass.
Three crystalline phases have been reported for synthetic
BiVO4: the monoclinic sheelite type, the tetragonal sheelite
type, and the tetragonal zircon type.23,24,27-29 The crystalline
phase depends on the synthetic method used for its preparation.
The tetragonal and monoclinic phases have been reported to be
selectively obtained depending on the Bi/V stoichiometric ratio
in solution, with excess Bi(III) leading to the tetragonal zircon-
11354 J. Phys. Chem. B, Vol. 110, No. 23, 2006
Figure 1. SEM photograph of the surface of BiVO4 electrodes prepared
by the MOD method and calcined at 500 °C.
type phase.23,24 The tetragonal zircon-type phase changed
irreversibly to the monoclinic sheelite-type at 397-497 °C.27-29
The monoclinic BiVO4 converted reversibly to the tetragonal
sheelite-type at >255 °C.29 Monoclinic sheelite-type BiVO4 has
been reported to show good photocatalytic activity for O2
evolution from AgNO3 aqueous solution compared to the
tetragonal zircon-type and the tetragonal sheelite phases.23,24
Figure 2a shows the XRD pattern of the BiVO4/FTO electrode
prepared by the MOD method at 500 °C. All peaks (V) were
assigned as sheelite-type, and its main peak was at 29°, in
addition to the FTO glass peaks (*). The difference between
the monoclinic and tetragonal sheelite phases can be judged by
the existence of a peak at 15° and splitting of peaks at 18.5°
and 35°. The XRD peaks of the BiVO4 film on the conducting
glass were weak for distinguishing this difference because the
film was very thin. The XRD pattern of BiVO4 powder prepared
by the calcination of the same MOD solution at 500 °C was
clearly assigned to the monoclinic sheelite-type (inset, Figure
2b). The tetragonal sheelite BiVO4 heated at 500 °C changed
to the monoclinic BiVO4 during the cooling process to room
temperature.29 Therefore, it is concluded that the BiVO4 film
electrode was the monoclinic sheelite-type. The tetragonal
zircon-type phase with its main peak at 24° and other phases,
Bi2O3 and V2O5, were not observed. Raman spectra of the
BiVO4/FTO electrode (Figure 3a) and the BiVO4 powder
prepared by solid-state methods as a reference sample of
monoclinic sheelite-type BiVO4 (Figure 3b) were almost
equivalent. The peaks at 822, 365, 325, and 219 cm-1 were
assigned to the symmetric stretch mode of V-O, the symmetric/
asymmetric deformation mode of VO43-, and the external mode
of the monoclinic BiVO4.26,29
Figure 4a shows the current-potential properties of the
BiVO4 film electrode, and the electrolyte was Na2SO4 aqueous
solution without additives. The dark current was observed only
above 1.3 V (vs Ag/AgCl). The anodic photocurrent was
Sayama et al.
observed at more than open-circuit potential (Vop ) -0.06 V)
under UV and visible light, and the photocurrent increased
steadily with applied positive potential. The absorption spectrum
of the BiVO4 film is shown in Figure 5. The threshold of the
absorption was ca. 500-520 nm, which is in accord with that
of the monoclinic BiVO4.23,24 The band gap was estimated at
ca. 2.4 eV. The dependence of the IPCE on the wavelength in
Na2SO4 (aq sol) is also shown (Figure 6a). The IPCE decreased
with longer wavelength, and the shape of the IPCE action
spectrum was similar to that of the absorption spectrum. But,
the edge of the IPCE spectrum seems to be blue-shifted
compared with that of the absorption spectrum. In the case of
the photon with low energy in the longer wavelength region,
the photon penetration depth is larger and the electron diffusion
length was longer. Therefore, it is considered that the probability
of the charge recombination during the long diffusion increased
and then the IPCE decreased around the light absorption edge.
In the case of the water splitting on the semiconductor
photoelectrodes without any sacrificial reagents in the electro-
lyte, measurement of O2 and H2 evolution is very important;
however, reports on gas measurement in the photoelectrochemi-
cal cell are very few. We investigated H2 and O2 evolution from
the BiVO4 cell using a closed gas-circulating system. Evolution
of H2 and O2 evolution at a stoichiometric ratio (H2/O2 ) 2)
was observed under visible-light irradiation (Figure 7). There
was no gas evolution in the dark under the same conditions.
The total amount of evolved gas was almost identical with that
calculated by the total passage of photoelectrons.
The promotion effect of the photocurrent by the addition of
organic compounds was reported for various semiconductor
photoelectrodes.5,6,19,30 Investigation of the oxidation properties
of organic compounds on the BiVO4 electrode is meaningful
for degradation of harmful compounds and for H2 production,
using biomass under visible light. The photocurrent almost
doubled with the addition of methanol at a positive potential
above +0.5 V (Figure 4b). Similar behavior on the improvement
of photocurrent was reported by Nakato et al., though the
photocurrent was very small.19 The open-circuit potential was
shifted slightly from -0.06 to -0.13 V by addition of methanol.
The photocurrent increased more than two times at low applied
potential. It is suggested that the charge recombination was
predominant at low applied potential without methanol and that
the charge recombination was suppressed by the methanol
addition owing to the hole-scavenging effect of methanol.5
Figure 6b shows the IPCE spectra of the BiVO4 electrode with
and without methanol addition. The IPCE also nearly doubled
with methanol addition, suggesting the possibility of a current-
doubling effect caused by electron injection from oxidized
radical intermediates.5,30
3.2. Band Structure of BiVO4. It is speculated, from the
results of photoemission and the redox potential of Bi5+/Bi3+,
that the top of the valence band of BiVO4 may be formed by
both O-2p and Bi-6s orbitals and that the top of the Bi-6s orbital
may be more negative than that of O-2p.23,31 However, the band
structure of BiVO4 has not yet been measured experimentally.
Herein we investigate the band structure of BiVO4 in detail using
photoelectrochemical measurements, the band-structure calcula-
tion based on DFT, and the valence-band XPS measurement.
Figure 8 shows the density of states (DOS) of the monoclinic
sheelite-type BiVO4. The bottom of the conduction band of
BiVO4 was formed mainly by the V-3d orbital, and the O-2p
orbital was also hybridized. The potential of the conduction band
edge (Ecb) is considered to be related to the open-circuit potential
(Vop) under irradiation. The Vop of the BiVO4 electrode under
Photoelectrochemical Decomposition of Water
Figure 2. (a) XRD pattern of the BiVO4/FTO electrode prepared by the MOD method at 500 °C: (V) monoclinic sheelite-type BiVO4; (*) FTO
conducting glass. (b) XRD pattern of BiVO4 powder prepared by calcination of the same MOD solution at 500 °C.
Figure 3. Raman spectra of (a) the BiVO4 film electrode prepared by
the MOD method calcined at 500 °C and (b) the BiVO4 powder
prepared by solid-state methods as a reference sample of monoclinic
sheelite-type BiVO4.
Figure 4. Current-potential plots for the BiVO4 film electrode in
various electrolyte solutions: (a) Na2SO4 aqueous solution without
additives and (b) with methanol (10 vol %). Unfiltered whole light
from a Xe lamp was used for irradiation. The pH was adjusted to 5.8.
unfiltered light irradiation was between -0.2 and -0.05 V (vs
Ag/AgCl). The Vop was influenced by light intensity. The Vop
range of the BiVO4 electrode was similar to that of the
nanocrystalline WO3 electrode when these photocurrents were
adjusted to the same level for our experimental results. If the
Ecb of BiVO4 and WO3 are equal, then the valence-band
potential edge (Evb) of BiVO4 is estimated to be more negative
than that of WO3, because the band gap of BiVO4 (2.4 eV) is
smaller than that of WO3 (2.7 eV).
Figure 9a shows the XPS spectrum of the BiVO4/FTO
electrode at around 0 eV binding energy. The main peak at 6
eV had shoulders on both sides, and another peak at 12 eV was
J. Phys. Chem. B, Vol. 110, No. 23, 2006 11355
Figure 5. Light-harvesting efficiency (LHE) spectrum of the BiVO4/
FTO electrode.
Figure 6. Dependence of IPCE on the wavelength in Na2SO4 (aq
sol): (a) without additives and (b) with methanol (10 vol %). The
applied potential was +1.0 V versus Ag/AgCl.
observed. The shape of the XPS spectrum was similar to the
shape of the valence band of the total DOS in Figure 8,
suggesting that the result of the DFT calculation on the valence
band was qualitatively in accord with the XPS measurement.
The peak at 12 eV in the XPS spectra of BiVO4 was assigned
mainly to the Bi-6s orbital, according to the DFT calculation
in Figure 8. The XPS measurement of various semiconductor/
FTO electrodes (Figure 9a-e) was conducted carefully with
both electron and Ar+ ion neutralizer systems. The semiconduc-
tor on the FTO conducting glass was very thin (<1 µm) to avoid
the charge-up effect; at the same time, no Sn-3d5/2 signal from
the conducting glass was confirmed, suggesting no pinholes in
the semiconductor film. The XPS spectra were proportionately
shifted with the bias to the sample holder within 0.05 eV.
Therefore, it is concluded that the charge-up effect was
negligible under this experimental condition. The spectrum
thresholds of BiVO4 and Bi2O3 were always lower than those
of WO3, TiO2, and V2O5 in both cases of the C-1s and the O-1s
corrections of the binding energy: {WO3, TiO2, V2O5} > BiVO4
> Bi2O3. Therefore, we believe that Bi-containing semiconduc-
11356 J. Phys. Chem. B, Vol. 110, No. 23, 2006
Figure 7. Time course of H2 and O2 evolution under visible-light
irradiation (>420 nm). The applied bias was 1.6 V to the Pt counter
electrode.
Figure 8. Density of state (DOS) of monoclinic sheelite-type BiVO4
calculated by the DFT method. Note that the x axis is inverted compared
to the Figure 9 XPS and that “zero energy” refers to the occupied level.
Figure 9. XPS spectra of various semiconductors on FTO conducting
glass. The binding energy was referenced to the C-1s at 284.8 eV: (a)
BiVO4, (b) Bi2O3, (c) V2O5, (d) WO3, and (e) TiO2.
tors easily discharged the electron and that the top of Evb of
BiVO4 and Bi2O3 was shifted negatively toward those of
conventional Bi-free oxide semiconductors.
The flat-band potential (Efb) of semiconductor electrodes is
usually measured by Mott-Schottky analysis.10,17 Figure 10
shows the Mott-Schottky plot of the BiVO4 electrode. The Efb
of the BiVO4 was -0.6 ( 0.1 V (vs Ag/AgCl). Values of Efb
for the WO3 and TiO2 electrodes in the same electrolyte solution
were ca. -0.6 and -0.8 V, respectively. Efb is strongly related
Sayama et al.
Figure 10. Mott-Schottky (1/C2 versus applied potential, where C is
the capacitance) plot of the BiVO4 electrode in the dark at 600 Hz.
to the bottom of the Ecb and is considered to be located just
under the Ecb for n-type semiconductors. According to the small
band gap of BiVO4, the top of Evb of BiVO4 was calculated to
be more negative than those of TiO2 and WO3.
Absolute values of Ecb and Evb of semiconductors are very
important but are controversial in each method mentioned above.
The comparison method for Voc was simple; however, Voc was
sensitive to light intensity, electrolyte solution, and quality of
film preparation. In the case of XPS measurement, complete
neutralization for the charge-up effect and precise correction
of the binding energy are essential. The Efb from the Mott-
Schottky analysis was affected by the Helmholtz capacitance
for dielectric semiconductors.32 It is considered that the dielectric
property of BiVO4 might cause the upward deviation of the plots
below -0.5 V in Figure 10.32,33 However, it should be
emphasized that all results from these three methodss
comparison of Voc, XPS measurement, and Mott-Schottky
analysissindicated that the top of Evb of BiVO4 was shifted to
less positive potentials in comparison with the values for the
conventional semiconductors without Bi. The negative shift of
the valence band is beneficial because it decreases the band
gap of oxide semiconductors without the positive shift of the
conduction band, leading to the decrease of applied bias.
According to the DFT calculation in Figure 8, the Bi-6s orbital
was mainly located -10 eV apart from the valence band made
mainly of O-2p. However, we also found that the top of the
valence band contained a slight amount of the Bi-6s component
(O-2p, 97%; Bi-6s, 2%; V-3d, 1%) and the Bi-6s peak at -10
eV also contained an O-2p component (O-2p, 15%; Bi-6s, 84%;
V-3d, 1%), suggesting hybridization between the O-2p and Bi-
6s orbitals.34 This hybridization may have contributed to the
upper shift of the BiVO4 valence band. Similar behavior about
the shift of valence band was also suggested in the Bi-6s, the
Pb-6s, or Ag-4d hybrid orbitals of PbBi2Nb2O9 and (AgBi)0.5-
MO4 (M ) W and Mo).35,36 We suggest that the transfer of
holes on the valence band becomes easy with the formation of
a hybrid Bi-6s-O-2p orbital. We also investigated other MVO4
(M ) Y, In) electrodes; however, high efficiencies were not
obtained. These results suggest that the Bi orbital probably
played an important role in the high efficiency of the BiVO4
electrode.
3.3. Stability of the BiVO4 Electrode and the Ag Treat-
ment Effect. Figure 11a shows the time course of the photo-
current for the BiVO4 electrode. The photocurrent decreased
gradually, but it remained constant at ca. 0.5 mA/cm2 for more
than 10 h. The turnover number of observed photoelectrons to
the BiVO4 unit was ca. 60 for 1 h. No change in the BiVO4
electrode after a 10-h photoreaction was observed in the XRD,
XRF, and UV-vis spectra, suggesting that the bulk of BiVO4
was intrinsically stable for the photoelectrochemical reaction.
Photoelectrochemical Decomposition of Water
Figure 11. Time course of the photocurrent of BiVO4 electrodes: (a)
no AgNO3 treatment and (b) after AgNO3 treatment. The applied bias
was 1.2 V to the Pt counter electrode.
Figure 12. Potential-current curve of the BiVO4 electrodes. The
applied bias was 1.2 V to the Pt counter electrode. Unfiltered whole
light from a Xe lamp was used for irradiation. (Upper panel) In Na2-
SO4 aqueous solution: (a) no AgNO3 treatment and (b) after AgNO3
treatment. (Lower panel) In Na2SO4 aqueous solution with methanol
addition (10 vol %): (c) no AgNO3 treatment and (d) after AgNO3
treatment.
The photocurrent was restored to 70% of the initial efficiency
by keeping it in the dark for 1 day or by cyclic voltammetry. It
is speculated that slight changes, for example, in the valence
state in BiVO4 or in the surface structure, may influence the
photocurrent stability.
In the study of photocatalysts, surface modifications and
loading of cocatalyst have often been investigated for the
promotion of the charge separation and the formation of active
J. Phys. Chem. B, Vol. 110, No. 23, 2006 11357
Figure 13. Dependence of IPCE on wavelength in Na2SO4 (aq sol):
(a) no AgNO3 treatment and (b) after AgNO3 treatment. The applied
potential was +1.0 V versus Ag/AgCl.
TABLE 1: Dependence of Treatment Time of AgNO3
Aqueous Solution on Photocurrent and Stabilitya
initial
treatment photocurrent photocurrent after
treatment time (mA/cm2) 30 min (mA/cm2)
no treatment - 1.2 0.8
AgNO3 treatment 1 min 1.9 0.9
in the dark 1h 2.2 2.3
3h 2.1 2.2
12 h 2.0 2.1
AgNO3 treatment 1 min 2.1 1.3
with light
a
Two-electrode system; applied bias, 1.2 V; AgNO3 concentration,
0.01 mol/L.
reaction site. On the other hand, reports on surface modifications
of photoelectrodes are limited.14,15,17,18,25 Ohno et al. reported
an improvement in the IPCE of a TiO2 single-crystal photo-
electrode by adsorption of Fe3+ ion.25 We investigated surface
modifications of the BiVO4 electrode by aqueous solutions (0.01
mol/L, 12 h) containing various metal nitrates and chlorides,
such as AgNO3, Pd(NO3)2, Cr(NO3)3, Cu(NO3)2, Ni(NO3)2, Fe-
(NO3)3, RuCl3, RhCl3, H2PtCl6, and HAuCl4. Among them,
treatment with AgNO3 aqueous solution improved the photo-
current significantly. Figure 12 (upper panel) shows the
potential-current curve of BiVO4 without (a) and after (b) the
AgNO3 treatment. The photocurrent increased sharply with a
positive potential sweep in the case of the Ag-treated electrode.
The IPCE of the BiVO4 electrode in the visible-light region
nearly doubled with AgNO3 treatment (see Figure 13). The
maximum IPCE at 420 nm was 44%. This value was the second
highest to that of the nanocrystalline WO3 electrode among
oxide semiconductor electrodes under the visible-light region
and was highest among mixed-oxide semiconductor electrodes,
suggesting the great potential for porous thin-film electrodes
with use of various mixed-metal oxide semiconductors. The
photocurrent and stability were not improved by treatment with
HNO3 and many other nitrates, except AgNO3, suggesting that
H+ and NO3- ions did not contribute to the promotion of
photocurrent but that Ag+ ions did contribute to the promotion
effect. The promotion effect was observed even at low
concentrations of AgNO3 aqueous solution (1 mmol/L).
AgNO3 treatment improved not only the IPCE but also the
stability of the photocurrent (see Figure 11b), whereas the
photocurrent without AgNO3 treatment decreased gradually with
irradiation time (Figure 11a). The photocurrent with AgNO3
treatment was maintained at around 4 mA/cm2. The turnover
number of total electrons per BiVO4 unit was found to be more
than 200 for 1 h. The Ag in the BiVO4 electrode was not
detected by XRF measurement, suggesting that the total amount
of Ag was less than the measurement’s limit of detection (<1
wt % of BiVO4). If the Ag amount was 1 wt %, then the turnover
11358 J. Phys. Chem. B, Vol. 110, No. 23, 2006 Sayama et al.

TABLE 2: Measurement of Surface Condition by XPS

surface Ag amount binding energy (eV)a half peak width (eV)
(surface atom %) V/Bi ratio Ag3d5/2 Bi4f7/2 V2p3/2 Bi4f7/2 V2p3/2
no treatment 0 0.85 159.35 516.30 1.05 0.90
AgNO3 treatmentb 3.2 0.64 367.50 159.00 516.20 1.05 1.10
no treatment f 1 h photoreactionc 0 0.22 158.85 515.80 1.20 0.90
AgNO3 treatmentb f 1 h photoreactionc 0.4 0.09 367.65 158.95 515.95 1.20 1.00
AgNO3 treatmentb f 1 h photoreactionc f Ar+ etchingd 1.8 1.03 368.10 159.50 515.85 1.30 2.55
+157.50
a
Binding energy was corrected by C1s ()284.8 eV). b AgNO3 treatment conditions: 0.01 mol/L, 12 h in the dark. c Photoreaction conditions:
two-electrode system, 1.2 V applied bias for 1 h. d Argon ion etching at 3 kV for 2 min, 5 × 5 mm raster area.

number of total electrons per Ag unit was calculated at more

than 6500. Table 1 shows the dependence of treatment time
with an aqueous solution of AgNO3 on photocurrent and
stability. The photocurrent increased with only a 1-min treatment
with AgNO3 solution; however, the photocurrent decreased to
half its original value after a 30-min photoreaction. On the other
hand, a stable photocurrent was also observed with treatments
that were longer than 1 h. It is considered that the simply
adsorbed Ag+ ion on the BiVO4 surface desorbed easily and
quickly during the photoreaction and that some changesssuch
as strong interaction between Ag+ and the BiVO4 surfaces
might occur during a treatment time that was longer than 1 h.
The Ag0 metal could be photodeposited on the surface of the
BiVO4 electrode by short time (1 min) irradiation in AgNO3
aq sol without bias. The photoelectrochemical behavior of the
electrode covered with electrodeposited Ag0 was similar to that
with 1-min AgNO3 treatment in the dark, as shown in Table 1.
It was found that the metallic color of Ag0 was removed after
the photoelectrochemical reaction in Na2SO4 aq sol under anodic
bias.
Table 2 summarizes the results of XPS measurements on the
surface of the various BiVO4 electrodes. The surface atomic
ratio of V to Bi on the initial BiVO4 electrode without treatment
(V/Bi ) 0.85) was smaller than the stoichiometric ratio, and it
decreased more after AgNO3 treatment for 12 h in the dark.
After 1 h of photoreaction, the surface atomic ratio of V/Bi
decreased significantly at both electrodes, both with and without
AgNO3 treatment. The bulk composition of the electrode was
almost ideal from the data of the V/Bi ratio after a short period
of Ar+ etching. The XRD pattern, the bulk ratios of V/Bi
measured by XRF, and the UV-vis spectrum of the BiVO4
electrodes with/without AgNO3 treatment were not changed after
1 h of photoreaction. It is also confirmed that the V2O5 electrode
dissolved, whereas the Bi2O3 electrode was stable in Na2SO4
during the photoreaction, and that the photocurrents of these
electrodes were small compared to the photocurrent of the
BiVO4 electrode. It is concluded that only the surface V atoms
dissolved from the BiVO4 surface during the photoreaction and
that the BiVO4 was covered with a thin Bi-rich layer. This thin
Bi-rich layer may help prevent further erosion of BiVO4.
The amount of surface Ag decreased after the photoreaction
because of desorption from the surface with dissolution of
surface V. However, the intensity of XPS of surface Ag
increased after the short period of Ar+ etching. It is suggested
that a silver atom penetrated the BiVO4, as in an ion-exchange
reaction. The valence state of Ag in/on the BiVO4 after the
photoreaction was not clear from the XPS measurement because
the chemical shift of Ag-3d was small and the intensity of the
Auger spectra of Ag-3d4d4d was too weak to determine the
Ag valence. The redox potential of Ag+/Ag0 (+0.80 V vs NHE,
pH 0) is more negative than that of O2/H2O (+1.23 V). The
photodeposited Ag0 with metallic color on the BiVO4 electrode
was removed during the photoreaction under anodic bias;
Figure 14. Speculated reaction mechanism of O2 evolution on the
BiVO4 electrode. The real BiVO4 layer was more porous and consisted
of many particles, but it was simplified here. (i) Forward reaction with
water and holes to evolve O2 gas, (ii) backward reaction with O2 and
electrons.
therefore it is reasonable to assume that Ag+ ion in/on the BiVO4
probably remained in an oxidized state during photogeneration
of oxygen by the hole in the valence band under anodic bias
during the photoreaction for O2 evolution. BiVO4 has ion-
exchange ability because it can be synthesized by ion-exchange
from KV3O8 and Bi3+ ion.23 According to the ion radii, the Ag+
(1.15 Å) may be ion-exchanged at the Bi3+ (1.03 Å) site rather
than at the V5+ site (0.54 Å) in the BiVO4. The difference of
the charge was probably compensated by the valence change
of Bi3+ to Bi5+ partially around the Ag+.
In both casesswith and without the AgNO3 treatmentsthe
binding energy of Bi-4f7/2 and V-2p3/2 decreased and the half
peak width of Bi-4f7/2 was broadened after the photoreaction,
suggesting some changes of surface valence state during the
photoreaction for both cases. Thus the effect of the AgNO3
treatment could not be explained directly by this change of
surface valence state and the change of surface V/Bi ratio
measured by XPS.
In the case of the BiVO4 photocatalyst, high O2 evolution
activity was observed with Ag+ ion as an electron acceptor,23,24
and the degradation activity of alkylphenols was improved by
the loading of oxidized Ag particles (AgOx) as cocatalysts.35
We investigated AgNO3 treatment for other porous semiconduc-
tor electrodes, such as TiO2 and WO3; however, no positive
effects on the photocurrent and stability were observed. These
results suggested a unique interaction between BiVO4 and Ag.
It is speculated that the Ag+ ion-exchange layer formed on the
semiconductor surface played an important role for the BiVO4
electrode (Figure 14).To investigate the mechanism of AgNO3
treatment, the cathode currents by the reduction of O2 gas (the
backward reaction of O2 formation) on the BiVO4 electrodes
with and without treatment were measured. The cathode current
Photoelectrochemical Decomposition of Water
Figure 15. Cathodic current of the BiVO4 electrode in the dark: (a)
N2 purge and no AgNO3 treatment; (b) N2 purge and AgNO3 treatment;
(c) O2 purge and no AgNO3 treatment; and (d) O2 purge and AgNO3
treatment.
of O2 reduction on BiVO4 was not decreased by Ag treatment,
as shown in Figure 15. Therefore, it is considered the inhibition
of the backward reaction, which is O2 reduction with an electron
in the BiVO4 conduction band (process i in Figure 14), was
not the main consequence of the Ag treatment.
In a report on a Ag-loaded BiVO4 photocatalyst, partially
oxidized silver (AgOx) on the BiVO4 was considered to
contribute to the acceleration of charge separation and increase
of adsorption of alkylphenols.37 With reference to our experi-
ments, we also speculated that charge separation was accelerated
at the interface of the internal BiVO4 and the surface Ag+/BiVO4
layer, if the band structure of the Ag+/BiVO4 was different from
that of BiVO4. However, it should be noted that the difference
of photocurrent of the BiVO4, with and without Ag treatment,
in the presence of methanol was not significant compared to
the difference in the absence of methanol (see Figure 12c,d).
Therefore, the Ag treatment contributed only to O2 formation,
and not to charge separation or methanol oxidation. The
photocurrent of the Ag-treated BiVO4 electrode increased
sharply with applied potential compared to that without treat-
ment (see Figure 12a,b). The photocurrent of the TiO2 electrode
was reported to increase sharply with Fe3+ treatment, and this
behavior was explained by catalysis of an Fe3+ ion to promote
O2 formation via decomposition of intermediates.25 The role of
Ag and Au metal loading on the Fe2O3 photoelectrodes was
also explained by the catalytic effect in the case of low light
intensity, though the promotion effect was very limitted.17 From
all of the results mentioned above, it is surmised that the Ag+
ions in/on the BiVO4 catalyzed the intrinsic O2 formation with
holes (process ii in Figure 14).
The solar energy conversion efficiency (ηsun) is very important
practically, and it was estimated by the following eq 3.
ηsun (%) ) Jsc × (1.23 - VNHE)/nSun (3)
The maximum ηsun was obtained at ca. 0.3 V (vs Ag/AgCl),
that is, VNHE ) ca. +0.85 V (vs NHE, pH 0). The Jsc at 0.85
VNHE was calculated from the I-V curve, and it was estimated
at about ca. 1.3 mA/cm2 under 2.6 Sun condition. Therefore,
the maximum ηsun was roughly calculated at ca. 0.2%.
4. Summary
We investigated the photoelectrochemical properties of porous
BiVO4 thin-film electrodes on conducting glass for water
decomposition into H2 and O2 under visible-light irradiation.
J. Phys. Chem. B, Vol. 110, No. 23, 2006 11359
The BiVO4 particles in the porous electrode were 90-150
nm in diameter. The crystalline phase of the BiVO4 film was
monoclinic sheelite-type. The band gap was estimated at ca.
2.4 eV. Evolution of H2 and O2 at the stoichiometric ratio (H2/
O2 ) 2) was observed under visible-light irradiation. The
photocurrent increased with addition of methanol.
The band structure of BiVO4 was also investigated in detail.
All results indicated that the top of Evb of BiVO4 was shifted
negatively compared to those of the conventional semiconduc-
tors without Bi. The hybridization between the O-2p and Bi-6s
orbitals might have contributed to the negative shift of the
BiVO4 valence band.
Treatment with a AgNO3 aqueous solution significantly
improved the photocurrent of the BiVO4 electrode. The maxi-
mum IPCE at 420 nm was 44%. This value was just below that
of the nanocrystalline WO3 electrode when compared with other
oxide semiconductor electrodes under the visible-light irradiation
and the highest among mixed-oxide semiconductor electrodes,
suggesting great future potential of porous thin-film electrodes
with various mixed-metal oxide semiconductors. The AgNO3
treatment improved not only the IPCE but also the stability of
the photocurrent.
Acknowledgment. This study was partially supported by
the Industrial Technology Research Grant Program (04A20507c)
from NEDO of Japan.
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