Journal of Catalysis 328 (2015) 308–315

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Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat

Z-scheme water splitting using particulate semiconductors immobilized

onto metal layers for efficient electron relay
Qian Wang a, Yanbo Li a,1, Takashi Hisatomi a,b, Mamiko Nakabayashi c, Naoya Shibata c, Jun Kubota a,
Kazunari Domen a,b,⇑
a
Department of Chemical System Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
b
Japan Technological Research Association of Artificial Photosynthetic Chemical Process (ARPChem), 5-1-5 Kashiwanoha, Kashiwa-shi, 277-8589 Chiba, Japan
c
Institute of Engineering Innovation, The University of Tokyo, 2-11-16, Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan

a r t i c l e i n f o a b s t r a c t

Article history: A major challenge in developing high-performing Z-scheme water splitting systems lies in achieving effi-
Received 11 September 2014 cient transfer of electrons between the H2 and O2 evolution photocatalysts. Here, we report a Z-scheme
Revised 16 November 2014 system consisting of H2 evolution photocatalyst (HEP)/metal layer (M)/O2 evolution photocatalyst (OEP),
Accepted 11 December 2014
taking SrTiO3:La,Rh/Au/BiVO4 as a prototype. SrTiO3:La,Rh/Au/BiVO4 systems exhibit photocatalytic
activities for overall water splitting that are 6 and 20 times higher than powder suspensions and SrTiO3:-
La,Rh/BiVO4 systems without metal layers, respectively. The SrTiO3:La,Rh/Au/BiVO4 system achieves an
Keywords:
apparent quantum yield of 5.9% under monochromatic light irradiation at 418 nm and a solar-to-hydro-
Z-scheme water splitting
Photocatalyst
gen conversion efficiency of 0.2%. The high performance of this system is due to the presence of the Au
Hydrogen production layer that transfers photogenerated electrons from BiVO4 to SrTiO3:La,Rh in an effective manner. The
SrTiO3:La,Rh/Au/BiVO4 present study offers a new design concept for HEP/M/OEP solid-state devices to overcome the limitations
Solid-state device of earlier Z-scheme systems and thus enable efficient photocatalytic water splitting.
Particle transfer Ó 2014 Elsevier Inc. All rights reserved.
Electron transfer

1. Introduction band gap should straddle the H2 and O2 evolution potentials.

Hydrogen has attracted growing attention as a next-generation
clean and sustainable energy carrier. Topsøe et al., for example,
invented a process for the production of hydrogen-rich gas from a
feedstock-containing dimethyl ether and/or methanol by steam
reforming in 1998 [1]. Recently, solar-driven water splitting has
been studied extensively as another promising approach for pro-
ducing hydrogen, because the solar energy irradiating the Earth’s
surface is larger than the global human energy consumption by
approximately four orders of magnitude and hydrogen produced
from water using the solar energy is in principle carbon neutral.
Two approaches have been reported for photocatalytic water
splitting using suspensions of particulate semiconductors [2–8].
One approach is using a single photocatalyst that meets the thermo-
dynamic requirement for overall water splitting, namely, that the
⇑ Corresponding author at: Department of Chemical System Engineering, School
of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656,
Japan. Fax: +81 3 5841 8838.
E-mail address: domen@chemsys.t.u-tokyo.ac.jp (K. Domen).
1
Current address: Joint Center for Artificial Photosynthesis, Lawrence Berkeley
National Laboratory, 1 Cyclotron Road, Berkeley, CA 94720, United States.
GaN–ZnO and ZnGeN2–ZnO solid solutions [9,10] can split water
into H2 and O2 under visible light illumination. The apparent quan-
tum yield (AQY) has been improved to 5.1% at 410 nm by optimizing
the cocatalysts and post-treatments [11]. However, the number of
photocatalysts that are capable of overall water splitting under
visible light irradiation is limited because of the stringent thermo-
dynamic requirement. The other approach is Z-scheme water split-
ting based on two-step photoexcitation of a H2 evolution
photocatalyst (HEP) and an O2 evolution photocatalyst (OEP) [4–
8]. The HEP and OEP harvest sunlight independently, each generat-
ing charges, and drive water reduction and oxidation reactions,
respectively. The remaining charges recombine through reversible
redox reactions of redox couples or interparticle electron transfer
[11]. Therefore, this reaction scheme necessitates eight electrons
to split two water molecules into two hydrogen and one oxygen
molecules, twice larger than the water splitting reaction on a single
photocatalyst. Some visible-light-driven metal oxide, metal (oxy)-
nitride, and metal (oxy)sulfide semiconductors have been found
to be active for H2 or O2 evolution with the proper sacrificial electron
donors or acceptors, but not for overall water splitting. Such photo-
catalysts can be employed as a HEP or OEP in Z-scheme water split-
ting. Thus, the choices for material combinations can be extended.

http://dx.doi.org/10.1016/j.jcat.2014.12.006
0021-9517/Ó 2014 Elsevier Inc. All rights reserved.
 Q. Wang et al. / Journal of Catalysis 328 (2015) 308–315
Redox couples, such as Fe3+/Fe2+ [12–16], IO 3 /I

[17–24],
3+/2+ 3+/2+
[Co(bpy)3] and [Co(phen)3] [25], mediate the electron relay
between HEP and OEP in Z-scheme water splitting. However, the
presence of redox mediators also causes undesirable side reactions
and shading of the photocatalysts from incident light. Therefore,
the development of redox-mediator-free Z-scheme systems is
desirable. Earlier studies by Kudo et al. and our group revealed that
Ru-loaded SrTiO3 doped with Rh (Ru/SrTiO3:Rh) [11,26–28] and
Ru-loaded SrTiO3 doped with Rh and La (Ru/SrTiO3:La,Rh) [29] func-
tioned as HEPs in Z-scheme water splitting, even without a shuttle
redox mediator, when combined with an OEP such as BiVO4
[11,27], PRGO/BiVO4 [28], and Ta3N5 [26,29]. The system comprising
Ru/SrTiO3:Rh and BiVO4 was the most active in redox-mediator-free
Z-scheme water splitting, exhibiting an AQY of 1.7% at 420 nm and a
solar-to-hydrogen energy conversion efficiency (STH) of 0.12% [11].
We also demonstrated that SrTiO3:La,Rh exhibited higher water
splitting rates than SrTiO3:Rh when combined with Ir/CoOx/Ta3N5
in redox-free Z-scheme water splitting [29]. In these systems, the
pH of the reactant solution must be selected such that the two kinds
of photocatalysts have surface potentials with opposite signs
[11,26,28]. Interparticle electron transfer can be established
between the respective photocatalyst particles in the reactant sus-
pension by adjusting the pH value, which generates an electrostatic
attractive force. However, it was suggested that the electron transfer
between the two kinds of photocatalysts is the rate-determining
step in the Ru/SrTiO3:Rh–BiVO4 Z-scheme system [11]. Therefore,
photoreduced graphene oxide (PRGO) was used as a solid-state elec-
tron mediator in this system, contributing to the enhanced activity
[28]. Nevertheless, the pH value was still a crucial factor in achieving
efficient electron transfer and overall water splitting. Through elec-
trostatic interactions, the PRGO/BiVO4 and Ru/SrTiO3:Rh particles
attracted each other at pH 3.5; the same particles repelled each other
at pH 7. Recently, Kudo’s group developed composites of SrTiO3:Rh
and BiVO4 by synthesizing BiVO4 in the presence of SrTiO3:Rh via
liquid–solid reactions [27]. This procedure allowed intimate contact
between the two kinds of the photocatalysts. However, the activity
was still limited, presumably because of chemical reactions of the
two photocatalysts during synthesis and the low degree of control
over the contact between the photocatalyst particles. The challenge
of developing a redox-mediator-free Z-scheme water splitting sys-
tem lies in ensuring efficient transfer of electrons between HEP and
OEP without deteriorating their intrinsic photocatalytic properties.
We recently demonstrated that photocatalyst particles immobi-
lized onto metal layers by the particle transfer method benefited
from the intimate mechanical and electrical contact between the
semiconductor particles and the metal layers, which led to a lower
resistance and enhanced photocurrent in the photoelectrochemical
water splitting reaction [30]. On the basis of these results, it is
expected that bridging HEP and OEP with metallic conducting lay-
ers by the particle transfer method will provide an effective means
of improving the efficiency of electron transfer and thus increase
water splitting activity.
We report here an all-solid-state device for redox-mediator-free Z-
scheme water splitting, that is, a plate consisting of HEP and OEP par-
ticles and a conductive layer for efficient electron transfer. Taking the
combination of SrTiO3:La,Rh and BiVO4 as a prototype, this work
discusses the effectiveness and advantages of the all-solid-state
structure design over conventional Z-scheme systems based on inter-
particle electron transfer for the overall water splitting reaction.
2. Experimental
2.1. Synthesis of SrTiO3:La,Rh and BiVO4 particles
SrTiO3:La,Rh (La/(La + Sr) = Rh/(Rh + Ti) = 4 mol%) was prepared
by a two-step solid-state reaction (SSR) [29]. In the initial step,
309
SrTiO3 was synthesized by a conventional SSR. Commercially avail-
able SrCO3 (Kanto Chemicals, 99.9%) and rutile-type TiO2 (rutile,
Kanto Chemicals, 99.0%) powders were mixed in a mortar at a ratio
of Sr:Ti = 1.03:1. The mixture was placed into an alumina crucible,
heated up to 1373 K at 10 K min1 and kept at the target temper-
ature for 10 h. The sample was allowed to cool naturally to room
temperature. Subsequently, the resulting SrTiO3 was mixed in eth-
anol with La2O3 (Kanto Chemicals, 99.99%), which had been freshly
calcined in air at 1273 K for 12 h, and Rh2O3 (Kanto Chemicals,
99.9%). The ethanol was added to mix the oxide particles well
and to lower the friction force between the particulate oxides
and a mortar. Finally, the mixture was heated at 1373 K for 6 h.
The heating-up and cooling procedures were carried out in the
same way with the first step.
BiVO4 was prepared via a solid–liquid reaction [28]. The starting
materials Bi(NO3)35H2O (Wako Distilled Chemical Industries,
99.9%) and V2O5 (Wako Distilled Chemical Industries, 99.0%) were
stirred in 0.75 mol L1 of an aqueous nitric acid solution (50 mL)
for 48 h at room temperature. The BiVO4 obtained was collected
by filtration and washed with distilled water before drying at
343 K.
2.2. Preparation of SrTiO3:La,Rh/Au/BiVO4 plates
SrTiO3:La,Rh/Au/BiVO4 (HEP/M/OEP) plates were prepared by a
particle transfer method [30]. The fabrication procedure is illus-
trated in Fig. 1c. First, a mixture of 10 mg of SrTiO3:La,Rh and
10 mg of BiVO4 powders were suspended in isopropanol and
deposited on a glass substrate (3  3 cm2). After drying at room
temperature, a thin contact layer (ca. 200 nm) was deposited by
vacuum evaporation (VFR-200 M/ERH, ULVAC KIKO Inc.). Au, Ag,
Ni, Al, or Rh was used as a contact layer to form contacts with
semiconductor particles. To obtain sufficient conductivity and
mechanical strength, an additional gold conductor layer (ca.
800 nm) was formed on the top of the contact layer by the vacuum
evaporation at an evaporation rate of approximately 10 nm s1.
The metal film holding the particulate photocatalysts was bonded
to a second glass plate (3  3 cm2) with an adhesive carbon tape
(Nisshin EM Co. Ltd.) and then lifted off the primary glass plate.
The photocatalyst plate obtained was ultrasonicated twice, for
2 min each time, in distilled water to remove excess particles piling
on the particle layer. When the weight fractions of SrTiO3:La,Rh
and BiVO4 were varied, the total amount of photocatalysts was
maintained at 20 mg. For comparison, photocatalyst plates without
the thin gold layer (HEP/OEP) were prepared as well (Fig. 1b). The
photocatalytic activity of a suspension of SrTiO3:La,Rh and BiVO4
particles was also tested (Fig. 1a).
2.3. Characterization
The samples were characterized by UV–visible diffuse reflec-
tance spectroscopy (DRS; V-670, JASCO), scanning electron micros-
copy (SEM; S-4700, Hitachi; JSM-7001FA, JEOL), and scanning
electron microscopy with energy dispersive X-ray fluorescence
spectroscopy (SEM-EDX; JSM-7001FA, JEOL).
2.4. Photocatalytic reactions
Ruthenium was chosen as a cocatalyst because it did not cause
the backward reaction to form water from evolved H2 and O2 sig-
nificantly in the Z-scheme water splitting reaction [16]. Ru species
were loaded on the photocatalyst plates by photodeposition from
RuCl33H2O (0.35 lmol) dissolved in distilled water (40 mL).
H2SO4 (aq.) was used to adjust the pH of the solution to 3.5 if nec-
essary. The photodeposition for a powder suspension system con-
sisting of SrTiO3:La/Rh and BiVO4 (10 mg each) was carried out in
310 Q. Wang et al. / Journal of Catalysis 328 (2015) 308–315
Fig. 1. Preparation procedure for (a) powder suspension, (b) HEP/OEP plate, and (c) HEP/M/OEP plate systems. SrTiO3:La,Rh, BiVO4, and Au were used as HEP, OEP, and a
conductor layer, respectively.
an aqueous solution containing RuCl33H2O (0.35 lmol) with pH
adjusting by H2SO4 (aq.) (pH  3.5). The photodeposition reactions
were carried out in a Pyrex top-irradiation reaction vessel con-
nected to a glass closed gas circulation system under illumination
from a Xe lamp with a cut-off filter (300 W, k > 420 nm,
9.1  1021 photon h1). The reaction system was evacuated several
times to ensure complete removal of air. Subsequently, argon
(40 Torr) was introduced into the system as a circulation gas. The
reactions were performed until steady gas evolution rates were
obtained, typically for 5–10 h as shown in Fig. A.1 in the Appendi-
ces. Nanoparticulate Ru species could be deposited on both
SrTiO3:La,Rh and BiVO4 photocatalysts.
Z-scheme water splitting reactions were carried out in the same
closed gas circulation system with top irradiation. In plate systems,
samples (3  3 cm2) were placed at the bottom of the reaction cell
containing the reactant solution (40 mL). For powder suspension
systems, the powder mixture was dispersed in the reactant solu-
tion (40 mL). The pH of the solution was adjusted with H2SO4
(aq.) or NaOH (aq.) when necessary. In some experiments, metha-
nol (10 vol%) and silver nitrate (20 mmol L1) were added as sacri-
ficial electron donor and acceptor, respectively. Argon gas (40 Torr)
was introduced into the reaction system as a carrier gas inside the
closed circulation system after removing air. The reaction cell was
illuminated by a 300 W Xe lamp (Lamp house, R300-3J) fitted with
a cut-off filter (k > 420 nm). The amounts of gases produced were
measured by gas chromatography (Shimadzu GC-8A with a TCD
detector and MS-5A column, using argon as a carrier gas).
2.5. Quantum efficiency measurement
The AQY of the Z-scheme water splitting system with a two-step
photoexcitation process was measured using the same experimen-
tal set-up, except for the use of a series of band-pass filters (central
wavelength 417.2 nm, full width at half maximum 9.4 nm; central
wavelength 435.1 nm, full width at half maximum 17.2 nm; central
wavelength 471.3 nm, full width at half maximum 13.8 nm; central
wavelength 499.6 nm, full width at half maximum 13.9 nm; and
central wavelength 518.7 nm, full width at half maximum
15.6 nm). The number of incident photons from a Xe lamp with var-
ious types of band-pass filters was listed in Table A.1. The AQY val-
ues were calculated using the following equation:
AQY ð%Þ ¼ ½4  nðH2 Þ=nðphotonsÞ  100; ð1Þ
where n(H2) and n(photons) denote the number of evolved H2 mol-
ecules and the number of incident photons, respectively. As stated
in the introduction, it was supposed that eight photons were used
to generate two hydrogen molecules. The total number of incident
photons was measured using a grating spectroradiometer (EKO
Instruments Co., Ltd., LS-100) over the wavelength range of 350–
1100 nm.
2.6. Solar-to-hydrogen conversion efficiency measurement
Photocatalytic water splitting was performed in the same
experimental apparatus, except under illumination from a solar
simulator (Sanei Electric Co., Ltd., XES-40S2-CE). The STH was cal-
culated as follows:
STH ð%Þ ¼ ½RðH2 Þ  DG =½P  S  100; ð2Þ
where R(H2), DG°, P, and S denote the rate of hydrogen evolution
(mol s1) in the redox-free Z-scheme water splitting system, the
change in Gibbs free energy that accompanies water splitting
(237  103 J mol1), the energy intensity of the solar light irradia-
tion, and the irradiation area (9 cm2), respectively. The energy
intensities of the simulated sunlight and the standard AM1.5D
and AM1.5G were 70.7, 70.3, and 79.1 mW cm2 over the wave-
length range of 350–1100 nm, and 19.1, 19.2, and 23.4 mW cm2
over 350–540 nm, respectively (Fig. A.2). Considering the better
matching of the power spectra, the intensity of the simulated sun-
light was assumed to be equal to the standard AM1.5D
(90.1 mW cm2).
3. Results and discussion
3.1. Morphology of the SrTiO3:La,Rh/Au/BiVO4 photocatalyst plate
Comparing the top-view SEM images of a SrTiO3:La,Rh/Au/
BiVO4 plate (Fig. 2A) with the SEM images of SrTiO3:La,Rh and
BiVO4 particles (Fig. A.3 in the Appendices) reveals that both
SrTiO3:La,Rh and BiVO4 particles were dispersed on the substrates.
SEM-EDX mapping images allow us to distinguish SrTiO3:La,Rh and
BiVO4 particles as well as the underlying Au layer. The particle
 Q. Wang et al. / Journal of Catalysis 328 (2015) 308–315
sizes of SrTiO3:La,Rh mostly ranged from 0.2 to 0.7 lm on the pho-
tocatalyst plate. BiVO4 particles formed larger particles, approxi-
mately 3 lm in size, in addition to aggregates of submicron
particles. These findings agree well with the morphologies of the
individual photocatalysts (Fig. A.3). This means that morphological
properties of the photocatalyst were unaffected by the preparation
of the photocatalyst plate. The photocatalyst particles covered
approximately 80% of the underlying Au layer (as revealed in
Fig. 2. (A) Top-view and (B) cross-sectional images of SrTiO3:La,Rh/Au/BiVO4
photocatalyst plates. (a and b) SEM images. (c–f) SEM-EDX mapping images for (c)
Bi, (d) Sr, (e) Au, and (f) superimposition of (c–e).
311
Fig. 2A-f). Fig. 2B shows cross-sectional images of a SrTiO3:La,Rh/
Au/BiVO4 plate transferred and embedded within an epoxy resin
for cross-sectional polishing. It should be noted that the thickness
of the photocatalyst particle layer in this specimen was approxi-
mately 10 lm and thicker than those in actual samples (typically,
a few microns thick), transferred using an adhesive carbon tape
because of the penetration of the soft epoxy. At the junction of
the photocatalyst particles and the Au layers, both SrTiO3:La,Rh
and BiVO4 particles were directly and firmly anchored onto the
Au layer. The above SEM-EDX analysis revealed that the photocat-
alyst plate prepared by the particle transfer method had a desirable
architecture: both HEP and OEP particles contacted the metal layer.
Thus, electrons could be transferred through the metal between
HEP and OEP particles.
Ideally, the particle layers should be as thin as possible to min-
imize the number of grain boundaries, which increase the resis-
tance to charge transfer within the particle layer. On the other
hand, the particle layers should be dense and thick enough to cover
the underlying Au layer and absorb sufficient incident light. In the
present experiments, the SrTiO3:La,Rh and BiVO4 particles stacked
on the metal layer without precise control. A detailed study on the
influence of the morphology of the particulate photocatalyst layer
on photocatalytic activity necessitates synthetic and processing
techniques that allow precise control over the particle size, spatial
distribution of particulate materials, and thickness of particulate
photocatalyst layers. These issues need to be addressed in future
work. Nevertheless, the present SrTiO3:La,Rh/Au/BiVO4 photocata-
lyst plate systems exhibited promising activity for overall water
splitting, as demonstrated in the following section.
3.2. Photocatalytic activity of Z-scheme systems of SrTiO3:La,Rh and
BiVO4
The water splitting activity of Z-scheme systems of SrTiO3:La,Rh
and BiVO4 with various modes under visible light illumination is
shown in Table 1, where the gas evolution rates were divided by
the geometric projection areas of the samples (9 cm2 for the pho-
tocatalyst plate and 13 cm2 for the powder suspension systems).
In the conventional powder suspension system of SrTiO3:Rh and
BiVO4, aggregation of the photocatalyst particles occurred upon
acidification of the suspension, and the highest activity was
obtained at pH 3.5 in the pH range from 3 to 9 [11]. Thus, the pH
value of the reaction solution for water splitting was adjusted to
3.5. The photocatalytic activity of the powder suspension system
was enhanced as the amounts of SrTiO3:La,Rh and BiVO4 were
increased, reaching a maximum at 10 mg of each powder (entry
1), after which the gas evolution rates saturated (Fig. A.4 in the
Appendices). This suggested that 10 mg each of SrTiO3:La,Rh and
BiVO4 was enough to harvest the photons from the Xe lamp. The
SrTiO3:La,Rh/BiVO4 (HEP/OEP) photocatalyst plate without a Au
layer (entry 2) exhibited a lower activity than the powder suspen-
sion system, presumably because of the restricted physical contact
between SrTiO3:La,Rh and BiVO4 due to the carbon tape. Another
possible reason for the worse performance of the HEP/OEP system
is that particles on the top surface prevented mass transfer of
water and evolved gas at the bottom part of the photocatalyst par-
ticle layer, as was suggested for photocatalyst panels of GaN:ZnO
[31]. Importantly, when SrTiO3:La,Rh and BiVO4 were fixed
together on Au layers, simultaneous evolution of H2 and O2
occurred at a H2/O2 ratio of 2:1. The water splitting rates of the
SrTiO3:La,Rh/Au/BiVO4 (HEP/M/OEP) system were 6 and 20 times
higher than those of the powder suspension system and the
SrTiO3:La,Rh/BiVO4 (HEP/OEP) system, respectively. The water
splitting activity was negligible when the plates of SrTiO3:La,Rh/
Au or BiVO4/Au were measured (entries 4 and 5, respectively).
Besides, the SrTiO3:La,Rh photocatalyst did not evolve a detectable
312 Q. Wang et al. / Journal of Catalysis 328 (2015) 308–315
Table 1
Photocatalytic activity of redox-mediator-free Z-scheme water splitting under visible light irradiation using SrTiO3:La,Rh and BiVO4 with various modes.
Entry Type Photocatalysts
H2
1 Powder suspensiona SrTiO3:La/Rh
2 HEP/OEP plateb SrTiO3:La/Rh
3 HEP/Au/OEP plateb SrTiO3:La/Rh
4 HEP/Aub SrTiO3:La/Rh
5 OEP/Aub – BiVO4
Reaction conditions: reactant solution, 40 mL water with pH adjustment using H2SO4 (aq.) (pH  3.5); light source, 300 W xenon lamp (k > 420 nm). ‘‘n.d.’’ stands for ‘‘not
detected’’. The gas evolution rates were divided by the irradiation areas. The detection limits for H2 and O2 were 0.007 and 0.02 lmol h1 cm2, respectively. Photodeposition
was carried out in an aqueous solution (40 mL) containing RuCl33H2O (0.35 lmol) with pH adjustment using H2SO4 (aq.) (pH  3.5) under 300 W xenon lamp illumination
(k > 420 nm).
a
Catalysts: 10 mg each; irradiation area: 13 cm2.
b
Irradiation area: 9 cm2.
amount of oxygen from an aqueous AgNO3 solution (10 mM,
40 mL) under the irradiation of a Xe lamp (k > 420 nm) or solar
simulator (not shown). These results suggest that H2 and O2 were
evolved by two-step photoexcitation over the SrTiO3:La,Rh and
BiVO4 particles and charge transfer through the Au layer. A gold
layer of 350 nm in thickness was thick enough to transfer the
charges, as presented in Fig. A.5 The gas evolution rates decreased
slightly with the thickness of gold layer increased. A thicker gold
layer needed a longer time for deposition and the temperature in
the vacuum evaporation chamber became higher. It is thus sus-
pected that the photocatalysts might be deteriorated by heating
under vacuum. Note that some photocatalyst particles, namely
those that were not anchored to the Au layer, were removed from
the photocatalyst plates during ultrasonication. The photocatalyst
plate showed a higher water splitting rate despite a lower amount
of photocatalyst.
The significant enhancement in the activity of the SrTiO3:La,Rh/
Au/BiVO4 plate is attributable to the presence of the Au layer,
rather than an optical effect due to surface plasmon resonance.
The diffuse reflectance spectrum of the Au/glass prepared by vac-
uum evaporation in the identical condition did not exhibit any
optical absorption peak between 500 and 650 nm (Fig. A.6 in the
Appendices) typical of the surface plasmon resonance of gold
nanoparticles [32–35]. This rules out the possibility that the gold
layer beneath the photocatalyst particle layer might have caused
excitation of surface plasmon resonance below 520 nm, where
the SrTiO3:La,Rh/Au/BiVO4 system showed water splitting activity.
It is thus reasonable to conclude that the Au layer behaved as an
electron conductor. The metal layer received excited electrons
from BiVO4 as an OEP and released them to SrTiO3:La,Rh as a HEP.
The schematic band diagram of the SrTiO3:La,Rh/Au/BiVO4 sys-
tem is presented in Fig. 3. The standard potential of H+/H2 was
4.5 eV below the vacuum level and more positive than the bottom
of conduction band of SrTiO3:La,Rh. Therefore, electrons generated
near the interface of SrTiO3:La,Rh and water can reduce water to H2
on the Ru cocatalyst. On the other hand, the standard potential of
O2/H2O is positioned above the top of the valence band of BiVO4.
Holes generated near the interface of BiVO4 and water can oxidize
water to O2. Note that only the forward carrier injection processes
are described for simplicity in Fig. 3. Unfavorable backward injec-
tion to the back metal contact would occur when the minority car-
riers are generated near the back metal contact. However, most of
minority carriers should be generated near the photocatalyst/water
interface because the photocatalyst plates were illuminated from
the front side. It is therefore expected that the forward carrier injec-
tion shown in Fig. 3 is the major process. It should be noted that the
Fermi level of Au is 5.1 V (relative to the vacuum level) [36], which
is more positive than the Fermi level of BiVO4 (5.0 V relative to the
vacuum level) [37]. On the other hand, the Fermi level of
SrTiO3:La,Rh was measured by Mott–Schottky analysis (Fig. A.7 in
Activity (lmol h1 cm2)
O2 H2 O2
BiVO4 0.8 0.4
BiVO4 0.2 0.1
BiVO4 4.5 2.2
– n.d. n.d.
n.d. n.d.
the Appendices) to be 6.3 V relative to the vacuum level, which
is more positive than that of Au. As a result, a Schottky junction that
is unfavorable for injection of the majority carriers would be
formed between Au and both semiconductors when the Fermi lev-
els were equilibrated. The choice of the metal contact layer could be
important for obtaining high photocatalytic activity because it
affects the height of the Schottky barriers. Thus, different kinds of
metals, other than Au, were deposited by vacuum evaporation.
Table 2 tabulates the water splitting activities of SrTiO3:La,Rh/M/
BiVO4 (HEP/M/OEP) photocatalyst plates (M = Al, Ag, Rh, Au, and
Ni) and the work functions of the metals. The Rh layer produced
an activity comparable to that of the Au layer, while the Al, Ag,
and Ni layers exhibited lower activity. Considering that Ag could
also cause excitation of surface plasmon resonance, the low activity
resulting from the Ag contact layer suggests that the metals pre-
pared by vacuum evaporation behaved as an electron conductor
and did not induce an optical effect. The Al and Ni layers had partly
corroded during the reaction. Because of the chemical stability of
the metal layers, the influence of the work function could not be
determined unambiguously. The mechanisms whereby electrons
can migrate across Schottky barriers efficiently are still under
investigation. Possibly, the carriers could migrate across the inter-
facial energy barriers due to tunneling of barriers or to conduction
through mid-gap surface states created by diffusion of metal ions.
3.3. Effect of the reaction conditions
The photocatalytic activity of the SrTiO3:La,Rh/Au/BiVO4 plate
for overall water splitting was almost independent of the pH of
the aqueous reactant solutions, as illustrated in Fig. 4. The activity
was barely higher in acidic solutions, maxing at pH 3.5–5.5 pre-
sumably because of changes in the kinetics of redox reactions
involving protons. It is worth noting that the dependence on pH
in the SrTiO3:La,Rh/Au/BiVO4 system was distinct from the case
of the powder suspension system [11]. The photocatalytic activity
of the SrTiO3:Rh-BiVO4 powder suspension decreased markedly at
pH > 4.0 because of the electrostatic repulsion between SrTiO3:Rh
and BiVO4 particles, which prevented the aggregation of particles
necessary for interparticle electron transfer [11]. These observa-
tions provide further evidence that in the SrTiO3:La,Rh/Au/BiVO4
system, electron transfer relies on the metal layer, rather than
the aggregation of particles. The weak sensitivity of the photocat-
alytic activity of HEP/M/OEP systems to pH is beneficial. Various
photocatalytic materials can be applied to Z-scheme water split-
ting because the choice of materials is not limited by the signs of
surface charges at the working pH. In addition, HEP/M/OEP sys-
tems operate in neutral solutions without redox couples. Because
HEP and OEP are located nearby, the concentration overpotential
of reactant species such as H+, OH, and redox couples, if present,
 Q. Wang et al. / Journal of Catalysis 328 (2015) 308–315 313

Fig. 3. Schematic energy diagrams of SrTiO3:La,Rh/Au/BiVO4 systems (a) before contact, (b) under equilibrium conditions in darkness, and (c) under band gap excitation.

Table 2
The water splitting activity of SrTiO3:La,Rh/M/BiVO4 (HEP/M/OEP) photocatalyst
plates (M = Al, Ag, Rh, Au, and Ni) and the work functions of the metals.

Metals Work function (eV) [38] Activity (lmol h1 cm2)

H2 O2
Al 4.3 5.4 n.d.
Ag 4.3 0.6 0.2
Rh 5.0 5.6 2.8
Au 5.1 4.6 2.3
Ni 5.2 1.5 0.7

Reaction conditions: reactant solution, 40 mL water without adjusting the pH

(pH  6.8); light source, 300 W xenon lamp (k > 420 nm), irradiation area: 9 cm2.
‘‘n.d.’’ stands for ‘‘not detected’’. The gas evolution rates were divided by the irra-
diation area. The detection limits for H2 and O2 were 0.007 and 0.02 lmol h1 cm2,
respectively. Photodeposition was carried out from an aqueous solution (40 mL)
containing RuCl33H2O (0.35 lmol) without pH adjustment under 300 W xenon
lamp (k > 420 nm) illumination.
should be minimized, unlike Z-scheme water splitting in
two-compartment cells.
To discuss factors limiting the photocatalytic activity of
SrTiO3:La,Rh/Au/BiVO4 plates for Z-scheme water splitting, the
mass ratio of SrTiO3:La,Rh and BiVO4 was varied and the photocat-
alytic activity was evaluated in the presence and the absence of
sacrificial electron donors (methanol) and acceptors (silver ions)
[2,3,6]. Oxidation of water occurs only over BiVO4 on a
SrTiO3:La,Rh/Au/BiVO4 photocatalyst plate, because SrTiO3:La,Rh
is practically inactive for the water oxidation reaction. Methanol
is thermodynamically more easily oxidized than water on both
SrTiO3:La,Rh and BiVO4. Therefore, the photocatalytic reaction is
free from limitations due to electron transfer via the Au layer or
water oxidation kinetics on BiVO4, and the H2 evolution rate from
an aqueous methanol solution should reflect the maximum
capability of SrTiO3:La,Rh on a SrTiO3:La,Rh/Au/BiVO4 plate to
Fig. 4. Dependence of the photocatalytic activity of a SrTiO3:La,Rh/Au/BiVO4 plate
on pH. Reaction conditions: reactant solution, 40 mL water with pH adjusted using
H2SO4 (aq.) or NaOH (aq.); light source, 300 W xenon lamp (k > 420 nm), irradiation
area: 9 cm2. Photodeposition was carried out in an aqueous solution (40 mL)
containing RuCl33H2O (0.35 lmol) with pH adjustment using H2SO4 (aq.)
(pH  3.5) under 300 W xenon lamp illumination (k > 420 nm). The gas evolution
rates were divided by the irradiation area.
evolve H2 under illumination. Note that H2 evolution still occurs
only on SrTiO3:La,Rh in the presence of methanol because the con-
duction band edge of BiVO4 is more positive than the hydrogen
evolution potential. Likewise, the silver cation is thermodynami-
cally more easily reduced than a proton. Ag+ cations are reduced
on both SrTiO3:La,Rh and BiVO4 on a plate, while O2 evolution pre-
dominantly occurs on BiVO4. Therefore, it is expected that the
maximum capability of BiVO4 to evolve O2 on a SrTiO3:La,Rh/Au/
BiVO4 plate under illumination can be estimated by adding AgNO3
as a sacrificial reagent. The overall reactions in the presence of
methanol and silver cations can be expressed by Eqs. (1) and (2),
respectively:
314 Q. Wang et al. / Journal of Catalysis 328 (2015) 308–315

Table 3
Gas evolution rates over SrTiO3:La,Rh/Au/BiVO4 photocatalyst plates with various mass ratios of SrTiO3:La,Rh and BiVO4 from reaction solutions containing sacrificial reagents.

Mass ratio of SrTiO3:La,Rh to BiVO4 Sacrificial reagents Gas evolution rate (lmol h1 cm2)
H2 O2
2:1 Nonea 3.3 1.6
CH3OHb 7.2 n.d.
AgNO3c n.d. 3.3
1:1 Nonea 4.0 2.0
CH3OHb 6.5 n.d.
AgNO3c n.d. 4.7
1:2 Nonea 1.7 0.9
CH3OHb 6.2 n.d.
AgNO3c n.d. 8.2

Light source, 300 W xenon lamp (k > 420 nm); irradiation area: 9 cm2. ‘‘n.d.’’ stands for ‘‘not detected’’. The gas evolution rates were divided by the irradiation area. The
detection limits for H2 and O2 were 0.007 and 0.02 lmol h1 cm2, respectively. Photodeposition was carried out from an aqueous solution (40 mL) containing RuCl33H2O
(0.35 lmol) without pH adjustment under 300 W xenon lamp (k > 420 nm) illumination.
a
pH  6.8, 40 mL.
b
An aqueous methanol solution (10 vol%), 40 mL.
c
An aqueous AgNO3 solution (20 mmol L1), 40 mL.

CH3 OH þ H2 O ! CO2 þ 3H2 ð3Þ rates of SrTiO3:La,Rh/Au/BiVO4 samples at pH  6.8 under 300 W
þ
4Ag þ 2H2 O ! O2 þ 4Ag þ 4H þ
ð4Þ xenon lamp irradiation (k > 420 nm) ranged from 3.5 to
5.8 lmol h1 cm2 for 10 individual samples (4.5 ± 1.5 lmol h1 -
As shown in Table 3, negligible amounts of O2 and H2 were cm2 at a confidence level of 95%). This in turn suggests that the
evolved from aqueous solutions of methanol and AgNO3, respec- photocatalyst activity of the SrTiO3:La,Rh/Au/BiVO4 plate system
tively. The gas evolution rates in the presence of sacrificial reagents could be promoted further through decreasing the number of grain
reflected the mass ratios of SrTiO3:La,Rh and BiVO4. The H2 evolu- boundaries across the photocatalyst particle layers by controlling
tion rate from aqueous methanol solution increased with increas- the particle sizes and morphologies and by reducing the thickness
ing mass fraction of SrTiO3:La,Rh, because the ratio of of the particle layers.
SrTiO3:La,Rh available for the hydrogen evolution reaction Fig. 5 shows the dependence of the AQY of Z-scheme water split-
increased, as explained above. Likewise, the O2 evolution rate from ting using a moderately active SrTiO3:La,Rh/Au/BiVO4 plate on the
aqueous AgNO3 solution increased with increasing ratio of BiVO4. incident light wavelength. The time course of the gas evolution
The enhancement factors, that is, the ratio of the H2 evolution under Xe lamp illumination (k > 420 nm) using the same specimen
rates in the presence and absence of methanol and the ratio of as in Fig. A.8 shows that the rates of H2 and O2 evolution were 4.6
the O2 evolution rates in the presence and absence of silver nitrate and 2.3 lmol h1 cm2, respectively. The SrTiO3:La,Rh/Au/BiVO4
were compared. When the mass ratios of SrTiO3:La,Rh and BiVO4 system split water into H2 and O2 under irradiation up to 520 nm.
were 2:1, 1:1, and 1:2, the enhancement factors for oxygen evolu- This wavelength is in agreement with the absorption edge of BiVO4
tion were 2.0, 2.3, and 9.3, respectively. The enhancement factor (Fig. 5c). The AQY of Z-scheme water splitting was measured to be
increased dramatically with increasing BiVO4 content. This is rea- 5.9% at 418 nm in distilled water (pH  6.8) and decreased with
sonable, because the 2:1 sample had a sufficient density of reaction increasing wavelength of incident photons up to 520 nm. The
sites for photoexcited electrons (on SrTiO3:La,Rh) in Z-scheme SrTiO3:La,Rh/Au/BiVO4 system exhibited a higher AQY at 420 nm
water splitting. In contrast, electron consumption on SrTiO3:La,Rh
was limited for the 1:2 sample. Allowing the BiVO4 in this speci-
men to consume electrons by adding silver cations should enhance
the O2 evolution rate the most. However, the enhancement factors
for H2 evolution were 2.2, 1.6, and 3.6 for the 2:1, 1:1, and 1:2 sam-
ples, respectively. The enhancement factor was unexpectedly the
largest for the 1:2 sample, which had the smallest amount of
SrTiO3:La,Rh and thus the least room for enhancement of H2 evolu-
tion by rapid consumption of photoexcited holes with methanol.
This might be due to the relatively small size of the SrTiO3:La,Rh
particles. As seen in Fig. A.3, SrTiO3:La,Rh particles 0.2–0.7 lm in
size were loosely aggregated, although individual particles could
still be distinguished. This implies that the particles did not fuse
well and increased grain boundary resistance in the photocatalyst
particle layers. Therefore, a certain portion of the BiVO4 particles
would not have intimate electrical contact with SrTiO3:La,Rh parti-
cles. As such, facilitation of hole consumption on BiVO4 by adding
methanol did not provide electrons to SrTiO3:La,Rh effectively.
Consequently, the enhancement factor for H2 evolution could be Fig. 5. (a) Dependence of apparent quantum yield of Z-scheme water splitting
limited in the case of SrTiO3:La,Rh-rich specimens. using a SrTiO3:La,Rh/Au/BiVO4 photocatalyst plate on incident light wavelength.
As described earlier, the degree of photocatalyst particle stack- Diffuse reflectance spectra for (b) SrTiO3:La/Rh and (c) BiVO4 are shown for
ing on the SrTiO3:La,Rh/Au/BiVO4 plate could not be precisely con- comparison. Reaction conditions: distilled water (pH  6.8, 40 mL); light source,
300 W xenon lamp equipped with various band-pass filters; irradiation area: 9 cm2.
trolled. This would inevitably lead to variations in the gas
Photodeposition was carried out from an aqueous solution (40 mL) containing
evolution rate of SrTiO3:La,Rh/Au/BiVO4 plates prepared under RuCl33H2O (0.35 lmol) without pH adjustment under 300 W xenon lamp
equivalent conditions but at different times. The water splitting (k > 420 nm) illumination.
 Q. Wang et al. / Journal of Catalysis 328 (2015) 308–315 315

splitting can be achieved by understanding and controlling the

effect of morphology on HEP/M/OEP devices and semiconductor/
metal junction properties.

Acknowledgments

This work was financially supported by Grants-in-Aid for Spe-

Fig. 6. Time course of Z-scheme overall water splitting using a SrTiO3:La,Rh/Au/
BiVO4 photocatalyst plate under simulated sunlight irradiation. Reaction condi-
tions: suspension in distilled water (pH  6.8, 40 mL); light source: solar simulator
(AM1.5D, 90.1 mW cm2); irradiation area: 9 cm2. The photodeposition was carried
out from an aqueous solution (40 mL) containing RuCl33H2O (0.35 lmol) without
pH adjustment under 300 W xenon lamp (k > 420 nm) illumination.
cially Promoted Research (No. 23000009) and for Young Scientists
(B) (No. 25810112), the Global Center of Excellence (GCOE) Pro-
gram for Chemistry Innovation through Cooperation of Science
and Engineering, and the A3 Foresight Program of Japan Society
for the Promotion of Science (JSPS). A part of work was conducted
in Research Hub for Advanced Nano Characterization, The Univer-
sity of Tokyo, supported by the Ministry of Education, Culture,
Sports, Science and Technology (MEXT), Japan. The authors thank
Prof. Yuichi Ikuhara and Mr. Shigeru Otsuka of The University of
Tokyo for their assistance in SEM-EDX mapping measurements.
Appendix A. Supplementary material

Supplementary data associated with this article can be found, in

than the BiVO4–Ru/SrTiO3:Rh and Ru/SrTiO3:RhBiVO4- the online version, at http://dx.doi.org/10.1016/j.jcat.2014.12.006.
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