Article

pubs.acs.org/JPCC

Strategic Modification of BiVO4 for Improving Photoelectrochemical

Water Oxidation Performance
Hye Won Jeong,† Tae Hwa Jeon,‡ Jum Suk Jang,§ Wonyong Choi,‡ and Hyunwoong Park*,†
†
School of Energy Engineering, Kyungpook National University, Daegu 702-701, Korea
‡
School of Environmental Science and Engineering, §Beamline Research Division, Pohang Accelerator Laboratory, POSTECH,
Pohang 790-784, Korea
*
S Supporting Information

ABSTRACT: To improve the photoelectrochemical (PEC)

performance of BiVO4, three different modifications (doping,
heterojunction, and catalyst deposition) using earth-abundant
elements are performed and their effects are compared in a 0.1
M phosphate electrolyte at pH 7 under AM1.5 light (100 mW/
cm2). When a hexavalent element (Cr6+, W6+, or Mo6+) is
doped at various levels, the Mo6+-doping effect is most
significant at 10 atomic % with about two times higher
photocurrent generation at the oxygen evolution potential
(1.23 VRHE). Such enhancement is attributed to a decrease in
charge transfer resistance (Rct) by donor doping, resulting in
an approximate 2-fold increase in charge separation efficiency (ηsep) to about 25%. W6+ is less effective than Mo6+, whereas Cr6+
has a detrimental effect. To further improve the charge separation efficiency of Mo6+-doped BiVO4 (Mo-BiVO4), a approximate
600 nm thick WO3 layer is deposited under a similarly thick Mo-BiVO4 layer. This binary heterojunction (WO3/Mo-BiVO4)
exhibits ηsep of about 50% along with more than 3 times higher photocurrent generation. On the other hand, an oxygen evolving
cobalt-phosphate (Co-Pi) catalyst electrodeposited to Mo-BiVO4 (Mo-BiVO4/Co-Pi) enhances charge injection efficiency (ηinj)
from ∼50 to ∼70% at 1.23 VRHE. These two binaries are coupled into a ternary heterojunction (WO3/Mo-BiVO4/Co-Pi) in
order to improve the charge transfer efficiencies (ηsep and ηinj). The PEC performance of this ternary is significantly high with
photocurrent density of about 2.4 mA/cm2 at 1.23 VRHE (corresponding to the solar-to-hydrogen efficiency of ca. 3%) due to ηsep
and ηinj of ∼60 and 90%, respectively.

■ INTRODUCTION
Photoelectrochemical (PEC) water oxidation is essential for
sustainable solar hydrogen and artificial photosynthesis.1−3
Water oxidation with simultaneous oxygen evolution is a four-
proton-coupled electron transfer process with an approximately
3 orders of magnitude lower rate than the hydrogen evolution
reaction in water electrolysis. A range of semiconductor
photoanodes for PEC water oxidation are available. Among
these, BiVO4 is unique and promising4−7 owing to its bandgap
of ∼2.4 eV (monoclinic) and its ability to produce a maximum
photocurrent of ∼7.5 mA/cm2 at 1.23 VRHE (volts vs a
reversible hydrogen electrode) under AM1.5G light (1 sun: 100
mW/cm2). Therefore, the maximal solar-to-hydrogen (STH)
conversion efficiency is approximately 9.2%, which is close to
the entrance level for commercialization.
Nevertheless, the typical STH of BiVO4 is disappointingly
low (<1%) with a photocurrent of <1 mA/cm2 at 1.23 VRHE.
The overall photocurrent for oxygen evolution is a function of
light absorption, charge separation, and charge injection
(catalysis). The former is related to the degree of absorption,
which is critically influenced by film thickness, particle size/
shape, porosity, degree of wetness, and so on. The charge
separation efficiency refers to the fraction of photogenerated
holes that reach the semiconductor electrode and solution
interface and is closely related to bulk recombination. On the
other hand, the charge injection efficiency refers to the fraction
of the holes that reach the interface and are subsequently
transferred to the solution for water oxidation. Hence, it should
be a signpost to estimate the surface recombination. These
parameters need to be optimized to obtain high efficiency water
oxidation. Many approaches have been adopted thus far5,8 and
the followings have been found to be effective: element-
doping,9−17 heterojunction,18−22 and coupling with oxygen-
evolving catalysts (OECs)14,23−27 (Scheme 1). Doping is an
effective way of increasing the electric conductivity and
improving the PEC performance. BiVO4 is often doped with
a range of elements9,28,29 but mostly hexavalent W13,15,17,30 and
Mo.11,13,23,31 Doping of W6+ or Mo6+ into the V5+ site of BiVO4
strengthens the n-type characteristics by supplying additional
free electrons, resulting in an increase in the electric
conductivity of BiVO4. Instead of the single element-doping,
codoping of W and Mo further improved the PEC performance
Received: January 14, 2013
Revised: April 9, 2013

© XXXX American Chemical Society A dx.doi.org/10.1021/jp400415m | J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
Scheme 1. Illustration of the Strategic Modifications of
BiVO4a
a
(a) Doping with hexavalent elements (M: Mo6+, W6+, or Cr6+), (b)
binary heterojunction with WO3, (c) coupling with cobalt-phosphate
(Co-Pi) as an oxygen evolving catalyst, and (d) ternary heterojunction
with WO3 and Co-Pi.
of BiVO4 in 0.1 M Na2SO4 solution.10,32 The heterojunction
couples two different semiconductors with dissimilar bandgaps
and band energy levels (e.g., WO3/BiVO418,19,33 and Co3O4/
BiVO434). Once the energy levels are matched, cascaded charge
transfer can occur and high efficiency PEC conversion can be
obtained. In some cases, WO3 nanorod arrays were used to
enhance the PEC performance of the heterojunction due to
high surface area.19 The coupling of semiconductors and OECs
is also necessary to enhance the charge injection efficiency for
the oxygen evolution reaction.24 Despite the sufficient energy
difference between the valence band and oxygen evolution
potential, multihole transfer to interfacial water molecules is
limited. The use of OECs can overcome this kinetic limit,
thereby enhancing the overall PEC water oxidation perform-
ance.
With this in mind, this study examined the effects of doping
on the PEC performance of bare and heterojunction BiVO4
electrodes at pH 7 under simulated solar irradiation (AM1.5;
100 mW/cm2) in terms of the charge separation and charge
injection. As dopants, Cr6+, W6+, and Mo6+ were selected and
their (single and codoping) effects were compared because they
could reduce the effective mass of the holes on top of the
valence band and increase the hole mobility (i.e., electrical
conductivity).13 Indeed, the latter two elements enhanced the
PEC performance of BiVO4 significantly.5,10,11,13,14,17 For the
heterojunction structure, WO3 was coupled to bare and doped
BiVO4 because the Ecb and Evb of WO3 are more positive of
those of BiVO4, respectively. This structure is expected to be
beneficial for improving the charge separation efficiency.
Finally, as an OEC, cobalt-phosphate (Co-Pi) was electro-
deposited on bare and doped BiVO4 electrodes to enhance the
charge injection efficiency for water oxidation. For example,
Pilli et al. showed that the PEC performance of Mo-doped
B dx.doi.org/10.1021/jp400415m | J. Phys. Chem. C XXXX, XXX, XXX−XXX
Article
BiVO4 is double upon the deposition of Co-Pi.23 In this study,
the optimized ternary heterojunction (WO3/Mo-BiVO4/Co-
Pi) generated approximately 2.4 mA/cm2 at 1.23 VRHE (STH
efficiency of ca. 3%) with charge separation and injection
efficiencies of about 60 and 90%, respectively.
■ EXPERIMENTAL SECTION
Preparation of BiVO4 Electrodes. Bare and Doped
BiVO4. Fluorine-doped SnO2 (F:SnO2, FTO)-coated glass
(Pilkington Co., 3 mm thick with an ∼50 nm thick FTO
layer, size: 1.5 × 3 cm2) was cleaned ultrasonically in ethanol
(99.0%; Aldrich) for 10 min, rinsed with distilled water, and
dried. For the BiVO4 precursor solutions, 0.2 M Bi-
(NO3)3·5H2O (Aldrich), and 0.03 M vanadium(IV) acetyla-
cetonate (Aldrich), as Bi and V precursors, respectively, were
dissolved separately in 2,4-pentanedione (Aldrich). Both
solutions were mixed with a Bi and V stoichiometric ratio of
1:1, and 200 μL of the solution was spread on FTO and spin-
coated at a spin rate of 1000 rpm (JS-301-100; Jaesung Eng.
Co.) for 6 s (repeated twice per coating cycle). After drying in
air, the coated BiVO4 electrodes were annealed at 500 °C for 10
min. This procedure was repeated for nine cycles to increase
the film thickness. In the final cycle, the BiVO4 electrodes were
annealed at the same temperature for 2 h. For the single
element-doped BiVO4, Na2Cr2O7·2H2O (Aldrich), Na2WO4
(Aldrich), and MoO3 (Aldrich) were dissolved separately in
2,4-pentanedione at 30 μM, which were then mixed with the
precursor solutions of Bi and V at Bi/V/dopant ratios of 1:1 −
x:x (0 ≤ x ≤ 0.15). For codoped BiVO4, the amount of W6+
was varied between 2 and 10% under a fixed Mo6+ level of 10%.
Coupling of WO3 and BiVO4. Tungsten acid (H2WO4,
Aldrich) and NH4OH (Aldrich) were dissolved in deionized
water to a W concentration of 5%. This solution (200 μL) was
placed dropwise on FTO glass and spin-coated at 1000 rpm for
6 s (repeated once more). After drying in air, the sample was
annealed at 500 °C for 30 min. The coating-annealing process
was repeated five times to obtain an ∼600 nm thick WO3 film.
The bare and doped BiVO4 films were prepared over the WO3
film using the following the aforementioned procedure for
BiVO4. The film thickness of the BiVO4 overlayer (∼550 nm)
was similar to the WO3 underlayer (Figures 3 and S3).
Deposition of Co-Pi. Co-Pi was loaded on bare, doped, or
WO3-coupled BiVO4 films using an electrodeposition meth-
od.24 A BiVO4 electrode (working electrode), a saturated
calomel electrode (SCE; reference electrode), and a graphite
rod (counter electrode) were immersed in a 0.1 M potassium
phosphate buffer solution (pH 7) containing 0.5 mM CoCl2
(Aldrich), to which a constant potential of 1.125 V versus SCE
was applied with a potentiostat (Ivium Compact Stat) for 5
min. After electrodeposition, the samples were dried at room
temperature.
Photoelectrochemical Study. The PEC study of the as-
prepared BiVO4 electrodes was performed using a three-
electrode system in 0.1 M potassium phosphate buffer at pH 7
(with or without 50 mM H2O2) using a graphite rod and an
SCE as the counter and reference electrodes, respectively. A
150 W Xenon arc lamp (ABET Tech.) equipped with an
AM1.5G filter was used as a light source with a light intensity of
1 Sun (100 mW/cm2). Light was irradiated to the backside of
the BiVO4 electrodes (FTO side), and the irradiated electrode
area was 0.635 cm2. To examine the PEC performance of the
sample electrodes, a linear potential sweep was applied from
−0.5 to 1.5 VSCE at a scan rate of 10 mV·s−1 in the absence or
The Journal of Physical Chemistry C Article

presence of light. Where necessary, a constant potential of
0.576 VSCE (equivalent to 1.23 VRHE) was applied with the light
on or off. For convenience, the potentials versus SCE were
converted to the RHE using the following relationship (eq 1).
VRHE = VSCE + 0.241 + 0.059 pH
(1)
For impedance analysis (Nyquist plots), alternating current
(AC) impedance measurements were carried out by the
application of a bias potential of −0.5 VSCE in a 0.1 M
potassium phosphate solution with the frequency range, 1000
to 0.01 Hz, and an AC voltage of 50 mV rms (Ivium Compact
Stat) in the dark and under AM1.5 light. Flat band potentials
were determined from the Mott−Schottky analysis at 1 kHz to
for water oxidation. In this regard, they are signposts to
estimate the bulk recombination (br) and surface recombina-
tion, respectively (i.e., Ibr = Iabs − Isep).14,30,35
Surface Analysis. The top and side views of samples were
analyzed by a field emission scanning electron microscope (FE-
SEM; Zeiss nd Kleindiek Supra-55VP, PW). An X-ray
photoelectron spectroscopy (ESCA Lab 220i XL, MgKα
source; VG Scientific) was used to examine the binding
energies of Bi, V, O, Cr, W and Mo. An X-ray diffractometer
(XRD; Rigaku D/Max-2500) was used to examine the sample
crystallite structures and particle sizes using Cu Kα radiation (λ
= 0.15406 nm) with 40 kV and 100 mA at a 0.02° scan rate. A
UV−vis spectrometer (Shimadzu UV-2450) was used to
measure the absorbance.

■
0.1 Hz in a 0.1 M potassium phosphate buffer solution (pH 7)
by applying the potential range from −0.8 to +0.8 VSCE with a
scan rate of 50 mW·s−1 (Ivium Compact Stat). RESULTS AND DISCUSSION
The charge separation and injection efficiencies (ηsep and ηinj, Photoelectrochemical Behavior of Metal (Cr, Mo, W)-
respectively) were estimated using the following equation:14,35 Doped BiVO4 Films. Figure 1a shows linear sweep voltammo-
H 2O
Iph = Iabs × ηsep × ηinj (2)
where IHph2O
and Iabs are the photocurrent density at 1.23 VRHE
(water oxidation) and the photon absorption rate expressed as
the photocurrent density, respectively. Iabs was determined by
estimating the overlapped areas between the UV−vis
absorption spectra of sample electrodes and an AM1.5G solar
irradiance (i.e., P = 10−A × P0, where P0 and P refer to the
powers of photons (W·m−2·nm−1) entering and coming from a
sample, respectively, while A is absorbance at each wavelength
(see Figure S7 for more information).26 The integrated power
(W·m−2) was then divided by 1.23 V to convert it into Iabs. For
comparison, we have actually measured the light intensities
passing through samples (P) using a calibrated silicon diode
detector (McScience Inc., K801S−K009) and found that as-
prepared BiVO4 film absorbed about 64.3% of AM1.5G light (1
Sun). This corresponds to about 4.82 mW/cm2 on the basis of
100% absorption (∼7.5 mA/cm2). For reference, as-prepared
WO3 film absorbed 61.5% of 1 Sun, corresponding to ∼3 mA/
cm2 (∼4.8 mA/cm2 per 100% absorption of 1 Sun). It should
be noted that the degree of absorption is critically influenced by
film thickness, particle size/shape, porosity, degree of wetness,
and so on. The optical property will affect the overall
performance. In this study the estimated Iabs values, however,
were not much different among bare and doped BiVO4 samples
(only 2% variation) and can be used for reliably estimating
Figure 1. (a) Light-irradiated linear sweep voltammograms of bare and
charge separation and injection efficiency. When hydrogen
doped BiVO4 electrodes in 0.1 M phosphate electrolyte (pH 7) in the
peroxide (H2O2) is used as a hole scavenger, ηinj becomes 100% presence or absence of H2O2 (50 mM) under AM1.5 light (100 mW/
because surface recombination is completely suppressed. cm2). W6+ and Mo6+ were doped at 8 and 10 atomic %, respectively.
Because H2O2 is transparent to UV and visible light, the (b) Effects of the dopant atomic % on the photocurrent generation of
photocurrent for H2O2 oxidation becomes BiVO4 at 1.23 VRHE in 0.1 M phosphate electrolyte.
H 2O2
Iph = Iabs × ηsep (3)
grams of the bare and doped BiVO4 films in a 0.1 M potassium
Combining these two equations results in the following phosphate electrolyte (pH 7) in the absence or presence of
equations: hydrogen peroxide (50 mM) under AM1.5 light (100 mW/
H 2O2
cm2). All BiVO4 electrodes have the dark onset potentials of
ηsep = Iph /Iabs (4) approximately 1.9 VRHE (Figure S4), whereas the bare BiVO4
shows an onset photopotential of ∼0.5 VRHE. Although
H 2O H 2O2
ηinj = Iph /Iph (5)
irradiation makes bare BiVO4 active at the equilibrium oxygen
evolution potential (1.23 VRHE), the main photoeffect is a
Note that ηsep corresponds to the fraction of photogenerated substantial increase in photocurrent at E > ∼1.65 VRHE. Due to
holes that reach the semiconductor electrode and solution the overpotential of about 0.4 V for water oxidation, the water
interface, while ηinj refers to the fraction of the holes that reach oxidation photocurrent at 1.23 VRHE is as low as 0.25 mA/cm2,
the interface and are subsequently transferred to the solution corresponding to a STH of ∼0.3%.
C dx.doi.org/10.1021/jp400415m | J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
The low PEC performance of n-type oxide semiconductor
electrodes is mainly attributed to the low mobility of holes,1,2,5
resulting in rapid charge recombination. To improve the PEC
water oxidation photocurrent, three donor elements (W6+,
Mo6+, and Cr6+) were doped into the V5+ site of BiVO4 at
dopant concentrations of up to 15 atomic %. XPS of the bare
and doped BiVO4 samples was performed to determine if the
elements were doped successfully (Figure 2). The doped
Figure 2. XPS spectra of (a) Bi4f, (b) O1s, and (c) W4f, Mo3d, and
Cr2p for bare and doped BiVO4 films. W6+, Mo6+, and Cr6+ were
doped at 8, 10, and 2 atomic %, respectively.
BiVO4 films display different binding energies of Bi4f, V2p, and
O1s (Figure 2a,b; for the V2p spectra, see Figures S5) with
0.2−0.3 eV shifts to higher binding energies compared to bare
BiVO4. These shifts are attributed to the stronger interaction of
doped hexavalent elements with Bi, V, and O atoms. Cr, W, and
Mo are located at binding energies of approximately 578 eV
(Cr2p), 34.5 eV (W4f), and 231.5 eV (Mo3d; Figure 2c),
which is indicative of all hexavalent ions (Cr6+, W6+, and Mo6+)
being doped. On the other hand, the atomic percentage of the
elements (Cr, 0.47%; W, 4.93%; Mo, 3.34%) are lower than
those of the precursor solutions (2, 8, and 10%, respectively).
The reduced dopant atomic percentages are attributed to their
inhomogeneous distribution throughout the BiVO4 structure.
D dx.doi.org/10.1021/jp400415m | J. Phys. Chem. C XXXX, XXX, XXX−XXX
Article
Such a difference is normally observed in metal-doped
semiconductors.1,5,16,36 A comparison of the stabilized photo-
currents of the bare and doped BiVO4 electrodes at 1.23 VRHE
shows that Mo6+ is very effective in improving the photo-
currents by 2 times at 10% (Figures 1b and S6). W6+ also has a
similar effect to Mo6+, but Cr6+ has a negative effect, making
BiVO4 almost photoinactive (Figure 1a). Cr always has an
adverse effect irrespective of the Cr atomic percentage (Figure
1b), which is opposite to the theoretical calculations that Cr is
as effective as Mo and W.13 In contrast to W and Mo, Cr
doping can create an isolated impurity energy band at ∼1.77 eV
away from the valence band minimum in the forbidden band.13
This impurity band can work as a recombination center (e− +
Cr6+ → Cr5+; h+ + Cr5+ → Cr6+). Furthermore, the effective
mass of an electron in the conduction band is increased ∼2.6-
fold by Cr6+ doping, whereas the effective mass of the hole in
the valence band is relatively unchanged.13 Therefore, charge
transfer is more sluggish with Cr doping.
To further examine the doping effects on the morphologies,
BiVO4 and Mo-BiVO4 (as a representative doped one) were
analyzed with FE-SEM and XRD. The FE-SEM analysis for
bare BiVO4 showed that the average particle size is quite
uniform with about 100 nm (Figure 3a). The particle size is
increased slightly by 10% Mo doping (Figure 3b) likely due to
the role of dopant as a nucleic site for interparticle
aggregation.36 As-prepared, BiVO4 exhibits a clinobisvanite
(monoclinic scheelite) structure with a crystallite size of 19−28
nm (Figure S1). It is of note that the crystallite size is typically
smaller than the particle grain size. Mo doping does not change
the structure (Figure S1) along with a slightly larger crystallite
size of 22−30 nm. No Mo-oriented XRD peak is observed,
indicating that Mo is not segregated out of the BiVO4 lattice.
Meanwhile, the diffraction peaks of BiVO4 (e.g., 112 and 011
peaks) are slightly shifted upon Mo doping (Figure S2). A
similar diffraction peak shift was also observed upon W
doping.30 The shift by the Mo doping is additional evidence
that Mo is actually doped into the BiVO4 lattice, not located on
the surface. The film thicknesses of bare and Mo-BiVO4 (single
layers) are quite similar with about 580 nm (10% variation;
insets in Figure 3a,b), while the Mo-BiVO4 layer coated on
WO3 layer (∼600 nm) is ∼550 nm thick (Figure S3). This
comparison indicates that the employed coating process is
reliable and reproducible.
To compare the doping effects in terms of the charge
separation efficiency (ηsep) and charge injection efficiency (ηinj;
eqs 2−5), the photon absorption rates (expressed as the
photocurrent densities, Iabs) were estimated by overlapping the
AM1.5G light spectrum (100 mW/cm2) with the absorption
spectra of the bare and doped BiVO4 films (Figure S7). Linear
sweep voltammograms of bare and doped BiVO4 were also
obtained in the presence of 50 mM H2O2 as a hole scavenger to
determine IHph2O2 at 1.23 VRHE (Figure 1a). As shown in Figure 4,
ηsep increases with increasing bias potential due to the enhanced
band-bending and reduced charge recombination. Compared to
W- and Mo-BiVO4, ηsep increases abruptly at E > 1.5 VRHE for
bare and Cr-BiVO4. This suggests that the bare and Cr-BiVO4
electrodes require more sufficient band-bending to achieve
comparable charge separation. The high ηsep of W- and Mo-
BiVO4 is due most likely to the increased charge mobility
resulting from decrease in charge transfer resistance (Rct).
Electrochemical impedance analyses were carried out on the
bare and doped BiVO4 electrodes to determine how the
dopants affect the charge transfer resistance. In this study, the
The Journal of Physical Chemistry C Article

Figure 3. FE-SEM images (top views) of (a) bare BiVO4, (b) Mo-BiVO4 (Mo: 10 atomic %), and (c, d) WO3. Insets show the side views of the
corresponding films. All scale bars are identically 200 nm, except 1 μm for (c).

Figure 4. Comparison of the bare and doped BiVO4 electrodes in
terms of the charge separation efficiency (ηsep, solid lines) and charge
injection efficiency (ηinj, broken lines) under AM1.5 light (100 mW/
cm2). W6+, Mo6+, and Cr6+ were doped at 8, 10, and 2 atomic %,
respectively.
Figure 5. Impedance analysis (Nyquist plots) of bare and modified
BiVO4 electrodes in a 0.1 M phosphate solution (pH 7). W6+, Mo6+,
and Cr6+ were doped at 8, 10, and 2 atomic %, respectively. Inset
shows the flat band potentials of bare and doped BiVO4 in a 0.1 M
phosphate solution (pH 7).

electrochemical cell was considered to represent the classical
Randles circuit composed of the solution resistance (Rs),
interfacial charge transfer resistance, and capacitance associated
with the Helmholtz layer at the electrode/solution interface
(CH; Figure S8). As shown in the Nyquist plots in Figure 5, the
electrodes show semicircles with different radii. The fitting of
the semicircles indicate that bare BiVO4 has an Rct of ∼4.9 kΩ,
which is decreased to ∼3.9 and ∼3.1 kΩ by W and Mo doping,
respectively. In contrast, Cr doping increases the resistance by
approximately 40% (∼6.8 kΩ). The reverse tendency of the
change in Rct from that of the PEC performance strongly
suggests that photogenerated charge transfer is a critical factor
in determining the photoelectrochemical performance of
BiVO4. The increase in Rct by Cr doping may result from
heavier electrons. The Mott−Schottky analysis further shows
E dx.doi.org/10.1021/jp400415m | J. Phys. Chem. C XXXX, XXX, XXX−XXX
that W and Mo doping shift the flat band potential of bare
BiVO4 cathodically by ∼0.15 V (from 0.4 to 0.25 VRHE: see
Figure 5 inset). The cathodic shift of the potential suggests that
W- and Mo-BiVO4 electrodes have larger band-bending
compared to bare BiVO4, consequently enhancing charge
separation.
Figure 4 also shows ηinj changes as a function of the bias
potential. Bare BiVO4 exhibits similar ηinj values of 30−40%
over the entire potential range, whereas ηinj of W-BiVO4
becomes greater than that of bare BiVO4 from ∼1.3 VRHE.
This suggests that the positive PEC effect of W6+ doping is due
to the enhanced charge separation efficiency, not from the
charge injection efficiency at 1.23 VRHE. On the other hand, the
Mo6+ doping effect on ηinj appears from ∼1 VRHE, and the
injection efficiency reaches a plateau of ca. 50% at 1.2 VRHE.
The Journal of Physical Chemistry C Article

This is only about 12% enhancement compared to the ηinj value

of bare BiVO4 (ca. 40%), suggesting that Mo6+ doping primarily
increases ηsep. The hexavalent W and Mo dopants appear to
trap photogenerated holes (e.g., Mo6+ + h+ → Mo5+),
effectively inhibiting bulk recombination. Similar to ηsep, Cr6+
doping is quite detrimental to ηinj.
Improving the PEC Performance of Mo-BiVO 4.
Codoping. Codoping with two different elements is often
performed to further improve the photocatalytic and photo-
electrocatalytic performance of single element-doped semi-
conductors.37,38 Recently, Berglund et al. reported that the
coincorporation of 6% Mo6+ and 2% W6+ into BiVO4 enhances
the photoelectrochemical performance significantly.10 In this
study, various atomic percentages of W6+ (2−10%) were doped
into Mo-BiVO4 electrodes at 10% of Mo6+. However, only 2%
W6+ doping enhances the PEC performance marginally, and
higher doping levels of W6+ reduce the performance
significantly (Figure S9). The different result from literature
may result from the different codoping process and the reduced
performance may be due to the degeneration of BiVO4. The
doping effect of 2% W6+ on photocurrent generation is
increased slightly with increasing bias potential.
Heterojunction. A heterojunction WO3/BiVO4 structure
was tested as well (Scheme 1b). In the construction of an
effective heterojunction, WO3 should be located beneath BiVO4 Figure 6. Light-irradiated linear sweep voltammograms of bare and
(i.e., FTO/WO3/BiVO4; see Figure S3) because the bandgap of doped BiVO4 with (a) WO3 underlayer and (b) Co-Pi catalyst and
WO3 is ∼0.3 eV wider. Under the condition of back WO3 underlayer in 0.1 M phosphate electrolyte (pH 7) under AM1.5
light (100 mW/cm2). W6+ and Mo6+ were doped at 8 and 10 atomic
illumination (to the FTO side), WO3 absorbs photons of λ < %, respectively. In (a), “+” refers to a simple sum.
∼440 nm and BiVO4 absorbs the photons of ∼440 nm < λ <
∼500 nm if all the high energy photons are absorbed by the respectively. These photocurrent values are also greater than
WO3 layer. In addition, the valence and conduction bands of those of WO3 + Mo-BiVO4 and WO3 + W-BiVO4, respectively,
WO3 are positive of those of BiVO4, respectively. This relative indicating synergistic effects. Analyses of WO3/Mo-BiVO4 for
energy level configuration will allow the photogenerated holes charge transfer also show that ηsep of Mo-BiVO4 (∼25%) is
to transport to and be collected at BiVO 4 with the doubled by coupling with WO3 (Figure 4 vs Figure 7),
photogenerated electrons moving to WO3. As a result,
electron−hole pairs are separated more effectively with
enhanced photocurrents. Before coupling BiVO4 and WO3,
their linear sweep voltammograms are compared under
irradiation (Figure 6a). The photocurrent generation of
BiVO4 follows exponential growth-like behavior, whereas the
photocurrent increases linearly at WO3. This suggests that WO3
may be better for generating photocurrent in the region of E <
1.8 VRHE and exhibit a similar photocurrent value at 1.23 VRHE
compared to BiVO4 (Figure S10)
When WO3 and BiVO4 are coupled, the shape of the linear
sweep voltammogram was more similar to that of bare WO3
than BiVO4. Because the most photons of λ < ∼440 nm are
absorbed primarily by WO3, the contribution of BiVO4 to
photocurrent generation might be limited in that wavelength Figure 7. Comparison of modified BiVO4 electrodes in terms of the
range. A comparison of the WO3 + BiVO4 (photocurrent sum) charge separation efficiency (solid lines) and charge injection efficiency
and WO3/BiVO4 samples reveals the superiority of the (broken lines) under AM1.5 light (100 mW/cm2). W6+ and Mo6+ were
heterojunction in that the photocurrent of the latter is doped at 8 and 10 atomic %, respectively.
approximately 50% higher than that of the former (Figure
S10). Although BiVO4 may exhibit limited absorption of high suggesting that bulk recombination is significantly inhibited due
energy photons due to underlying WO3, the potential gradient to cascaded charge transfer. The inhibition of the bulk
created across WO3 and BiVO4 should enhance charge transfer recombination may be attributed to reduced charge transfer
of both semiconductors. In this heterojunction, WO3 serves as resistance. As shown in Figure 5, the charge transfer resistance
an electron acceptor, whereas BiVO4 acts as a hole acceptor. To of WO3/Mo-BiVO4 is approximately 1.8 kΩ, corresponding to
enhance the PEC performance further, Mo-BiVO4 and W- ∼58% of that of Mo-BiVO4. WO3 also enhances moderately the
BiVO4 are used for the heterojunction because the hole charge injection efficiency of Mo-BiVO4 (∼48%) to ∼70% at
mobility of bare BiVO4 is inherently low. As shown in Figure 6a 1.23 VRHE.
(also see Figure S10), WO3/Mo-BiVO4 and WO3/W-BiVO4 The synergistic effect of this heterojunction can be attributed
exhibit ∼60 and 25% higher photocurrents than WO3/BiVO4, to a so-called necking effect. If BiVO4 particles penetrate into
F dx.doi.org/10.1021/jp400415m | J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
the pores created by WO3 particles (if WO3 layer is sufficiently
porous), then photogenerated charges can migrate from one
particle (WO3 and BiVO4) to neighboring particles through the
filled BiVO4 particles. This necking effect is often observed in
photocatalysis and photoelectrocataysis.8,39,40 To examine this
possibility, as-prepared WO3 film was analyzed by FE-SEM and
compared to BiVO4 (Figure 3). WO3 film is composed of
closely packed particles of ∼200 nm (Figure 3c,d). They are
interconnected (i.e., necked) among themselves and no pores
are observed. BiVO4 particles (Figure 3a,b) are also fully
packed, leaving no obvious void. Due to their large particle size
of ∼100 nm, BiVO4 particles are unlikely filled into WO3 layer.
In addition, Figure S3 (the side view of WO3/Mo-BiVO4)
obviously shows that WO3 and BiVO4 layers are distinctly
separated and BiVO4 particles do not intrude into the WO3
layer. In this regard, the necking effect may be minor.
Coupling with Oxygen Evolving Catalyst. Finally, cobalt-
phosphate (Co-Pi) is electrodesposited to bare and doped
BiVO4. As shown in Figure 6b, BiVO4/Co-Pi generates a dark
current from ∼1.75 VRHE, which is approximately 0.15 V
negative of the dark onset potential at bare BiVO4, due to the
catalytic effect of Co-Pi. Mo6+ doping shifts cathodically the
dark onset potential further to ∼1.6 VRHE, which is attributed to
the more metallic properties of BiVO4 (i.e., increase in electrical
conductivity). Upon irradiation, BiVO4/Co-Pi generates a
photocurrent from ∼0.5 VRHE but still requires a large
overpotential to obtain high photocurrent. The onset potential
is relatively unaffected by Mo6+ doping but the photocurrent is
increased dramatically. The stabilized photocurrent region at
1.0−1.6 VRHE also suggests that almost full charge separation is
accomplished in the potential region. An increase in photo-
current from ∼1.6 VRHE results from the catalytic effect of Co-
Pi. The effect of Co-Pi is due primarily to an increase in the
charge injection efficiency of Mo-BiVO4. As shown in Figure 7,
ηinj of Mo-BiVO4/Co-Pi is approximately 80% at 1.23 VRHE,
suggesting that around 80% of the interfacial holes (i.e.,
photogenerated and separated) are used for water oxidation.
The primary effect of Co-Pi therefore is the inhibition of
surface recombination.30 The volcano-shaped ηinj is due to the
maximized Co-Pi effect at the low potential region and the
kinetic bottleneck effect of Co-Pi at the high potential region. It
is usually found that the Co-Pi effect is reduced with increasing
bias potential over 1.23 VRHE, because the charge transfer
efficiency is already sufficient without Co-Pi due to the large
band-bending and positive shift of the valence band.5,14,30
Despite the superior catalytic effect, ηsep of Mo-BiVO4/Co-Pi is
very similar to that of Mo-BiVO4 (30%) (Figure 4 vs 7),
indicating the insignificant effect of Co-Pi on the inhibition of
bulk recombination. The impedance analysis shows that the
effect of Co-Pi on the charge transfer resistance is insignificant
(Figure 5). This confirms that bulk recombination is less
affected by Co-Pi.
To enhance ηsep of Mo-BiVO4/Co-Pi along with high ηinj,
WO3 was coupled with Mo-BiVO4 and Co-Pi was then
deposited on the WO3/Mo-BiVO4 binary. This ternary
structure is found to be very promising in generating
photocurrents (Figure 6b). Although the onset potential is
similar to that of Mo-BiVO4/Co-Pi, the photocurrent of the
ternary increases exponentially, reaching approximately 2.4
mA/cm2 at 1.23 VRHE (corresponding to the STH efficiency of
∼3%). As expected, ηsep of the ternary is increased significantly
to ∼60% at 1.23 VRHE (Figure 7). In particular, ηinj of the
ternary is even higher than those of the binaries (Mo-BiVO4/
G dx.doi.org/10.1021/jp400415m | J. Phys. Chem. C XXXX, XXX, XXX−XXX
Article
Co-Pi and WO3/Mo-BiVO4) and is maintained at more than
80% in the region between 1.0 and 1.8 VRHE. This indicates that
the ternary configuration of WO3/Mo-BiVO4/Co-Pi is effective
in enhancing ηsep and ηinj. Decrease in ηinj of the ternary at high
bias potentials (E > ∼1.8 VRHE) may be attributed to the
relatively enhanced photocurrent for H2O2 oxidation (or ηsep)
compared to that for H2O oxidation (eqs 4 and 5). Co-Pi can
effectively catalyze the single electron oxidation of H2O2
without a kinetic limit even at high bias potentials, whereas
the four sequential electron oxidation of water is kinetically
limited by the reduction rate of high valence cobalt (Co3+ and
Co4+) to low valence cobalt (Co2+). This kinetic bottleneck
effect of Co-Pi is commonly observed in photoelectrochemical
reactions.24,26,41,42
■ CONCLUSIONS
Strategic modification is employed to improve the photo-
electrochemical water-oxidation performance of BiVO4 by
decreasing bulk and surface recombination. BiVO4 is doped
with hexavalent elements (W6+, Mo6+, and Cr6+), among which
Mo6+ is found to be most effective in enhancing the
photocurrent generation at 1.23 VRHE. The doping effect is
attributed primarily to the more than 2-fold improved charge
separation efficiency (from ∼12 to ∼25%), resulting from a
decrease in charge transfer resistance, along with a marginal
increase in charge injection efficiency (from ∼40 to ∼50%).
The binary heterojunction of Mo-BiVO4 with either WO3 or
Co-Pi is constructed to further increase the charge transfer
efficiency. The primary effect of the former is an increase in the
charge separation efficiency (∼50%) due to cascaded charge
transfer, whereas the latter results from enhanced charge
injection efficiency (∼80%) due to Co-Pi mediated catalysis.
Therefore, a ternary heterojunction of Mo-BiVO4 with both
WO3 and Co-Pi is very effective in charge separation (∼60%)
and charge injection (∼90%) at 1.23 VRHE by inhibiting the
bulk and surface recombination, respectively. This ternary
structure produces approximately 2.4 mA/cm2 at 1.23 VRHE in a
phosphate electrolyte (pH 7), corresponding to a STH of ∼3%,
without the use of noble metals or strong acids/bases. Although
the basic concept of the modification is not so novel, this study
obviously shows that a systematic experimental approach
promises a high efficiency.
■
ASSOCIATED CONTENT
*
S Supporting Information
XRD patterns of Mo-BiVO4 (Figures S1 and S2), SEM image
of WO3/Mo-BiVO4 (Figure S3), linear sweep voltammograms
of bare and modified BiVO4 (Figure S4), XPS spectra of V2p
for doped BiVO4 (Figure S5), photocurrent time profiles of
bare and doped BiVO4 (Figure S6), comparison of AM1.5 light
spectrum and UV−vis absorption spectra of bare and modified
BiVO4 (Figure S7), Randle circuit (Figure S8), linear sweep
voltammograms of W and Mo codoped BiVO4 (Figure S9), and
photocurrent time profiles of single and heterojunction
electrodes (Figure S10). This material is available free of
charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*Phone: +82-53-950-8973. E-mail: hwp@knu.ac.kr.
Notes
The authors declare no competing financial interest.
The Journal of Physical Chemistry C
■
ACKNOWLEDGMENTS
This research was supported by the Basic Science Research
Programs (Nos. 2012R1A2A2A01004517, 2010-0002674, and
2011-0021148) and the Korea Center for Artificial Photosyn-
thesis (KCAP; No. 2012M1A2A2671779) through the Na-
tional Research Foundation (NRF) funded by MEST, Korea.
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