i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 2 0 7 3 6 e2 0 7 4 3

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Facile and simple fabrication of an efficient

nanoporous WO3 photoanode for visible-light-
driven water splitting

Xiaohong Zhang a,b, Debraj Chandra a, Masashi Kajita a,

Hidehito Takahashi a, Li Dong a, Akinori Shoji a, Kenji Saito a,
Tatsuto Yui a, Masayuki Yagi a,c,*
a
Department of Materials Science and Technology, Faculty of Engineering, Niigata University, 8050 Ikarashi-2,
Niigata, 950-2181, Japan
b
College of Chemistry and Chemical Engineering, Qiqihar University, Wenhua Street 42, Qiqihar, 161006, China
c
Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST),
4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan

article info abstract

Article history: Tungsten trioxide (WO3) films with nanoporous morphology were prepared by a facile and
Available online 4 July 2014 simple method utilizing commercially available WO3 nanopowder with polyethylene glycol
to guide porosity of a nanostructure, and the resulted photoanode was working efficiently
Keywords: for visible-light-driven water oxidation. The SEM observation and XRD measurement
Tungsten trioxide revealed formation of interparticulate nanopores between the well-connected WO3 crys-
Photoelectrocatalysis taline particles of dimension ca. 100e200 nm. The nanoporous WO3 electrode generated a
Nanoporous structure significant photoanodic current density of 1.8 mA cm
2 due to water oxidation at 1.0 V
Water oxidation versus Ag/AgCl on visible light irradiation (l > 390 nm, 100 mW cm
2). The onset potential
of the WO3 electrode was 0.67 V versus a reversible hydrogen electrode (RHE), being lower
by 0.56 V than the theoretical potential for water oxidation (1.23 V versus RHE). The inci-
dent photon to current conversion efficiency (IPCE) reached 45% at 400 nm of light wave-
length and 1.04 V versus Ag/AgCl of an applied potential. The photoanodic current and
photostability of the WO3 electrode were improved by addition of Co2þ ions in the elec-
trolyte solution during photoelectrocatalysis.
Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

[1e3]. The conversion of solar energy into hydrogen repre-

Introduction sents an attractive but challenging alternative in photo-
electrochemical (PEC) cells [4,5], following the pioneer work on
Concern over climate change due to global warming becomes a TiO2 photoanode for water splitting by Honda and Fujishima
increasingly important, and in this regard hydrogen has [6]. Unfortunately a wide band gap of TiO2 (3.0e3.2 eV) causes
featured prominently as a clean and renewable energy source to absorb only an ultraviolet fraction of a solar spectrum

* Corresponding author. Department of Materials Science and Technology, Faculty of Engineering, Niigata University, 8050 Ikarashi-2,
Niigata, 950-2181, Japan. Tel./fax: þ81 25 262 6790.
E-mail address: [email protected] (M. Yagi).
http://dx.doi.org/10.1016/j.ijhydene.2014.06.062
0360-3199/Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 2 0 7 3 6 e2 0 7 4 3 20737

(accounts for just 4% of solar irradiation) and consequently Seiyaku Co. An indium tin oxide (ITO)-coated glass substrate
responsible for low efficiency in utilization of solar light [4,7,8]. was obtained from Asahi Glass Co. Millipore water was used
Therefore, intensive researches have been focused on mate- for all the experiments. All other chemicals unless mentioned
rials with a relatively narrower band gap than TiO2 to expand otherwise were of analytical grade and used as received.
light absorption to a visible region. Several single component
and composite materials (WO3, Fe2O3, Ta3N5, TaON, BaZ- Preparation of electrodes
rO3eBaTaO2N, etc.) have been investigated to achieve efficient
visible-light-driven water splitting [9e20]. A nanoporous WO3 film-coated ITO (ITO/WO3) electrode was
WO3, an n-type semiconductor has attracted immense prepared by using a doctor-blade technique. Before coating,
attention as a photoanode material for water oxidation in PEC an ITO glass substrate (1.0 cm2 area) was cleaned up by the
cells because of its visible light response (band gap, UV-Ozone treatment (SEN LIGHTS Co., Photo Surface Proces-
Eg ¼ 2.6e2.8 eV), a thermodynamically possible valence band sor PL16-110) for 15 min. In a typical procedure, 300 mL water
edge position for water oxidation (3 V versus the normal was added to a mixture of 200 mg WO3 nanopowder, 100 mg
hydrogen electrode) and good photochemical stability under PEG and 20 mg marpolose. The mixture was stirred for 2 ~ 4 h
acidic conditions [9e12,21e23]. So far, several efforts for until a smooth paste was formed. The resulting paste was
nanostructural control of WO3 have been paid to increase a squeezed over the ITO glass substrate by a doctor-blade coater
contact area between an electrode and electrolyte solution and dried at 80  C for 15 min. After repeating the procedure for
and to make electron transport in WO3 layers easier, intended 2 times, it was calcined at 550  C for 90 min to obtain the
for enhancing performance of PEC water oxidation at WO3 nanoporous WO3 film on the ITO glass substrate.
electrodes [9,11,24e27].
WO3 films have been prepared by several techniques, e.g., Structural characterization
vacuum evaporation [28], chemical vapor deposition [29,30],
solegel precipitation [23e26,31], spin coating [32], sputtering The crystalline phase of the nanoporous WO3 film was char-
[33] and electrodeposition [34e38]. The low-cost chemical acterized by powder X-ray diffraction (XRD; Rigaku, Mini-
procedure like a solegel technique is selected for a wide range FlexII) using monochromated Cu Ka (l ¼ 1.54 Å) radiation. The
of applications [23e26,31]. Santato et al. reported the prepa- nanoporous structure of the film was imaged by scanning
ration of a transparent crystalline WO3 film with inter- electron microscopy (SEM; JEOL, JSM-6510LV), and prior to SEM
connected nanoparticulate structures by a spin-coat of the observation the samples were gold-coated by sputtered
colloidal tungstic acid precursor solution (obtained by passing deposition (Sanyu Electron, Quick Coater SC-701). UVevisible
an aqueous solution of sodium tungstate through a proton diffuse reflectance spectra (DRS) were recorded on a JASCO V-
exchange column) and followed by calcination under oxygen 670 spectrophotometer.
atmosphere at 550  C [24e26]. However, one needs to be pro-
ficient in preparation of the precursor solution involving a Photoelectrochemical measurements
somewhat complicated procedure for reproducible fabrication
of the WO3 film. Sayama et al. reported the fabrication of a Photoelectrochemical measurement was carried out in a two-
WO3 film from an oxygen rich amorphous peroxo-tungstic compartment electrochemical cell separated by a Nafion
acid precursor prepared using a relatively easy technique membrane using an electrochemical analyzer (Hokuto, HZ-
[39e41]. Our aim is to develop a simple and reproducible 3000). A three-electrode system has been employed by using
fabrication technique for a WO3 film without a complicated ITO/WO3 and Ag/AgCl electrodes in one compartment as
procedure of precursor preparation, which is beneficial for working and reference electrodes, respectively and a Pt wire in
general researcher especially out of a chemistry field. Herein the other compartment as a counter electrode. An aqueous
we report a facile, simple and low-cost method for the prep- 0.1 M phosphate solution were used as an electrolyte in both
aration of the nanoporous WO3 film utilizing commercially the compartments, which was saturated with Ar gas prior to
available WO3 nanopowder (instead of laboratory-made the electrochemical measurement. For the study on effect of
tungsten precursors) with polyethylene glycol (PEG) to guide Co2þ ions on the photoelectrocatalytic performance, 0.1 mM
porosity of a nanostructure. The high performance of photo- Co(NO3)2.6H2O was contained in the electrolyte solution of the
electrocatalytic water oxidation of the nanoporous WO3 film is working electrode compartment. The cyclic voltammogram
presented, and furthermore the photostability of the nano- (CV) was recorded at a scan rate of 50 mV s
1 at 25  C under Ar
porous WO3 electrode during photoelectrocatalysis is atmosphere. Light (l > 390 nm) was irradiated from a backside
discussed. of the working electrode using a 500 W xenon lamp (Ushio
Inc., Optical ModuleX) with a UV-cut-filter (L39) and a liquid
filter (0.2 M CuSO4) for cutting of heat ray. The output of light
Experimental section intensity was calibrated as 100 mW cm
2 using a spectror-
adiometer (Ushio Inc., USR-40). IPCE data were calculated
Materials using Equation (1):

IPCEð%Þ ¼ ½1241$IP =ðl$4Þ  100 (1)

Tungsten trioxide (WO3) nanopowder (particle size, <100 nm)

2
2
was purchased from Aldrich. Polyethylene glycol (PEG, mo- where IP (mA cm ), l (nm), and 4 (mW cm ) denote photo-
lecular weight ¼ 2000) was obtained from Wako Chemical Co. current density recorded at given conditions, wavelength and
Marpolose (60 MP-50) was purchased from Matsumoto Yushi- intensity of incident photon, respectively. Monochromatic
20738 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 2 0 7 3 6 e2 0 7 4 3

irradiation was carried out using a 500 W xenon lamp in The SEM images of the ITO/WO3 film prepared under
combination with a monochromator (Jasco Corp., M10). Pho- typical conditions and then calcined at 550  C are shown in
toelectrocatalysis was conducted at 25  C under the poten- Fig. 1. The top-view of the SEM image at a low magnification
tiostatic conditions of 0.5 V vs Ag/AgCl under illumination of (Fig. 1a) exhibits a flawless and smooth porous network,
light (l > 390 nm; intensity 100 mW cm
2) for 1 h. The amounts extended over several micrometer without any significant
of H2 and O2 evolved were determined from the analysis of the crack formation. The SEM image at higher magnification
gas phase (headspace volume: 87.3 mL) of counter and work- (Fig. 1b) shows that a nanoporous network is composed of
ing electrode compartments, respectively using a gas chro- embedded ball-like WO3 particles of ca. 100e200 nm in di-
matography (Shimadzu, GC-8A with a TCD detector and ameters, being well-connected to each other. From the cross-
molecular sieve 5A column and Ar carrier gas). sectional SEM image the film thickness was measured to be ca.
20 mm. The X-ray diffraction (XRD) patterns of the ITO/WO3
film calcined at 200e600  C are shown in Fig. 2. The films
Results and discussion exhibited sharp and intense peaks for all the calcination
temperatures employed due to preattainment with optimum
When a WO3 film was prepared on the ITO substrate from only crystallization of WO3 nanopowders used in the coating paste.
a dispersion of WO3 nanopowder (200 mg) in water (3.0 ml), a The d-spacings calculated from the corresponding peaks of
reproducible film was not obtained due to low viscosity of the the XRD patterns are in good agreement with phase-pure
dispersion medium. In case of either PEG or marpolose monoclinic WO3 (JCPDS number: 43e1305). This crystalline
(120 mg) included in the dispersion medium (200 mg WO3 in nanoporous structure of the connected WO3 particles is
3.0 ml water) for preparation of a coating paste, the quality of important to yield a large interface between the electrolyte
the resulted WO3 film was better than that prepared without and film and efficient electron transport through the film,
PEG or marpolose but it was not sufficiently homonegeous. which are consequently expected to work efficiently for PEC
However, the use of both PEG (100 mg) and marpolose (20 mg) water oxidation since the electron and hole pairs generated by
in the coating paste gave a highly reproducible and homoge- photoexcitation of WO3 would have less chance to recombine
neous WO3 film exhibiting a significant photocurrent before participating in a water oxidation reaction at the WO3
response as discussed in the latter section. Marpolose helps to surface.
attach the coating paste on the ITO substrate by increasing The PEC water oxidation at the nanoporous ITO/WO3
viscosity of the dispersion medium, which is necessary to electrode (calcined at 550  C) was studied in a 0.1 M phosphate
produce an uniform layer of coating by a doctor blade method. solution. On cyclic voltammograms (CVs) at pH ¼ 6.0 in the
PEG acts as a binder between WO3 particles as well as guides dark, no redox response was observed in a range of
porosity of a nanostructure [11]. The organic additive is well-
0.2 ~ 1.0 V vs. Ag/AgCl except a response based on WO3/
defined to play a role as a template for formation of various HxWO3 below 0 V (black line in Fig. 3a). Upon visible light
nanostructures of the metal oxides [11,25,42,43]. irradiation (l > 390 nm, 100 mW cm
2) the significantly high

Fig. 1 e (a and b) Top view and (c) cross-sectional scanning electron microscopic (SEM) image of the nanoporous ITO/WO3
electrode prepared under the typical conditions.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 2 0 7 3 6 e2 0 7 4 3 20739

60

50

40

IPCE (%)

KM
30

20

10

0
380 400 420 440 460 480 500
Wavelength / nm

Fig. 4 e Action spectrum of IPCE (black line and symbols)

Fig. 2 e X-ray diffraction (XRD) patterns of (a) WO3 for the nanoporous ITO/WO3 electrode in a 0.1 M
nanopowder, (b) bare-ITO, and the WO3 films calcined at (c) phosphate buffer solution of pH ¼ 6.0 at 1.04 V vs. Ag/AgCl.
25, (d) 200, (e) 300, (f) 400, (g) 500 and (h) 600  C. The red line shows is UVevisible diffuse reflection spectra
as Kubelka-Munk (KM) function of the nanoporous ITO/
WO3 electrode. (For interpretation of the references to color
in this figure legend, the reader is referred to the web
photoanodic current was observed above 0.12 V vs. Ag/AgCl version of this article.)
and reached 1.76 mA cm
2 at 1.0 V. The potential values of CV
data were converted from Ag/AgCl to reversible hydrogen
electrode (RHE) according to Equation (2): penetration restriction. The photocurrent was measured by
 changing light intensity from 0 to 172 mW cm
2 (Fig. 3c). It
ERHE ¼ EAg=AgCl þ ð0:059  pHÞ þ EAg=AgCl (2)
increased linearly with an increase in light intensity up to
where ERHE is the calculated potential versus RHE, EAg/AgCl is 100 mW cm
2, indicating that the photocurrent generation is
the measured potential vs Ag/AgCl and E Ag/AgCl ¼ 0.199 V at controlled by a photoexcitation process up to 100 mW cm
2
25  C. The onset potential of the nanoporous ITO/WO3 elec- light intensity. The downward deviation of the photocurrent
trode is 0.67 V versus RHE and it is lower by 0.56 V than the from the linear relationship could be ascribed to controlled
theoretical potential for water oxidation (1.23 V versus RHE). diffusion of the holes and electrons and/or a water oxidation
Fig. 3b shows the dependence of the generated photocurrent reaction at the surface taking place after photoexcitation.
at 1.0 V vs. Ag/AgCl on the thickness of the nanoporous ITO/ Action spectrum of IPCE for the nanoporous ITO/WO3
WO3 electrode. The photocurrent increased up to 20 mm of the electrode in a phosphate solution at pH ¼ 6.0 and 1.04 V versus
film thickness, showing that 20 mm of the WO3 layer from the Ag/AgCl are shown in Fig. 4. The photocurrent was generated
ITO interface is effective for the PEC reaction due to light in a visible light region below 480 nm, and IPCE reached 45% at

Potential / V vs. RHE

0.4 0.6 0.8 1.0 1.2 1.4 1.6 2.5
2.0
a) b) 2.5 c)
2.0
Current density / mA cm
Current denisty / mA cm

1.5
Current density / mA cm

Light 2.0

1.0 1.5
1.5

0.5 1.0
1.0
Dark

0.0 0.5 0.5

E
-0.5 0.0 0.0
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 0 10 20 30 40 0 30 60 90 120 150 180
Potential / V vs. Ag/AgCl Film thickness /μm Light intensity / mW cm

Fig. 3 e (a) Cyclic voltammograms (CVs), (b) plots of photocurrent density versus film thickness and (c) plots of photocurrent
density versus light intensity for the nanoporous ITO/WO3 electrode in a 0.1 M phosphate buffer solution of pH ¼ 6.0. Visible
light (l > 390 nm, 100 mW cm¡2) was irradiated from an ITO substrate side. Photocurrent density at 1.0 V versus Ag/AgCl is
used for plots in (b) and (c). CVs and plots of photocurrent density versus light intensity were measured using an ITO/WO3
electrode of thickness 20 mm.
20740 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 2 0 7 3 6 e2 0 7 4 3

400 nm. The edge of the action spectrum of IPCE agreed with a
band gap energy of 2.64 eV (470 nm), estimated from the 0.6
diffuse reflectance spectrum of the WO3 film (Fig. 4). This
result indicates that the photocurrent is generated by band
0.5

Eon / V vs. Ag/AgCl

gap excitation of WO3. The IPCE of the ITO/WO3 electrode at
0.4
400 nm was measured to be 33% and 42% at 0.5 V and 0.8 V
versus Ag/AgCl respectively. The former IPCE value at 0.5 V is
0.3
inferior to that of efficient small mesopore WO3 film (43% at
0.5 V) [9], but significantly higher than those of inter-
0.2
particulate and bulk WO3 films prepared from peroxo-tungstic
acid precursors using a similar fabrication technique (16 and
0.1
6% respectively at 0.5 V [9]) The latter IPCE value at 0.8 V is
comparable to that of macroporous 3D photonic crystal WO3 0.0
films (40e45% at 0.8 V) [44].
The flat band potential of the nanoporous ITO/WO3 elec- 0 2 4 6 8 10 12
trode was estimated from the onset potential (Eon) of the pH
photoanodic current at various pH of the electrolyte solution.
Fig. 5 e Plots of onset potential (Eon) versus pH for the
Although WO3 is known to be less stable in basic conditions
nanoporous ITO/WO3 electrode in a 0.1 M phosphate
[45], the reliably analyzable CV data of the ITO/WO3 electrode
solution. Eon was calculated as the intersection potential of
were recorded even at pH ¼ 10. Eon was defined as the inter-
the tangential lines of the initial photocurrent rise and x-
section potential of the tangential lines of the initial photo-
axis of the potential in CV data.
current rise and x-axis of the potential in CV data. We can
classify the Eon values into two groups, as shown in Fig. 5. In
the first group, the plot of Eon versus pH gave straight line
below pH ¼ 8.0 with the slope of
69 mV/pH (close to
59 mV/ the small mesopore WO3 film reported earlier [9], but
pH), indicating that the PEC reaction at the surface involves a much higher than those of interparticulate WO3
proton-couple electron transfer reaction with nearly equiva- ðnO2 ¼ 0:9 mmol; FEO2 ¼ 61%; rps ¼ 22%Þ and bulk WO3
lents of electron and proton. Most likely, the water oxidation ðnO2 ¼ 0:4 mmol; FEO2 ¼ 44%; rps ¼ 30%Þ prepared using a
reaction at the surface could occur as represented in Equa- similar fabrication technique [9]. The photocatalytic currents
tions (3) and (4) involving adsorbed hydroxy radical species at pH ¼ 3 and 9 for the nanoporous ITO/WO3 electrode were
(OHads). [46] lower than that at pH ¼ 6 by 1.5 and 1.8 times at 1 min,
respectively (Fig. 6c and d). ðnO2 Þ increased in a pH region from
2H2 Oads /2OH$ads þ 2e
þ 2Hþ (3) 3 to 6, although rps remains almost unchanged in this pH re-
gion, as shown in Fig. 7 (with nearly same ðFEO2 Þ, Table 1). The
2OH$ads /O2 þ 2e
þ 2Hþ (4) increase of ðnO2 Þ is ascribed to easier water oxidation accord-
ing to Nernst equation as pH increases. ðnO2 Þ decreased dras-
where the subscript “ads” means adsorbed species on the WO3 tically above pH ¼ 7 concomitantly with decreases of rps and
surface. In the second group, the same plot above pH ¼ 8.0
gave the straight line but the slope (
30 mV/pH) is low (as
absolute value), indicating that the PEC reaction involves
another process of 2 equivalents of electron per a proton, 1.0
competing with the water oxidation reaction at the surface
-2
Current density / mA cm

above pH ¼ 8. 0.8
Photoelectrocatalysis over the nanoporous ITO/WO3 elec-
trode was conducted in a 0.1 M phosphate solution under the
0.6 a)
potentiostatic conditions at 0.5 V versus Ag/AgCl for 1 h upon
visible light irradiation (l > 390 nm, 100 mW cm
2). The b)
0.4
photocurrent-time profile at pH ¼ 6.0 (Fig. 6) exhibits an initial
spike in the photocurrent upon illumination (related with the c)
capacitance component at the solideliquid interface), fol- 0.2
d)
lowed by a photocatalytic current. The photocurrent density
at 1 min was 0.69 mA cm
2, which decreased to 0.37 mA cm
2 0.0
0 10 20 30 40 50 60
after 1 h. When defining the degree (rps) of photocurrent sta-
Time / min
bility as the photocurrent ratio of 1 min to 1 h to evaluate
stability of photoelectrocatalysis, the rps value at pH ¼ 6 was Fig. 6 e Photocurrent densityetime profiles for the
54%. The charge amount passed during the 1 h photo- nanoporous ITO/WO3 electrode in the (a) presence and
electrocatalysis is 1.69C and the amount ðnO2 Þ of O2 evolved (bed) absence of 0.1 mM Co2þ ion in a 0.1 M phosphate
was 2.6 mmol (59% Faradaic efficiency ðFEO2 Þ), as summarized solution of (a,b) pH 6.0, (c) pH 3.0 and (d) pH 9.0 at 0.5 V vs.
in Table 1. The performance of PEC water oxidation is Ag/AgCl. Visible light (l > 390 nm, 100 mW cm¡2) was
lower than that ððnO2 ¼ 4:2 mmol; FEO2 ¼ 79%; rps ¼ 76%ÞÞ for irradiated from an ITO substrate side.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 2 0 7 3 6 e2 0 7 4 3 20741

Table 1 e Summary of photoelectrocatalytic water oxidation at different pH using nanoporous ITO/WO3 photoanodes in a
0.1 M phosphate solution.
pH Charge/C ðnO2 =mmolÞ ðFEO2 ð%ÞÞa ðnH2 =mmolÞb ðFEH2 ð%ÞÞc rpsd (%)
3.0 1.03 1.7 65 4.7 88 56
4.0 1.12 1.7 59 5.0 87 53
5.0 1.37 2.1 59 6.3 89 52
6.0 1.69 2.6 59 7.4 85 54
6.0e 2.14 3.8 69 9.5 86 74
7.0 1.38 2.3 64 6.3 88 41
8.0 1.37 1.8 50 6.1 86 27
9.0 0.61 0.52 33 2.7 85 18
10.0 0.56 0.64 44 2.5 87 7.6
a
Faradic efficiency of O2 evolution.
b
nH2 is the amount of H2 evolved in the Pt counter electrode compartment.
c
Faradic efficiency of H2 evolution.
d
rps is a degree of photocurrent stability, calculated as the photocurrent ratio of 1 min to 1 h during photoelectrocatalysis
e
Photoelectrocatalysis was conducted in the presence of 0.1 mM Co2þ ion in a 0.1 M phosphate solution.

FEO2 due to photocorrosion of WO3 film under basic conditions evidence for the formation of either Co-Pi [48] or CoOx [49]
[45], which is consistent with the mechanistic change in the catalysts during photoelectrocatalysis, as discussed in
proton-coupled PEC reactions in Fig. 5. earlier report [9]. This enhancement could be explained by
The photocurrent decrease and low FEO2 during photo- acceleration of the water oxidation reaction at the WO3 sur-
electrocatalysis at acidic and neutral conditions could be face by Co2þ ions adsorbed, being predominant to the photo-
attributed to photo-oxidation of WO3 by the accumulated oxidation of WO3. However, the performance of PEC water
holes to form inactive tungsten-peroxo adducts at the surface oxidation was not sufficiently improved by addition of Co2þ
[22]. We earlier reported that the photo-oxidation was sup- ions (rps ¼ ~73%, FEO2 ¼ e69%), when comparing with that
pressed by Co2þ ions in an electrolyte solution to enhance the (rps ¼ ~95%, FEO2 ¼ 81%) under the same conditions for the
performance of PEC water oxidation at the small mesopore small mesopore WO3 photoanode reported earlier [9]. The
WO3 film [9]. The similar enhancement effect by Co2þ ions in high photostability of the small mesopore WO3 photoanode is
an electrolyte solution was reported for PEC water oxidation at attributed to low effective concentration of the accumulated
a hematite photoanode [47]. In the presence of 0.1 mM Co2þ holes at the surface caused by their high surface-to-volume
ions in the phosphate buffer solution of pH ¼ 6, the perfor- ratio.
mance of PEC water oxidation at the nanoporous ITO/WO3
electrode was enhanced compared with those in the absence
of Co2þ ions (Fig. 6a, Table 1). Consequently the amount of O2 Conclusions
evolved (3.8 mmol) was about 1.5 times higher compared with
that (2.6 mmol) in the absence of Co2þ ion. We do not have any A nanoporous WO3 film was prepared on an ITO electrode by a
facile, simple and low cost method using commercial WO3
nanopowder. PEG additive was used as a binder between the
70 3.0 WO3 particles and guided nanoporosity in the film composed
of well-connected crystalline WO3 particles of diameter
60 2.5 ~100e200 nm. The WO3 film worked efficiently as a photo-
anode for PEC water oxidation and the photoelectrocatalytic
50
2.0 performance was further improved by addition of Co2þ ions in
nO2 / μmol

the electrolyte solution. The WO3 film is available as a

rps (%)

40
1.5 benchmark photoanode for water oxidation required for a PEC
30 water splitting device because a reproducible film is easily
1.0 prepared without a complicated procedure of precursor
20
preparation, especially for general researcher out of a chem-
0.5 istry field.
10

0 0.0
2 3 4 5 6 7 8 9 10 11
pH Acknowledgment

Fig. 7 e Plots of degree of photocurrent stability (rps) and This work was partially supported by the JST PRESTO program
the amount ðnO2 Þ of O2 evolved versus pH for the and Grant-in-Aid for Scientific Research (B) from the Ministry
nanoporous ITO/WO3 electrode in a 0.1 M phosphate of Education, Culture, Sports, Science and Technology (No.
solution. rps was calculated as the photocurrent ratio of 24350028). DC thanks JSPS for providing postdoctoral
1 min to 1 h during photoelectrocatalysis. fellowship.
20742 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 2 0 7 3 6 e2 0 7 4 3

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