128 Electrochemistry

― Communication ―

Utilization of Fe3+/Fe2+ Redox for the Photodegradation of

Organic Substances over WO3 Photocatalyst
and for H2 Production from the Electrolysis of Water
Takeo ARAI, Masatoshi YANAGIDA, Yoshinari KONISHI, Hideki SUGIHARA, and
Kazuhiro SAYAMA*
Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology (AIST),
(Tsukuba Central 5, 1-1-1 Higashi, Tsukuba 305-8565, Japan)

Received July 31, 2007 ; Accepted November 6, 2007

WO3 is a visible-light-responsive photocatalyst, but the potential of its conduction band is not negative enough to
produce H2 from water or to reduce O2 in the photodegradation reaction of various waste organic materials, environ-
mental pollutants, and biomass. The activity of WO3 for the photodegradation of various organic substances into CO2
was markedly enhanced by the addition of Fe3+, mainly due to the electron-accepting effect of the reduction of Fe3+
to Fe2+. WO3 in the presence of Fe3+ was more active than TiO2 even under ultraviolet-visible light for the degrada-
tion of lower-molecular-weight organic substances. The Fe2+ generated in the photocatalytic reaction could be oxi-
dized to Fe3+ by means of a hybrid system of electrolysis and photocatalysis accompanied by the production of H 2
from water at a low external bias (＜ 1 V).

Key Words : Photocatalyst, Tungsten Oxide, Ferric Ion, Photodegradation, Hydrogen Generation

1 Introduction using a renewable energy source is important. It is con-

Photocatalysis with sunlight has the potential to be a
beneficial technology for environmental purification and
solar energy conversion for H2 production. TiO2 under
UV light is in practical use for the degradation of harm-
ful organic substances. However, for more efficient uti-
lization of sunlight, the development of materials that are
active under visible light is necessary. WO3 is a visible-
light-responsive photocatalyst for O2 generation using
sacrificial reagents,1,2）but reports on the degradation of
organic compounds with WO3 are limited.3-8）The conduc-
tion band of WO3 has a positive potential (ca. +0.5 V vs.
NHE) compared with that of TiO 2 . 9） Therefore, the
reduction of O2 (O2/O2･−＝−0.563 V vs. NHE) over WO3 is
expected to be difficult. Fe3+ reportedly accelerated the
photocatalytic activity of TiO2 and X-doped TiO2 powder
(X ＝ S, N).10,11）The redox potential of Fe3+/Fe2+ (+0.77 V
vs. NHE) is more positive than the bottom potential of
the WO3 conduction band; therefore, an electron on WO3
can reduce Fe3+ to Fe2+ in aqueous solution. To achieve a
total catalytic reaction, Fe2+ must be reoxidized to Fe3+,
but the oxidation of Fe2+ by O2 dissolved in water is gen-
erally slow at acidic and neutral pH. We previously pro-
posed a photocatalysis-electrolysis hybrid system for the
economical splitting of water into H2 and O2 using an
Fe3+/Fe2+ redox reaction; O2 evolution accompanies the
reduction of Fe3+ on the WO3 photocatalyst, and H2 evo-
lution accompanies the oxidation of Fe2+ using an elec-
trolyzer.12）The electrolyzer for H2 production using Fe2+
is already being established on a pilot-plant scale at a
low external bias (＜ 1 V),13）whereas the normal elec-
trolyzer bias from water is 1.6-2 V. Therefore, the devel-
opment of an efficient system for the production of Fe2+
sidered that the photocatalytic activity on the Fe 3+
reduction to Fe2+ is improved by using water-soluble bio-
mass and wastewater containing organic compounds as
hole scavengers. In this study, we investigated the effect
of Fe3+ on WO3-catalyzed photodegradation of various
organic compounds, and the possibility of using the pho-
tocatalysis-electrolysis hybrid system both for H2 produc-
tion and for the purification of aqueous solutions contain-
ing organic compounds.
2 Experimental
In the photodegradation experiment, 150 mg of WO3
powder (Kanto Chemical, Japan) was used as a visible-
light-responsive photocatalyst, and 15 mg of TiO2 (P-25,
Nippon Aerosil, Japan) was used as a reference photocat-
alyst. A solution containing Fe3+ was prepared by dis-
solving 1.4 g of Fe2(SO4)3･nH2O (Wako Pure Chemical
Industries, Japan, n ＝ 6-9) in 25 ml of ion-exchanged
water. Ethanol, formic acid, acetic acid, phenol, sucrose,
polyethylene glycol 300 (PEG 300), and hydroxyethyl cel-
lulose (HEC) were used as organic substances. The
organic substances (10 µl) were added to 1 ml of ion-
exchanged water or Fe2(SO4)3 solution. These solutions
were used as reaction solutions. A borosilicate glass vial
(4.4 ml) was used as a reaction vessel. The photocatalyst
powder and the reaction solution were introduced into
the vial, and the vial was capped with a septum. The
bottom of the vial (area : 1.1 cm2) was irradiated with
light from a xenon lamp (Cermax LX-300, PerkinElmer,
USA) equipped with a cold mirror and an infrared-reduc-
ing filter. A 420-nm cutoff filter (L-42, Hoya, Japan) was
used with the xenon lamp for visible light irradiation.
76，No. 2（2008） 129

The amount of CO 2 generated in the photocatalytic O2/O2･− (−0.563 V vs. NHE) and because the concentra-
degradation reactions of the organic substances was tion of Fe3+ in the aqueous solution was higher than that
measured using a gas chromatograph (GC-14B, of dissolved O2. When WO3 was utilized in Fe3+ solution
Shimadzu, Japan) with a flame ionization detector at low concentration (2 µmol as Fe3+), the CO2 generation
equipped with a methanizer. rate was also improved in the first stage of reaction.
Photoelectrochemical measurement and electrochemi- However, it was decreased after the stoichiometric
cal measurement were performed using an electrochemi- amount of CO2 (1 µmol) toward the reduction of Fe3+ ion
cal analyzer (Model 630A, ALS, Japan) and a two-com- was formed (Fig. 1(b)). This result suggests that the oxi-
partment cell with a Nafion membrane. In the photoelec- dation rate of Fe2+ to Fe3+ by air in aqueous solution is
trochemical measurements, a WO3 film electrode and a probably slower than the reduction rate of Fe3+ in the
Pt wire were used as the working and counter elec- photocatalytic reaction under this reaction condition.
trodes, respectively. The porous WO3 film electrode was The effect of Fe3+ was confirmed in the photoelectro-
prepared from a precursor solution reported by chemical measurement using a two-electrode system
Augustynski et al.14）Conductive glass (F-doped SnO2, 10 consisting of a WO3 photoanode and a Pt cathode in a
Ω/sq cm) was coated with the precursor solution by two-compartment cell (Fig. 2). In this measurement, the
means of a spin-coater and fired at 550 ℃. H2SO4 solution absolute potential level depends on the condition of the
(1 mol/L, pH 0) was used as the electrolyte. A 500-W
xenon lamp (UXL-500D-0, Ushio, Japan) was used as the
light source. In the electrochemical measurements, two
Pt wires were used as the working and counter elec-
trodes. For an electrolyte, H2SO4 solution (pH 0) was
used in the counter electrode. A suspension of WO3 pow-
der in an Fe2(SO4)3 solution containing formic acid was
used in the working electrode. To generate Fe2+ by pho-
tocatalytic reaction, the suspension was irradiated with a
xenon lamp (Cermax, LX-300) for 1 h. The electrolyzer
current before and after the photocatalytic reaction was
measured at 0.9 V of applied bias.

3 Results and Discussion

The presence of Fe 3 + in the solution drastically
improved the activity of WO3 (Fig. 1). The presence of
Fe3+ was also effective for TiO2, but the combination of
WO3 powder and Fe3+ was more active than the TiO2
and Fe3+ combination under ultraviolet and visible light
(UV-vis) conditions, as well as under visible light (vis)
conditions. Note that the solution containing Fe3+ without
a photocatalyst decomposed formic acid into CO2 slightly
under UV-vis conditions, owing to direct photoexcitation
of Fe3+,15）but the amount of CO2 produced was low com-
pared with that produced in the presence of photocata-
lysts. The activity of WO3 was lower than that of TiO2 in
the absence of Fe3+. The low photooxidation activity of
WO3 in aqueous solution may be due to slow O2 reduc-
tion because of the positive potential of the WO3 conduc-
tion band (ca. +0.5 V vs. NHE). When the photoreactions
were carried out in water without Fe3+, both the WO3
powder and the TiO2 powder changed to a dark blue
color after the photoreaction, whereas when the reac-
tions were carried out with Fe3+, the powders did not
change color. This result suggests that the photoexcited
electrons in WO3 and TiO2 were consumed not only by
the reduction of O2 but also by the reduction of WO3 and
TiO2 themselves. However, in the presence of Fe3+, the
photoexcited electrons in WO3 and TiO2 were consumed
quickly by the reduction of Fe3+ to Fe2+ instead of by O2
reduction. It is considered that the rate of reaction of Fig. 1 Time course of CO 2 formation during
electrons with Fe 3+ was fast enough to prevent the photocatalytic degradation of formic acid over WO3 and
reduction of WO3 and TiO2, because the Fe3+/Fe2+ redox TiO2 photocatalysts with and without Fe3+ under UV-vis
potential (+0.771 V vs. NHE) is more positive than that of conditions (a) and vis conditions (b).
130
Fig. 2 Potential-current curve of the WO3 photoelectrode
in the presence and absence of Fe3+.
The two-electrode measurement was performed in a two-
compartment cell with a Nafion membrane. H2SO4 solution
(25 ml, pH 0) was used as the electrolyte in both cells.
Formic acid (25 ml) was introduced into the WO3 electrode
side, and Fe2(SO4)3 solution (1 ml) was introduced only into
the Pt electrode side.
Fig. 3 The enhancement of current by Fe2+ generated in
the photocatalytic reaction.
Two platinum wires were used as the working and
counter electrodes. H2SO4 solution (30 ml) was used as the
electrolyte on the counter electrode side. On the working
electrode side, WO3 powder was dispersed in a solution of
15 ml of H2SO4 solution, 15 ml of Fe2(SO4)3 solution and 0.5
ml of formic acid. The applied bias between the two
electrodes was 0.9 V.
Pt electrode, and the x-axis refers to the difference of
potential between the Pt electrode and the conductive
glass substrate of the WO3 electrode. At 0 V without
external bias, the photocurrent was almost zero in spite
of the presence of O2 in the solution on the Pt side, and
the photocurrent was markedly enhanced, to ca. 1 mA,
by the addition of Fe 2 (SO 4 ) 3 solution on the Pt side.
These results suggest that little O2 reduction occurred
and that Fe3+ was reduced on the Pt counter electrode
by an electron from WO3 without bias, as explained by
the difference between the redox potentials of Fe3+/Fe2+
and O2/O2･−. The photocurrent of the WO3 electrode was
drastically increased by utilizing the reduction reaction
of Fe3+, which was probably the reason for the enhance-
Electrochemistry
Fig. 4 Amount of CO 2 produced by photocatalytic
degradation of various organic substances over WO3 and
TiO2 photocatalysts in the presence and absence of Fe3+.
Formic acid, acetic acid, ethanol, and PEG 300 were used as
provided. Commercial sugar was used as sucrose. Phenol
and HEC were dissolved in ion-exchanged water at 0.5 M
and 5 wt%, respectively. Organic substances (10 µl, except
100 µl for HEC) were introduced into solution. The amount
of CO2 generated in each experiment was measured after 3
h irradiation under UV-vis conditions and normalized by
the amount generated from TiO2 in water.
ment of the photocatalytic reaction.
Fe3+ is reduced to Fe2+ in the photodegradation of an
organic substance over WO3. In the case of the photo-
catalysis-electrolysis hybrid system, Fe2+ can be used to
decrease the electrolysis bias for the production of H2
from water.13）Figure 3 shows the time course of the cur-
rent in the electrolyzer at 0.9 V before and after photo-
catalytic reaction. The current for H2 production during
the electrolysis of the Fe2(SO4)3 aqueous solution before
the photocatalytic reaction was very small. In contrast,
after the photocatalytic reaction, the current was
markedly enhanced, to ca. 4 mA, because anodic oxida-
tion of Fe2+ to Fe3+ took place instead of O2 production.
The amount of H2 generated in the electrolysis for 15
minutes was estimated as ca. 18 µmol. The hydrogen
generation rate will be improved by the optimization of
working and counter electrodes, electrolyte and applied
potential. These results suggest that the Fe2+ accumulat-
ed during photocatalysis is available for H2 generation
when photocatalysis is hybridized with electrolysis. The
oxidation rate of Fe2+ by air in aqueous solution is very
slow as described previously. It is advantage for photo-
catalysis-electrolysis hybrid system because Fe2+ can be
consumed preferentially for the electrolysis to generate
hydrogen without considering the loss by the oxidation
by air.
To investigate the availability of Fe3+ in the photocat-
alytic reaction, we photodegraded various organic sub-
stances over WO3 and TiO2 photocatalysts in aqueous
solution in the presence and absence of Fe3+ under UV-
vis conditions (Fig. 4). For all the organic substances, the
activity of WO3 was markedly enhanced by the presence
of Fe3+. In the photodegradation of formic acid, acetic
acid, ethanol, and phenol, the activity of WO3 in Fe2(SO4)3
76，No. 2（2008）
solution was higher than that of TiO2. In contrast, the
activity of WO3 was equivalent to that of TiO2 in the
photodegradation of sucrose, and lower than that of TiO2
in the photodegradation of PEG 300 and HEC. These
results suggest that the WO3 photocatalyst is more suit-
able than TiO2 especially for the degradation of lower-
molecular-weight organic substances. Note that the WO3
photocatalyst with Fe3+ is useful for the photodegrada-
tion of harmful organic substances, such as phenol, or for
organic substances derived from biomass, such as
sucrose. The combination of the photocatalytic degrada-
tion of organic substances and electrolysis at low bias
using redox mediators is expected to be practical both
for environmental purification and for H 2 production
from wastewater and biomass.
4 Conclusion
Photocatalytic oxidation of organic substances over
WO3 powder was enhanced by the addition of Fe3+. In
the presence of Fe3+, WO3 powder showed higher activi-
ty than TiO2 (P-25) under UV-vis conditions, as well as
under vis conditions. The results of photoelectrochemical
measurement indicated that the photocurrent of the
WO3 electrode was increased drastically in the presence
of Fe3+, and confirmed the electron-accepting effect due
to the reduction of Fe 3 + to Fe 2+ . We attribute the
enhancement of the photocatalytic reaction to this effect.
Utilization of an Fe3+/Fe2+ redox couple would permit
the use of a visible-light-responsive material with a posi-
tive conduction band potential, such as WO3, to decom-
pose organic substances efficiently under visible light
irradiation. Fe2+ generated by photocatalytic reduction of
Fe3+ can reduce the potential for the generation of H2
from the electrolysis of water. The combination of pho-
todegradation of organic substances and electrolysis in
solution is expected to be useful for both environmental
purification and energy production.
131
Acknowledgement
This study was partially supported by the New
Energy and Industrial Technology Development
Organization (NEDO) of Japan.
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