Review
Photocatalysis
Photocatalytic Water Splitting for Solar Hydrogen
Production Using the Carbonate Effect and
the Z-Scheme Reaction
Yugo Miseki and Kazuhiro Sayama*
The development of innovative technologies for solar energy conversion and
storage is important for solving the global warming problem and for estab-
lishing a sustainable society. The photocatalytic water-splitting reaction using
semiconductor powders has been intensively studied as a promising tech-
nology for direct and simple solar energy conversion. However, the evolution
of H2 and O2 gases in a stoichiometric ratio (H2/O2 = 2) is very difficult owing
to various issues, such as an unfavorable backward reaction and mismatched
band potentials. Two important findings have widened the variety of photo-
catalysts available for stoichiometric water-splitting, viz. the carbonate anion
effect and the Z-scheme photocatalytic reaction using a redox mediator. The
bicarbonate anion has been found to act as a redox catalyst via preferential
peroxide formation and subsequent decomposition to O2. As the Z-scheme
reaction using a redox mediator mitigates band potential mismatches, it is
widely applicable for various visible-light-active photocatalysts. This review
describes the development of photocatalytic water-splitting for solar hydrogen
production using the carbonate anion effect and the Z-scheme reaction.
Moreover, recent developments in photocatalysis–electrolysis hybrid systems,
an advanced Z-scheme reaction concept, are also reviewed for practical and
economical hydrogen production.
1. Introduction
It is clear that innovative renewable energy technologies
should be developed for a solution to global warming by CO2
from fossil fuel consumption and for an establishment of a
sustainable society. Solar light is the largest renewable energy
resource and is the original power source among wind, sea
wave, hydraulic power, biomass, and ancient fossil fuels. The
total amount of solar energy irradiated on the earth per hour
is almost equivalent to the total amount of energy consumed
by human social activity in the world per year.[1] However,
solar energy has two serious disadvantages, i.e., low-energy
density and fluctuations with weather; therefore, technologies
Dr. Y. Miseki, Dr. K. Sayama
Research Center for Photovoltaics (RCPV)
National Institute of Advanced Industrial Science and Technology (AIST)
Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
E-mail: k.sayama@aist.go.jp
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.201801294.
DOI: 10.1002/aenm.201801294
Adv. Energy Mater. 2018, 1801294 1801294  (1 of 15)
www.advenergymat.de
for the direct utilization of solar energy
have been very limited. Technologies for
photovoltaic, solar thermal, and biomass
energies have been realized commer-
cially, but it is unclear whether the global
energy problem will be solved in future
by these simple extensional technologies.
Thus, it is essential to develop new and
simpler technologies with lower costs per
area than photovoltaics to use low-energy-
density solar energy. Photovoltaics have
a serious disadvantage, as the electricity
cannot be accumulated without an expen-
sive battery. The cost of H2 production
using a simple combination of conven-
tional photovoltaics and an electrolyzer
will be highly expensive. As a promising
candidate for the direct conversion of solar
energy into chemical energy and solar
energy accumulation, the photocatalytic
splitting of water into H2 and O2 has been
intensively investigated in the research
fields of artificial photosynthesis and solar
hydrogen technologies.
Since the Honda–Fujishima effect
was first reported,[2] TiO2 semiconductor
photo­ anodes have been used for water splitting to achieve
low-cost H2 production, and various photoanodes and powder
photocatalysts have been widely studied.[3–10] In particular,
oxide semiconductors have been widely investigated because
they can be simply prepared by calcination in air and are stable
for the O2 evolution reaction. Figure  1 shows the reaction
mechanisms for water splitting into H2 and O2 in photocatalyst
and photoanode systems. In the case of n-type semiconductor
photoanodes, O2 is evolved on the photoanode and H2 is
evolved on the metal cathode, and an external bias is generally
applied between the electrodes to supply a surplus potential for
the reaction. In the case of powdered photocatalysts, a cocata-
lyst is often loaded on the semiconductor surface to accelerate
the reaction. As both the oxidation and reduction reactions are
completed on the small semiconductor particles, photocatalytic
reactors can be simplified and easily enlarged for wide-scale
use. The reaction mechanisms shown in Figure 1 are similar
to the photoexcitation mechanism of semiconductors in photo-
voltaics; thus, the theoretical and maximum solar energy con-
version efficiencies are very high (up to 30%).[11] It has been
evaluated that the photocatalytic reactor cost for water splitting,
where an oxide photocatalyst powder is suspended within an
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aqueous solution in a plastic film package (without a gas sepa-
ration system), could be reduced to ≈$3 m−2.[12] This value is
one-thirtieth of that of a typical solar panel (≈$100 m−2). Thus,
if the solar energy conversion efficiency and lifetime of a photo­
catalytic reactor were equivalent to those of solar panels in
future, the energy conversion cost into chemical energy using
photocatalytic technology would be one-thirtieth cheaper than
that using solar panels. As a solution for the low energy den-
sity of solar light, the very cheap theoretical cost per area of
photocatalytic reactors is an attractive advantage. According to
the DOE report, the efficiency targets of the systems utilizing
powdered photocatalysts or photoelectrodes were estimated to
be 5–15% of solar energy conversion efficiencies.[12c] There-
fore, the general priority in this research field is to develop the
photocatalyst materials showing such a high solar energy con-
version efficiency. Thus, overall water splitting for the produc-
tion of H2 using various semiconductors particle has been
extensively studied by many researchers.[3–10]
The reaction mechanism of photocatalysts is very simple, as
mentioned above, but the water-splitting reaction does not typi-
cally proceed when a semiconductor powder in water is irra-
diated. The following four conditions are required for water
splitting:
(i) suitable conduction and valence band potentials,
(ii) acceleration of the surface reaction,
(iii) suppression of the backward reaction, and
(iv) stability of the photoreaction.
For condition (i), the conduction band potential must be more
negative than that of H+/H2 and the valence band potential
must be more positive than that of O2/H2O. Moreover, a cata-
lyst surface has to possess catalytic properties promoting both
water reduction and water oxidation reactions (condition (ii)).
Various backward reactions containing a water regeneration
reaction must be suppressed (condition (iii)). Of course, a cata-
lyst material needs to be stable during photocatalytic reaction
(condition (iv)). The variety of semiconductors and reaction
solutions that satisfy conditions (i)–(iv) is very limited. In early
papers, only a small amount of H2 gas was detected during the
initial reaction and/or O2 was not detected. To evaluate whether
photocatalytic water splitting actually occurs, it is very important
to make the following observations: steady and stoichiometric
H2 and O2 gas evolution rates (H2/O2  = 2), enough amount of
Figure 1.  Reaction mechanisms of water splitting into H2 and O2 in a) powdered photocatalyst
and b) photoanode systems.
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Yugo Miseki was born in
Tokyo. He received his Ph.D.
degree from Tokyo University
of Science in 2009. Currently,
he is a senior researcher at
the Advanced Functional
Materials Team in AIST. His
research interests include
photocatalysts and photo-
electrodes for water split-
ting and valuable chemical
productions.
Kazuhiro Sayama received his
Ph.D. degree in 1997 from the
Tokyo Institute of Technology.
He became a researcher
at the National Institute
of Materials and Chemical
Research in 1990. He studied
photoelectrochemistry at
the University of Geneva in
1998–1999. Currently, he is
a principal researcher and
team leader of the Advanced
Functional Materials Team in AIST. His research inter-
ests include dye-sensitized solar cell, photocatalysts, and
photoelectrodes for water splitting and valuable chemical
productions.
total gas evolutions than the amount of photocatalyst (larger
turnover number > 1), and long-term stability without changing
the photocatalyst. By the early 1980s, only four photocatalysts
(RuO2–TiO2(G),[13] NaOH-coated Pt–TiO2(G),[14] RhOx–SrTiO3,[15]
and NiOx–SrTiO3[16]) were recognized for reproducible photo-
catalytic water splitting. RuO2–TiO2 and NaOH-coated Pt–TiO2
only worked for gas phase reactions with water vapor (G), not
with liquid water, suggesting the importance of the reaction con-
ditions. By 1990, more photocatalysts, such as Ni-K4Nb6O17,[17]
Ni-Rb4Nb6O17,[18] and RuO2–Na2Ti6O13,[19] had been reported,
but increasing the types of available photocatalysts has been
difficult, even under intense deep UV light,
which is scarcely contained in solar light.
Our group has developed various reaction
methods and conditions for photocatalytic
water splitting to increase the variety of avail-
able photocatalysts and utilize solar energy
effectively, as shown in Figure  2. The find-
ings marked as ★ in this figure were the first
reports in the world. Our strategy is to first
develop reaction methods for practical appli-
cations of solar energy and then to screen
new materials optimized for each new reac-
tion method.
In 1992, it was found that photocata-
lytic water splitting occurred on Pt–TiO2
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Figure 2.  Development of milestone reactions for photocatalytic water splitting by AIST.
suspended in aqueous solution when carbonate salts were
added.[20] The variety of available photocatalysts was signifi-
cantly increased using this carbonate effect.[21–28] Recently, our
group found that H2O2 could be formed and accumulated by
the oxidative reaction of water on photocatalysts and photo­
anodes using the carbonate effect.[29,30] In the second section
of this paper, we review photocatalytic water splitting using this
unique carbonate effect and discuss the reaction mechanism of
the carbonate effect based on our research results over 25 years.
In addition, it is necessary to develop innovative reac-
tion methods to utilize visible light effectively, being away
from the regulation of (i)–(iv) conditions on the conven-
tional photo­catalyst (Figure 1a) mentioned above. Our group
was the first to develop two breakthrough reaction methods,
namely the “photocatalytic Z-scheme reaction” and the “photo­
catalysis–electrolysis hybrid reaction.” The former is a two-step
photoexcitation reaction using powder photocatalysts and a
redox mediator, mimicking the Z-scheme mechanism in nat-
ural photosynthesis as an artificial photosynthesis technology.
The latter is a progression from the photocatalytic Z-scheme
reaction to produce H2 economically and practically within a
shorter period. Developments and recent results on these reac-
tion methods are reviewed in the third and fourth sections of
this paper as a special issue “Energy Research in AIST.”
2. Carbonate Anion Effect on Photocatalytic
Water Splitting
In the early 1990s, our group studied CO2 reduction into CO
or organic compounds using water as an electron donor on
semiconductor photocatalysts such as Pt–TiO2 suspended in
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NaHCO3 aqueous solution with CO2 gas
bubbling. By chance, instead of CO2 reduc-
tion, we found the carbonate effect[20] for
photocatalytic water splitting into H2 and O2
in 1992.
2.1. Carbonate Anion Effect for Water
Splitting over TiO2-Based Photocatalysts
Pt–TiO2 is the typical photocatalyst, and
it has been reported that NaOH-coated
Pt–TiO2 decomposes water stoichiometri-
cally in gas-phase reactions.[14] However, in
the case of liquid-phase reactions, it is diffi-
cult to decompose water on Pt–TiO2. Table 1
shows the rates of photocatalytic H2 and O2
evolution on Pt–TiO2 suspended in several
Na-salt solutions. In the case of no additive
or added NaOH, NaCl, Na2SO4, Na3PO4, and
Na2HPO4, a small amount of H2 was evolved
initially and then H2 evolution gradually
stopped, and no O2 evolution was observed.
In contrast, upon the addition of Na2CO3,
NaHCO3, and K2CO3, the H2 evolution rate
increased dramatically. Furthermore, O2
evolution occurred simultaneously at the
stoichiometric ratio expected for H2O decomposition. The pro-
duction of CO or organic compounds by CO2 reduction was not
observed. The total amount of evolved gases (24.3 mmol H2
and 12.1 mmol O2) was much higher than the amount of TiO2
photocatalyst (3.8 mmol), suggesting a turn over number >1.
Further, no change was observed in the used catalyst after
a long reaction time. These results suggested that the photo-
decomposition of water in this system was indeed a catalytic
reaction.
The evolution rates depended on the concentration of the
carbonate salts. The water-splitting reaction hardly occurred in
dilute solutions at the same pH as in concentrated solutions.
The pH of the carbonate solutions was varied between 8.4 and
11.8, overlapping with those of other solutions without car-
bonate (between 5.5 and 12.0). It was concluded that neither
the pH of the solution nor the cations directly contributes to
water splitting, and that concentrated CO32− or HCO3− anions
are essential for both stoichiometric water splitting and acceler-
ation of the gas evolution rate over Pt-TiO2. At higher pH > 12,
O2 evolution was not observed, even when CO32− anions were
present, suggesting that HCO3− anions are more important
than CO32− for photocatalytic water splitting into H2 and O2.
Moreover, the carbonate effect was also observed in suspen-
sions of RuO2–TiO2 and NiOx–TiO2 (Table 1).[21]
When using a Pt cocatalyst, the influence of the backward
reaction on Pt to form water from H2 and O2 should be con-
sidered. The backward reaction on Pt–TiO2 in carbonate solu-
tions was suppressed by covering of Pt with titanium carbonate
and titanium hydroxide, and the suppression effect increased
as the solution pH increase.[20,25] In contrast, the influence
of the backward reaction on RuO2 or NiOx cocatalysts can be
excluded. Thus, it is suggested that a direct mechanism of
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Table 1. H2 and O2 evolution from various solutions over TiO2 demonstrated that photocatalytic water splitting into H2 and
photocatalysts. O2 occurred under real solar light using the carbonate effect
over NiOx–TiO2 or RuO2–TiO2 photocatalysts.[26–28] In the case
Photocatalyst Additive Amount [mol] Activity pH of NiOx (3 wt%)–TiO2 suspended in Na2CO3, the amounts of
[µmol h−1]a)
evolved H2 and O2 gases over 6.5 h were 420 and 184 mL m−2,
H2 O2 respectively. The quantum efficiency in the UV region was esti-
Pt (0.3 wt%)/TiO2 None – 1 0 7.9 mated as ≈1.7%. The solar energy conversion efficiency was ca.
Na2CO3 0.1 3 1 10.9 0.03% (Tsukuba city, Japan, fine day).
0.38 316 158 11.0
0.76 568 287 11.0
2.2. Carbonate Anion Effect for Water Splitting over Various
0.76 (+ NaOH) 4 0 13.0 Semiconductor Photocatalysts
NaHCO3 0.36 4 2 8.4
K2CO3 1.45 20 10 11.8 Subsequently, various semiconductor materials with cocata-
NaOH 0.0003 4 0 11.0
lysts were investigated for photocatalytic water splitting using
the carbonate anion effect. It was found that many new photo-
Na2SO4 0.38 4 0 5.5
catalysts, such as Ta2O5 and ZrO2, had the ability to split water
Na3PO4 0.25 5 0 12.0 into H2 and O2, and that the activity of some reported photo-
Na2HPO4 0.38 2 0 8.6 catalysts could be improved by the carbonate effect.[22–24,26–28]
NaBO2 0.76 5 0 12.0 K4Nb6O17 is a layered compound with cation-exchange ability.
Na3PO4 0.18 (+ Na2HPO4) 3 0 11.0
The activity of a Pt-intercalated K4Nb6O17 photocatalyst was
improved significantly in carbonate aqueous solution.[31] In
Na2SO4 0.38 (+ NaOH) 1 0 11.0
conclusion, the carbonate effect is very useful for screening
RuO2 (1 wt%)/TiO2 Na2CO3 0.76 34 17 11.0 new photocatalysts owing to the general versatility of this
None – tr 0 7.9 approach.
NiOx (1 wt%)/TiO2 Na2CO3 0.76 64 32 11.0 Photocatalysts newly found to exhibit the carbonate effect
include Pt–TiO2, Cu–TiO2, Pt–Na2Ti6O13, RuO2–K4Nb6O17,
None – 1 0 7.9
NiOx–Ta2O5, RuO2–Ta2O5, ZrO2, Pt–ZrO2, NiOx–ZrO2, and
NiOx(1 wt%)/SrTiO3 Na2CO3 0.76 41 20 11.0
RuO2–ZrO2. Photocatalysts that showed improved activity
None – 9 4 7.9 with the carbonate effect include RuO2–TiO2, NiOx–TiO2,
NiOx(1 wt%)/Ta2O5 Na2CO3 0.76 41 20 11.0 NiOx–SrTiO3, RuO2–Na2Ti6O13, and Pt–K4Nb6O17.
None – 9 4 7.9
ZrO2 Na2CO3 0.38 142 75 11.0
2.3. Carbonate Anion Effect for Water Splitting and CO2
NaHCO3b) 0.33 309 167 8.3
Reduction over ZrO2 Photocatalysts
None – 72 36 7.9
Cu(1 wt%)/ZrO2 NaHCO3b) 0.33 19 11 8.3 It is noted that ZrO2 can decompose water stoichiometrically
Pt(0.3 wt%)/K4Nb6O17 Na2CO3 0.76 451 217 11.0 into H2 and O2 without any cocatalyst loading, and the activity
was significantly increased in carbonate aqueous solution.
None – tr 0 7.9
ZrO2 absorbs light at wavelengths less than 250 nm owing to
RuO2(1 wt%)/Na2Ti6O13 Na2CO3 0.76 55 25 11.0
its wide band gap of >5 eV.[22] Further, the activity of ZrO2 in
None – 5 2 7.9 NaHCO3 was much higher than that in Na2CO3. We found
RuO2(1 wt%)/K2Ti6O13 Na2CO3 0.76 49 24 11.0 that Cu–ZrO2 suspended in NaHCO3 aqueous solution pro-
None – 11 1 7.9 duces CO as well as H2 and O2 (19 µmol h−1 H2, 2.5 µmol h−1
CO, and 11 µmol h−1 O2). This was the first report on a photo-
RuO2(1 wt%)/BaTi4O9 Na2CO3 0.76 36 18 11.0
catalytic reaction in which O2 was observed with H2 and CO
None – 30 13 7.9
in a stoichiometric ratio ((H2  + CO)/O2  =  ≈2), suggesting that
a)Photocatalyst:
1 g (TiO2, 0.3 g), water: 350 mL, inner irradiation quartz reactor, both the water-splitting (Equation (1)) and the CO2 reduction
high pressure Hg lamp; b)CO was formed. (Equation (2)) reactions proceeded “catalytically.”[22,24]

positive effect of carbonate solution is present on TiO2 surface
(see Section 2.5).
Most research on photocatalytic water splitting has used
intense UV light from artificial light sources, such as high-pres-
sure Hg lamps and Xe lamps. It has been difficult to realize
activity under real solar light because of the wide band gap of
semiconductors and the low activity. There have been a few
reports on H2 evolution under solar light, but the evolution
of O2 gas has not been measured so far. In 1997, it was first
2H2O → 2H2 + O2 ∆G = +238 kJ mol −1 (1)
2CO2 → 2CO + O2 ∆G = +258 kJ mol −1 (2)
Photocatalytic CO2 reduction with water has been very dif-
ficult without a sacrificial electron donor, such as a strong
reduction reagent, and the stoichiometric production of O2 in
this work is real evidence for the usage of water as an electron
donor.

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2.4. Carbonate Anion Effect for Water Splitting and Oxida-
tive H2O2 Production from Water on Photocatalysts and
Photoanodes
In addition to photocatalytic reactions, photoelectrochemical
reactions have been widely investigated for water splitting
(Figure 1b). In particular, porous photoanodes using n-type
oxide semiconductors (TiO2, WO3, Fe2O3, etc.), which are
simply prepared by wet coating on conductive glass with a pre-
cursor solution and calcination in air, have been intensively
studied.[32] The charge separation mechanism on the semi-
conductor particles in a porous photoanode is similar to that
in photocatalyst particles; therefore, porous photoanodes are
called photocatalyst electrodes. The pores between particles
in a photoanode are filled with an electrolyte solution. Porous
photoanodes have the advantages that the quantum efficiency
can be improved by the short diffusion length of holes (h+) in
the minor carrier and that the charge separation can be acceler-
ated by an external bias.
Our group and Augustynski and co-workers found a unique
carbonate effect on the photoelectrochemical properties of a
porous TiO2 photoanode.[33] A two-step photocurrent–potential
curve was observed in carbonate electrolyte solutions, whereas
those in other solutions simply increased and were saturated.
The saturated photocurrents increased in the order: NaHCO3 >
Na2CO3  > other electrolytes. By considering the unusual two-
step shape observed in carbonate electrolyte solutions, it was
surmised that some intermediates of carbonates might be gen-
erated during the photoreaction that are then oxidized at the
potential of the second increase in the two-step curve.[33]
Since our first report in 2003[34] that bismuth vanadate
(BiVO4) can be utilized as a photoanode material to decom-
pose water into O2 under visible light, the water-splitting reac-
tion using porous BiVO4 photoanodes has been intensively
investigated.[35] BiVO4 was a semiconductor reported by Kudo
et al. as a powder photocatalyst for O2 evolution using Ag+ as
a sacrificial reagent.[36] The photoelectrochemical properties of
BiVO4 photoanodes were considerably improved in a carbonate
electrolyte solution,[37,38] and the photocurrent in NaHCO3
was much higher than that in Na2CO3. Recently, it was found
that H2O2 can be produced and accumulated on BiVO4 photo-
anodes when carbonate electrolyte solutions were used at low
temperature (Figure  3), whereas H2O2 was hardly observed
in other electrolyte solutions, such as phosphate, sulfate, and
borate.[29,30] H2O2 was not generated in carbonate solution
when the pH was greater than 12. The initial faradaic efficiency
of H2O2 on a BiVO4 photoanode in aqueous solution con-
taining HCO3− was almost 100%,[37,38] suggesting that water
with HCO3− anions was selectively oxidized to H2O2 via a two-
electron process (Equation (3)), not to O2 via a four-electron
process.
Moreover, e− in the BiVO4 conduction band has the poten-
tial to reduce O2 into H2O2 (Equation (4)), but cannot reduce
water into H2. It was demonstrated that H2O2 is produced both
on a photoanode and a Au cathode without an external bias
in KHCO3 solution (Figure 3a, Equation (5)).[30] As an appli-
cation of the photoanode mechanism, our group also demon-
strated H2O2 production on a Au-loaded BiVO4 photocatalyst
powder, both by oxidative and reductive reactions under
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Figure 3. Reaction mechanisms of H2O2 production on a) a BiVO4
photoanode and b) Au-loaded BiVO4 photocatalyst powder in an aqueous
carbonate solution.
visible light, as shown in Figure 3b.[30] The overall reaction for
H2O2 production from H2O and O2 (Equation (5)) is an uphill
reaction (△G > 0).
2H2O + 2h + → H2O2 + 2H+ (3)
O2 + 2e − + 2H+ → H2O2 (4)
2H2O + O2 → 2H2O2 ∆G = +204 kJ mol −1 (5)
2.5. Reaction Mechanism of the Carbonate Anion
Effect for Water Splitting
To discuss the reaction mechanism of the carbonate anion
effect for water splitting over photocatalysts, it is informative
to refer to the results for the carbonate anion effect on photo-
anodes, as the mechanisms of photocatalysts and photoelectro-
chemical systems are very similar. In a photoelectrochemical
system, it is easy to discuss the oxidative and reductive reac-
tions separately. It should be emphasized that the initial fara-
daic efficiency of H2O2 production and accumulation on a
BiVO4 photoanode in carbonate solution was almost 100%[37,38]
whereas H2O2 was hardly observed in other solutions.[29] The
carbonate effect on photocatalysts and photoanodes was not
observed at high pH (>12). From these results, it was con-
cluded that HCO3− anions directly affect the selective produc-
tion of H2O2 and that O2 gas observed in photocatalytic and
photoelectrochemical reactions after long-term irradiation is
produced through H2O2 decomposition by heat, UV, and cata-
lytic reaction (Equation (6)).
2H2O2 → 2H2O + O2 (6)
Next, the reaction mechanism of the carbonate anion effect
for water splitting is discussed in detail (Figure  4). Carbonate
species are generally absorbed on the surface of oxides such
as TiO2, ZrO2, and BiVO4, as observed by Fourier transform
infrared spectroscopy and X-ray photoelectron spectros-
copy.[21,25,29] It is also known that various anions, such as sul-
fate, phosphate, and borate, as well as carbonate, are generally
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Figure 4.  Reaction mechanism of the carbonate anion effect for water
splitting. a) with and b) without the carbonate anion.
absorbed on oxide surfaces. Therefore, a special mechanism
including direct reaction with carbonate anions may occur,
explaining the uniqueness of the carbonate effect widely
observed on various photocatalysts and photoanodes. It has
been reported that some peroxocarbonates (H2CO4, H2C2O6)
are formed by electrolysis in carbonate solutions at low tem-
perature.[39] These peroxides could immediately produce H2O2
and HCO3− by hydrolysis in aqueous solution.[40] Using com-
putational chemistry, it was predicted that HCO3− on a GaN
semiconductor will function as a better hole acceptor than H2O
and that carbonate radicals and percarbonate (HCO4−) will be
generated oxidatively.[41] From these results, it is reasonable that
some intermediates of oxidized carbonates, such as peroxocar-
bonates, are produced during photocatalytic and photoelectro-
chemical reactions in carbonate solution.
During the water-splitting reaction, the forward and the
backward reactions compete with each other. Charge recombi-
nation of e− and h+ through the redox reaction of intermediates
on the surface (Figure 4b) is a serious problem, and the prompt
desorption of intermediates may be the most important process
for avoiding backward reactions. The desorption of H2O2 from
the surface is not easy because of its reversible formation reac-
tion, and it is known that H2O2 is strongly adsorbed on oxide
surface such as TiO2.[21] However, peroxocarbonates are not
stable and easily decompose into H2O2 and CO2 gas, and the
desorption of H2O2 from the surface is accelerated by the irre-
versible emission of CO2. Subsequently, CO2 gas is solved as
carbonate in water, suggesting that CO2 and carbonate act as a
catalyst for the formation of H2O2. Further, free H2O2 is easily
decomposed to O2 through self-decomposition. This unique
reaction mechanism (Figure 4a) might cause the improvement
of the performance of photocatalysts without Pt cocatalyst (such
as ZrO2, RuO2–TiO2, and NiOx–TiO2), and be widely applicable
for various semiconductors in photocatalytic and photoelectro-
chemical reactions. In the case of Pt–TiO2, the optimum pH
condition was ≈10.[25] This pH dependence is explained by the
balance between two effects, that is, the positive effect of O2
evolution by increasing HCO3− at lower pH and the negative
effect of the backward reaction on exposed Pt-metal surface
at lower pH because Pt metal was covered with metal oxide at
higher pH.[24,25]
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3. Water Splitting by the Z-Scheme Reaction
Using Redox Mediators and Photocatalysts
The variety of photocatalysts showing activity for water split-
ting into H2 and O2 under UV light has been broadened by the
carbonate effect, as described above, and by increased atten-
tion from many researchers in this field. However, photocata-
lytic water splitting under visible light was not demonstrated
until 2000 because the narrow band gaps of oxide semiconduc-
tors make it difficult to satisfy conditions (i)–(iv) mentioned in
Section 1. The valence bands of typical oxides originate from
the O–2p orbital, and the tops of these valence band are located
at similar potentials of ≈3 V versus the reversible hydrogen
electrode (RHE).[42] Therefore, the bottom potentials of the con-
duction band become positive when the band gap is reduced
to less than 3 eV, that is, condition (i) cannot be satisfied for
typical oxide semiconductors in the case of the conventional
one-photon excitation mechanism (Figure 1a). Most sulfides
and nitrides, which have suitable band potentials for condi-
tion (i) and narrow band gaps for visible light absorption, are
unstable for O2 evolution reactions. There are two strategies
that can be used to solve this serious dilemma. One strategy
is to use new, stable semiconductors of mixed anions of sulfur
and/or nitrogen with oxygen. Domen et al. have developed var-
ious semiconductors, such as oxynitrides and oxysulfides, for
photocatalytic water splitting under visible light.[43,44] The other
strategy is to build a two-photon excitation reaction system
using a reversible redox shuttle mediator, as first demonstrated
by our group,[45] using a mechanism similar to that of natural
photosynthesis (Z-scheme reaction, Figures 5 and 6b).
3.1. Advantages of the Z-Scheme Reaction[45–47]
The concept of Z-scheme water splitting using powdered
photo­ catalysts to mimic photosynthesis was not new, but a
demonstration of the reactions of both PSI [H2] and PSII [O2]
(PS: photosystem) in Figure 5 to produce H2 and O2 stoichio-
metrically had not been achieved. The realization of Z-scheme
photocatalytic water splitting was very difficult, even under UV
light, because the activities of the PSII [O2] and PSI [H2] reac-
tions require further improvement and that the concentration
regions of the redox mediators for both PSII [O2] and PSI [H2]
reactions should overlap, as shown in Figure 7. Moreover, theo-
retical limit of solar energy conversion efficiency is half com-
pared to conventional direct water splitting system because
Z-scheme type water splitting need to the amount of double
photons compared to a direct water splitting mechanism.
It must be considered the shielding effect derived from the
absorption properties of redox solution. However, Z-scheme-
type photocatalytic water-splitting reactions have many advan-
tages. The utilization of the low-energy photons of visible light
is easy because the excitation energy is divided into two systems
compared with the conventional one-photon reaction.
Many types of photocatalysts, such as dye-sensitized, dye,
complex, and unstable semiconductor photocatalysts, including
sulfides, can be utilized in PSI [H2] through simple redox media-
tors that use one or two electrons, whereas semiconductors should
be stable for O2 evolution from water via a four-electron process in
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www.advancedsciencenews.com
Figure 5.  Mimicking the natural photosynthesis mechanism (Z-scheme reaction) for artificial photosynthesis. PS: photosystem.
the conventional reaction. As the requirement of condition (i) is
mitigated by using a redox mediator, the variety and combinations
of photocatalysts and redox mediators are significantly broadened.
Moreover, H2 and O2 gases can be produced separately. Since our
initial reports[45–47] on Z-scheme-type photocatalytic water-splitting
reactions, many new systems have been developed.[7–10]
The Z-scheme system in natural photosynthesis emerged
in cyanobacteria gigayears ago owing to two innovative events:
the fusion of PSI and PSII units, which originated in other bac-
teria, and acquisition of the ability to evolve O2 by water oxida-
tion. The completed Z-scheme system in cyanobacteria, which
was inherited by green plants, has not changed for a long time.
Therefore, it is reasonable that an analogous Z-scheme system
for photocatalytic water splitting is the most suitable method to
harvest and utilize solar light. The realization of our Z-scheme
water-splitting system, with the many advantages mentioned
above, is a breakthrough technology in the research field of arti-
ficial photosynthesis. Here, we review our developments and
successful results on Z-scheme water-splitting reactions.
3.2. Realization of Water Splitting by the Z-Scheme
Reaction Using an Fe3+/Fe2+ Redox Mediator under
Visible and UV Light[45]
Graetzel and co-workers reported that O2 was evolved from an
aqueous solution containing Fe3+ ions over a RuO2−WO3 photo-
catalyst under visible light.[48]
Figure 6.  Various technologies for water splitting into H2 and O2.
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2H2O + 4Fe3+ → O2 + 4Fe 2+ + 4H+ ∆G ( eV ) = ( +0.46 − 0.059pH ) (7)
First, our group planned to combine the reaction shown in
Equation (7) as PSII [O2] with a dye-sensitized photocatalytic
reaction as PSI [H2], as shown in Equation (8), to realize water
splitting by the Z-scheme reaction (Equation (9) (Equation (7)+
Equation (8)) = Equation (1)). However, an effective dye-
sensitized PSI [H2] with Fe2+ ions as the electron donor could
not be found. Next, we investigated various PSI [H2] reactions
using Fe2+, finally demonstrating a new Z-scheme reaction to
produce H2 and O2 stoichiometrically under both UV and vis-
ible light (Equation (9), Figure 6b2) in 1997.[45]
4H+ + 4Fe 2+ → 2H2 + 4Fe3+ ∆G ( eV ) = ( +0.77 + 0.059pH) (8)
2H2O → 2H2 + O2 ∆G ( eV ) = +1.23 (9)
Under steady-state condition, the ratio of evolved H2 and
O2 was 2 when a RuO2-WO3 photocatalyst suspended in an
aqueous solution containing Fe3+/Fe2+ ions in a quartz cell
was irradiated by both UV and visible light from a high-pres-
sure Hg lamp. The total amount and the turnover numbers of
H2 and O2 gases were much higher than those of the photo-
catalyst and Fe3+/Fe2+ ions, and the RuO2–WO3 photocatalyst
was very stable over a long photoreaction time. This was the
first report on photocatalytic Z-scheme water splitting into H2
and O2 stoichiometrically.[45] The reaction mechanism of this
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www.advancedsciencenews.com
Figure 7.  Requirements of the Z-scheme reaction for water splitting into
H2 and O2.
process is very unique, as shown in Figure 6b2. O2 was evolved
by water oxidation and Fe2+ was formed by Fe3+ reduction on
the photocatalyst under visible light. Fe2+ ions can be photoex-
cited directly by UV light of <280 nm, and excited Fe2+ ions can
reduce water directly to H2 with self-oxidation to Fe3+.
Moreover, sequential and separate evolution of H2 and O2
gases was demonstrated.[45] Only O2 gas was evolved when the
photocatalyst in the reactor was irradiated with light of >280 nm.
In contrast, only H2 gas was evolved when the solution in
the reactor was irradiated with light of <280 nm. The sepa-
rated gas evolution achieved by the Z-scheme reaction is safer
than the mixed evolution of detonating gas in conventional
photocatalysis; thus, this approach will become very economical
as no gas separation system is required.
3.3. Water Splitting by the Z-Scheme Reaction Using
an IO3−/I− Redox Mediator under Visible Light Only[47,49]
The development of new redox mediators is very important to
realize effective Z-scheme reactions for solar energy utiliza-
tion. Ohno and co-workers reported a complicated Z-scheme
water-splitting system using a two-compartment cell with an
ion-exchange membrane and Pt–Pt wired electrodes under UV
light, where H2 was evolved on Pt–TiO2 (rutile) with a Br−/Br2
redox mediator in one compartment and O2 was evolved on
TiO2 (rutile) with an Fe3+/Fe2+ redox in the other compart-
ment.[50] Our group demonstrated Z-scheme water splitting in
a one-compartment cell under UV light, where a mixture of a
Pt-TiO2 (anatase) photocatalyst as PSI [H2] and a TiO2 (rutile)
photocatalyst as PSII [O2] was suspended in a NaI aqueous
solution.[46] IO3−/I− acted as the redox mediator under neutral
pH conditions (Equation (10)) in the Z-scheme water-splitting
system, as shown in Figure 6b1. The ratio of evolved H2 and O2
gases was 2 in the steady state over a long time.
I− + 6OH− + 6h + = IO3 − + 3H2O (10)
Next, our group tried to demonstrate photocatalytic water
splitting by the Z-scheme reaction under visible light only
Adv. Energy Mater. 2018, 1801294
www.advenergymat.de
using the IO3−/I− redox mediator under visible light only.[47]
For PSI [H2] using I− ions as the electron donor, we investi-
gated various dye-sensitized photocatalysts and metal-doped
photocatalysts under visible light. Among them, H2 evolution
was observed in NaI solution over a Pt-SrTiO3 photocatalyst
doped with Cr and Ta (Pt-SrTiO3:Cr,Ta). This orange-colored
photocatalyst, originally reported by Kudo and co-workers
using methanol solution as a sacrificial reagent, absorbed
visible light by excitation from the donor level of Cr in the
forbidden band to the conduction band of SrTiO3.[51] In this
system, a Pt cocatalyst was essential for H2 evolution from
water. For PSII [O2] using IO3− as an electron acceptor, it was
found that Pt-loaded WO3 was the best photocatalyst under
visible light. Pt loading was essential in this system, and it was
surmised that Pt acted as an effective cocatalyst for the reduc-
tion of IO3− to I−.
Subsequently, we combined these PSI [H2] and PSII [O2]
reactions with the IO3−/I− redox mediator. It was found that
the ratio of evolved H2 and O2 gases was 2 in the steady state
when a mixture of Pt-SrTiO3:Cr,Ta and Pt-WO3 photocatalysts
suspended in NaI aqueous solution was irradiated by visible
light using a UV cutoff filter (>400 nm).[47] Among photocata-
lytic reactions, this was the first report of water splitting in
a stoichiometric ratio under visible light only. The quantum
efficiency at 420 nm was ≈0.1%. It should be noted that a Pt
cocatalyst was found to be unfavorable owing to the back-
ward reaction for water formation from H2 and O2, but it was
essential for H2 evolution and IO3− reduction. It was found
that the Pt surface could be covered with iodine to prevent
the backward reaction, similar to the effect observed for car-
bonate. Recently, our group improved the photocatalytic
performance of Pt–WO3 by surface modification using an
aqueous Cs-salt solution (see Section 4.4.1), achieving highly
quantum efficiency for the overall water-splitting reaction
(1.5% at 420 nm).[52]
3.4. Other Mediators for Z-Scheme Reactions: Fe3+/Fe2+,
NO3−/NO2−, VO2+/VO2+, I3−/I−, Co(bpy)33+/2+
Since the successful demonstration of water splitting in a
Z-scheme system using IO3−/I−, a variety of semiconductor
photocatalysts and redox mediators have been reported.[7–10]
Kudo and co-workers have reported that Pt/SrTiO3:Rh[53] shows
high performance for H2 production under visible light in the
presence of methanol as an electron donor, and have demon-
strated visible-light-induced water splitting using Pt/SrTiO3:Rh
as PSI [H2], BiVO4[36] as PSII [O2], and Fe3+/Fe2+ as the redox
mediator.[54] Kudo and co-workers also revealed that the back-
ward (water regeneration) reaction can be suppressed by using
Ru instead of Pt as a cocatalyst.[55]
Our group has reported that surface-modified WO3 (see
Section 4.4.1) shows high activity as PSII [O2] in the pres-
ence of a VO2+ solution as an electron acceptor.[56] Further,
we have demonstrated overall water splitting by using a
VO2+/VO2+ redox mediator in a Z-scheme system combined
with Ru/SrTiO3:Rh as PSI [H2]. An interesting feature of
this Z-scheme system is its ability to suppress undesirable
backward reactions. For PSI [H2], it is necessary that water
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reduction and oxidation of the redox reductant (Red) occur
selectively. However, as the redox oxidant (Ox) concentration
increases, the PSI [H2] performance decreases as Ox reduc-
tion proceeds preferentially over water reduction owing to
thermodynamic advantages. For PSII [O2], red oxidation,
which is an undesirable reaction, proceeds easily upon
increasing the Red concentration, resulting in an apparent
reduction in PSII [O2] performance (Figure 7). However,
photocatalytic O2 evolution proceeded steadily on surface-
modified WO3 until the total quantity of evolved O2 reached
150 µmol, which is the stoichiometric quantity expected
in the presence of 600 µmol VO2+ in the reaction solution
(Figure  8a). Moreover, H2 evolution also proceeded rapidly
on Ru/SrTiO3:Rh until the stoichiometric quantity, calcu-
lated based on the presence of 600 µmol VO2+ in the reac-
tion solution, was obtained (Figure 8b). Consequently, our
group demonstrated efficient solar water splitting to give
H2 and O2 not only via the conventional one-pot method,
but also via a stepwise operation. A solar energy conversion
efficiency of 0.06% was estimated for the stepwise operation,
which was demonstrated for the first time in the context of
separated production of H2 and O2. Moreover, this efficiency
was relatively high compared with those of typical one-pot
Z-scheme systems (Ru/SrTiO3:Rh-Ir/CoOx/Ta3N5: 0.013%,[57]
Pt/BaZrO3-BaTaO2N-PtOx/WO3: 0.0067%,[58] Ru/SrTiO3:Rh-
RuO2/TiO2:Ta/N: 0.02%,[59] and Ru/SrTiO3:Rh-BiVO4:
0.1%[60]) despite H2 being evolved separately from O2.
A unique Z-scheme system utilizing the photodecomposi-
tion of NO3− to NO2− and O2 was also developed.[61] The valence
band potential of TiO2 is ≈+ 2.3 V versus the normal hydrogen
electrode (NHE; pH 11), and is very positive compared to the
redox potential of NO3−/NO2− (+ 0.186 V vs NHE (pH 11)).
Therefore, the photogenerated holes in TiO2 have potential to
oxidize NO2− to NO3−. In addition, it is known that OH radicals,
which can oxidize NO2− into NO3− via an intermediate,[62,63]
Figure 8.  a) Photocatalytic O2 evolution using VO2+ over surface-modified
WO3. b) Photocatalytic H2 evolution using VO2+ over Ru/SrTiO3:Rh. WO3:
0.4 g, Ru/SrTiO3:Rh: 0.1 g, redox concentration: 2 × 10−3  m, light source:
300 W Xe lamp with an L42 cut-off filter. The dashed lines indicate the
upper stoichiometric limits of O2 or H2 evolution expected from 600 µmol
VO2+ or VO2+. Adapted with permission.[56] Copyright 2017, American
Chemical Society.
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are produced on the TiO2 surface by the reaction between
OH− and photogenerated holes. As a result, TiO2 can produce
H2 accompanied by NO2− oxidation (PSI [H2]). In contrast, it
has been reported that NO3− ions photoexcited by UV light at
wavelengths less than 260 nm decompose into NO2− and O2
via various intermediates (PSII [O2]). However, the overall
water-splitting reaction does not proceed steadily by simply
combining these PSI [H2] and PSII [O2] reactions. Thus, the
effect of coexisting anions on the photocatalytic performance
was investigated. Water splitting was found to proceed steadily
in the presence of coexisting carbonate ions, and the turnover
number of NO2− ions for the amount of H2 produced reached
4.7.
Abe et al. have reported a Z-scheme system utilizing the
I3−/I− redox couple and a dye-sensitized photocatalyst as PSI
[H2].[64] Dye-sensitized photocatalysts can absorb a wide range
of wavelengths below 700 nm. Kudo and co-workers have
reported that sulfide photocatalysts can be utilized as PSI [H2]
in a Z-scheme system using a Co(bpy)33+/2+ redox couple.[65] The
fact that various nonoxide materials can be applied to the water-
splitting system is an important advantage of the Z-scheme
system. The variety of combination of PSI [H2] and PSII [O2]
photocatalysts has been rapidly increased with increasing the
kinds of redox mediators.[10]
4. Overall Water Splitting via a “Photocatalysis–
Electrolysis Hybrid System”
4.1. Principles and Advantages of the Photocatalysis–
Electrolysis Hybrid System
In the water-splitting reactions via conventional photocatalysis
techniques discussed in the previous section, there are several
serious hurdles for practical use, as listed below.
(v) Solar energy conversion efficiencies remain low.
(vi) Hydrogen is simultaneously produced with oxygen as a
detonating gas.
(vii) A transparent, large, leak-free cover is required to accu-
mulate hydrogen gas.
(viii) A precious metal is necessary to achieve excellent hydro-
gen production sites on the photocatalyst.
Unless these issues are resolved, expanding conventional
water-splitting systems to a practical scale is difficult. We have
studied a photocatalysis–electrolysis hybrid system using an
Fe3+/Fe2+ redox mediator[12a,b,66] as another candidate for prac-
tical water splitting, where PSI [H2] in the Z-scheme system is
replaced by an electrolytic reaction (Figure 6c, Figure 9). In this
system, solar energy is converted and stably accumulated in the
redox solution as chemical energy by a photocatalytic PSII [O2]
reaction with a positive ∆G value (Equation (7)) as described
in the previous section. In the electrolytic reaction ES [H2], H2
is produced under conditions of accumulated Fe2+ with a low
applied bias of <0.8 V[66] (similar to the potential difference
between Fe3+/Fe2+ and H+/H2) owing to the low overpotential of
Fe2+ oxidation (Equation (8)).[67,68] As a result, the overall water-
splitting reaction proceeds to give H2 and O2 (Equation (9)). In
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Figure 9.  Image of a photocatalysis–electrolysis hybrid system. Figure 10. Cost estimation for the photocatalysis–electrolysis hybrid
system using an Fe3+/Fe2+ redox mediator. Adapted with permission.[12b]
contrast, the applied bias of conventional water electrolysis is Copyright 2014, AIST.
generally more than 1.6 V owing to the high overpotential of O2
production (1.23 V + high overpotential). Pure H2 can be pro- the typical large-scale water electrolysis system using power at
duced separately from O2 and accumulated easily in the closed 8 yen kWh−1 would be ≈41 yen N m−3 H2. This calculation shows
cathode chamber, as in a conventional water electrolysis system; that the photocatalysis–electrolysis hybrid system is capable of
thus, a large cover over the photocatalysis pool is not needed for producing H2 at a lower cost than the conventional method of
H2 accumulation. Further, the electrolytic reaction for H2 pro- combining photovoltaic generation and water electrolysis.
duction can be time-shifted because the Fe2+ ions accumulated
in the aqueous solution are stable for a long time. Thus, this
hybrid system has the potential to resolve issues (v)–(viii). 4.3. Theoretical Limit of Solar Energy Conversion Efficiency
in the Photocatalysis–Electrolysis Hybrid System Using
an Fe3+/Fe2+ Redox Mediator
4.2. Cost Estimation for the Photocatalysis–Electrolysis
Hybrid System An estimation of the theoretical limit of solar energy conver-
sion efficiency (ηsun) is necessary to determine the potential
When discussing practical applications, it is necessary to esti- of the photocatalysis–electrolysis hybrid system for practical
mate the cost of the entire system and to compare the cost of applications. Figure  11 shows the photoabsorption wavelength
hydrogen production for various candidates. Therefore, we threshold (Lmax) of the semiconductor and ηsun when the
have reported a cost estimation for the photocatalysis–elec- quantum efficiency is assumed to be 100% based on solar
trolysis hybrid system (Figure 10).[12b] Reports from the Central spectrum data (JIS-C-8911, AM 1.5G).[12b] It was assumed that
Research Institute of Electric Power Industry[69] and the Depart-
ment of Energy (DOE)[12c] were used as references for the elec-
trolysis and photocatalysis parts, respectively. A large-scale solid
polymer hydrolysis device (32 000 N m3 h−1) was assumed as
a comparable water electrolysis device. For the electricity cost,
8 yen kWh−1 at 40% operation is assumed. The solar energy
conversion efficiency (ηsun) of photocatalysis is assumed as 3%.
The photocatalyst pool area needed to achieve the above
production level of hydrogen is 3 km2. The photocatalyst pool
has a cost of 268 yen m−2, which is similar to that in the DOE
report (≈300 yen m−2). The premium over the costs related to
the photocatalyst pool (facility, pump, cost of labor, land cost,
management fee, interest, etc.) is about 3 yen N m−3. If the
electrolysis voltage of the electrolyte solution containing Fe2+ is
set at 0.8 V, the cost of electric power can be reduced by half,
and the cost merit of this part is extremely high compared
with that of conventional electrolysis. Using the above assump-
tions, the hydrogen production cost of the photocatalysis–elec- Figure 11.  Theoretical limit of solar energy conversion efficiency for the
trolysis hybrid system was estimated to be ≈25 yen N m−3 H2. photocatalytic water oxidation reaction using an Fe3+/Fe2+ redox medi-
Under the same conditions, the hydrogen production cost of ator. Adapted with permission.[12b] Copyright 2014, AIST.

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irradiated light at wavelengths shorter than Lmax was 100%

absorbed by the semiconductor material (no loss by light reflec-
tion or permeation). Notably, in natural photosynthesis, the
potential difference between individual redox mediators in
various electron transfer processes is about 0.2 V. If iron redox
mediators are used with the minimum loss value derived from
the required overpotential (0.4 V for the sum of two-electron
transfer process), solar light with an energy greater than 0.86 V
will be required. Therefore, the photocatalytic reaction can be
driven by light with wavelengths up to 1440 nm, which corre-
sponds to a maximum ηsun value of 24%. Thus, the target effi-
ciency of 3% assumed in the previous section (Section 4.2) is
an achievable value.

4.4. Methods of Improving Photocatalytic Performance in

Systems Using an Fe3+/Fe2+ Redox Mediator

To realize the photocatalysis–electrolysis hybrid system, it is
important to achieve a solar to chemical energy conversion
efficiency of ≈3%. In this section, efforts toward improving the
photocatalytic performance of systems using an Fe3+/Fe2+ redox
mediator are reviewed.
4.4.1. Surface Treatment of WO3[70]
It was reported that Fe2+ can be produced efficiently over a
WO3 photocatalyst under visible light using sacrificial electron
donors such as organic compounds.[71] However, the photocata-
lytic activity of Fe2+ production and O2 formation without sacri-
ficial electron donors was very low (quantum efficiency < 0.4%
at 405 nm).[48] Thus, our group aimed to construct a surface
structure that promoted the water oxidation reaction. Owing
to surface modification of the WO3 particles, the photocatalytic
performance of WO3 was remarkably improved following
thermal treatment at 773 K using MCl (M = Na, K, Rb, and Cs)
and AgNO3 aqueous solutions. WO3 treated with an aqueous
Cs-salt solution (Cs-WO3) showed the best activity. The X-ray
diffraction patterns, Raman spectra, and diffuse reflection
spectra of the WO3 and Cs-WO3 photocatalysts were similar,
suggesting that the bulk of WO3 was unchanged by the surface
modification process.
Figure  12 shows the time course of O2 evolution over WO3
with and without Cs treatment. Cs-WO3 showed the highest
activity when an aqueous CsCl solution (2.2 mol% relative to
WO3) was impregnated at 773 K for 30 min. The total amount
of O2 gas reached ≈300 µmol over Cs-WO3, in agreement with
the stoichiometric amount expected from Fe3+ (1200 µmol) in
the solution. Further, the expected stoichiometric amount of
Fe2+ was detected in the solution after the photoreaction, but
no Fe3+ was detected after the photoreaction. The activity of the
second run over Cs-WO3 (Figure 12c) was much higher than
that of the first run (Figure 12b), though no improvement in
the second run was observed for WO3 without Cs treatment.
Therefore, it was determined that the further improvement was
derived from changes in the surface condition of the Cs-WO3
photocatalyst during the photoreaction. Using various charac-
terization techniques, we concluded that the surface structure
Figure 12. Photocatalytic O2 evolution over a) WO3, b) Cs-WO3 (first
run), and c) Cs-WO3 (second run) under visible-light irradiation. The
second run was performed by exchanging the reactant solution from the
first run with fresh Fe2(SO4)3 aqueous solution. Catalyst: 0.4 g, reactant
solution: 300 mL of 2 × 10−3  m Fe2(SO4)3, light source: 300 W Xe lamp
with an L42 cut-off filter. The initial pH of the reactant solution was always
adjusted to 2.3 using H2SO4. Reproduced with permission.[70] Copyright
2014, the Royal Society of Chemistry.
formed by Cs treatment of the WO3 photocatalyst has ion
exchangeable sites, and the photocatalytic performance of the
WO3 photocatalyst was further improved by ion-exchange treat-
ment with H+ and Fe2+ ions.
The ability of the surface structure formed on WO3 by Cs
treatment to realize ideal reaction selectivity for water oxida-
tion reaction using an Fe3+/Fe2+ redox system was evaluated.
Figure 13 shows the influence of the concentration of Fe2+ ions
coexisting with 2 × 10−3  m Fe3+ over the WO3 photocatalyst,
with and without surface modification, on the photocatalytic
activity for water oxidation into O2. The activity of native WO3
significantly decreased when 0.5 × 10−3  m Fe2+ ions coexisted
in the reactant solution (Figure 13a), indicating that Fe2+ ions
are more easily oxidized than water on the unmodified WO3
Figure 13.  Effect of the concentration of Fe2+ over WO3 photocatalysts
a) with and b) without surface ion-exchange sites on the photocatalytic
reaction rate for water oxidation in the presence of Fe3+ ions. Reproduced
with permission.[70] Copyright 2014, the Royal Society of Chemistry.

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surface. In contrast, the activity of the Cs-WO3 photocatalyst

was unaffected by the concentration of Fe2+ ions (Figure 13b).
Moreover, an excellent suppression effect for the undesirable
reaction between photogenerated holes and Red was obtained,
regardless of the type of redox reagent. Undesirable reactions
were also effectively suppressed when IO3− or VO2+ were used
in the redox system, but the activity of native WO3 drastically
decreased when 0.5 × 10−3  m I− or VO2+ was also present in the
reactant solution. The fact that ideal reaction selectivity can be
attained by simple surface treatment of a powdered photocat-
alyst is an important result for photocatalytic reactions using
reversible redox systems.

4.4.2. Structure of Fe Ion Complexes[70,72]

In the case of Fe3+ reduction, the reactant solution conditions

are important because Fe3+ ions must arrive preferentially
at the photocatalyst surface and receive photogenerated elec-
trons smoothly.[73] Fe3+ ions form various types of complexes,
depending on the coexisting anion species.[74–76] Therefore,
we evaluated the effect of the structure of Fe3+ complexes on
the photocatalytic performance of Cs-WO3. The activities were
found to strongly depend on the iron source. This coexisting
anion species effect was also observed for other photocatalysts,
such as native WO3, BiVO4, and TiO2. The photocatalytic activi-
ties of WO3, BiVO4, and TiO2 using a Fe(ClO4)3 solution were
4.4, 4.7, and 12 times higher, respectively, than those using a
Fe2(SO4)3 solution.
The cyclic voltammetry (CV) profiles of various Fe3+ solu-
tions depended on the type of iron solution (Figure  14). The
order of redox potentials estimated from the CV profiles was:
SO42− (+0.72 vs RHE) < Cl− (+0.77 vs RHE) < NO3−  = ClO4−
(+0.79 vs RHE). Further, there was a good correlation between
the redox potential and the reaction rate. A negative shift of Figure 15.  a) Amount of adsorbed Fe3+ over BiVO4 as a function of pH.
b) Photocatalytic reaction rates as a function of adsorbed Fe3+ on BiVO4.
(black): 20 °C, (blue): 35 °C, and (red): 50 °C. BiVO4: 0.4 g, 2 × 10−3  m
Fe(ClO4)3: 150 mL, light source: solar simulator (AM 1.5G), irradiation
area: 9 cm2. Measurement errors in the photocatalytic performance data
were less than 3%. Reproduced with permission.[77] Copyright 2018, the
Royal Society of Chemistry.

the redox potential indicates that it is thermodynamically

Figure 14. Cyclic voltammetry profiles at a Pt electrode (surface area:
0.01 cm2) with a) 2.0 × 10−3 m Fe2(SO4)3 in 0.1 m Na2SO4, b) 4.0 × 10−3 m
FeCl3 in 0.1 m NaCl, c) 4.0 × 10−3  m Fe(NO3)3 in 0.1 m NaNO3, and d)
4.0 × 10−3  m Fe(ClO4)3 in 0.1 m NaClO4. The pH values of the iron solu-
tions were adjusted to 2.3 using a) H2SO4, b) HCl, c) HNO3, and d)
HClO4. Scan rate: 5 mV s−1. Reproduced with permission.[70] Copyright
2014, the Royal Society of Chemistry.
difficult to reduce Fe3+ ions. Fe3+ ions in aqueous Fe2(SO4)3
or FeCl3 solutions mainly form Fe(SO42−)x(H2O)6−x or
Fe(Cl−)x(H2O)6−x, whereas Fe(H2O)6 is formed in aqueous
Fe(NO3)3 and Fe(ClO4)3.[74–76] The different coordinate species
for Fe3+ ions may affect the reducibility of complexed Fe ions.
For instance, it may be more difficult to reduce Fe3+ ions if
SO42− or Cl− ions are introduced into the Fe3+ complex than
if there is only H2O coordination. Therefore, it was concluded
that the photocatalytic reaction rates were strongly affected by
the coordination and the thermodynamic reducibility of the
Fe3+ complexes. The apparent quantum efficiency of TiO2 for
the reaction using aqueous Fe(ClO4)3 solution reached ≈51% at
365 nm, indicating that a simple powdered system can achieve
a high quantum efficiency. The quantum efficiency and ηsun
of Cs-WO3 were estimated to be 31% (at 420 nm) and 0.38%,
respectively.

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4.4.3. Amount of Fe3+ Ions Absorbed Table 2.  Recent progress on photocatalytic O2 evolution employing Fe3+ ion.
over BiVO4[77]
Photocatalyst Reactant solution Photocatalytic performancea)
As mentioned in Sections 4.4.1 and 4.4.2, O2 evolution rate [µmol h−1] AQY ηsund)
the Cs-treated WO3 powder showed high WO −3
1 × 10  m Fe2(SO4)3 8 1% at 420 nm –
3
activity for the PSII [O2] reaction using Fe3+.
Cs-WO3 1 × 10−3 m Fe2(SO4)3 116 – –
However, this performance is not sufficient
−3
because only visible light up to 460 nm is Fe-H-Cs-WO3 1 × 10  m Fe2(SO4)3 200 – –
absorbed on WO3. To efficiently harness Fe-H-Cs-WO3 2 × 10−3 m FeCl3 241 – –
solar energy, longer wavelength absorption Fe-H-Cs-WO3 2 × 10−3 m Fe(NO3)3 290 – –
as well as higher quantum efficiencies over
Fe-H-Cs-WO3 2 × 10−3 m Fe(ClO4)3 297 31% at 420 nm 0.38%
the entire visible-light spectrum is neces-
−3
sary. BiVO4 can absorb visible light up to TiO 2 1 × 10   m Fe2(SO4)3 30 b)
– –
× −3 m Fe(ClO )
520 nm and has been used for the PSII TiO 2 2 10 4 3 370 b)
51% at 365 nm 0.24%
[O2] reaction in Z-scheme water-splitting WO3 1 × 10−3 m Fe2(SO4)3 8 – –
systems with an Fe3+/Fe2+ redox medi- WO 2 × 10−3 m Fe(ClO4)3 35 – –
3
ator.[54,60,78] However, the highest reported −3
BiVO4 1 × 10  m Fe2(SO4)3 47 – –
quantum efficiency for BiVO4 remains low
−3
(18.3% at 440 nm);[78] this efficiency was BiVO4 2 × 10  m Fe(ClO4)3 221 – –
evaluated using Ag(I), which is an irrevers- BiVO4 2 × 10−3 m Fe(ClO4)3 1100c) 38% at 420 nm 0.65%
ible electron scavenger. Thus, we elucidated
a)
the factors affecting the photocatalytic per- Catalyst: 0.4 g, reactant solution: 300 mL (pH2.4), reactant solution temperature: 293 K, light source:
300 W Xe lamp attached with L42 cut off filter (λ < 420 nm); b)300 W Xe lamp without cut of filter was used
formance of the PSII (O2) reaction using as a light source (λ  < 300 nm); c)Temperature and pH of reactant solution were controlled to 308 K and
Fe3+/Fe2+ to improve the photocatalytic per- pH2.5 (300 mL); d)ηsun was estimated by using solar simulator controlled to AM 1.5 (100 mW cm−2).
formance of BiVO4.
Figure 15 shows the effects of pH and reac-
tion-solution temperature on the amount of adsorbed Fe3+ and which suggests that artificial photosynthesis technology using
the photocatalytic performance over BiVO4. It was found that photocatalysts has progressed toward the next step for practical
the amounts of adsorbed Fe3+ increased with both increasing applications.
pH and temperature (Figure 15a). BiVO4 exhibited the highest
activity at each reaction temperature when the amount of
adsorbed Fe3+ was ≈3–8 µmol g−1 (Figure 15b). As 1 g of BiVO4 5. Conclusion and Outlook
has a surface area of 1.0 m2 g−1, the surface coverage of Fe3+
ions on BiVO4 was determined as 20%–60% at the optimum In this paper, the unique carbonate anion effect and various
adsorption amounts, if the ionic radius of the Fe3+ complex is two-step reactions using redox mediators for the photocatalytic
assumed as 2 Å. Hence, we propose that the activity is improved splitting of water into H2 and O2 were reviewed. In the future
by increasing the level of adsorbed Fe3+ when the adsorption of this research field, two directions are predicted for practical
amount is less than ≈8 µmol g−1, whereas high adsorption applications: (A) drastic improvement of ηsun of photocatalysts
levels decrease the activity. This behavior indicates that the ratio and (B) photocatalytic production of higher value-added chemi-
between surface sites for reduction and for oxidation is impor- cals than H2.
tant, as surface sites for water oxidation to O2 might be covered For direction (A), ηsun of photocatalysts must be further
at high Fe3+ adsorption levels. Table 2 summarized the recent increased to produce H2 at a cost lower than that of fossil
progress on the photocatalytic O2 evolution employing Fe3+ ion. energy. To achieve this, the photocatalysis–electrolysis hybrid
We successfully improved the reaction efficiency of powdered system is one of the most promising approaches. The effi-
photocatalysts focusing on the surface structure of catalyst, ciency target (ηsun  = 3%) in photocatalysis–electrolysis hybrid
the structure of Fe3+ complex ion, and the amount of Fe3+ ions systems is realistic, as the theoretical maximum ηsun (24%) is
absorbed over catalyst. Quantum efficiency and ηsun values of much higher, as shown in Section 4.3. However, ηsun should be
38% (at 420 nm) and 0.65%, respectively, were achieved using improved by more than four times relative to the present effi-
BiVO4 catalyst. This is the best performance reported for a pow- ciency (0.65%) of BiVO4 photocatalysts. Theoretically, ηsun > 3%
dered photocatalyst suspended in a reaction solution containing can be achieved using BiVO4 if all photons up to 520 nm were
reversible redox mediators. Although the conversion efficiency utilized with a high quantum efficiency of ≈100%. Photon loss
of this system is considerably lower than those of photovoltaics, by reflection and scattering at the surface of the reactor must
it is comparable with those for photosynthesis in natural green be avoided. Approaches for improving the quantum efficiency
plants. In the case of corn and switch grass, the solar energy to nearly 100% will likely be developed, as the fundamental
conversion efficiencies for organic compounds, such as carbohy- photocatalyst mechanism is similar to that of photovoltaics
drates or celluloses, are ≈0.79% and 0.22–0.56%, respectively.[79] and photoelectrodes, where quantum efficiencies of 100% are
It should be emphasized that a high efficiency similar to that common. The first priority for achieving ηsun > 3% is to develop
for photosynthesis could be obtained in our simple reactor with new semiconductors that utilize more photons by absorbing at
an oxide photocatalyst powder suspended in aqueous solution, wavelengths greater than 520 nm. The theoretical ηsun value is

Adv. Energy Mater. 2018, 1801294 1801294  (13 of 15) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
5.6% when all photons up to 600 nm can be utilized for the
Fe3+/Fe2+ reaction. Semiconductors that absorb light at wave-
lengths greater than 520 nm for PSII [O2] are very limited,
and their activities are not sufficient. To realize faster devel-
opment of new semiconductors, investigations of automated
high-throughput screening of materials will become important.
Our group developed an original high-throughput screening
system for new photoreactive semiconductors.[80] Various semi-
conductor films were prepared by a wet process on conducting
glass and the charge separation activities of each film were
measured photoelectrochemically. The screening rate achieved
using this system (maximum of 384 films per day) was more
than an order of magnitude greater than that by hand. More-
over, screening of materials using artificial intelligence based
on a huge amount of data from automated high-throughput
screening systems and computational chemistry should be real-
ized in the future.
For research direction (B), the photocatalytic production of
higher value-added chemicals than H2 and O2 is one of the
most promising practical applications for the near future.[81]
For example, H2O2 could be produced by both reductive and
oxidative reactions (Equation (5)) over Au-loaded BiVO4 in
KHCO3 aqueous solution.[30] H2O2, which produces only
H2O or O2 after utilization, has received substantial attention
as a versatile and clean reagent for selective organic conver-
sion, environmental purification, bleaching, cleaning, sterili-
zation against viruses and bacteria, and as an energy source
for H2O2 fuel cells. H2O2 is produced worldwide in enormous
quantities (4.5 million metric tons annually),[81] but total CO2
emissions resulting from H2O2 processing (24 million metric
tons) are also high. The CO2 emission factor per electron (kg
CO2 kmol−1 e−) for H2O2 is 90.1, which is much larger than
those for H2 and O2 (2.5 and 1.1, respectively).[81] In Japan,
the price per electron for H2O2 is ≈140-fold higher than that
for O2 and ≈18-fold higher than that for H2. Therefore, it is
possible that the realization of efficient photocatalytic produc-
tion of H2O2 would not only be highly economical but also
contribute to alleviating global warming. For both research
directions, it is important to develop a lot of more ideal mate-
rials utilizing solar energy effectively. To solve this issue, we
need to improve understanding some fundamental properties
affecting these performances, such as electrical conduction,
hydration of the material surface,[82] electron spin polariza-
tion,[83] and so on. Moreover, approximation between experi-
mental and theoretical effort on previously studied candidate
materials may be important.[84] We also need to utilize the
overall reaction containing various molecular catalysis like
natural photosynthesis.[85]
The study of solar energy conversion for artificial photo-
synthesis and solar hydrogen production has been influenced
significantly by the fluctuating prices of fossil fuels, such as
oil and natural gas. Public interest in solar energy conversion
tends to decrease with decreases in the price of fossil energy.
However, considering the global warming problem resulting
from CO2 emissions and the goal of the Paris Agreement, it
is essential to reduce the use of fossil energy and to construct
a renewable energy society as soon as possible. Thus, studies
on solar energy conversion using simple photocatalyst systems
should continue to be progressed.
Adv. Energy Mater. 2018, 1801294 1801294  (14 of 15)
www.advenergymat.de
Acknowledgements
This study was partially supported by the International Joint Research
Program for Innovative Energy Technology (METI), JSPS KAKENHI
Grant Number JP17H06439 in Scientific Research on Innovative Areas
“Innovations for Light-Energy Conversion (I4LEC)”, and the JSPS
KAKENHI Grant-in-Aid for Young Scientists (B) (Project no. JP17H14528).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
hydrogen, photocatalysts, redox mediators, solar fuels, water splitting
Received: April 29, 2018
Revised: June 6, 2018
Published online:
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