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DOI 10.1007/s10562-014-1397-z
Kazunari Domen
Received: 30 September 2014 / Accepted: 6 October 2014 / Published online: 16 October 2014
Ó Springer Science+Business Media New York 2014
Abstract Some particulate semiconductors loaded with thermal catalytic reactions. Importantly, by utilizing exci-
nanoparticulate catalysts exhibit photocatalytic activity for ted states generated from photon energy, reactions that are
the water-splitting reaction. The photocatalysis is distinct energetically prohibitive under given reaction conditions
from the thermal catalysis because photocatalysis involves (e.g., at room temperature) can be achieved in photocata-
photophysical processes in particulate semiconductors. lytic reactions. That is, some of the photon energy can be
This review article presents a brief introduction to photo- harvested as chemical energy as a result of the formation of
catalysis, followed by kinetic aspects of the photocatalytic photocatalytic products. This ability is the principal reason
water-splitting reaction. why photocatalysis has attracted growing interest in terms
of solar energy conversion technology. Because the solar
Keywords Photocatalyst Solar energy energy irradiating the surface of the Earth (1.3 9 105 TW)
Semiconductor Water splitting Hydrogen Hydrogen exceeds the current global human energy consumption
evolution reaction (HER) Oxygen evolution reaction (1.6 9 101 TW in 2010 [1]) by approximately four orders
(OER) of magnitude, efficient photocatalytic solar energy con-
version on a large scale should have a significant impact on
energy and environmental issues as well as the economy, as
1 Introduction to Photocatalytic Water Splitting described later.
Figure 1 shows a simplified schematic of the reaction
Photocatalytic reactions differ from thermocatalytic reac- processes involved in overall water splitting using a single
tions in many ways. Photocatalysis involves photophysical particulate photocatalyst [2]. Excited electrons and holes
processes, which are initiated by photon absorption to are generated in the bulk of the semiconductor photocata-
generate excited states (new chemical potentials). This lyst particles upon band gap excitation. Photoexcited car-
process is followed by photochemical or electrochemical riers with opposite signs are separated and transferred to
redox reactions. These processes involve excited states surface active sites by either diffusion or electric fields
with finite lifetimes, which determines the efficiency of the associated with the semiconductor-electrolyte and semi-
system and differentiates photocatalysis from conventional conductor-cocatalyst interfaces. The photocatalysis then
culminates in surface electrochemical redox reactions,
wherein electrons and holes must be consumed at the same
T. Hisatomi K. Domen (&) rate. The adsorption, desorption and mass transport of
Department of Chemical System Engineering, The University
reactants and products should proceed effectively. How-
of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
e-mail: domen@chemsys.t.u-tokyo.ac.jp ever, the majority of photoexcited carriers are often lost by
carrier recombination, which occurs largely in the bulk of
K. Takanabe the semiconductor, generating either heat or photolumi-
Division of Physical Sciences and Engineering, KAUST
nescence. The photocatalytic efficiency (i.e., photocatalytic
Catalysis Center (KCC), King Abdullah University of Science
and Technology (KAUST), 4700 KAUST, Thuwal 23955-6900, rate) is determined by a multiplication of the efficiencies of
Saudi Arabia these consecutive processes. Therefore, a specific reaction
123
96 T. Hisatomi et al.
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Photocatalytic Water-Splitting Reaction 97
conversion efficiency / -
When solar energy conversion is of interest, a simulated 0.20 60%
Solar-to-hydrogen
solar spectrum can be used as incident light (using the
entire spectrum rather than monochromatic light). The 40%
0.15
benchmark efficiency for solar hydrogen production via
water splitting and the diagnostic efficiencies for the STH = 10%
0.10
investigation of material performance were recently
reviewed [3, 4]. The solar-to-hydrogen efficiency (STH) STH = 5% 20%
can be calculated from the product of the hydrogen pro- 0.05
duction rate (rH2) and an increase in the Gibbs free energy
(DG) of 237 kJ mol-1: 0.00
400 600 800 1000
output energy rH DG
STH ¼ ¼ 2 ; ð2Þ Maximum wavelength of photons
Energy of incidence solar light PSun S
available for water splitting / nm
where Psun is the energy flux of sunlight and S is the area of
Fig. 2 Relationship between STH and photon wavelengths available
the reactor. ASTM-G173 AM 1.5 global tilt is commonly
at different AQYs for photocatalytic water splitting. It is assumed that
used as the standard solar irradiation, with an energy flux of two water molecules are split into two hydrogen molecules and one
1.0 9 103 W m-2 and a well-defined power spectrum. oxygen molecule in four-photon processes
STH is an absolute and practical standard for the perfor-
mance of photocatalysts under sunlight. It is recommended
gap semiconducting photocatalysts for practical operation
that the irradiance (photon number as a function of wave-
despite the present low activity of photocatalysts with
length) used for the measurement be reported with the STH
absorption edge wavelengths longer than 600 nm for the
values for clarity.
overall water-splitting reaction. Solar hydrogen plants with
A techno-economical analysis of the commercial value
areas of 25 km2 consisting of photocatalysts with 10 %
of hydrogen produced in various photocatalytic and pho-
STH and incidental equipment for gas separation and
toelectrochemical systems was recently reported [5]. Given
purification can generate 570 tons of hydrogen from
an STH of 10 % and a lifetime of ten years for a particulate
5,100 tons of water daily [6]. Hydrogen may be converted
photocatalyst, the price of hydrogen was estimated to be
into liquid fuels, such as methanol or methylcyclohexane,
1.6 USD kg-1, which could meet the target hydrogen price
for easy transportation and storage by catalytic processes.
of 2–4 USD kg-1 (0.18–0.36 USD Nm-3) suggested by
Approximately 10,000 such solar hydrogen plants
the United States Department of Energy. Particulate pho-
(250,000 km2) are needed to provide one-third of the
tocatalytic systems suffer from difficulty in improving the
projected energy needs of human society in 2050 from
STH and safe separation of the hydrogen and oxygen
solar energy. Therefore, photocatalytic systems must be
produced, although particulate systems with unique plastic
designed bearing scalability in mind.
baggie reactors were considered less expensive than rele-
vant photoelectrochemical systems in the report. STH
values of 5 % or higher could be regarded as a requirement
for the practical operation of photocatalytic solar hydrogen 3 Energy Diagram
plants. One might wonder what requirements the photo-
catalysts should meet to achieve 5 and 10 % STH. To A semiconductor photocatalyst has a forbidden band (band
answer this question, Fig. 2 presents the relationship gap) between the conduction band and valence band. When
between STH and the wavelengths of photons available in a photocatalyst absorbs photons with energies higher than
AM 1.5 at different AQYs for photocatalytic water split- its band gap energy, the electrons in the valence band are
ting. AQYs of 62, 40, and 30 % are needed to achieve excited into the conduction band, leaving positive holes in
10 % STH when using solar photons with wavelengths the valence band. For efficient photocatalysis, this elec-
shorter than 600, 700, and 800 nm, respectively, at the tron–hole pair (exciton) must be separated, and both the
constant AQYs. The STH of a photocatalyst that absorbs excited electron and excited hole should travel to the
only UV light (k \ 400 nm) is limited to 1.7 % even if the respective surfaces. These photogenerated carriers can
AQY is unity because of the limited number of photons in drive reduction (electrons) and oxidation (holes) reactions
the UV range and the dissipation of more than half of the when the charge injections are thermodynamically favor-
energy of the UV photons as heat while producing H2. able. To achieve an overall water-splitting reaction, the
Thus, it is necessary to develop and activate narrow-band- band gap of a semiconductor must straddle the reduction
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98 T. Hisatomi et al.
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Photocatalytic Water-Splitting Reaction 99
[26–28]. However, the primary reaction steps have not during OER is decreased if the computed O p-band center
been identified experimentally in an unambiguous manner is sufficiently close to the Fermi level. The O p-band of
because of the instability of the electrode surface at the Ba0.5Sr0.5Co0.8Fe0.2O3–d was overly close to the Fermi
oxygen evolution potentials and the difficulty of identify- level, causing the amorphization of the material during
ing the reaction intermediates. Considering only the surface OER. (Pr0.5Ba0.5)CoO3 produced the best activity and
species, the four electron reaction paths are assumed to be durability among the double perovskite-type cobalt oxides
as follows [28]: examined. The above findings will facilitate the develop-
H2 O þ HO þ Hþ þ e ð6Þ ment of efficient cocatalysts for oxygen evolution in pho-
tocatalytic systems for water splitting. The redox properties
HO O þ Hþ þ e ð7Þ of the cocatalysts may endow the intermediate states with
O þ H2 O HOO þ H þ e þ
ð8Þ extended lifetimes, enhancing the charge separation.
123
100 T. Hisatomi et al.
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Photocatalytic Water-Splitting Reaction 101
123
102 T. Hisatomi et al.
123
Photocatalytic Water-Splitting Reaction 103
Fig. 8 Diffuse reflectance spectra of (a) TaON and (b) ZrO2/TaON. The number of the photons is calculated by integrating from 280 to
Adapted from Ref. [57] with permission. Copyright Ó 2008 The 600 nm of AM 1.5G
Chemical Society of Japan
enables oxygen evolution on Rh-doped SrTiO3 in the
presence of sacrificial reagents. The reactivity of photo-
Subsequently, the coloading of a core/shell-type excited holes in impurity levels for the oxidation of water is
hydrogen evolution cocatalyst and an oxygen evolution not typically high because of the low mobility and short
cocatalyst was found to enable overall water splitting using lifetimes of the holes. Loading of IrO2 improved the oxy-
ZrO2/TaON [56]. ZrO2/TaON was modified with a RuOx/ gen evolution activity of SrTiO3:Rh,Sb, as confirmed by
Cr2O3 core/shell-type hydrogen evolution cocatalyst and the sacrificial OER. Interestingly, the loading of IrO2 also
then with IrO2 as an oxygen evolution cocatalyst. ZrO2/ improved the photocatalytic activity of the sacrificial HER.
TaON modified with RuOx/Cr2O3 exhibited some activity Thus, IrO2, a well-known cocatalyst for O2 evolution,
for overall water splitting under UV illumination, although enhanced both the hydrogen and oxygen evolution in water
the gas evolution rates decreased over time because of the splitting using SrTiO3:Rh,Sb. It was suggested that that
deactivation of the photocatalyst. When IrO2 was coloaded partially reduced IrO2 worked as an active site for H2
as an oxygen evolution cocatalyst on ZrO2/TaON with evolution.
RuOx/Cr2O3, overall water splitting proceeded steadily. By
optimizing the preparation conditions for the photocatalyst/
cocatalyst composite, overall water splitting was achieved, 7 Kinetic Aspects
even under visible light irradiation. Coloading with RuOx
and IrO2 did not lead to oxygen evolution. These results 7.1 Light Intensity and Cocatalyst Loading Amounts
highlight the importance of activation and stabilization of
the photocatalyst by the coloading of hydrogen and oxygen Photocatalytic reactions are initiated by the absorption of
evolution cocatalysts and the suppression of side reactions photons by photocatalysts. This absorption generates
by the ultrathin chromia layer. electron–hole pairs that dissociate into photoexcited elec-
trons and holes (electron vacancies). The photocatalyst
particle size plays an important role in determining how
6.4 Doped SrTiO3 Photocatalysts many photons are absorbed by a particle. Table 2 shows
the number of photons that strike the cross-section of a
Overall water splitting was also achieved under visible single spherical particle per unit time and its inverse, which
light using rhodium- and antimony-codoped SrTiO3 represents the expected time difference between photons
(SrTiO3:Rh,Sb) loaded with IrO2, RuO2, or Ru as cocata- striking a single particle, as a function of particle diameter
lysts [58]. Among the three cocatalysts, IrO2 produced the [40]. The number of incident photons per unit area is
highest activity for overall water splitting. In this photo- estimated based on the solar flux of standard AM 1.5G
catalyst, donor levels consisting of trivalent Rh species are from UV to 600-nm visible light. Increasing the photo-
excited under visible light. Electrons and holes are gener- catalyst particle size will clearly increase the number of
ated in the conduction band composed by Ti 3d orbitals and photons that strike a photocatalyst particle. However, a
the impurity levels consisting of Rh species. Codoping with particle with a typical diameter of 100 nm will receive 107
Sb5? ions stabilizes the donor level formed by Rh3? and photons s-1, which corresponds to a time of only 0.1 ls
123
104 T. Hisatomi et al.
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Photocatalytic Water-Splitting Reaction 105
123
106 T. Hisatomi et al.
photocatalyst. The H–D isotope effect also became stron- associated with surface electrochemical reactions, consid-
ger when the amount of loaded cocatalyst was decreased to ering the relatively low electrochemical activity of Ni. The
suppress HER. However, the H–D isotope effect was at apparent activation energy for HER on Ni was reported to
most two, even when the photocatalytic water splitting was be 56 kJ mol-1 [64]. However, the apparent activation
carried out using Rh2-yCryO3/Ga2O3:Zn at decent rates. energy is often considerably lower for photocatalytic
These results suggest that in most cases, the photocatalytic reactions than for electrochemical HER using correspond-
water-splitting rate is mainly determined by bulk processes ing electrodes because bulk processes have a dominant
inside the photocatalyst particles. effect on the apparent activation energy.
When (Ga1-xZnx)(N1-xOx) was modified with RuO2
7.3 Activation Energy instead of Rh2-yCryO3, the apparent activation energy
decreased from 8 to 0 kJ mol-1 and the water-splitting rate
The effect of reaction temperature on the photocatalytic decreased to 40 % [2]. This change in the water-splitting
activity for water splitting was investigated using (Ga1-x rate cannot be explained by the apparent activation energy
Znx)(N1-xOx) and Ga2O3:Zn modified with various cocat- alone. Side reactions, such as oxygen reduction, compete
alysts. It is natural to expect that the apparent activation with hydrogen evolution on RuO2, whereas Rh2-yCryO3 is
energy of photocatalytic water splitting reflects the acti- selectively active for hydrogen evolution [49]. As a result,
vation energy of the slowest reaction step and that reaction the water-splitting rate on RuO2/(Ga1-xZnx)(N1-xOx)
processes involving the cleavage and formation of chemi- decreases drastically in the presence of oxygen. Such
cal bonds have higher activation energies than physical competing reactions could significantly complicate the
processes, such as charge migration. kinetics of photocatalysis.
The apparent activation energy for photocatalytic water
splitting using Rh2-yCryO3/(Ga1-xZnx)(N1-xOx) and Rh2-y
CryO3/Ga2O3:Zn was 8 kJ mol-1 from 298 to 323 K [59, 8 Concluding Remarks
60]. This apparent activation energy is significantly lower
than that for the electrochemical HER on Rh electrodes Some examples of powder photocatalysts for successful
(31 kJ mol-1) [61]. Moreover, the apparent activation overall water splitting and their reaction kinetics are
energies for D2O splitting, water splitting in the presence of overviewed. The photocatalytic reactions using a particu-
sacrificial reagents, and gas-phase water vapor splitting late semiconductor are distinct from thermocatalytic reac-
were highly similar when Rh2-yCryO3/(Ga1-xZnx)(N1-xOx) tions, as the former involves photophysical processes
was used [59, 62]. This observation indicates that the inside semiconductors, which regulates how many charge
apparent activation energy is associated with processes carriers are available in surface electrochemical redox
occurring inside the photocatalyst rather than the formation reactions. Consequently, the kinetic parameters of photo-
and dissociation of chemical bonds involving hydrogen or catalytic water splitting, such as the H–D isotope effect and
the diffusion, adsorption, and desorption of chemical spe- apparent activation energy, can be significantly lower than
cies. This association likely occurs because only electrons those for electrochemical water splitting and thermocata-
that have successfully escaped recombination with photo- lytic reactions. Considering that AQYs lower than 10 %
excited holes can contribute to the photocatalytic HER on have been reported for water-splitting reactions in visible
the surface, whereas the electrons needed to drive hydrogen light regions, a major challenge lies in the efficiency and
evolution can be supplied immediately, depending on the selectivity of the separation of photoexcited charge carriers
potential of the electrode in the electrochemical HER. generated in visible-light-driven photocatalysts and their
The apparent activation energy depends on the type of transfer to cocatalysts that work as active sites for surface
cocatalyst. For example, loading Ni instead of Rh2-yCryO3 redox reactions. Semiconductor photocatalysts for overall
on Ga2O3:Zn increased the apparent activation energy from water splitting should be highly crystalline to prevent
8 to 15 kJ mol-1 while lowering the water-splitting rate at photoexcited charge carriers from becoming trapped and
room temperature to 40 % [60]. This result suggests that recombining at defective sites. At the same time, the
reaction processes involving both the photocatalyst and dimension of photocatalyst particles must be chosen based
cocatalysts, such as electron transfer from the photocatalyst on the diffusion length of minority carriers so that they can
to the cocatalyst, contributed to the apparent activation reach the surface active sites before recombination. Thus, it
energy. In fact, surface-enhanced infrared spectroscopy is necessary to balance the crystallinity and dimension of
under potential control revealed that there was a potential photocatalytic materials with the visible light response.
barrier for electron migration at the interface between an The weight or surface area of a photocatalytic material is
n-type GaN single crystal and deposited Pt particles [63]. not a primary concern unless the photocatalytic reactions
The slightly higher activation energy of Ni could also be involve the cleavage of metal cations and organic
123
Photocatalytic Water-Splitting Reaction 107
pollutants at low concentrations. In such a case, where the Acknowledgments This work was financially supported by Grant-
rate is proportional to the reactant concentration, the pho- in-Aids for Specially Promoted Research (No. 23000009) and for
Young Scientists (B) (No. 25810112) of the Japan Society for the
tocatalytic reaction may be regulated by the adsorption of Promotion of Science (JSPS) and King Abdullah University of Sci-
the reactants, and thus, high photonic efficiency cannot be ence and Technology. Further financial support came from the
expected. International Exchange Program of the A3 Foresight Program of JSPS
Cocatalysts loaded on a photocatalyst play key roles in and Companhia Brasileira de Metalurgia e Mineração (CBMM).
not only charge separation but also electrocatalytic func-
tions. A correlation may be found between the electrocat-
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