Review Article

https://doi.org/10.1038/s41929-019-0242-6

Reaction systems for solar hydrogen production

via water splitting with particulate semiconductor
photocatalysts
Takashi Hisatomi   1 and Kazunari Domen   1,2*

Photocatalytic water splitting using particulate semiconductor materials has been studied as a simple means of hydrogen
production. However, there are still many obstacles to the development of complete, practical and renewable solar hydrogen
production processes. This review discusses particulate photocatalyst systems intended for large-scale solar hydrogen produc-
tion via water splitting, focusing on their current status and potential impact. The cost and efficiency targets for solar-to-fuel
conversion on a practical scale are also reviewed, based on the maximum allowable cost of solar hydrogen production systems,
which has been estimated to be US$102 m–2, at most. Particulate photocatalyst material design principles are discussed, using
efficient oxide photocatalysts as examples. Approaches to constructing photocatalytic reactors extensible to large areas are
also introduced. Finally, challenges related to the development of efficient and inexpensive photocatalyst systems and poten-
tially useful analytical methods are outlined.

G
lobal primary energy consumption has increased by 1.7%
annually on average over the past 10 years, reaching 17.9 TW
(terawatts) in 20171. This value is estimated to further increase
to 22 TW by 2030. Because fossil fuels will account for almost 80%
of this energy in the evolving transition scenario2, carbon diox-
ide emissions are also predicted to increase over the next several
decades. Heavy dependence on fossil fuels has raised concerns
regarding the sustainability and environmental impact of modern
day energy production. The use of thermal catalysts in the chemical
industry has addressed some of these concerns, by decreasing the
energy input required to produce chemicals at satisfactory rates, via
reductions in activation energies and improvements in selectivity.
Photocatalysts based on heterogeneous semiconductor materials
that absorb light and catalyse reactions using the collected energy
have also received increasing attention with regard to the produc-
tion of renewable solar hydrogen.
In the early 1970’s, Fujishima and Honda reported photoelectro-
chemical water oxidation on a titanium oxide single crystal pho-
toanode3. Although an electrical or chemical bias was necessary
to drive the reaction, this phenomenon, nowadays known as the
Honda–Fujishima effect, showed the potential of semiconducting
materials in conversion of light energy into chemical energy, and
storage as fuels via the up-hill water splitting reaction. Thereafter,
a variety of particulate semiconductor materials have been studied
for applications in unbiased photocatalytic sunlight-driven water
splitting, as well as other artificial photosynthetic reactions4–29.
The amount of solar energy reaching the Earth’s surface (roughly
1.3 × 105 TW) is more than three orders of magnitude greater than
the current global energy consumption, although the intensity of
solar radiation fluctuates with time and region, and is often intense
at locations distant from areas where energy is intensively utilized.
Hydrogen is energetically dense by weight, storable and transport-
able. These properties make hydrogen attractive as a fuel for the
storage and transport of solar energy. In addition, hydrogen is a
feedstock for a variety of catalytic processes, and can be used to fix
carbon dioxide and nitrogen to produce liquid fuels for easier han-
dling11,30,31. The hydrogenation of aromatic molecules — for exam-
ple, toluene to methylcyclohexane — at hydrogen production sites,
followed by the recovery of hydrogen at sites where it is to be used,
has also been suggested32. Toluene and methylcyclohexane are both
liquids at ambient temperature, have relatively low toxicities and can
be hydrogenated and dehydrogenated in cycles using state of the art
technology owing to progress in the performance and understand-
ing of dehydrogenation catalysts33,34. For all these reasons, photo-
catalytic solar hydrogen production is closely linked to a variety of
catalytic processes that could potentially address challenges related
to both energy supplies and environmental degradation, and con-
tribute to the realization of sustainable societies. However, there are
still many obstacles to the development of complete, practical and
renewable solar hydrogen production processes.
In this review article, we focus on particulate photocatalyst sys-
tems intended for large-scale solar hydrogen production via water
splitting. The cost and efficiency targets of solar-to-fuel conver-
sion on a practical scale are also assessed. Subsequently, the design
principles for particulate photocatalyst materials are discussed,
using oxide photocatalysts that feature excellent apparent quantum
yields (AQYs) during water splitting as case studies. Approaches to
constructing large-scale photocatalytic water splitting systems and
associated challenges are also presented. Finally, analytical tech-
nologies potentially useful to the development of active photocata-
lysts and efficient systems are suggested. This review article does
not cover photocatalysts intended for environmental purification
because the requirements for such materials are very different26.
Readers who are interested in photocatalytic environmental puri-
fication and associated surface processes are encouraged to refer to
other review articles35,36.
Targets of solar-to-fuel conversion
In 2011, the United States Department of Energy (US DOE) esti-
mated that the maximum cost of hydrogen in 2020 that would

Center for Energy & Environmental Science, Interdisciplinary Cluster for Cutting Edge Research, Shinshu University, Nagano, Japan. 2Department of
1

Chemical System Engineering, School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo, Japan. *e-mail: domen@chemsys.t.u-tokyo.ac.jp

Nature Catalysis | VOL 2 | MAY 2019 | 387–399 | www.nature.com/natcatal 387

Review Article NATUre CATAlySiS

was estimated to be US$1.6 and US$3.2 kg–1 for single and dual bed
Table 1 | Comparison of unit energy costs
particle suspension systems, respectively, assuming STH values
Energy Cost (¥ MJ–1) Timeframe of 10% and 5% and a common lifetime of five years. In contrast,
Gasoline 1.8–2.6 In 2010
photoelectrochemical systems based on fixed planar and tracking
concentrator arrays were estimated to produce hydrogen at US$10.4
Petroleum 1.4–1.8 In 2010, thermal
and US$4.0 kg–1, respectively, with assumed STH values of 10% and
efficiency of 39%
15% and a common lifetime of 10 years. Suspended photocatalyst
Liquid natural gas 0.7–1.7 In 2010, thermal systems incorporating simple plastic bag reactors were expected to
efficiency of 51% be less expensive than photoelectrochemical systems owing to the
Coal <0.3 In 2010, thermal low capital costs, and could potentially meet the target hydrogen
efficiency of 42% price of US$2–4 kg–1 suggested by the US DOE in conjunction with
Fossil fuel (average) 1.0 In 2010 a moderate STH and lifetime. Sathre et al. modelled the life cycle
Fossil fuel (average) 1.5 Estimation for 2030 of photoelectrochemical water splitting technology and determined
that increasing the STH and extending the cell life are the primary
Hydrogen 2.4 Target for 2020
requirements for the net energy viability of this technology42. If the
PV 6.4–10.6 In 2013 STH and cell life are improved significantly, additional energy and
PV 1.9 Target for 2030 material inputs may be allowable on an overall basis even though
PV and water-electrolysis 10.9 In 2014 this technology is too energy and material intensive at present.
Figure 2 shows an overview of a solar hydrogen production plant
Wind power 2.6–6.4 In 2010, estimated to be
proposed by Maeda et al. in 201011. Each plant has an area of 25 km2
similar for 2030
and is capable of splitting water with an STH of 10% for 7.6 hours
Biomass-fired power 4.8–8.9 In 2010 daily in response to irradiation by sunlight (air-mass (AM)1.5 G,
Biomass-ethanol 1.7–4.3 Target 1 kW m–2). In this scenario, 570 tons of hydrogen can be produced
Adapted from ref. 37, Optronics Magazine.
from 5100 tons of water daily. It is important to note that ten thou-
sand of these solar hydrogen plants would be needed to produce
one third of the global energy requirements in 2050. Therefore,
these facilities must be efficient but also inexpensive and scalable.
make it an economically viable fuel was US$2–4 kg–1 (https://www. In earlier evaluations, the feasibility of solar hydrogen production
energy.gov/eere/fuelcells/doe-technical-targets-hydrogen-produc- was estimated based on assessing the capital and operating costs of
tion-photoelectrochemical-water-splitting). The cost of hydrogen the systems15. However, the allowable cost of photocatalytic reac-
produced by photoelectrochemical processes was predicted to be tion systems can also be evaluated using the value of the resulting
US$5.7 kg–1 in 2020 and to decrease to US$2.1 kg–1 in the more hydrogen and oxygen products, as reported by Setoyama et al23. On
distant future based on market competition. On the other hand, in this basis, the allowable cost of photocatalytic reaction systems was
2017, the Ministry of Economy, Trade and Industry of Japan sug- calculated to be US$136 m–2, assuming an STH of 10%, daily AM1.5
gested future cost targets for hydrogen of ¥30 Nm–3 (equivalent to G irradiation for 7.6 hours (corresponding to 317 W m–2), a lifetime
US$2.9 kg–1 if US$1 equals ¥115) by 2030 and ¥20 Nm–3 at a later date of 10 years, an annual depreciation rate of 4%, a hydrogen price of
(http://www.meti.go.jp/english/press/2017/pdf/1226_003b.pdf ). US$3.5 kg–1 and an oxygen price of US$0.1 kg–1. However, the solar
These target hydrogen costs for future commercial use are almost irradiance is typically 240 W m–2 at most15, 75% of the assumed value.
equal, and this coincidence has been explained by Sayama37, who The corresponding affordable cost will be thus US$102 m–2. This is
suggested using the unit energy cost (based on mega joules, MJ) a simple but clear cost target derived from the value of products.
as a measure for comparison of different energy resources, because Thus, in order to enable building and operating a solar hydrogen
cost is likely the strongest market driver. Table 1 shows the unit production process within this cost target, and with the assumed
energy costs of various energy resources as calculated by Sayama37. or even better STH and lifetime to ensure profitable solar hydro-
The average cost of fossil fuels in 2010 was ¥1.0 MJ–1, whereas all gen production, it is necessary to innovate materials and systems
renewable energy sources, including photovoltaics, wind power radically, because no solar hydrogen production system has met
and biomass, were more expensive, and the cost of hydrogen pro- such a cost target so far. It was estimated for photovoltaic-assisted
duced by electrolysis powered by photovoltaics was even greater. water electrolysis and photoelectrochemical water splitting systems
The future cost of fossil fuels was predicted to increase to ¥1.5 MJ–1 that the balance of system (BoS) expenses alone would exceed the
on average, with a value of ¥2.0 MJ–1 specifically for petroleum. cost target of US$102 m–2 (ref. 38). In the case of photocatalytic sys-
Here, the hydrogen cost targets of ¥30 and ¥20 Nm–3 correspond tems, however, the lower technological maturity offers large space
to energy costs of ¥2.4 and ¥1.6 MJ–1, respectively. Based on these for innovation. In this perspective, it is crucial to demonstrate scal-
values, the cost of hydrogen could conceivably become comparable able solar hydrogen production systems and identify problems in
to that of fossil fuels. Accordingly, a significant cost reduction will construction and operation before detailed estimation, because the
be required before renewable energy resources are adopted by the total cost of a system and the ratio of capital, hard BoS and soft BoS
market, particularly in the case of photovoltaic-assisted water elec- costs should vary with the progress of the research and develop-
trolysis. Shaner et al. also pointed out the high cost of the photovol- ment, and be optimised by system design43.
taic-assisted water electrolysis in 201638. According to their analysis, STH values of 5% and 10% have been assumed in the cost analy-
this process cannot be cost-competitive with electrolysis powered sis of photocatalytic water splitting systems. Therefore, it is worth
by nuclear or thermal power plants using present-day technology, considering the efficiencies required to achieve these STH values in
even taking into account that the solar-to-hydrogen energy conver- terms of the AQY and the irradiation wavelength. The AQY is the
sion efficiency (STH) values for such systems have been improved ratio of the number of photons contributing to an intended reac-
drastically, and high STH values exceeding 20% have been demon- tion (that is, water splitting) to the number of photons imparted to
strated under natural and simulated sunlight39–41. the photocatalytic reactor, and serves as a measure of photocatalytic
Pinaud et al. conducted a techno-economic analysis of the cost activity. The dependence of the STH of a photocatalytic water split-
of hydrogen produced by various types of photocatalytic and pho- ting system on the absorption edge wavelength of the photocatalyst
toelectrochemical systems in 2013 (Fig. 1)15. The cost of hydrogen has previously been discussed21,24. The absorption edge wavelength

388 Nature Catalysis | VOL 2 | MAY 2019 | 387–399 | www.nature.com/natcatal

NATUre CATAlySiS Review Article
a 4H++ 4e– 2H2

Single bed particle suspension nm–µm

STH efficiency 10%
2H2O + 4H+

O2 + 4H+
Particle slurry Baggies Transparent film

Driveway
0.1 m

12.2 m

b 4hυ + 4H++ 4A– 2H2+ 4A 4hυ + 2H2O + 4A O2 + 4H++ 4A–

Dual bed particle suspension

STH efficiency 5%
Perforated Porous Particle
pipes bridge slurry Transparent film

Driveway
0.1 m

O2 Baggie H2 Baggie 2m 1m

c O2
H2 outlet
Plastic case outlet

Electrolyte, O2
Fixed panel array 2m Panel
STH efficiency 10% TC anode
electrode
PV-1
PV-2
Metal cathode
Electrolyte, H2 35° Water inlet

1m

d Parabolic cylinder reflector

(10:1 solar concentration) 6m
O2
outlet
Tracking concentrator array
STH efficiency 15% H2
outlet 3m
El C a -1
ec
tro nod
T

lyt e
Me ectr

PV -2 ode

e,
El

PV ath , H 2
tal olyt

O2
c e

Linear PEC
cell

Water inlet

Fig. 1 | Schematics of four reactor types. a, A type 1 reactor cross-section showing the particle slurry contained within bags separated by an access
driveway. b, A type 2 reactor cross-section showing the particle slurries contained within bag assemblies with alternating full and half size bags for H2
and O2 evolution. c, A type 3 reactor design showing the encased composite panel oriented toward the sun with buoyant separation of gases. d, A type 4
reactor design with an offset parabolic cylinder receiver that concentrates sunlight onto a linear photoelectrochemical (PEC) cell. Drawings not to scale.
Reproduced from ref. 15, RSC.

must be longer than 526 nm even if the reaction is assumed to occur
at a constant AQY of unity at wavelengths shorter than this value,
because the proportion of photons in sunlight below this wavelength
is too small to allow an STH of 10%. This threshold wavelength cor-
responds to a band gap energy of 2.36 eV, and so it is essential to
develop and activate photocatalytic materials that have narrower
band gaps than this to ensure practical solar hydrogen production.
Electron donors such as methanol are sometimes added to
water as sacrificial reagents in research examining the properties of
photocatalysts. Such additives irreversibly react with photoexcited
holes, thus suppressing the recombination of electrons and holes,
and increasing the AQY of the hydrogen evolution reaction18,26.
However, the Gibbs energy change (∆Gr) for this reaction is much
less than that for the overall water splitting reaction (H2O → H2 +
1/2 O2, ∆Gr = 237 kJ mol–1 under standard conditions at 298 K).
Therefore, the addition of sacrificial electron donors is not useful in
terms of solar energy conversion. In addition, the fate of sacrificial
reagents in terms of the complete reaction must be known to cor-
rectly determine the reaction efficiency29.
Photocatalytic materials
The ability of photocatalysts to drive nonspontaneous reactions at
moderate temperatures and pressures and produce energetic carri-
ers is unique, and distinct from the behaviour of thermal catalysts.

Nature Catalysis | VOL 2 | MAY 2019 | 387–399 | www.nature.com/natcatal 389

Review Article
Under air-mass 1.5 G irradiation (7.6 hours day–1)
Solar energy
27 TJ km–2 day
Solar hydrogen plant
Conversion efficiency: 10%
25 km2 (5 km x 5 km)
570 tons day–1
Water supply
5,100 tons day–1
Fig. 2 | A proposed scheme for large-scale hydrogen production via solar water splitting. Reproduced from ref. 11, American Chemical Society.
A photocatalytic reaction is initiated by photoelectric conversion in
a semiconducting material, similar to photovoltaic power genera-
tion22. However, in a photocatalytic system, photoelectric conver-
sion and catalytic functions that evolve hydrogen and oxygen from
water are merged in a single particle, or at most within a composite
that includes several photocatalyst and cocatalyst particles, which
serve as active sites for surface redox reactions. In contrast, pho-
tovoltaic cells must be combined with external electrocatalysts if
chemical fuels are to be produced. Moreover, hydrogen and oxygen
are evolved at macroscopically distant places in electrolysers as well
as in photoelectrochemical cells. Therefore, the design principle of
photocatalytic systems is not identical to those of photovoltaic and
photoelectrochemical systems, and photocatalytic systems are also
believed to be less expensive15. Unfortunately, the STH values for
photocatalytic systems are lower than those for photovoltaic-assisted
electrolysis systems at present, because of the restrictions on the
design of such systems20,22,39. In particular, substantial advancements
in STH are needed to allow practical photocatalytic solar hydrogen
production. A scalable photocatalytic system design is also neces-
sary, owing to the low areal density of solar energy (1 kW m–2 for
AM 1.5 G irradiation), which is equivalent approximately to a cur-
rent density of 10 mA cm–2 given a STH value of 10%. Conversely,
research on electrolysers is commonly focused on reducing the sys-
tem size by increasing the current density at the order of 0.1–1 A
cm–2, in order to suppress the capital cost44.
The water splitting reaction on particulate semiconductor photo-
catalysts has been extensively investigated with regard to materials,
thermodynamics and kinetics4–27. A number of reviews and edito-
rial comments on the best practices for the correct measurement
and reporting of photocatalytic and energy conversion efficien-
cies have been published28,29. Briefly, when a particulate semicon-
ductor photocatalyst absorbs a photon, an electron is excited from
the valence band to the conduction band, while a positive hole is
left in the valence band. These excited charge carriers can respec-
tively drive the reduction and oxidation reactions on a photocata-
lyst particle. Based on thermodynamic principles, a semiconductor
photocatalyst can generate both hydrogen and oxygen from water
when its band gap straddles the potentials for the hydrogen evolu-
tion reaction (0 V versus reversible hydrogen electrode, RHE) and
the oxygen evolution reaction (+1.23 V versus RHE) (Fig. 3a)18. In
390
NATUre CATAlySiS
Oxygen
Chemicals
Chemical such as methanol
plant
Hydrogen
addition, two different photocatalysts can be connected in series so
that hydrogen and oxygen are generated on the respective materi-
als (Fig. 3b)18; this approach, based on two-step photoexcitation, is
termed Z-scheme water splitting. In a Z-scheme system, photocata-
lysts that do not have the ability to evolve both hydrogen and oxy-
gen can still be applied if they can evolve either hydrogen or oxygen
from an aqueous solution containing certain reversible electron
mediators. This allows a wider range of photocatalytic materials to
be employed. In order to drive photocatalytic reactions efficiently,
it is generally necessary to load nanoparticulate metals and metal
oxides as cocatalysts onto the photocatalysts. Surface modifica-
tions are also important to suppress backward reactions as well as
the self-decomposition of narrow band gap semiconductor photo-
catalysts45–47. Further details are available in a recent review by the
authors’ group24.
Semiconductor photocatalysts that are active for water splitting
can be classified into two categories: compound materials based
upon transition metal cations that do not have d-electrons in their
outmost orbitals (that is, those that have d0 electronic configura-
tions) and those based on metal cations whose outmost d-orbitals
are fully occupied (that is, those that have d10 electronic configu-
rations)7,9. In general, metal cations form the conduction band of
compound semiconductors while anions constitute the valence
band. However, in the case of oxide semiconductors incorporat-
ing Cu+, Ag+, Sn2+, Pb2+ and Bi3+ ions, the valence band edge is
composed of filled 3d (Cu), 4d (Ag), 5s (Sn), 6s (Pb) or 6s (Bi)
orbitals, because these orbitals are located at energy positions more
negative than those of oxygen 2p orbitals9. Certain (oxy)nitrides
and oxychalcogenides also have band structures suitable for overall
water splitting under visible light because nitrogen 2p, sulfur 3p
and selenium 4p orbitals are also situated at levels more negative
than those of oxygen 2p orbitals, owing to the lower electronega-
tivities of these elements7. Additionally, elemental and compound
semiconductors free from metal species, including black phos-
phorous48–50, carbon nitride (C3N4) and its derivetives51–55 and
1,3-diyne-linked conjugated microporous polymer nanosheets56,57,
have emerged as photocatalysts. Plasmonic systems have also been
applied to water splitting58–60, and certain photocatalytic systems
have been reported to efficiently split water without cocatalysts.
In any case, it is important to understand the band structure and
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NATUre CATAlySiS Review Article
a b (–)
(–)
e–
CB e– 2H+
e– H+/H2
Potential (V) versus NHE (pH 0)

Potential (V) versus NHE (pH 0)

+
H /H2 H+/H2
0 H2 (0 V) e–
CB hν
Band gap
(Eg) e–
Ox/Red
+1.0 Ox/Red
hν e–
O2 /H2O hν
+2.0 O2 /H2O h+
O2 /H2O
O2 +4H+ (1.23 V) e– H2 evolution
photocatalyst
+3.0
VB h+
VB h+ 2 H2O
(+) (+) O2 evolution
Photocatalyst photocatalyst

Fig. 3 | Energy diagrams for photocatalytic water splitting. a, One-step excitation and b, Two-step excitation (Z-scheme) processes. Reproduced from
ref. 18, RSC. CB, conduction band; VB, valence band; NHE, normal hydrogen electrode.

NiO ultra fine particle

H2
H+ H+ O2
3–15
NiO H 2O nm
H2 H 2O
O2
e–
– +
h+ h+
e h – +
La doping e h
NiO/N TaO3
2–3 µm
NiO/NaTaO3:La
0.1–0.7 µm

Fig. 4 | Mechanism of highly efficient photocatalytic water splitting over NiO/NaTaO3:La photocatalysts. Reproduced from ref. 64, American
Chemical Society.

carrier dynamics when developing and activating photocatalytic particles can be selectively loaded on the edges of nanosteps on
materials and systems. La-doped NaTaO3. As a result, reaction sites for hydrogen evolution
(that is, reduction) and oxygen evolution (oxidation) can be spa-
Design of efficient oxide photocatalysts tially separated (Fig. 4)64. This is believed to contribute to the highly
Oxide photocatalysts have been the target of continuing research efficient photocatalytic water splitting observed over NiO-loaded
effort since the first reports of photocatalytic water splitting using La-doped NaTaO3 photocatalysts.
TiO2 and SrTiO3 in 1980 (refs. 61–63) up to recent work focusing on Ga2O3 codoped with Zn and Ca and loaded with a rhodium
scaled-up systems, and are considered as representative systems in chromium oxide (RhCrOx) as a hydrogen evolution cocatalyst also
the following section. NaTaO3 doped with La and loaded with NiO splits water into hydrogen and oxygen with a high AQY value of
as a hydrogen evolution cocatalyst is reported to exhibit a high AQY 71% at 254 nm69. Doping with either Zn2+ or Ca2+ individually effec-
value of 56% during overall water splitting at 270 nm64. In this mate- tively suppresses charge recombination because these ions modify
rial, the La3+ species are partly situated in the bulk but also found the bulk state of the Ga2O3 and affect the mobility of electrons and
on the NaTaO3 surface. La3+ ions have an ionic radius of 150 pm in holes. Notably, the use of Ca-doped Ga2O3 as a host material for the
the twelve-coordinated state, which is closer to the radius of Na+ doping of Zn2+ species further improves the water splitting activity.
(153 pm in the twelve-coordinated state) than that of Ta5+ (78 pm The optimal Ca2+ concentration was found to be 0.89 mol% rela-
in the six-coordinated state), and thus are believed to preferentially tive to the amount of Ga, and this relatively low amount does not
replace Na+ in NaTaO3. However, analyses using X-ray diffractom- affect the crystal structure or the particle morphologies. The results
etry, Raman spectroscopy and X-ray absorption spectroscopy have obtained with these materials indicate the synergistic effects of dop-
shown that Sr2+ ions, which have a similar ionic radius (132 and 158 ing with Zn and Ca species on photocatalytic activity.
pm for six- and twelve-coordinated states, respectively) to La3+, are Recently, Al-doped SrTiO3 loaded with a RhCrOx cocatalyst has
doped into both the Ta5+ and Na+ sites to form core-shell-structured been shown to split water into hydrogen and oxygen at an AQY of
NaTaO3−SrSr1/3Ta2/3O3 solid solutions, in which a Sr-rich shell cov- 56% at 365 nm70. The Al3+ species are believed to be situated at Ti4+
ers a Sr-poor core65,66. Doping with these species reduces the par- sites following calcination of SrTiO3 and Al2O3 powders in an alu-
ticle size from several micrometres to hundreds of nanometres and mina crucible in the presence of a SrCl2 flux. Even without adding
induces characteristic nano-step structures on the surface of the Al2O3, Al-doped SrTiO3 is produced because Al species are supplied
NaTaO3 (Fig. 4), but does not alter the optical properties or degrade from the crucible. The synthesis under molten salt environments
the bulk crystallinity of the material. The high degree of crystallinity results in SrTiO3 particles that grow into micrometre-sized trun-
and smaller particle sizes of the product both favour photocatalytic cated cubes71. However, additional Al2O3 effectively prevents the
water splitting because excited carriers can be efficiently transferred growth of overly large SrTiO3 particles, yielding highly-crystalline
to active sites on the surface. It has also been observed that dop- Al-doped SrTiO3 particles of 200–500 nm in size, which improves
ing increases the population of excited electrons in response to both the AQY during overall water splitting70. Reducing the particle size
pulsed and steady photoexcitation67,68. In addition, catalytic NiO is beneficial with regard to photocatalytic water splitting, so long

Nature Catalysis | VOL 2 | MAY 2019 | 387–399 | www.nature.com/natcatal 391

Review Article
as a high degree of crystallinity is maintained, as in the cases of
La-doped and Sr-doped NaTaO3 (ref. 64). Furthermore, the AQY
value of this same photocatalyst can be further increased to 69% by
additional deposition of molybdenum oxide (MoOy)72. It has been
suggested that the Mo species modify the chemical states of Rh
and Cr species in the RhCrOx cocatalyst and thus affect hydrogen
evolution processes, although the detailed mechanism is yet to be
clarified. Because Al-doped SrTiO3 exhibits an excellent AQY value
in response to irradiation with light in the near-UV region (which
is included in sunlight), this material splits water more efficiently
than most other photocatalysts, and produces hydrogen from pure
water under sunlight at STH values of 0.4% at room temperature
and 0.6% at 331 K. Doping with metal cations other than Al3+ also
enhances the water splitting activity of SrTiO3, provided that these
cations have oxidation numbers lower than that of the host cation
species. These low valence metal cations are believed to decrease the
concentration of reduced Ti species73.
It has been reported that the site-selective co-loading of Pt and
Co3O4 as hydrogen evolution and oxygen evolution cocatalysts
improves the AQY of an eighteen-faceted SrTiO3 photocatalyst dur-
ing overall water splitting74. The anisotropic nature of this material
and the intrinsic potential at the semiconductor-liquid junction,
resulting from the exposition of different facets, may allow for the
preferential migration of electrons and holes, and thereby enhance
charge separation. A similar effect has been reported in works
based on BiVO4 and Cu2O using spatially-resolved surface photo-
voltage spectroscopy75,76. However, it is still unclear if exposing spe-
cific facets and the site-selective loading of cocatalysts enhance the
water splitting activity of SrTiO3, because the absolute AQY real-
ized by the eighteen-faceted SrTiO3 photocatalyst was below that
obtained from a featureless Al-doped SrTiO3 photocatalyst. It will
be necessary to optimize the quality of the SrTiO3 photocatalyst,
the cocatalyst species and the loading process to draw an unam-
biguous conclusion.
Examples of highly efficient oxide photocatalysts demonstrate
that reducing particle sizes to the submicron level and obtaining a
high degree of crystallinity are very likely to improve photocatalytic
water splitting. Doping with certain metal cations can realize these
factors simultaneously, although critical problems remain regarding
the large band gap energies of such materials. Oxide photocatalysts
that are active during overall water splitting based on one-step exci-
tation primarily absorb only UV light, because the valence bands in
these photocatalysts, composed of oxygen 2p orbitals are too positive
(approximately +3.0 V versus RHE). When such materials absorb
sufficient visible light, it is often the case that their conduction band
edges are too positive to evolve hydrogen from water77. However,
Z-scheme water splitting has allowed the utilization of these photo-
catalysts in water splitting under visible light10,13. Moreover, a num-
ber of doped oxide photocatalysts have been investigated with the
aim of obtaining a visible light response while controlling electronic
properties and morphologies6,78,79.
The fundamental effects of doping on the photocatalytic activity of
metal oxides was reviewed by Kudo et al6. The doping of perovskite-
type oxides has been studied in detail because these compounds
readily undergo elemental substitution and tolerate the presence of
defects. Doping with transition metal cations can provide visible light
activity during hydrogen and oxygen evolution in the presence of
sacrificial reagents for wide band gap oxides acting as host photocat-
alyst materials. This visible light response is due to electron excitation
from donor levels created by the dopants to the conduction bands
of the host photocatalysts. However, most transition metal cations
can have multiple oxidation states, and the incorporation of foreign
ions generally deteriorates the crystallinity of the host material such
that charge recombination is enhanced and the AQY is drastically
decreased. Therefore, it is important to control the chemical states,
amounts and locations of doped transition metal cations.
392
NATUre CATAlySiS
Codoping is an effective strategy for controlling the valence
states of dopants through charge compensation6. As an example,
TiO2 doped with Rh shows no activity during oxygen evolution
from an aqueous AgNO3 solution. The Rh species doped into the
Ti4+ sites are primarily tetravalent and predominantly function as
recombination centres. However, codoping with Sb5+ transitions
the Rh4+ ions to Rh3+ and generates active donor levels because of
charge compensation, leading to photocatalytic oxygen evolution
under visible light irradiation. Notably, the first demonstrations of
Z-scheme water splitting under visible light were based upon the use
of transition metal-codoped oxide photocatalysts, such as SrTiO3
codoped with Cr3+ and Ta5+, as hydrogen evolution photocatalysts
(HEPs)80. Codoping of anion species (N3– and F–) also allowed TiO2
to exhibit visible light activity in sacrificial oxygen evolution reac-
tions and function as an oxygen evolution photocatalyst (OEP) in
Z-scheme water splitting under visible light81. Efficient Z-scheme
water splitting with STH values exceeding 1.0% has been realized
with particulate photocatalyst sheets incorporating SrTiO3 codoped
with La3+ and Rh3+ as the HEP82,83. These La and Rh species have
been found to be localized near the surface of the highly crystalline
SrTiO3 to form a core-shell-type structure84. This configuration is
thought to maintain the crystallinity of the material whilst accom-
modating high dopant concentrations. In 2013, one-step excitation
overall water splitting was achieved under visible light irradiation
using Rh- and Sb-codoped SrTiO3 modified with IrO2, RuO2, and
Ru as cocatalysts85. In this photocatalyst, electrons and holes are
generated in the conduction band composed of titanium 3d orbit-
als and impurity levels associated with Rh species, respectively.
Codoping with Sb5+ ions evidently stabilizes the donor level formed
by Rh3+ and enables oxygen evolution on Rh-doped SrTiO3 in the
presence of sacrificial reagents.
As described above, there are some successful cases in which
doping improves the properties of photocatalysts. Doping may
modify morphology, electronic and optical properties of host semi-
conductor photocatalysts favourably. However, doped species gen-
erally deteriorate the crystallinity of the host materials and enhance
charge recombination. Due to this trade-off, the functionality of
dopants should be analysed and doping methods should be con-
trolled carefully.
Reactors for fixed particulate photocatalysts
Particulate photocatalyst systems are described as featuring some
advantages in terms of fabrication cost and scale-up potential
compared with photovoltaic and photoelectrochemical systems15.
However, the scale-up of photocatalytic water splitting systems even
to the square metre scale has rarely been demonstrated, despite the
eventual necessity of fabricating plants with footprints of tens of
square kilometres. In contrast, photovoltaic power generation facili-
ties have been commercialized and installed over wide areas. This
represents a continuing challenge to the use of photocatalytic water
splitting as a means of solar fuel production.
Conventionally, photocatalytic water splitting has been studied
using suspensions of photocatalyst powders in flask-type reactors
on the laboratory-scale9,28,86. However, the difficulty in scale-up
of suspension systems may be inferred from the absence of large-
scale demonstrations of sunlight-driven overall water splitting with
appreciable STH values. In fact, this approach is troublesome on
large scales for several reasons. Firstly, it is challenging to minimize
reactor costs, considering that water is required in large volumes.
As an example, even for a depth of just 1 cm, the mass of water in
a reactor reaches values of 10 kg per square metre, and so these
reactors tend to be bulky and costly. This would not be feasible on
a large scale considering that the maximum cost allowed for the
whole hydrogen production systems is estimated to be US$102 m–2,
as discussed earlier23. Secondly, the particulate photocatalysts tend
to gravitate to the lower part of the reactor and thus do not receive
Nature Catalysis | VOL 2 | MAY 2019 | 387–399 | www.nature.com/natcatal
NATUre CATAlySiS
incident light effectively unless the reactor is perfectly levelled
or stirred. Tubular reactors coupled with a compound parabolic
concentrator (CPC) have been examined for large-scale outdoor
operation of photocatalytic hydrogen evolution reactions in the
presence of sacrificial reagents87. No daily light tracking is required
for CPCs in principle. In the works by Jing et al., CPCs had the
maximum half incident angle of 14°, aperture length of 0.4 m, and
total length of 1.5 m, and reactor tubes made of Pyrex glass 1.6 m
in length were utilized. This configuration resulted in a concentra-
tion factor of four. However, turbulent flow in the reactor must be
maintained by pumping so that sedimentation of the photocatalyst
leading to ineffective light absorption could be avoided. Thirdly,
recovering the suspended catalytic powder by filtration or centrifu-
gation is energy- and time-consuming. Processes associated with
spent photocatalyst replacement should be simpler considering the
large footprints of photocatalytic water splitting systems. The use of
fixed particulate photocatalysts addresses all of these problems, and
so it has been suggested that photocatalysts should be processed
into modular planar panels such as those used in photovoltaic sys-
tems for large-scale applications.
Water splitting using photocatalyst powders thinly fixed on
substrates has been reported in several recent publications88–90. It is
possible to fix particulate photocatalysts onto substrates by drop-
cast methods using silica binders70,88. Controlling the hydrophilic-
ity and porosity of these layers is important in terms of preserving
the intrinsic activity of the particulate photocatalysts fixed onto the
substrates. For example, photocatalyst particles densely fixed onto
glass substrates exhibit lower activity than suspensions of the same
materials70,88. This is because the penetration of water into and
desorption of gaseous products from the dense particulate photo-
catalyst layer are inefficient. The addition of hydrophilic silica par-
ticles accelerates the water splitting rate of the photocatalyst panels
because the hydrophilic silica particles create voids among the pho-
tocatalyst particles, and thus promote the diffusion of the aqueous
solution and product gas bubbles. The properties of Z-scheme-
type photocatalyst sheets based on HEP and OEP particles fixed
onto substrates with conductive materials are reviewed in recent
publications by the authors’ group83,91,92. Z-scheme-type photo-
catalyst sheets can be regarded as micro p/n-photoelectrochemical
cells based upon photocathodes of the HEP and photoanodes of
the OEP sharing the same back contact material in the dimension
of particles, a few micrometres at most in size. The water splitting
activity of photocatalyst sheets are unaffected by the pH value, pH
gradients, or the resistance of the reaction solution, because the
photocatalyst particles are directly fixed into a conductive film and
hydrogen and oxygen are generated in close proximity. Therefore,
the photocatalyst sheet can be directly scaled up without any spe-
cial consideration given to the electron and mass transfer between
the HEP and OEP particles. However, it is favourable to use large
and small work function materials for HEP and OEP materials,
respectively, to minimize the Schottky-type barrier, which could
not be realized by single conductor materials. In addition, back-
ward reactions such as the oxygen reduction reaction are enhanced
on certain conductor materials. It is effective in creating addi-
tional charge transfer pathways by surface modifications of pho-
tocatalysts and applying electrochemically inert conductors83,93,94.
Originally, vacuum processes were necessary during the fabrica-
tion to establish electric contact between particulate photocatalysts
and conductive materials during the water splitting reaction, and
to suppress oxygen reduction as a backward reaction83. However,
Z-scheme-type photocatalyst sheets that can be printed and used
under atmospheric conditions have been recently developed by
applying indium tin oxide nanoparticles as a transparent conduc-
tor inactive in the backward reaction93. In principle, particulate
photocatalyst sheets can be fixed over large areas using existing
solution processes.
Nature Catalysis | VOL 2 | MAY 2019 | 387–399 | www.nature.com/natcatal
Review Article
a b
3
3
51.5 cm
91 c
m
2 2
110 cm
1
4 1
10 7 6 11 10
5
4
86 cm
m
5 6
3c
9
8
11
7
8
11 113 cm
9
Fig. 5 | A largescale photoreactor for photocatalytic reactions with
an immobilized photocatalyst. a, A schematic flow diagram and b,
A photographic image. (1) The reaction chamber inlet, (2) the reaction
chamber with cross and longitudinal bracings and nine stainless steel
plates (each 28 × 30 × 0.1 cm) coated with Pt-loaded mp-C3N4, (3) a light
sensor calibrated with a solar cell in units of W m–2, (4) a storage tank (2 L),
(5) a webcam for volumetric tracking of H2 production, (6) a thermocouple,
(7) a peristaltic pump, (8) a gas line that connects the photoreactor with
(9) the volumetric quantification system (two graduated cylinders placed
in a water reservoir upside down and completely filled with water), (10) a
two-way valve for purging and (11) a computer to log the data. Reproduced
from ref. 90, Wiley.
Although it is vital to understand the reaction properties of fixed
photocatalysts and to increase their STH values, a further challenge
is to build scalable reactors that allow efficient photocatalysis as
well as transfer of product gases. Schröder et al. reported in 2015
a flat panel-type photocatalytic reactor with a light-acceptance area
of 0.76 m2 based on a C3N4 photocatalyst, using triethanolamine as
a sacrificial electron donor90. The panel-type reactor was primar-
ily composed of a reactor body made of an etched Teflon plate
(6 mm in depth), exchangeable stainless-steel plates coated with the
photocatalyst using a Nafion binder, a plexiglass window (8 mm in
thickness), a reaction solution reservoir (10 vol% aqueous trietha-
nolamine) and a pump for circulation of the solution (Fig. 5). The
amount of photocatalyst in the device was approximately 13 g m–2.
Due to the high hydrostatic pressure inside the reactor, the window
was stabilized by longitudinal bracings. The photocatalytic hydro-
gen evolution rate was found to decrease by 40% during continuous
operation over 30 days owing to detachment of the Pt catalyst from
the photocatalyst. Unfortunately, the STH value of this unit was not
correctly determined because the oxidation reaction potential of
the sacrificial reagent was not considered. In fact, the vast major-
ity of the energy stored as hydrogen originated from the chemical
energy of the sacrificial reagent, not from the solar energy harvested
by photocatalysis. In addition, forced convection was applied with
a pump, which would increase the energy required to sustain the
system. Nevertheless, this was a pioneering work that addressed
challenges associated with building a large-scale panel-type photo-
catalytic reactor for the generation of gaseous products.
The authors’ group has also examined problems associated
with panel-type reactors intended for large-scale photocatalytic
water splitting, using highly active SrTiO3:Al photocatalyst sheets70.
SrTiO3:Al has a wide band gap of 3.2 eV, corresponding to an
absorption edge wavelength of 390 nm. Due to the limited ability
of sunlight absorption, the STH values under sunlight illumination
393
Review Article
(AM1.5 G, 100 mW cm–2) are restricted to less than 1.4% (ref. 21).
Nevertheless, the high AQY in the near UV region produces high
water splitting rates over large areas using unfocused and ordinary
experimental UV-light sources such as Xe lamps and light emitting
diodes, as well yielding decent STH values of 0.4% and 0.6% at 288
and 331 K, respectively, under simulated sunlight irradiation. Such
features render SrTiO3:Al one of the most favourable photocatalyst
materials in the reactor engineering for large-scale sunlight-driven
overall water splitting.
SrTiO3:Al photocatalyst sheets were prepared by depositing the
SrTiO3:Al photocatalyst together with SiO2 as a binder on frosted
glass plates. The sheets were initially contained in a laboratory-scale
panel-type reactor (25 cm2) filled with water to a depth of 1 mm
and tilted at angles in the range of 10–20°. Under intense UV light
illumination over the entire photocatalyst sheet from a 1500-W Xe
lamp, the evolution rate of hydrogen and oxygen gas mixture was
found to reach 5.6 mL cm–2 h–1. During the reaction, small bub-
bles of hydrogen and oxygen migrated upward smoothly due to
the buoyant force without forced convection, and the photocata-
lyst sheet was kept wet as the window had been hydrophilized. If
the water splitting reaction occurs under AM1.5 G irradiation (100
mW cm–2) at a 10% STH, a gaseous mixture of hydrogen and oxygen
will be evolved at 5.6 mL cm–2 h–1. Although the gas evolution rate
of 5.6 mL cm–2 h–1 under irradiation from a 1500-W Xe lamp does
not correspond to a 10% STH, because the fluence of UV light was
greater than that of natural sunlight, the experiment demonstrated
that limiting the water depth to 1 mm does not cause mass-transfer
problems in the envisioned operation condition. Subsequently, one
square metre panel reactors were constructed using plexiglass plates
for the body and window, and SrTiO3:Al sheets and distilled water
were loaded into these devices (Fig. 6) using a photocatalyst amount
of approximately 8 g m–2. Here, it is worth noting that the material
cost of the photocatalyst (SrTiO3:Al) and the cocatalyst (RhCrOx)
used is not significant compared with the allowable cost of the
photocatalytic reactor (US$102 m–2). Given that the price of Rh is
US$81 g–1, the cost of Rh in the cocatalyst is US$0.6 m–2, just 0.6%
of the allowable cost of the system. Moreover, the total material cost
of the RhCrOx-loaded SrTiO3:Al and silica binder is estimated to
be below US$2 m–2 on the basis of the largest quantities of reagents
available from reagent companies when the SrCl2 flux used in the
synthesis is recycled. The material cost depends on photocatalysts
but can be at an allowable level. The STH of this one square metre
photocatalytic reactor for non-sacrificial sunlight-driven overall
water splitting was estimated to be 0.4% based on the amount of
gas generated and collected under exposure to natural sunlight, and
this value was comparable to that obtained during laboratory scale
experiments under simulated sunlight. The results above indicate
the ability of a panel-type reactor to sustain a high gas evolution
rate that is envisioned at 10% STH under AM1.5 G irradiation (100
mW cm–2) without forced convection as well as the potential for
scale-up to the square meter scale and beyond. Therefore, once
photocatalyst sheets realizing 10% STH under natural sunlight are
developed in the future, they can be mounted in a panel-type reac-
tor directly without concerns regarding mass transfer limitations.
The STH values obtainable from SrTiO3 photocatalysts during
solar hydrogen production are limited to less than 1.4% because of
the short absorption edge wavelength of this material (390 nm)21.
However, Z-scheme type photocatalyst sheets could also, in prin-
ciple, be accommodated in panel-type reactors for effective harvest-
ing of sunlight.
Summary and prospects
This review assesses particulate photocatalyst systems intended for
large-scale sunlight-driven water splitting. It is evident that signifi-
cant cost reductions are needed for solar hydrogen production tech-
nologies because existing approaches are all too expensive37,40. In
394
NATUre CATAlySiS
this work, a maximum allowable cost of US$102 m–2 is estimated, in
conjunction with an STH of 10% with a lifetime of 10 years and real-
istic product gas values23. We propose that fixing particulate photo-
catalysts in thin layers on substrates to form panel-type reactors may
be the best approach70, because this reduces the amounts of reactant
water and materials required to build reactors, and thus lowers costs.
The use of panel-type reactors does not lead to critical mass trans-
fer problems even at a gas evolution rate equivalent to 10% STH
under AM1.5 G irradiation (100 mW cm–2), which is envisioned in
future operation, and allows photocatalysts to exhibit their intrinsic
activities. The panel-type reactor concept can be scaled up to at least
the square metre scale and likely beyond. Nevertheless, the high-
est STH demonstrated to date with fixed particulate photocatalysts
is approximately 1%, using Z-scheme photocatalyst sheets based
on La and Rh-codoped SrTiO3 and Mo-doped BiVO4 (refs. 82,83).
With regard to durability, Al-doped SrTiO3 photocatalyst sheets are
reported to maintain 64% of their initial activity after 1,000 hours
of continuous irradiation with simulated sunlight70. Existing photo-
catalytic water splitting technologies are still far behind the targeted
performance in terms of the STH and lifetime. This situation not
only restricts freedom in the design of photocatalytic solar hydro-
gen production processes but will eventually cause such processes to
become inferior to competing energy-related technologies in terms
of practical applications37.
Photocatalytic materials capable of splitting water into hydro-
gen and oxygen with high efficiency remain limited to oxide semi-
conductors absorbing light up to approximately 500 nm at most.
Therefore, the activation of narrow band gap materials is a con-
tinuing and important challenge. Some particulate non-oxide pho-
tocatalysts such as (oxy)nitrides and (oxy)chalcogenides are also
applicable to water splitting under visible light94–98. As an example,
LaMg1/3Ta2/3O2N with appropriate surface modifications splits water
under irradiation at wavelengths up to 600 nm (ref. 95); however, the
AQY value is very low (0.18% at 440 nm)96, as is the STH value. The
situation is similar for Z-scheme systems. Z-scheme systems solely
based on photocatalyst materials with light absorption onsets of 600
nm and even longer, such as those using Ga-doped La5Ti2CuS5O7,
LaTiO2N, ZnRh2O4, Bi4V2O11 and AgSbO3, generate hydrogen and
oxygen simultaneously under visible light but at low AQY values
on the orders of 10–1% at most92,94,99,100. In addition, there are no
generally-accepted experimental protocols to evaluate the long-
term stability of such materials, even though improvement in the
lifetimes of photocatalytic systems is needed. Photocatalytic water
splitting reactions may be conducted under intense illumination in
acceleration tests101. However, the effects of greater concentrations
of photoexcited carriers and higher hydrogen and oxygen evolution
rates must be considered, because this may induce deviations in the
quasi-Fermi levels of charge carriers and mass transport behaviour,
compared with those under realistic operational conditions.
It appears that particulate semiconductor materials with nar-
row band gaps are typically poorly crystallized and are often defec-
tive owing to the difficulty in their synthesis. These materials are
also prone to energetically-favourable backward reactions and
charge recombination mediated by trap states (Fig. 7), regardless
of whether they are used for one-step or two-step excitation reac-
tions. The doping and charge compensation approaches that are
effective at improving oxides are not readily applicable to narrow
band gap materials because of the formation of anion defects and
the reduction of constituent metal cations. Therefore, it is necessary
to design synthesis methods giving well-crystallized materials with
low bulk defect densities, as well as surface modification methods to
passivate surface defects. Reductions in bulk and surface defect den-
sities will suppress charge recombination and backward reactions
mediated by charge trapping. In fact, Ta3N5 was, for the first time,
activated for the visible-light-driven overall water splitting through
modifications of the synthesis conditions102. This active Ta3N5 was
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NATUre CATAlySiS Review Article
a 10 mm b
Screw Gas outlet
1,080 mm

330 mm

30 cm

330 mm

1,190 mm
Acrylic plate (5 mm)
H2O (4mm)
Photocatalyst sheet (2 mm)
Spacer (2 mm)
Acrylic plate (5 mm)

Fig. 6 | 1 × 1 m Water-splitting panels containing SrTiO3:Al sheets. a, Schematics of the 1 × 1 m water-splitting panel. Nine photocatalyst sheets (each
33 × 33 cm) were arrayed in the reactor. A hydrophilized acrylic plate was used as the window and the panel had a 10° tilt. The weight of water in this
panel was approximately 4 kg because a surplus depth of 4 mm was adopted in consideration of the distortion of the panel under its own weight. b, A
photograph of a 1 × 1 m SrTiO3:Al panel. Adapted from ref. 70, Elsevier.

a b

(–) (–) CB
CB (v) Interface/surface
e– e– modifications

(i)
(ii) ηHER (iv)

H+/ H2 H+/H2

(iii)
Potential

Potential

hν 1.23 V hν 1.23 V
(vi)

O2 / H2O O2 /H2O

ηOER
(ii) (iv)
(i)

h+ +
h (v)
(+) (+)

VB VB

Photocatalyst Water Photocatalyst Water

Fig. 7 | Schematic diagrams of water splitting on narrow-band-gap semiconductor photocatalysts. a, A photocatalyst with a high defect density suffering
from (i) charge trapping, (ii) insufficient energy offsets for the hydrogen and oxygen evolution reactions and (iii) thermodynamically favoured backward
reactions (for example, the oxygen reduction reaction). b, A conceptual active photocatalyst benefitting from (iv) low bulk trap-state densities for effective
charge separation, (v) low interfacial energy barriers for efficient charge transfer and (vi) low surface defect densities leading to fewer opportunities for
undesired backward reactions. CB, conduction band; VB, valence band; ηHER, the energy offset between the bottom of the CB and the hydrogen evolution
potential; ηOER, the energy offset between the top of the VB and the oxygen evolution potential.

Nature Catalysis | VOL 2 | MAY 2019 | 387–399 | www.nature.com/natcatal 395

Review Article
directly generated on KTaO3 particles by short nitridation and was
composed of single crystal nanorods without inside grain bound-
aries. Engineering of the interfaces of semiconductor photocata-
lysts and cocatalysts is also important. There are many cases where
excellent electrocatalysts do not effectively catalyse the intended
redox reactions over photocatalysts and photoelectrodes103,104. It is
apparent that the behaviour of electrocatalysts loaded on conduc-
tive materials under potential control, and cocatalysts loaded on
semiconducting photocatalysts under photoexcitation is not iden-
tical. This is because the competition between charge separation
or migration and recombination largely dominates the efficiency
of photocatalysis21.
Research into catalysis is closely linked to the identification of
active species and sites with the aim of achieving drastic improve-
ments in certain reaction processes. In the case of photocatalysts for
solar energy conversion, it is beneficial to understand the behaviour
of photoexcited carriers during the material development process,
because photocatalysis results from a series of phenomena occur-
ring under non-equilibrium conditions and involves photoexcited
carriers with finite lifetimes as active species. Accordingly, analyti-
cal techniques with temporal resolution will play an important role.
Transient absorption spectroscopy has been used to elucidate the
carrier dynamics in photocatalysts and the effects of other materials
within composites67,68,103,105. The dynamics of carriers are sensitive to
their environment, and photocatalytic water splitting is conducted
in the presence of large amounts of water. In this context, oper-
ando analyses involving analytical techniques in aqueous solutions
in conjunction with photoexcitation will be vital for assessing the
intrinsic properties of particulate photocatalysts. It has also been
pointed out that chemical states of cocatalyst species may be dif-
ferent under darkness and illumination owing to the presence of
photoexcited carriers106.
Analytical information obtained from powdered materials typi-
cally represents an average over many particles unless the spatial
resolution is better than the dimensions of the particles. Considering
the significant variations in stoichiometry, crystallinity, size and
morphology among and within photocatalyst particles, technologies
that allow the high-spatial resolution imaging of charge separation
and surface redox reactions during photoexcitation will be power-
ful tools. Recently, it became possible to observe charge separation
and redox reactions occurring on single particles75,76,107. Spatially-
resolved surface photovoltage spectroscopy can also be used to
determine the facets of photocatalyst particles on which electrons
and holes preferentially migrate75,76. The visualization of reduction
and oxidation sites on photocatalyst particles has also been reported,
using single-molecule fluorescence microscopy in association with
redox-sensitive probe molecules107. Furthermore, transient absorp-
tion spectroscopy and X-ray photoelectron spectroscopy of individ-
ual particles have become useful techniques108,109. Such technologies
will allow examinations of particle morphology and size and their
effects on semiconductor properties and the reactivities of charge
carriers, and could be used to design composites consisting of pho-
tocatalysts, cocatalysts and conductor particles. Combinations of
operando and spatiotemporal analytical technologies are expected
to greatly advance the development of photocatalysts.
Along with the development of photocatalyst materials and reac-
tors exhibiting satisfactory performance, chemical processes must
be designed that maximize and balance the energy efficiency, cost,
stability and safety of solar hydrogen production systems. This rep-
resents a complex problem in the field of chemical process engi-
neering. In particular, the safe and energy-efficient separation of
hydrogen from oxygen in the product is a critical challenge related
to photocatalytic water splitting23. Moreover, the cost of H2/O2 sepa-
ration systems must be managed within the allowable cost of whole
solar hydrogen production systems. The Gibbs energy necessary to
separate a mixture of 1 mol of H2 at a partial pressure of 2p/3 and
396
NATUre CATAlySiS
0.5 mol of O2 at a partial pressure of p/3 with a volume of V into
1 mol of pure H2 and 0.5 mol of pure O2 at the pressure of p with
volumes of 2V/3 and V/3, respectively, is thermodynamically 2.4 kJ
mol–1 at room temperature if H2 and O2 behave as ideal gases. This
is the minimum energy loss associated with the separation of hydro-
gen and oxygen, and corresponds to 1.1% with respect to the Gibbs
energy change for the overall water splitting reaction. Therefore,
this energy expenditure can be reduced to an acceptable level if effi-
cient gas separation processes are available. Several types of mem-
branes materials have been studied for the separation of gaseous
hydrogen and oxygen for this purpose23. It was estimated that mem-
branes with a H2-permeance of 10–7 mol m–2 s–1 Pa–1 were needed to
separate hydrogen and oxygen generated at an STH of 10% when a
pressure difference of 0.1 MPa was provided. Zeolite membranes
satisfy the required permeance while the silica membranes exhibit
a sufficient H2 or O2 selectivity under dry conditions. Therefore, it
is probably possible to separate dry H2 and O2 at satisfactory per-
meance and selectivity by improving and combining these mem-
branes. In reality, water vapour at saturation pressure is included in
the gaseous product of water splitting and lowers the performance
of the separation membranes. It is necessary to improve the stability
of membranes against water vapour and to develop and integrate
systems for product gas compression and water removal into panel
reactors. It may also be feasible to generate a mixture of gaseous and
liquid products rather than a purely gaseous mixture of hydrogen
and oxygen, leading to spontaneous separation of the products110. It
has been shown that water can be split into hydrogen and hydrogen
peroxide by reduction and oxidation, respectively, using a photo-
electrochemical system, and this may represent an alternative target
also for photocatalytic systems. The faradaic efficiency of hydrogen
peroxide formation was shown to be improved by surface modifica-
tions masking materials that caused the decomposition of hydrogen
peroxide preferentially111,112. However, the efficiency, selectivity and
process design are still at the preliminary stage in terms of produc-
ing highly concentrated hydrogen peroxide for the purpose of solar
energy conversion.
Overall, both the understanding and demonstration of photocat-
alytic water splitting systems, as well as associated analytical tech-
nologies have advanced significantly, and such advances continue
to accelerate. Despite this, there are still numerous obstacles to real-
izing practical solar hydrogen production via photocatalytic water
splitting. Hopefully, this review will allow researchers in multidisci-
plinary fields to better appreciate the potential impact of photocata-
lytic water splitting, and will facilitate the integration of innovative
concepts and advanced techniques to overcome present-day chal-
lenges to the wide-scale implementation of such processes.
Received: 17 July 2018; Accepted: 28 January 2019;
Published online: 11 March 2019
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Acknowledgements
This work was financially supported by the Artificial Photosynthesis Project of the New
Energy and Industrial Technology Development Organization (NEDO), by a Grant-
in-Aid for Scientific Research (A) (no. 16H02417), a Grant-in-Aid for Young Scientists
(A) (no. 15H05494), and a Grand-in-Aid for Scientific Research on Innovative Areas
(no. 18H05156) from the Japan Society for the Promotion of Science (JSPS).
Competing interests
The authors declare no competing interests.
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