Review

Cite This: Chem. Rev. XXXX, XXX, XXX−XXX pubs.acs.org/CR

Particulate Photocatalysts for Light-Driven Water Splitting:

Mechanisms, Challenges, and Design Strategies
Qian Wang†,§ and Kazunari Domen*,†,‡
†
Department of Chemical System Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo
113-8656, Japan
‡
Center for Energy & Environmental Science, Shinshu University, 4-17-1 Wakasato, Nagano-shi, Nagano 380-8553, Japan

ABSTRACT: Solar-driven water splitting provides a leading approach to store the

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abundant yet intermittent solar energy and produce hydrogen as a clean and sustainable
energy carrier. A straightforward route to light-driven water splitting is to apply self-
supported particulate photocatalysts, which is expected to allow solar hydrogen to be
competitive with fossil-fuel-derived hydrogen on a levelized cost basis. More
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importantly, the powder-based systems can lend themselves to making functional

panels on a large scale while retaining the intrinsic activity of the photocatalyst.
However, all attempts to generate hydrogen via powder-based solar water-splitting
systems to date have unfortunately fallen short of the efficiency values required for
practical applications. Photocatalysis on photocatalyst particles involves three sequential
steps: (i) absorption of photons with higher energies than the bandgap of the
photocatalysts, leading to the excitation of electron−hole pairs in the particles, (ii)
charge separation and migration of these photoexcited carriers, and (iii) surface
chemical reactions based on these carriers. In this review, we focus on the challenges of
each step and summarize material design strategies to overcome the obstacles and limitations. This review illustrates that it is
possible to employ the fundamental principles underlying photosynthesis and the tools of chemical and materials science to
design and prepare photocatalysts for overall water splitting.

CONTENTS 3.2.1. Short Charge Carrier Migration Distan-

ces AF
1. Introduction B 3.2.2. Reduction of Defects AG
1.1. Solar Fuels from Water Splitting Using 3.2.3. Junctions AH
Particulate Semiconductors B 3.2.4. Facet Control AM
1.2. Thermodynamics and Kinetics of Photo- 4. Surface Chemical Reactions AO
catalytic Water Splitting B 4.1. Challenges AP
2. Photon Absorption C 4.1.1. Side and Back Reactions AP
2.1. Challenges C 4.2. Strategies AQ
2.1.1. The Solar Spectrum and Maximum 4.2.1. Cocatalysts AQ
Solar Light Conversion Efficiency C 4.2.2. Surface Modification AT
2.1.2. Semiconductor Materials D 5. Conclusion and Perspectives AT
2.2. Strategies F Author Information AW
2.2.1. Valence Band Potential Engineering Corresponding Author AW
and Other Photocatalyst Materials F ORCID AW
2.2.2. Doping S Present Address AW
2.2.3. Solid Solutions U Notes AW
2.2.4. Dye Sensitization W Biographies AW
2.2.5. Localized Surface Plasmon Resonance Acknowledgments AW
Effect Z Abbreviations Used AW
2.2.6. Quantum Confinement Effect AA References AX
2.2.7. Z-Scheme Configurations AC
3. Charge Separation and Transport AD
3.1. Challenges AF
3.1.1. Recombination AF
3.1.2. Trapping AF Special Issue: Nanoparticles in Catalysis
3.2. Strategies AF
Received: March 31, 2019

© XXXX American Chemical Society A DOI: 10.1021/acs.chemrev.9b00201

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1. INTRODUCTION
Solar energy is the most attractive renewable replacement for
fossil fuels because it is plentiful, inexhaustible, and widely
distributed. However, due to the diffuse and intermittent
nature of solar irradiation, energy harvested from the sun must
be efficiently converted into chemical fuels that are storable,
transportable, and usable upon demand.1,2 This requirement
has motivated the development of sustainable artificial
photosynthetic processes, with the aim of mimicking natural
photosynthesis to generate fuels from water and carbon
dioxide utilizing solar energy (Figure 1).3,4 Solar-to-chemical
energy conversion offers a highly useful means of storing solar
energy efficiently as sustainable energy carriers with minimal
environmental impact. Among the potential solar fuels
produced by artificial photosynthesis, hydrogen is one of the
most attractive as it offers high energy density and does not
generate pollutants during combustion.5,6 Combining solar
energy with water (a highly abundant resource) by way of solar
water splitting provides a platform for hydrogen production; a
schematic of a potential sustainable plant for hydrogen
generation and utilization is presented in Figure 2. In this
system, water is injected into a solar water splitting module and
converted into hydrogen, which is subsequently used in high-
efficiency power production systems, including internal
combustion engines and fuel cells. Thus, water and sunlight
are utilized to provide power. In addition, hydrogen can be
combined with carbon dioxide captured from the atmosphere
or from the emissions of coal or natural gas burning plants to
generate methanol and synthetic natural gas or precursors for
plastics and fertilizers.7 Sustainable processes such as these
would offer numerous advantages in terms of climate change
mitigation and compatibility with currently existing infra-
structure. One of the most significant challenges associated
with realizing such processes is the efficient, cost-effective
decomposition of water on the scale required to meet global
energy demands (that is, tens of terawatts).8
1.1. Solar Fuels from Water Splitting Using Particulate
Semiconductors
Light-driven water splitting can be achieved in relatively simple
systems by employing particulate semiconductor materials as
photocatalysts, such that both sunlight absorption and catalysis
take place on single particles. The estimated average cost of the
hydrogen produced by such powder-based photocatalytic
devices is in the range of 1.6−3.5 USD kg−1, assuming solar-
to-hydrogen conversion efficiency (STH) values of 5−10% and
a system lifetime of 5 years.9−11 The STH is defined by3,12
output energy as H 2
energy of incident solar light
(mmol H 2 s−1) × (237000 J mol−1)
=
(100 mW cm−2) × area (cm 2)
at standard conditions (1.1)
This range meets the United States Department of Energy’s
goal of achieving a cost of 2.00−4.00 USD kg−1 H2 by 2020 so
as to obtain an economically viable alternative to fossil fuels.9
Importantly, such powder-based systems can be processed into
large scale panel facilities while retaining the intrinsic activity
of the photocatalyst. As an example, our own group has
demonstrated the construction of 1 m2 photocatalytic water
splitting panels based on a fixed Al-doped SrTiO3 photo-
catalyst (Figure 3).13 Such panel reactors maintain the inherent
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photocatalytic activity of the powder regardless of size and thus
are extensible to the level of square meters and even larger.
Despite this potential for scale-up, all attempts to generate
hydrogen via powder-based solar water-splitting systems to
date have unfortunately fallen short of the efficiency values
required for practical applications. Assuming daily AM 1.5G
irradiation for 7.6 h (corresponding to 240 W m−2), to reach a
hydrogen price of 3.5 USD kg−1, the recent evaluation suggests
a photocatalytic reaction system with an STH of 10%, a
lifetime of 10 years, an annual depreciation rate of 4%, and an
allowable cost of 102 USD m−2.11 Thus, further fundamental
investigations regarding the design and development of
efficient photocatalysts are vital.
1.2. Thermodynamics and Kinetics of Photocatalytic Water
Splitting
Figure 4a presents a diagram of a typical semiconductor
particle, loaded with a hydrogen evolution cocatalyst (HEC)
and oxygen evolution cocatalyst (OEC) on its surface. Such
particles would be applied as a photocatalyst for overall water
splitting. The photocatalytic decomposition of water on
semiconductor photocatalysts to produce hydrogen and
oxygen comprises three sequential processes: (i) the
absorption of photons having energy values greater than the
semiconductor bandgap to excite electrons from the valence
band (VB) to the conduction band (CB), creating electron
(e−)/hole (h+) pairs, (ii) the separation of the photoexcited
carriers into free carriers and subsequent migration to
accumulate at the active sites on the particle surfaces, and
(iii) the initiation of redox reactions involving these charges to
generate hydrogen and oxygen with the assistance of the
cocatalysts. These reactions are summarized below.
Hydrogen evolution reaction (HER):
in an acidic aqueous solution: 2H+ + 2e− → H 2 (1.2)
in an alkaline aqueous solution: 2H 2O + 2e− → H 2 + 2OH−
(1.3)
Oxygen evolution reaction (OER):
in an acidic aqueous solution: 2H 2O → O2 + 4e− + 4H+
(1.4)
− −
in an alkaline aqueous solution: 4OH → O2 + 4e + 2H 2O
(1.5)
The overall solar energy conversion efficiency, ηtotal, takes into
account the efficiencies associated with these three funda-
mental processes and thus is determined as14,15
ηtotal = ηabsoprtion × ηseparation × ηreaction (1.6)
Here, the photon absorption efficiency, ηabsorption, is defined as
the fraction of electron−hole pairs excited by the incident
photon flux, the separation efficiency, ηseparation, is the fraction
of photogenerated charge carriers that separate and migrate to
the solid−liquid interface, and the reaction efficiency, ηreaction, is
the efficiency of the surface reaction involving the charge
carriers at the solid−liquid interface.
At pH 0, as illustrated in Figure 4b, the protons are reduced
by the electrons in the CB to generate hydrogen.
Simultaneously, oxygen is produced via the oxidation of
water molecules by photoexcited holes in the VB. Therefore, to
achieve the overall water splitting reaction, the CB minimum
(CBM) must be more negative than the H+ to H2 reduction
potential (0 V relative to normal hydrogen electrode (NHE) at
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pH 0), while the VB maximum (VBM) must be more positive
than the H2O to O2 oxidation potential (+1.23 V relative to
NHE at pH 0). Consequently, the minimum theoretical
bandgap required to drive the overall water splitting reaction is
1.23 eV, which corresponds to a wavelength of approximately
1000 nm. It is likely that some additional kinetic overpotentials
are necessary to initiate and drive the electron transfer process
as well as the HER and OER at reasonable rates, which
precludes semiconductors with bandgaps smaller than 1.6
eV.4,16 In addition to the band alignment of a photocatalyst
relative to the hydrogen and oxygen evolution potentials,
photocatalysts must exhibit excellent physicochemical stability
in the presence of oxidative and/or reductive photocorrosion
processes. For a photocatalyst to be thermodynamically stable,
its reductive decomposition potentials and CBM must be more
negative than the H+/H2 potential, while its oxidative
decomposition potentials and VBM must be more positive
than the O2/H2O potential.17 These constraints place severe
restrictions on the choice of suitable materials for photo-
catalytic water splitting. Essentially, these compounds are
required to harvest solar radiation efficiently, to exhibit long-
term stability, and to support rapid charge migration and
surface reactions.
The goal of this review is to provide an overview of the
fundamentals of photocatalytic overall water splitting, focusing
on the design of photocatalysts. Over the past decade,
significant progress has been achieved in elucidating the solar
water splitting mechanism and developing novel materials to
promote this process, and recent research concerning efficient
photocatalytic water splitting designs is summarized herein.
Several distinct strategies have been explored to meet
improved performance requirements, including extending the
spectral range of visible light absorption, enhancing photo-
generated charge separation and transport, and facilitating the
hydrogen and oxygen production reactions. This review
presents recent advances in photocatalytic water splitting to
illustrate several general approaches that are expected to
mitigate the various obstacles involved in achieving practical
solar hydrogen production.
2. PHOTON ABSORPTION
The semiconductor photocatalysis process to convert solar
energy into chemical fuels begins with photon absorption. The
irradiation of semiconductor particles results in optical
excitation in the case that the incident light has an energy
equal to or greater than the bandgap of the material, in which
case, electrons in the VB are excited to the CB on the
femtosecond time scale.18 Charge carriers can also be
generated in organic semiconductors, including dyes19,20 and
polymers,21 moving from the highest occupied molecular
orbital (HOMO) to the lowest unoccupied molecular orbital
(LUMO). The rapid relaxation of electrons and holes to the
bottom of the CB and the top of the VB, respectively, follows
excitation, on a similar time scale.18 Two types of bandgaps
arise in semiconductors: direct and indirect. In the case of a
direct bandgap, the momentum (wave vector) of an electron in
the VBM is equal to that of an electron in the CBM, as shown
in Figure 5. Thus, irradiation by a super bandgap photon (i.e.,
hν > Eg, where Eg is the bandgap energy), an electron is readily
promoted from the VB to the CB, with minimal variation in its
momentum. In contrast, in an indirect bandgap semi-
conductor, the states at the minimum of the CB and the
maximum of the VB do not have equal momenta. Thus, to
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conserve momentum, an electron must undergo a significant
change in its momentum to be excited across the bandgap and
produce an electron−hole pair in this material.22,23 This occurs
because the electron interacts not only with the initial photon
to obtain energy but also with a quantized lattice vibration
known as a phonon, which either increases or decreases its
momentum. Because the electron, photon, and phonon are all
involved in this indirect absorption process, it proceeds at a
lower probability and at a much slower rate than direct
absorption.
The absorption of light by a semiconductor particle can be
quantified based on the absorption coefficient of the material,
α(λ). For a given photon energy, E2 − E1 = hν (as in Figure 5),
this coefficient is summed over all possible band transitions
from the VB to the CB, as in the equation24
α(hν) ∝ ∑ P12 g V (E1)gC(E2) (2.1)
Here, P12 is the probability of the transition of an electron from
the initial state E1 to the final state E2, while gV(E1) and gC(E2)
are the electron densities in the initial and final states,
respectively.
The value of α(λ) varies with the intrinsic absorption
properties of the photocatalyst, such as its bandgap and band
positions, and whether light absorption proceeds directly or
indirectly. Because a phonon is involved in indirect bandgap
absorption, the absorption coefficient for indirect transitions is
relatively small compared to that for direct transitions. As a
result, light penetrates more deeply into indirect bandgap
semiconductors than direct bandgap semiconductors.24 The
absorption depth, α(λ)−1, determined by taking the inverse of
α(λ), refers to the distance below which the light intensity is
reduced to 1/e of the incident irradiation. This value
determines the optimal thickness of a photocatalyst film or
suspension or how many particles are required to obtain a
suitable degree of photocatalytic efficiency.14,18 It is therefore
important to note that the maximum photon absorption of a
given photoreactor should be determined using the optimal
conditions such that the value is not affected by the amount of
photocatalyst used, because otherwise photocatalytic perform-
ances reported by different laboratories cannot be compared.
Research has demonstrated that the diameter of a particle must
be at least 2.3 times α(λ)−1 to ensure 95% absorption of the
incident light.25,26 Means of determining α(λ) have been
described in detail by Gray et al.24 and Chen et al.14
2.1. Challenges
2.1.1. The Solar Spectrum and Maximum Solar Light
Conversion Efficiency. The sun emits radiation ranging from
X-rays to radio waves, but the most intense solar radiation
occurs in the visible light range (Figure 6), such that 43% of
the solar energy reaching the Earth’s surface is at visible
wavelengths from 400 to 700 nm. Assuming that only
ultraviolet (UV) light up to 400 nm is utilized, with a
quantum efficiency (QE) of 100%, the STH would be limited
to 2% (neglecting entropic losses),27,28 as illustrated in Figure
7. Extending absorption into the visible light region up to 700
and 1000 nm would drastically raise the ideal STH to 25% and
47%, respectively. As such, a QE of approximately 100% is
required for a photocatalyst with an absorption edge of 520 nm
to attain the target STH of 10%. In contrast, a semiconductor
capable of harvesting light up to 650 nm can have a QE of less
than 60% while still achieving the target STH. Therefore, in
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Figure 1. Schematic illustration of natural and artificial photosynthetic systems.

Figure 2. Potential sustainable hydrogen fuel cycle based on photocatalytic water splitting.

order to obtain a high STH, it is crucial to focus on
photocatalysts that harvest visible light.
2.1.2. Semiconductor Materials. The pioneering work
concerning the decomposition of water into hydrogen and
oxygen using heterogeneous photocatalysts was reported by
Fujishima and Honda in 1972. Their approach employed a
photoelectrochemical (PEC) cell consisting of TiO2 as the
photoanode and platinum as the counter electrode under UV
irradiation, with an external bias.29 This report revealed the
feasibility of generating hydrogen from water, a clean and
D DOI: 10.1021/acs.chemrev.9b00201
plentiful natural resource, and stimulated research into overall
water splitting using particulate photocatalysts. In 1977,
Schrauzer et al. determined that external energy inputs other
than light are not required to split water and demonstrated the
production of H2 over TiO2 powder under UV light.30 Since
then, many new semiconductor types have been investigated
and efforts have been devoted to identifying new photo-
catalysts. Table 1 summarizes the photocatalysts reported to
date for single-step overall water splitting without using
sacrificial reagents, of which approximately 80% have wide
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Figure 3. (a) Schematics and (b) a photograph of a 1 m × 1 m water splitting panel based on SrTiO3:Al powder. Reprinted with permission from
ref 13. Copyright 2018 Elsevier.
Figure 4. (a) Diagram showing the reactions during water splitting on
a semiconductor photocatalyst: (i) light absorption, (ii) charge
separation and transport, and (iii) redox reactions. (b) Energy
diagram for photocatalytic water splitting based on one-step
excitation.
bandgaps and thus are only active under UV light. Note that
the efficiencies of these materials, as reflected in QE, apparent
quantum yield (AQY) values at specific wavelengths (as
defined in Table 1) and STH values, could be directly
compared in principle, whereas the gas evolution rates cannot.
This is because the experimental conditions used to determine
gas evolution, including light sources and the scale of the
E DOI: 10.1021/acs.chemrev.9b00201
Review
reaction, differ among these various studies. The gas evolution
rates presented herein can be used to find the H2/O2 molar
ratios, which are an important means of determining if the
process is an overall water-splitting or sacrificial reaction.
Several review articles discuss how to report reliable and
comparable photocatalytic activity to ensure reproducibility
and effective benchmarking and are highly recommended for
further reading.12,31−33
Most metal oxide photocatalysts capable of splitting water
into H2 and O2 in Table 1 consist of metal cations with either
d0 (Ti4+, Zr4+, Nb5+, Ta5+, V5+, W6+ and Ce4+) or d10 (Zn2+,
In3+ , Ga 3+ , Ge4+, Sn4+ and Sb5+) configurations. The
conduction bands for d0 and d10 metal oxide photocatalysts
typically consist of the d and sp orbitals of the metal cations,
respectively, while the valence bands are composed of O 2p
orbitals, as shown in Figure 8. Alkali metal, alkaline earth
metal, and some lanthanide ions usually do not directly
contribute to band formation and simply construct the crystal
structure (for example, as A site cations in perovskite
compounds). Although there is a wide variety of metal oxides
with different crystal structures and electronic structures, the
key factors affecting water splitting activity are believed to be
the symmetry of the metal oxygen octahedral/tetrahedral
coordination and the VB and CB structures.34 A number of
review articles and book chapters on this subject have been
published.3,35−37
Because of the highly positive VB (located at approximately
+3 V relative to NHE at pH 0) formed by O 2p orbitals, it is
difficult to find an oxide semiconductor photocatalyst that has
both a CB sufficiently negative for H2 production and a
bandgap sufficiently to absorb visible light (λ > 400 nm). The
development of photocatalysts capable of water cleavage and
having a narrow bandgap and wide light absorption range is
therefore an important aspect of achieving efficient solar
hydrogen generation. However, to date, very few reproducible
photocatalytic systems have been found to exhibit simulta-
neous and stoichiometric hydrogen and oxygen generation
from pure water under visible light irradiation. In section 2.2,
we review the strategies that have been employed to improve
the photonic efficiencies of photocatalytic systems. These
strategies, which are illustrated in Figure 9, include VB control,
doping, solid solution formation, quantum dots (QDs),
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Figure 5. Photon absorption in (a) a direct bandgap semiconductor for an incident photon with energy hν = E2 − E1 > Eg, and (b) an indirect
bandgap semiconductor for a photon with energy hν < E2 − E1 and a photon with energy hν > E2 − E1.
Figure 6. AM 1.5 G solar spectrum based on the ASTM G173-03
reference spectrum.
Figure 7. Calculated STH values as functions of photon wavelength
for photocatalytic one-step overall water splitting using photocatalysts
with various QEs. The associated calculations assumed AM 1.5G solar
irradiance. Reprinted with permission from ref 28. Copyright 2010
American Chemical Society.
plasmon resonance, dye-sensitization, and Z-scheme con-
struction.
2.2. Strategies
2.2.1. Valence Band Potential Engineering and Other
Photocatalyst Materials. As discussed in section 2.1,
obtaining both H2 and O2 production over a metal oxide
having a VB consisting of O 2p orbitals requires that the
bandgap energy of the oxide exceeds 3 eV, such that it
straddles the potentials associated with proton reduction and
water oxidation. Tuning the VB potential using the p orbitals
of anions or the s orbitals of p-block metal ions has been found
to narrow the bandgap successfully.
F DOI: 10.1021/acs.chemrev.9b00201
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The past several decades have seen a surge in the evolution
of novel materials for visible-light-driven photocatalytic
reactions, including oxides, (oxy)nitrides, (oxy)sulfides, oxy-
halides, and chalcopyrites. Some metal elements, such as Ag,
Cu, Bi, Pb and Sn, have been found to contribute to the
formation of not only conduction band104,105,185−187 but also
valence band. As an example, the electron configurations of
Ag+,188 Cu+,189,190 Sn2+,191,192 Pb2+,193−195 and Bi3+ (refs
194,196) can construct new VBs appearing at more negative
potentials than O 2p orbitals and thus reduce the bandgap.
The insertion of transition metals with filled d orbitals or s
orbitals can give rise to a narrower bandgap.197 This effect is
typified by monoclinic BiVO4 (m-BiVO4), which has a
bandgap of 2.4−2.5 eV and has been reported to promote
water oxidation to give significant gas evolution rates in the
presence of Ag+ as a sacrificial electron acceptor (SEA).198,199
In this compound, the distortion of VO4 tetrahedra and BiO8
dodecahedra results in the hybridization of Bi 6s/O 2p lone
pair states at the top of the VB. Electronic structure predictions
based on density functional theory (DFT) indicate that the VB
consists primarily of O 2p orbitals, while the VBM comprises
nonbonding O 2pπ orbitals with a contribution from Bi 6s
orbitals.196 Similarly, the VB of SnNb2O6 is composed of Sn 5s
and O 2p hybrid orbitals, such that the VBM is more negative
than it would be if made solely of O 2p orbitals.191
Consequently, SnNb2O6 has a narrow bandgap of 2.3 eV and
exhibits photocatalytic activity during H2 and O2 evolution
from aqueous solutions containing sacrificial reagents (meth-
anol and Ag+) under visible light irradiation.192 Another
approach to VB tuning via the introduction of metal cations is
the substitution of alkali ions with Ag+ and Cu+ ions at the
interlayers in layered materials, such as RbLaTa2O7,200
K2La2Ti3O10,201 Li2TiO3, and Li2SnO3,202 or at and/or near
the surface of bulky materials like NaTaO3, as shown in Figure
10.201 The energy gaps of these metal oxide photocatalysts are
narrowed by 1.1−1.5 eV after introducing Ag+ or Cu+ ions
because the filled Cu 3d or Ag 4d orbitals form VBs at higher
energy levels than those resulting from O 2p orbitals. This
technique has also been applied to decrease the bandgaps of
metal sulfides, such that the bandgap of ZnGa2S4 (3.4 eV) was
reduced to 2.7 eV by cosubstituting Cu+ and Ga3+ at Zn2+
sites.203 In this case, the VBM was raised significantly following
substitution with Cu+, while the CBM was slightly lowered by
introducing Ga3+. Moreover, due to charge compensation, the
cosubstitution of Cu+ together with the high valence Ga3+ ions
suppressed the appearance of sulfur defects in the crystal
lattice.
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 Table 1. Photocatalysts for Light-Driven Single-Step Photocatalytic Water Splitting without Using Sacrificial Reagents
gas evolution rate
bandgap/eV reaction
photocatalyst (absorption range/nm) surface loading reactant H2 O2 light source duration efficiency ref
Ultraviolet Light-Responsive Photocatalysts
TiO2 3.2 (<385) Pt, RuO2 water with pH 2.8 mL/h 450-W Xe lamp 25 h QEa: 30 ± 10% at 310 nm 38
Chemical Reviews

adjustment (pH
1.5)
TiO2 (anatase) 3.2 (<385) NaOH, Rh water vapor 449 μmol/h 500-W Hg lamp (250 1.5 h 39
< λ < 400 nm)
TiO2 (anatase) 3.2 (<385) Pt Na2CO3 aq soln 568 μmol/h 287 μmol/h 400-W Hg lamp ∼200 h 40
(pH 11)
TiO2 (P25) Pt water 106 μmol/h ∼53 μmol/h 250-W Hg lamp 20 h QE: 1.4% 41
ZrO2 5.0 (<250) water 72 μmol/h 36 μmol/h 400-W Hg lamp 42
Ta2O5 4.0 (<310) NiOx water 3360 μmol/h 1630 μmol/h 450-W Hg lamp (λ > 5h 43
200 nm)
Ga2O3 4.5 (<275) NiO water 338 μmol/h 171 μmol/h 450-W Hg lamp 60 h 44, 45
α-Ga2O3/β-Ga2O3 NiOx water ∼130 ∼65 450-W Hg lamp 46
μmol/h/m2 μmol/h/m2
Ga2O3:In RuO2 water ∼900 ∼450 200-W Hg−Xe lamp 10 h 47
μmol/h μmol/h
Ga2O3:Zn 4.5 (<275) Ni water 2403 μmol/h 1400 μmol/h 450-W Hg lamp 6h 45
Ga2O3:Ca Ni water 950 μmol/h 550 μmol/h 450-W Hg lamp 45
Ga2O3:Sr Ni water 640 μmol/h 282 μmol/h 450-W Hg lamp 45

G
Ga2O3:Ba Ni water 765 μmol/h 348 μmol/h 450-W Hg lamp 45
Ga2O3:Cr Ni water 707 μmol/h 385 μmol/h 450-W Hg lamp 45
Ga2O3:Ta Ni water 534 μmol/h 256 μmol/h 450-W Hg lamp 45
CeO2:Sr 3.1 (<400) RuO2 water ∼110 ∼55 μmol/h 450-W Hg lamp 17 h 48
μmol/h
CeO2:Sm RuO2 water ∼500 ∼250 450-W Hg lamp 9h 49
μmol/h μmol/h
B/Ti oxide Pt water ∼22 μmol/h ∼11 μmol/h 400-W Hg lamp 3h 50
Mg/Ta oxide NiO water 102 μmol/h 51 μmol/h 450-W Hg lamp 30 h 51
SrTiO3 3.2 (<385) NiO water vapor 4.4 × 10−3 2.2 × 10−3 450-W Hg lamp ∼80 h 52
mL/h mL/h
SrTiO3:Al 3.2 (<385) RhCrOx, MoOy water ∼80 μmol/h ∼40 μmol/h solar simulator 1300 h AQYb: 56% at 365 ± 10 nm STH: 0.6% 13, 53−55
(AM 1.5G)
SrTiO3:Na 3.2 (<385) Rh0.3Cr1.7O3 water 1600 μmol/h 800 μmol/h 450-W Hg lamp 3−5 h AQY: 16% at 360 nm 56, 57
SrTiO3:Li Rh0.3Cr1.7O3 water ∼1650 ∼850 450-W Hg lamp 57
μmol/h μmol/h
SrTiO3:K Rh0.3Cr1.7O3 water ∼1420 ∼710 450-W Hg lamp 57
μmol/h μmol/h
SrTiO3:Rb Rh0.3Cr1.7O3 water ∼800 ∼410 450-W Hg lamp 57
μmol/h μmol/h
SrTiO3:Cs Rh0.3Cr1.7O3 water ∼790 ∼400 450-W Hg lamp 57
μmol/h μmol/h
SrTiO3:Mg Rh0.3Cr1.7O3 water ∼1500 ∼750 450-W Hg lamp 57
μmol/h μmol/h
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 Table 1. continued
gas evolution rate
bandgap/eV reaction
photocatalyst (absorption range/nm) surface loading reactant H2 O2 light source duration efficiency ref
Ultraviolet Light-Responsive Photocatalysts
SrTiO3:In Rh0.3Cr1.7O3 water ∼600 ∼300 450-W Hg lamp 57
Chemical Reviews

μmol/h μmol/h
SrTiO3:La 3.2 (<385) CoO Na2CO3 aq soln ∼280 ∼130 400-W Hg lamp 58
μmol/h μmol/h
SrTiO3:Ga 3.2 (<385) Rh2O3, Cr2O3 water ∼4400 ∼2100 450-W Hg lamp 5h 56
μmol/h μmol/h
Sr3Ti2O7 3.2 (<385) NiO water 144 μmol/h ∼75 μmol/h 400-W Hg lamp 10 h QE: 4.3 at 360 nm 59
Sr4Ti3O10 3.2 (<385) NiOx water ∼170 400-W Hg lamp QE: 4.5 at 360 nm 60
μmol/h
La2Ti2O7 3.2 (<385) NiOx water 474 450-W Hg lamp QE: 12% (<360 nm) 61, 62
μmol/h/g
La2Ti2O7:Ba 3.2 (<385) NiOx water 2010 μmol/h 450-W Hg lamp QE: 35% (<360 nm) 62
La2Ti2O7:Sr 3.2 (<385) NiOx water 1510 μmol/h 450-W Hg lamp 62
La2Ti2O7:Ca 3.2 (<385) NiOx water 850 μmol/h 450-W Hg lamp 62
La2TiO5 Ni water 442 450-W Hg lamp 62
μmol/h/g
La2Ti3O9 Ni water 386 450-W Hg lamp 62
μmol/h/g
LaTiO3 Ni water 137 450-W Hg lamp 62

H
μmol/h/g
La4Ti3O12 4.0 (<310) NiO water 357 μmol/h 179 μmol/h 400-W Hg lamp 63
Na2Ti6O13 3.1 (<400) RuOx water 7.3 μmol/h 3.5 μmol/h 400-W Xe lamp 20 h QE: 1.5% at 330−410 nm 64, 65
CaTiO3 3.5 (<355) Pt NaOH aq soln ∼30 μmol/h ∼17 μmol/h 500-W Hg lamp 10 h 66
Y2Ti2O7 3.5 (<355) NiOx water 850 μmol/h 420 μmol/h 400-W Hg lamp 67
Gd2Ti2O7 3.5 (<355) NiOx water ∼410 ∼210 400-W Hg lamp 67, 68
μmol/h μmol/h
Nd2Ti2O7 3.7 (<335) NiOx water 99 μmol/h/g 450-W Hg lamp 69
Dy2Ti2O7 NiOx water ∼150 ∼75 μmol/h 400-W Hg lamp 68
μmol/h
Ho2Ti2O7 NiOx water ∼520 ∼240 400-W Hg lamp 68
μmol/h μmol/h
Er2Ti2O7 NiOx water ∼390 ∼180 400-W Hg lamp 68
μmol/h μmol/h
Yb2Ti2O7 NiOx water ∼190 ∼90 μmol/h 400-W Hg lamp 68
μmol/h
Tm2Ti2O7 NiOx water ∼220 ∼100 400-W Hg lamp 68
μmol/h μmol/h
Eu2Ti2O7 NiOx water ∼10 μmol/h ∼5 μmol/h 400-W Hg lamp 68
Lu2Ti2O7 NiOx water ∼60 μmol/h ∼25 μmol/h 400-W Hg lamp 68
K2Ti6O13 RuO2 water ∼6 μmol/h ∼2.5 μmol/h 400-W Xe lamp 70
Rb2Ti6O13 RuO2 water ∼4 μmol/h ∼2 μmol/h 400-W Xe lamp 18 h 70
LiNbO3 RuO2 water 47 μmol/h 23 μmol/h 400-W Hg lamp 5h AQY: 0.7% at 254 nm 71
NaNbO3 3.5 (<355) NiO water ∼36 μmol/h ∼12 μmol/h 400-W Hg lamp 12 h 72
Review

Chem. Rev. XXXX, XXX, XXX−XXX

DOI: 10.1021/acs.chemrev.9b00201
K4Nb6Ol7 3.3 (<375) NiO water 77 μmol/h 37 μmol/h 450-W Hg lamp 50 h QE: 3.5 ± 0.5% at 330 nm 73, 74
 Table 1. continued
gas evolution rate
bandgap/eV reaction
photocatalyst (absorption range/nm) surface loading reactant H2 O2 light source duration efficiency ref
Ultraviolet Light-Responsive Photocatalysts
Ca2Nb2O7 4.3 (<290) Rh2−xCrxO3 water 1006 μmol/h 503 μmol/h 400-W Hg lamp 4h 61, 75
Chemical Reviews

Ca2Nb3O10 Na+, RuOx water 118 μmol/h 56 μmol/h 450-W Hg lamp 76

SrNb2O6 3.9 (<320) RuO2 water 435 205 400-W Hg lamp 10 h 77
μmol/h/g μmol/h/g
Sr2Nb2O7 4.1 (<300) Ni water ∼400 ∼180 450-W Hg lamp 5h QE: 23% (<300 nm) 61, 78
μmol/h μmol/h
Sr5Nb4O15 4.0 (<310) NiO water 2200 μmol/h 1100 μmol/h 400-W Hg lamp 63
La3NbO7 3.9 (<320) NiOx water 35 μmol/h 17 μmol/h 400-W Hg lamp 7h 67
ZnNb2O6 4.0 (<310) NiO water 54 μmol/h 21 μmol/h 450-W Hg lamp 5h 79
Cs2Nb4O11 3.7 (<335) NiO CsOH aq soln 212 μmol/h 98.3 μmol/h 400-W Hg lamp 8h 80
Rb4Nb6O17 3.5 (<355) Ni water 936 μmol/h 451 μmol/h 400-W Hg lamp 6h 81
Ba5Nb4O15 3.9 (<320) NiO water 4021 μmol/h 1972 μmol/h 400-W Hg lamp 4.5 h AQY: 15% at 270 nm 63, 82
NaTaO3 4.0 (<310) NiO water 2180 μmol/h 1100 μmol/h 400-W Hg lamp 6h AQY: 20% at 270 nm 83, 84
NaTaO3:La 4.1 (<300) NiO water 19800 9660 μmol/h 400-W Hg lamp 400 h AQY: 56% at 270 nm 85
μmol/h
NaTaO3:Pr 4.1 (<300) NiO water 5300 μmol/h 2660 μmol/h 400-W Hg lamp 86
NaTaO3:Nd 4.1 (<300) NiO water 5200 μmol/h 2550 μmol/h 400-W Hg lamp 86

I
NaTaO3:Sm 4.1 (<300) NiO water 5300 μmol/h 2600 μmol/h 400-W Hg lamp 86
NaTaO3:Gd 4.1 (<300) NiO water 4300 μmol/h 2100 μmol/h 400-W Hg lamp 86
NaTaO3:Tb 4.1 (<300) NiO water 4300 μmol/h 2200 μmol/h 400-W Hg lamp 86
NaTaO3:Dy 4.1 (<300) NiO water 4500 μmol/h 2200 μmol/h 400-W Hg lamp 86
NaTaO3:Ca 4.1 (<300) NiO water 4930 μmol/h 2600 μmol/h 400-W Hg lamp 87
NaTaO3:Sr 4.1 (<300) NiO water 13600 6690 μmol/h 400-W Hg lamp 5h 87
μmol/h
NaTaO3:Ba 4.1 (<300) NiO water 9780 μmol/h 4780 μmol/h 400-W Hg lamp 87
NaTaO3:K water ∼1050 ∼500 400-W Hg lamp 6h AQY: 2.8% (<310 nm) 88
μmol/h μmol/h
Na2Ta2O6 4.6 (<270) NiO NaOH aq soln 391 μmol/h 195 μmol/h 450-W Hg lamp 89
LiTaO3 4.7 (<260) water 430 μmol/h 220 μmol/h 400-W Hg lamp 84
KTaO3 3.6 (<345) water 29 μmol/h 13 μmol/h 400-W Hg lamp 84
KTaO3:Zr 3.8 (<325) NiO water 93.5 μmol/h 42.1 μmol/h 500-W Xe lamp 6h 90
KTaO3:Ga NiO water 67.7 μmol/h 23.3 μmol/h 500-W Xe lamp 90
KTaO3:Hf NiO water 98.5 μmol/h 39.8 μmol/h 500-W Xe lamp 90
K2Ta2O6 4.5 (<275) NiO NaOH aq soln 437 μmol/h 226 μmol/h 450-W Hg lamp 89
La3TaO7 4.6 (<270) NiOx water 164 μmol/h 80 μmol/h 400-W Hg lamp 7h 67
LaTaO4 3.9 (<320) NiOx water 115.6 51.5 μmol/h 400-W Hg lamp 91
μmol/h
AgTaO3 3.4 (<365) NiO water 20.7 μmol/h 9.5 μmol/h 300-W Xe lamp (λ > 65 h 92
300 nm)
BaTa2O6 4.1 (<300) NiO water 780 μmol/h 350 μmol/h 400-W Hg lamp 18 h 93
(orthorhombic)
Review

Chem. Rev. XXXX, XXX, XXX−XXX

DOI: 10.1021/acs.chemrev.9b00201
 Table 1. continued
gas evolution rate
bandgap/eV reaction
photocatalyst (absorption range/nm) surface loading reactant H2 O2 light source duration efficiency ref
Ultraviolet Light-Responsive Photocatalysts
Ba5Ta4O15 3.9 (<320) NiO water 7100 3600 450-W Hg lamp 6h 94
Chemical Reviews

mmol/h mmol/h
CaTa2O6 4.0 (<310) NiO water 72 μmol/h 32 μmol/h 400-W Hg lamp 95
Ca2Ta2O7 4.4 (<280) NiO NaOH aq soln 170 μmol/h 83 μmol/h 450-W Hg lamp 18 h 89
CaTa4O11 4.6 (<270) NiO water 403 μmol/h 207 μmol/h 100-W Hg lamp 8h AQY: 1.6% at 254 nm 96
Ca0.7Sr0.3Ta4O11 4.6 (<270) NiO water 575 μmol/h 291 μmol/h 100-W Hg lamp 8h AQY: 5.8% at 270 nm 96
Sr2Ta2O7 4.5 (<275) NiO water 1000 μmol/h 480 μmol/h 400-W Hg lamp 21 h AQY: 12% at 270 nm 78
SrTa2O6 4.4 (<280) NiO water 960 μmol/h 490 μmol/h 400-W Hg lamp 4h AQY: 7% at 270 nm 95
NiTa2O6 3.7 (<335) water 11 μmol/h 4 μmol/h 400-W Hg lamp 93
ZnTa2O6 4.4 (<280) NiO water 15 μmol/h 6 μmol/h 400-W Hg lamp 93
Rb4Ta6O17 4.2 (<295) Ni water 92 μmol/h 46 μmol/h 400-W Hg lamp 6h 81
Ca2Sb2O7 3.9 (<320) RuO2 water ∼3 μmol/h ∼1 μmol/h 200-W Hg−Xe lamp 16 h 97
(248 < λ < 643 nm)
Sr2Sb2O7 4.0 (<310) RuO2 water ∼8 μmol/h ∼3 μmol/h 200-W Hg−Xe lamp 16 h 97
(248 < λ < 643 nm)
NaSbO3 3.6 (<345) RuO2 water ∼1.7 μmol/h ∼0.8 μmol/h 200-W Hg−Xe lamp 12 h 97
(248 < λ < 643 nm)
BaCeO3 3.2 (<385) RuO2 water 59 μmol/h 26 μmol/h 400-W Hg lamp 98

J
Zn2GeO4 3.2 (<385) RuO2 water ∼22 μmol/h ∼10 μmol/h Hg−Xe lamp 12 h 99
LaInO3 RuO2 water ∼1.25 ∼0.5 μmol/h 200-W Hg−Xe lamp 12 h 100
μmol/h
YInO3 3.5 (<355) RuO2 water ∼6 μmol/h ∼2.5 μmol/h 200-W Hg−Xe lamp 10 h 101, 102
Sr2SnO4 4.6 (<270) RuO2 water ∼5 μmol/h ∼2.5 μmol/h 200-W Hg−Xe lamp 3h 103
SrSnO3 4.1 (<300) RuO2 water 227.2 113.5 400-W Hg lamp ∼90 h 104
μmol/h/g μmol/h/g
CaSnO3 4.4 (<280) RuO2 water 46 μmol/h/g 23.3 400-W Hg lamp 96 h 105
μmol/h/g
BaSnO3 3.1 (<400) RuO2 water 1.41 0.61 400-W Hg lamp 13 h 105
μmol/h/g μmol/h/g
BaZrO3 4.8 (<260) water 104.5 26.2 400-W Hg lamp ∼20 h AQY: 3.7% 106
μmol/h/g μmol/h/g
BaZrO3:Ta water 180 μmol/h 90 μmol/h 300-W Xe lamp 107
ZnGa2O4 4.2 (<295) RuO2 water ∼10 μmol/h ∼4 μmol/h 200-W Hg−Xe lamp 12 h 108
PbWO4 RuO2 water ∼24 μmol/h ∼12 μmol/h 200 W Hg−Xe lamp 16 h 109
InBO3 5.4 (<230) NiO water 352 μmol/h 178 μmol/h 400-W Hg lamp 8h 110
La4CaTi5O17 3.8 (<325) Ni water 499 μmol/h 450-W Hg lamp QE: 20% (<320 nm) 61
CaLa4Ti4O15 3.8 (<325) NiO water 593 μmol/h 276 μmol/h 400-W Hg lamp 63
SrLa4Ti4O15 3.8 (<325) NiO water 1171 μmol/h 546 μmol/h 400-W Hg lamp 63
BaLa4Ti4O15 3.9 (<320) NiO water 2300 μmol/h 1154 μmol/h 400-W Hg lamp 4h AQY: 15% at 270 nm 63
K2La2Ti3O10 3.5 (<355) Ni KOH aq soln 2186 μmol/h 1131 μmol/h 450-W Hg lamp 2h 111
KLaTiO4 3.6 (<345) NiO water 86 μmol/h/g 44 μmol/h/g 450-W Hg lamp 112
Review

KLaZr0.3Ti0.7O4 3.9 (<320) NiO water 230 116 450-W Hg lamp 112

Chem. Rev. XXXX, XXX, XXX−XXX

DOI: 10.1021/acs.chemrev.9b00201
μmol/h/g μmol/h/g
 Table 1. continued
gas evolution rate
bandgap/eV reaction
photocatalyst (absorption range/nm) surface loading reactant H2 O2 light source duration efficiency ref
Ultraviolet Light-Responsive Photocatalysts
Rb2La2Ti3O10 3.4−3.5 (<365) Ni RbOH aq soln 869 μmol/h 430 μmol/h 450-W Hg lamp 30 h 113
Chemical Reviews

Cs2La2Ti3O10 3.4−3.5 (<365) Ni water (pH 10.5) 700 μmol/h 340 μmol/h 450-W Hg lamp 113
Na2Li2Ti6O14 3.7 (<335) RuO2 LiOH aq soln 27 μmol/h 14 μmol/h 100-W Hg lamp 16 h 114
SrLi2Ti6O14 3.7 (<335) RuO2 LiOH aq soln 13 μmol/h 6.8 μmol/h 100-W Hg lamp 114
NdLaTi2O7 3.7 (<335) NiOx water 131 450-W Hg lamp 69
μmol/h/g
(Na, K)TaO3:Zr 3.9 (<320) water 4650 μmol/h 2310 μmol/h 350-W Hg lamp 6h 115
(Na, K)TaO3:Hf 3.9 (<320) water 4960 μmol/h 2460 μmol/h 350-W Hg lamp 6h 115
KBa2Ta3O10 3.5 (<355) Ni water 150 μmol/h 450-W Hg lamp QE: 8% (<350 nm) 61
K2LaTa5O15 4.0 (<310) NiO water 175 μmol in 74 μmol in 400-W Hg lamp 116
5h 5h
K2PrTa5O15 3.8 (<325) NiO water 1550 μmol/h 830 μmol/h 400-W Hg lamp 19 h 116, 117
K2NdTa5O15 4.1 (<300) NiO water 125 μmol in 60 μmol in 400-W Hg lamp 116
5h 5h
K2SmTa5O15 4.1 (<300) NiO water 623 μmol in 272 μmol in 400-W Hg lamp 116
5h 5h
K2GdTa5O15 4.1 (<300) NiO water 240 μmol in 73 μmol in 400-W Hg lamp 116
5h 5h

K
K2TbTa5O15 3.9 (<320) NiO water 174 μmol in 77 μmol in 400-W Hg lamp 116
5h 5h
K2DyTa5O15 4.1 (<300) NiO water 358 μmol in 172 μmol in 400-W Hg lamp 116
5h 5h
K2TmTa5O15 4.1 (<300) NiO water 173 μmol in 70 μmol in 400-W Hg lamp 116
5h 5h
H2SrTa2O7·nH2O 3.9 (<320) NiO water 940 μmol/h 459 μmol/h 400-W Hg lamp 75 h 118, 119
H1.81Sr0.81Bi0.19Ta2O7 3.9 (<320) water 2460 1110 350-W Hg lamp 6h 120
μmol/h/g μmol/h/g
K2SrTa2O7·nH2O 3.9 (<320) water 374 μmol/h 12 μmol/h 400-W Hg lamp 5h 118
K2Sr1.5Ta3O10 4.1 (<300) RuO2 water 100 μmol/h 39.4 μmol/h 400-W Hg lamp 65 h AQY: ∼2% at 252.5 nm 121
K2La2/3Ta2O7 4.0 (<310) water 146 μmol/h 66 μmol/h 400-W Hg lamp ∼6 h 119
K4La2Ta10O30 3.9 (<320) water 18.2 μmol/h 7.3 μmol/h 300-W Xe lamp 122
KCa2Ta3O10 4.2 (<295) NiOx water 177 μmol/h 81 μmol/h 400-W Hg lamp 123
KCaSrTa5O15 4.1 (<300) NiO water 4300 μmol/h 2260 μmol/h 400-W Hg lamp 20 h AQY: 6.6% at 254 nm 124
LiCa2Ta3O10 4.2 (<295) NiOx water 708 μmol/h 333 μmol/h 400-W Hg lamp 7h 123
NaCa2Ta3O10 4.2 (<295) NiOx water 293 μmol/h 162 μmol/h 400-W Hg lamp 123
CsCa2Ta3O10 4.2 (<295) NiOx water 89 μmol/h 53 μmol/h 400-W Hg lamp 123
RbCa2Ta3O10 4.2 (<295) NiOx water 180 μmol/h 91 μmol/h 400-W Hg lamp 123
RbNdTa2O7 3.8 (<325) water 234.8 126.4 400-W Hg lamp ∼48 h 125
μmol/h/g μmol/h/g
RbSmTa2O7 3.8 (<325) water 53.2 28.7 400-W Hg lamp 125
μmol/h/g μmol/h/g
RbLaTa2O7 3.8 (<325) water 1.2 μmol/h/g 0.6 μmol/h/g 400-W Hg lamp 125
Review

H2La2/3Ta2O7 4.0 (<310) NiO water 158 μmol/h 77 μmol/h 400-W Hg lamp ∼6 h 119

Chem. Rev. XXXX, XXX, XXX−XXX

DOI: 10.1021/acs.chemrev.9b00201
 Table 1. continued
gas evolution rate
bandgap/eV reaction
photocatalyst (absorption range/nm) surface loading reactant H2 O2 light source duration efficiency ref
Ultraviolet Light-Responsive Photocatalysts
H-SrBi2Ta2O9 3.9 (<320) water 162.7 44.2 μmol/h 250-W Hg lamp 126
Chemical Reviews

μmol/h
Ba3LaNb3O12 4.1 (<300) NiO water 1185 μmol/h 588 μmol/h 400-W Hg lamp 63
K2SmNb5O15 3.4 (<365) NiOx water 64 μmol/h 29 μmol/h 400-W Hg lamp 18 h 127
K2NdNb5O15 3.4 (<365) NiOx water 20 μmol/h 9 μmol/h 400-W Hg lamp 127
K2LaNb5O15 3.3 (<375) NiOx water 13 μmol/h 4 μmol/h 400-W Hg lamp 127
KSr2Nb5O15 3.5 (<355) NiOx water 10 μmol/h 3 μmol/h 400-W Hg lamp 127
KBa2Nb5O15 3.4 (<365) NiOx water 8 μmol/h 3 μmol/h 400-W Hg lamp 127
KCa2Nb3O10 3.5 (<355) Pt NaI aq soln ∼8.5 μmol/h ∼3.5 μmol/h 300-W Xe lamp (λ > 10 h AQY: 3% at 300 nm 128
300 nm)
CaZrTi2O7 3.6 (<345) NiOx water 150 μmol/h 75 μmol/h 400-W Hg lamp 10 h AQY: 0.2% at 270 nm 129
KTiNbO5 3.5 (<355) NiO water ∼29 μmol/h ∼10 μmol/h 450-W Hg lamp 18 h 130
K4Ta2Nb4O17 3.4 (<365) Ni water 409 μmol/h 198 μmol/h 400-W Hg lamp 81
K4Ta3Nb3O17 3.3 (<375) Ni water 233 μmol/h 111 μmol/h 400-W Hg lamp 81
K2Rb2Nb6O17 3.3 (<375) NiO water 78 μmol/h 39 μmol/h 450-W Hg lamp QE: 3.3% at 330 nm 131
K2PrNb5O15 3.1 (<400) NiOx water 13 μmol/h 4 μmol/h 400-W Hg lamp 127
Rb4Ta2Nb4O17 3.5 (<355) Ni water 362 μmol/h 179 μmol/h 400-W Hg lamp 81

L
Rb4Ta3Nb3O17 3.6 (<345) Ni water 126 μmol/h 62 μmol/h 400-W Hg lamp 81
Rb4Ta4Nb2O17 3.6 (<345) Ni water 101 μmol/h 48 μmol/h 400-W Hg lamp 81
LaZrTa3O11 4.4 (<280) NiO water 22 μmol/h 9.3 μmol/h 100-W Hg lamp 96
H-K0.5La0.5Bi2Ta2O9 4.0 (<310) water 189.3 57.3 μmol/h 250-W Hg lamp 126
μmol/h
H-BaBi2Ta2O9 4.3 (<290) water 119.5 30.5 μmol/h 250-W Hg lamp 126
μmol/h
Na4Nb8P4O32 3.2 (<385) RuO2 water ∼18 μmol/h ∼9 μmol/h 200 W Hg−Xe lamp 12 h 132
Na4Ta8P4O32 4.0 (<310) RuO2 water ∼50 μmol/h ∼25 μmol/h 200 W Hg−Xe Lamp 12 h 132
BaZr0.7Sn0.3O3 water 138 μmol/h 37 μmol/h 400-W Hg lamp 133
RbTaWO6 3.8 (<325) NiOx RbOH aq soln 69.7 μmol/h 34.5 μmol/h 1000-W Hg lamp 45 h 134
RbNbWO6 3.6 (<345) NiOx RbOH aq soln 11.4 μmol/h 4.3 μmol/h 1000-W Hg lamp 134
CsTaWO6 3.8 (<325) NiOx CsOH aq soln 19.7 μmol/h 8.8 μmol/h 1000-W Hg lamp 134
CsNbWO6 3.6 (<345) NiOx CsOH aq soln 10.1 μmol/h 4.7 μmol/h 1000-W Hg lamp 134
K3Ta3Si2O13 4.2 (<295) NiO water 773 μmol/h 406 μmol/h 400-W Hg lamp 5h AQY: 2.4% at 254 nm 135, 136
Ba3Ta6Si4O26 4.3 (<290) NiO water 134 μmol/h 68 μmol/h 400-W Hg lamp AQY: 0.2% at 254 nm 136
silicotungstic acid 3.4 (<365) water 32.8 μmol/h ∼16.4 450-W Hg lamp 137
(SWA)−silica μmol/h
K3Ta3B2O12 4.2 (<295) water 2390 μmol/h 1210 μmol/h 450-W Hg lamp ∼6 h 138
BaIn0.5Nb0.5O3 3.5 (<355) NiOx water 27.0 μmol/h 12.3 μmol/h 400-W Hg lamp 139
BaZn1/3Nb2/3O3 3.4−3.9 (<365) NiOx water 291.22 145.61 400-W Hg lamp 140
μmol/h/g μmol/h/g
RbLa2Ti2NbO10 3.4−3.5 (<365) Ni RbOH aq soln 79 μmol/h 30 μmol/h 450-W Hg lamp 113
CsLa2Ti2NbO10 3.4−3.5 (<365) Ni water 540 μmol/h 265 μmol/h 450-W Hg lamp 113
Review

Chem. Rev. XXXX, XXX, XXX−XXX

DOI: 10.1021/acs.chemrev.9b00201
 Table 1. continued
gas evolution rate
bandgap/eV reaction
photocatalyst (absorption range/nm) surface loading reactant H2 O2 light source duration efficiency ref
Ultraviolet Light-Responsive Photocatalysts
Rb1.5La2Ti2.5Nb0.5O10 3.4−3.5 (<365) Ni RbOH aq soln 725 μmol/h 358 μmol/h 450-W Hg lamp 113
Chemical Reviews

Cs1.5La2Ti2.5Nb0.5O10 3.4−3.5 (<365) Ni water 540 μmol/h 265 μmol/h 450-W Hg lamp 113
LiInGeO4 RuO2 water ∼25 μmol/h ∼12.5 200-W Hg−Xe lamp 9h 141
μmol/h
β-Ge3N4 3.6 (<345) RuO2 water ∼1500 ∼700 450-W Hg lamp 24 h AQY: 9% at 300 nm 142
μmol/h μmol/h
GaN 3.4 (<365) Rh2−xCrxO3 H2SO4 aq soln 19 μmol/h 9.5 μmol/h 450-W Hg lamp (λ > 50 h AQY: 0.7% at 300−340 nm 143
(pH 4.5) 300 nm)
GaN:Mg RuO2 water ∼650 ∼290 450-W Hg lamp ∼20 h 144, 145
μmol/h μmol/h
GaN:Zn RuO2 water ∼200 ∼100 450-W Hg lamp ∼10 h 144, 145
μmol/h μmol/h
GaN:Be RuO2 water ∼500 ∼250 450-W Hg lamp ∼12 h 145
μmol/h μmol/h
p-GaN/InGaN NaCl aq soln ∼6 mol/g ∼3 mol/g AM 1.5G 3h STH: 1.9% 146
(nanowire)
Visible Light-Responsive Photocatalysts
CoO water ∼11 mL ∼5.5 mL 0.9-W solid-state laser STH: 5% 147
(λ = 532 nm)

M
Cu2O 2.0 (<620) water 3.8 mmol in 1.9 mmol in 300-W Xe lamp (λ > 1900 h QE: 0.3% at 550−600 nm 148
1900 h 1900 h 460 nm)
TiO2 (rutile) 3.0 (<410) Pt water 3.4 μmol/h 1.6 μmol/h 300-W Xe lamp (λ < 2.5 h 30, 149
420 nm)
TiO2:Cr (anatase) Pt, RuO2 HCl aq soln 150 μL/h 30 μL/h 450-W Xe lamp (λ > ∼10 h 150
(pH 3) 415 nm)
TiO2:Br,Cl (P25) Pt Na2SO3 aq solnn ∼145 μL/h ∼50 μL/h 450-W Hg lamp 8h 151
GaFeO3:N 2.7 (<460) water 0.10 μmol/h 0.04 μmol/h 300-W Xe lamp (λ = 8h QE: 0.13 ± 0.01% at 450 ± 5 nm 152
450 ± 5 nm)
BiOBr 3.0 (<410) water (pH 7) ∼650 ∼300 350-W Hg lamp (λ > 153
μmol/h/g μmol/h/g 400 nm)
BiOI 2.0 (<620) water (pH 7) ∼1300 ∼650 350-W Hg lamp (λ > 153
μmol/h/g μmol/h/g 400 nm)
Bi2Ga4O9 2.9 (<430) RuOx water 19.3 9.7 μmol/h/g 300-W Hg lamp (λ > 5h 154
μmol/h/g 400 nm)
Bi2Ga3.6Fe0.4O9 RuOx water 41.5 19.6 300-W Hg lamp (λ > 35 h AQY: 0.09% at 420 nm 154
μmol/h/g μmol/h/g 400 nm)
Bi2GaVO7 2.1 (<590) water 46.8 μmol/h 22.9 μmol/h 400-W Hg lamp (λ = 20 h 155
390 nm)
Bi2YVO8 2.1 (<590) water 40.7 μmol/h 20.7 μmol/h 400-W Hg lamp 24 h AQY: 0.628% at 390 nm 156
(λ = 390 nm)
Bi0.5Y0.5VO4 Rh−Cr2O3 water 901.6 414.4 450-W Hg lamp (λ > ∼18 h 157, 158
μmol/h μmol/h 300 nm)
BiYWO6 2.7 (<460) Pt−Cr2O3 water 11.2 μmol/h 5.8 μmol/h 500-W Xe lamp (λ > 15 h AQY: 0.17% at 420 nm 159
420 nm)
Review

Chem. Rev. XXXX, XXX, XXX−XXX

DOI: 10.1021/acs.chemrev.9b00201
 Table 1. continued
gas evolution rate
bandgap/eV reaction
photocatalyst (absorption range/nm) surface loading reactant H2 O2 light source duration efficiency ref
Visible Light-Responsive Photocatalysts
Bi0.5Eu0.5VO4 Rh−Cr2O3 water ∼70 μmol/h ∼35 μmol/h 450-W Hg lamp (λ > 157
Chemical Reviews

300 nm)
Bi0.5Sm0.5VO4 Rh−Cr2O3 water ∼60 μmol/h ∼30 μmol/h 450-W Hg lamp (λ > 157
300 nm)
Bi0.5La0.5VO4 Rh−Cr2O3 water ∼25 μmol/h ∼10 μmol/h 450-W Hg lamp (λ > 157
300 nm)
Bi0.5Dy0.5VO4 Pt−Cr2O3 water 33.7 μmol/h 17.6 μmol/h 300-W Xe lamp (λ > 24 h 160
300 nm)
Bi0.5Nd0.5VO4 Pt−Cr2O3 water 11.1 μmol/h 5.6 μmol/h 300-W Xe lamp (λ > 160
300 nm)
Bi0.5Gd0.5VO4 Pt−Cr2O3 water 13.3 μmol/h 6.4 μmol/h 300-W Xe lamp (λ > 160
300 nm)
Bi0.5Eu0.25Y0.25VO4 Rh−Cr2O3 water ∼95 μmol/h ∼38 μmol/h 450-W Hg lamp (λ > 157
300 nm)
Bi0.5La0.25Y0.25VO4 Rh−Cr2O3 water ∼30 μmol/h ∼15 μmol/h 450-W Hg lamp (λ > 157
300 nm)
Bi1−xInxV1−xMoxO4 2.5 (<495) RuO2 ∼17 μmol/h ∼8 μmol/h 450-W Hg lamp (λ > 10 h AQY: 3.2% at 420−800 nm 161
420 nm)
Sr5Ta4O15 3.0 (<410) NiO water 1194 μmol/h 722 μmol/h 400-W Hg lamp 6h 162

N
InTaO4 2.6 (<475) NiOx water 3.2 μmol/h 1.1 μmol/h 300-W Xe lamp (λ > 163
420 nm)
In0.9Ni0.1TaO4 2.3 (<540) NiOx water 16.6 μmol/h 8.3 μmol/h 300-W Xe lamp (λ > ∼66 h QE: 0.66% at 402 nm 163
420 nm)
K4Ta4Nb2O17 3.0 (<410) Ni water 31 μmol/h 12 μmol/h 400-W Hg lamp 81
Pr2Ti2O7 3.0 (<410) NiOx water 150 450-W Hg lamp 69
μmol/h/g
BaTi4O9 3.0 (<410) RuO2 water ∼45 μmol/h ∼20 μmol/h 400-W Xe lamp ∼33 h 164−166
SrTiO3:Rh,Sb IrO2 H2SO4 aq soln ∼4 μmol/h ∼2 μmol/h 300-W Xe lamp (λ > ∼20 h AQY: 0.1% at 420 nm 167
(pH 3.0) 440 nm)
PrLaTi2O7 3.0 (<410) NiOx water 220 450-W Hg lamp 69
μmol/h/g
Ga2BiNbO7 2.6 (<475) water 72.6 μmol/h 35.7 μmol/h 400-W Hg lamp 18 h 168
In2BiNbO7 2.5 (<495) water 54.3 μmol/h 26.6 μmol/h 400-W Hg lamp 18 h 168
CaIn2O4 2.9 (<430) RuO2 water ∼22 μmol/h ∼11 μmol/h 400-W Xe lamp 4h 103, 169
SrIn2O4 2.9 (<430) RuO2 water ∼7 μmol/h ∼3.5 μmol/h 400-W Xe lamp 103, 169
SrIn2O4:Ba 2.9 (<430) RuO2 water ∼6 μmol/h ∼3 μmol/h 400-W Xe lamp (280 6h 100
< λ < 700 nm)
(Ga1−xZnx)(N1−xOx) 2.6 (<475) Rh2−yCryO3 H2SO4 aq soln ∼463 ∼231 450-W Hg lamp (λ > 180 days AQY: 2.5% at 420−440 nm 170, 171
(pH 4.5) μmol/h μmol/h 400 nm)
ZnO/GaN-P RuO2 water ∼29 μmol/h ∼14 μmol/h 300-W Xe lamp ∼10 h 172
(Zn1+xGe)(N2Ox) 2.7 (<460) Rh2−yCryO3 water ∼520 ∼260 450-W Hg lamp (λ > AQY: 2.0% at 420−440 nm 173
μmol/h μmol/h 400 nm)
ZrO2/TaON 2.5 (<495) IrO2, Cr2O3, water ∼3 μmol/h ∼1.5 μmol/h 450-W Hg lamp (λ > 9h 174
RuOx 400 nm)
Review

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DOI: 10.1021/acs.chemrev.9b00201
 Table 1. continued
gas evolution rate
bandgap/eV reaction
photocatalyst (absorption range/nm) surface loading reactant H2 O2 light source duration efficiency ref
Visible Light-Responsive Photocatalysts
CaTaO2N 2.4 (<510) TiOXH, water ∼0.14 ∼0.07 300-W Xe lamp (λ > 30 h AQY: 3 × 10−3% at 440 ± 30 nm 175
Chemical Reviews

RhCrOx μmol/h μmol/h 420 nm)

LaMg1/3Ta2/3O2N 2.1 (<590) TiOXH, water 22 μmol/h 11 μmol/h 300-W Xe lamp (λ > 22−27 h AQY: 0.18% at at 440 ± 30 nm 176, 177
SiOXH, 300 nm)
RhCrOx
LaScxTa1−xO1+2xN2−2x 2.1 (<590) TiOXH, water ∼11 μmol/h ∼5.5 μmol/h 300-W Xe lamp (λ > 178
RhCrOy 300 nm)
CDots-C3N4 2.8 (<440) water ∼8.4 μmol/h ∼4.1 μmol/h 300-W Xe lamp (λ > ∼200 days AQY: 16, 6.29 and 4.42% at 420 ± 20, 179
420 nm) 580 ± 15, 600 ± 10nm, respectively
STH: 2%
g-C3N4 2.8 (<440) Pt−Co water 1.2 μmol/h 0.6 μmol/h 300-W Xe lamp (λ > 510 h AQY: 0.3% at 405 nm 180
420 nm)
g-C3N4 (nanosheet) 3.0 (<410) Co1-phosphide water 126.8 64.5 300-W Xe lamp (λ > 12 h QE: 3.6%, 2.2% and 0.35% at 181
μmol/h/g μmol/h/g 420 nm) 420, 500, and 580 nm, respectively
Ta3N5 (nanorod) 2.1 (<590) Rh−Cr2O3 water ∼10 μmol/h ∼5 μmol/h 300-W Xe lamp (λ > 15 h STH: 0.014% AQY: 2.2%, 0.22% and 0.024% 182
420 nm) at 320, 420, and 500 nm, respectively
Mn(bpy)V4O11(bpy) 1.6 (<775) Pt water ∼92 ∼46 1000-W Xe lamp (420 7h 183
μmol/h/g μmol/h/g < λ < 800 nm)
CdS Pt, RuDTC acidic condition 8−12 0.1−0.3 20 mW/cm Xe lamp 184
(pH 6.0) μmol/h μmol/h (λ = 460 ± 50 nm)

O
a number of reacted electrons b number of reacted electrons
QE: quantum efficiency, defined by AQY: Apparent quantum yield, defined by
number of photons absorbed number of incident photons
Review

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DOI: 10.1021/acs.chemrev.9b00201
Chemical Reviews
Figure 8. Elements used to construct photocatalysts for photocatalytic water splitting and their roles.
A similar strategy for modifying the VB involves using the p
orbitals, specifically, N 2p or S 2p, of anions. (Oxy)nitrides
(having bandgaps of 1.7−2.0 eV) that absorb visible light have
been investigated by our own group. As a result of the lower
electronegativity of nitrogen compared to oxygen, the N 2p
orbitals of (oxy)nitrides form VBs at potentials more negative
than those of VBs resulting from O 2p orbitals, while the
potential of the CB is barely affected by introducing nitrogen.
As an example, compared to Ta2O5, the VBMs are shifted to
more negative potentials in TaON and Ta3N5 by replacing the
O2− anions in Ta2O5 with N3− anions (Figure 11).204 DFT
calculations of the associated electronic band structures suggest
that the VBs of Ta2O5, TaON, and Ta3N5 consist primarily of
O 2p, (O 2p + N 2p), and N 2p orbitals, respectively.
Accordingly, the light absorption spectra of TaON and Ta3N5
are expanded up to ca. 500 and 600 nm, respectively. Our
group has also researched perovskite oxynitrides with small
bandgap energies, such as LaMON2 (M = Nb, Ta), LaMO2N
(M = Ti, Zr), MNbO2N (M = Ca, Sr, Ba), and MTaO2N (M =
Ca, Sr, Ba).205−207 The majority of these materials are capable
of absorbing light with wavelengths up to 600 nm or even
longer. In addition, all these (oxy)nitrides are able to oxidize
water and/or reduce protons to generate oxygen and/or
hydrogen, respectively, under visible light in the presence of
sacrificial reagents (that is, half-reactions). However, until
recently, demonstrating overall water splitting using these
materials has represented a significant challenge due to the
high degree of charge recombination at crystal defects.
Nevertheless, in 2018, we achieved the successful growth of
Ta3N5 nanorods comprising well-defined single crystals free
from grain boundaries. This material produced H2 and O2 in
the expected stoichiometric molar ratio of 2:1 under both
P DOI: 10.1021/acs.chemrev.9b00201
Review
visible light and simulated sunlight,182 as discussed in detail in
section 3.
In addition to oxynitrides, metal chalcogenides are also
particularly promising candidates for visible-light-driven photo-
catalysis because their VBs typically consist of the p orbitals of
chalcogenide ions, which are shallower than O 2p orbitals. As
an example, CdS exhibits good charge transfer properties and
suitable band alignment with the potentials of the relevant
redox reactions. For these reasons, CdS is able to generate H2
with an extremely high QE of 93% at 420 nm following the
surface loading of Pt and PdS nanoparticles and in conjunction
with the scavenging of holes by sulfide and sulfite ions acting as
sacrificial electron donors (SEDs).209 Visible-light-responsive
metal sulfide photocatalysts with various crystal structures and
constituent metal cations having d0, d5, and d10 electron
configurations have been developed, including CuGa2In3S8,210
AgGa2In3S8,210 Cu2ZnGeS4,211 Cu2ZnSnS4,211 Ag2ZnGeS4,211
Ag2ZnSnS4,211 CuGaS2,212 CuInS2,212 Cu3VS4,213 Cu3NbS4,213
Cu3TaS4,213 BaLaCuS3,213 and MnGaInS4.213 Under visible
light, all these metal sulfides have been shown to produce
hydrogen in an aqueous solution containing SEDs.
Despite the narrow bandgaps of metal chalcogenides, it is
extremely difficult to decompose water into H2 and O2 over
these materials, primarily due to the facile oxidation of S2−
within the materials by holes near the VBM in the absence of
sacrificial reagents, resulting in self-photocorrosion without O2
evolution. Simultaneous H2 and O2 evolution have been
observed on CdS nanorods decorated with Pt nanoparticles as
the HEC and a Ru(tpy)(bpy)Cl2-based molecular OEC.184
However, the H2/O2 molar ratio was significantly different
from the expected stoichiometric value of 2 due to the
oxidation of S2− ions and the cysteine ligands by photo-
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

Figure 9. Schematics showing (a) visible light-inactive semiconductor with a wide bandgap and (b−h) strategies for obtaining a visible light
response: (b) VB potential engineering, (c) doping, (d) solid solution formation, (e) dye-sensitization, (f) localized surface plasmon resonance
(LSPR), (g) quantum confinement, and (h) a Z-scheme configuration.

generated holes. Oxysulfides are expected to be more stable O2 from aqueous solutions under visible light in the presence
than metal sulfides because they contain hydrated O 2p and S of an SED or an SEA without noticeable degradation.
Recently, oxyhalides have been intensively studied as
3p orbitals. Thus, the Ln2Ti2S2O5 series (Ln = Pr, Nd, Sm, Gd,
potential visible light responsive catalysts due to their narrow
Tb, Dy, Ho and Er),214,215 La3GaS5O,216 La5Ti2CuS5O7,217 bandgaps.187,195,219−222 Interestingly, some of these substances,
and La2Ta2ZrS2O8 (ref 218) have been shown to evolve H2 or such as Bi4NbO8Cl,187,220,221 have a shallow VBM not because
Q DOI: 10.1021/acs.chemrev.9b00201
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews
Figure 10. (a) Effect of treatment with CuCl2 on the structure of RbLaTa2O7. Reprinted with permission from ref 200. Copyright 2015 American
Chemical Society. (b,c) Effect of treatment with CuCl and on the diffuse reflectance spectra of (b) K2La2Ti3O10, K4Nb6O17, KLaNb2O7, and
RbCa2Ta3O10 layered oxides, and of (c) LiTaO3, NaTaO3, and KTaO3 bulk oxides. Reprinted with permission from ref 201. Copyright 2015 Royal
Society of Chemistry.
Figure 11. Band diagrams for Ta2O5, TaON, and Ta3N5 showing the
shift in the VBM upon nitridation. Reprinted with permission from ref
208. Copyright 2015 American Chemical Society.
they contain Cl 3p orbitals but due to the presence of highly
dispersed O 2p orbitals. Bi4NbO8Cl with a Sillén−Aurivillius
perovskite structure acts as a stable photocatalyst for water
oxidation under visible light. A Madelung analysis of
Bi4NbO8X (X = Cl, Br) and a comparison with Bi2GdO4X
and SrBiO2X (Figure 12) demonstrates that the oxide anions
(O1−O4) in the [Bi2O2] block, rather than the O5−O8 sites in
the perovskite [NbO4] slab, play a vital role in providing an
unusual VB in which the VBM is shifted upward.220
Furthermore, significant interactions between the O 2p and
Bi 6s orbitals have been identified in this compound that also
result in an upward shift of the VBM, which can be explained
by the revised lone-pair (RLP) model. 221 Similarly,
Bi6NbWO14Cl (ref 223) and PbBiO2X (X = Cl, Br),194 both
of which have small bandgaps of approximately 2.5 eV, have
been shown to be stable during visible-light-driven photo-
catalytic water oxidation without suffering from self-oxidative
R DOI: 10.1021/acs.chemrev.9b00201
Review
deactivation by photogenerated holes. The elevated VBM of
Bi6NbWO14Cl results from highly dispersed O 2p orbitals in
the VB,223 while that of PbBiO2X (X = Cl, Br) is due to the
high degree of hybridization of the Pb 6s and O 2p orbitals
(based on the RLP model).194 These studies have shown that
modifying the layers and stacking sequence as well as utilizing
post-transition-metal cations (including Sn2+, Sb3+, Pb2+, and
Bi3+) allows tuning of the VB structures of such Sillén
oxyhalides.
Conjugated polymers have sparked much interest as
photocatalysts because of their delocalized π-system and
diverse synthetic modularity, which allows visible light
absorption and systematic control over the electronic and
structural properties.224−226 As an example, polymeric C3N4
has emerged as promising materials for metal-free photo-
catalysts, which possesses peculiar properties including an
optical bandgap and hence semiconducting properties, out-
standing thermal, and chemical stability as well as tailorable
texture and structure.227 Overall water splitting using graphitic
carbon nitride (g-C3N4) modified with Pt, PtOx, and CoOx was
achieved by Wang et al. in 2016.180 This g-C3N4 was identified
as a visible-light-responsive photocatalyst with a bandgap of 2.8
eV, corresponding to an optical absorption edge of 442 nm.
The simultaneous evolution of H2 and O2 gases in a
stoichiometric ratio of 2:1 over the cocatalysts-modified g-
C3N4 happened under both UV and visible light irradiation
without using sacrificial reagents (Figure 13). The AQY for the
overall water-splitting reaction was calculated to be 0.3% at 405
nm, and the photocatalyst was stable for 510 h of reaction. The
bandgap of carbon nitride can be reduced by adding more N in
the CN framework, which enables the formation of
mesoporous carbon nitrides with C3N5 and C3N6 stoichiom-
etry, as reported by Vinu et al.228,229 The C3N5 and C3N6 with
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Chemical Reviews Review

Figure 12. Ionic energy levels for the anion sites in BiOX, Bi4NbO8X, Bi2GdO4X, and SrBiO2X (X = Cl, Br, and I) as calculated from the sum of
the Madelung potential and electron affinity. The red, blue, green, and orange symbols indicate oxygen, chlorine, bromine, and iodine anions,
respectively. Reprinted with permission from ref 220. Copyright 2017 American Chemical Society.

Figure 13. (a) Band structure diagram of g-C3N4 polymers and (b) time course of water splitting activities of Pt, PtOx, and CoOx-modified g-C3N4
polymers under visible light (λ > 420 nm) irradiation. Reprinted with permission from ref 180. Copyright 2016 Royal Society of Chemistry.

well-ordered porous structure alter the local arrangement of
the atoms and bandgap positions and provide much better
electronic properties than the analogues with less nitrogen
content. Other than carbon nitrite, there are a few examples of
organic materials have been found to act as photocatalysts for
hydrogen evolution from water in the presence of electron
donors, including pyrene-based conjugated polymers,224,230
bipyridyl-based conjugated polymers,231 benzothiadiazole-
based conjugated polymers,232 polyimide-based polymers,233
imine-linked conjugated poly(azomethine) networks,234 co-
valent triazine-based frameworks,235−237 and covalent organic
framework. 238−240 The reader is referred to previous
comprehensive reviews discussing the heterogeneous photo-
catalyst based on organic material in more detail.226,227,241−243
Recently, hybrid organic−inorganic materials featured as
solar energy transducers for hydrogen production.244−248
Maggard et al. developed manganese(II)−vanadate(V)/organ-
ic hybrids capable of producing hydrogen from water under
visible light illumination in the presence of SEDs.183,249 These
hybrid photocatalysts show structures assembled from metal-
oxide chains or layers that are linked together by organic
S DOI: 10.1021/acs.chemrev.9b00201
ligands. In particular, the Mn(bpy)V4O11(bpy) (bpy = 2,2′-
bipyridine) with a bandgap of 1.6 eV exhibits a photocatalytic
behavior of cleaving water into H2 and O2 in the stoichiometric
molar ratio of 2:1. The highest occupied crystal orbitals of the
Mn(bpy)V4O11(bpy) hybrid are composed of the high-spin d5
orbital contributions from Mn2+ and some contributions from
the N 2p orbitals on the bipyridine ligands, while the lowest
unoccupied crystal orbitals consist of π* orbital from the
bipyridine ligands coordinated to V. This compound
represents the first known hybrid solid with photocatalytic
activity for overall water splitting under visible light irradiation.
In addition, Wang and Huang et al. reported a composite of
methylammonium lead iodide perovskite (MAPbI3) with
reduced graphene oxide, enabling stable photocatalytic hydro-
gen production in aqueous HI solution saturated with MAPbI3
for 200 h.250
2.2.2. Doping. Doping by introducing foreign elements to
host materials is an effective strategy for modulating the
physicochemical and photophysical properties of photo-
catalysts. The properties that can be modified in this manner
include optical absorption, p/n characteristics,144,145 charge
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Chemical Reviews
density,90,115,251,252 charge mobility,253 charge separation,88,254
particle size,58,85,87 crystallinity,112 hydrophilicity,255 surface
structure,85 and defect density.13,53,56,57 Each of these
modifications can serve to improve the photocatalytic
efficiency of the material during water splitting. Here, we
limit our discussion to the effect of shifting the optical response
toward the visible region, known as a bathochromic shift.
Numerous researchers have proposed metal doping as an
efficient approach to extending the optical absorption of wide
bandgap semiconductor photocatalysts to the visible light
range. The introduction of metal cations with ionic radii
similar to those of the host ions can bring about bandgap
narrowing via the interactions of cation states with valence or
conduction bands or the creation of intrabandgap levels
(Figure 9c). In such cases, donors are dopants capable of
donating an electron to the CB and thus generating a hole,
while acceptors are dopants that can accept an electron from
the VB. The evident shift in the absorption edge of a metal-
doped material may have a complex origin. It has been
suggested that this effect can likely be attributed to metal ion
incorporation if it varies with the concentration of the dopant
or may be ascribed to the formation of metal clusters if related
to the annealing temperature.256 This distinction is important
because the origin of the shift is believed to be critical to the
photocatalytic activity of the doped material.256 In 1982,
Gratzel et al. split water into H2 and O2 under visible light
(400−550 nm) using Cr3+-doped TiO2 as a photocatalyst.150
In this case, the visible light absorption was attributed to the
photoexcitation of Cr3+ electrons to the CB of TiO2. Because
the CBM of TiO2 consists of Ti d states, substitutional doping
of other transition metals for Ti should lower the energy level
of d states in the bandgap.257 In fact, various metal ions, such
as Cr3+,150 Fe3+,258 Ni2+,259 V4+,260 Rh3+,260 and Mn3+,260 have
been introduced into TiO2 to produce an optical response shift
in an attempt to promote water oxidation and/or reduction
reactions under visible light. A systematic study of TiO2 doped
with V3+, V4+, V5+, Cr3+, Mn3+, Fe3+, Co3+, Ni2+, Ni3+, and Rh3+
using the DV-Xα software program (specifically, the SCAT
program developed by the Society for Discrete Variational Xα)
was conducted by Nakajima and co-workers, who determined
that the ionic radius is correlated with the degree of
bathochromic shift. That is, the shift of the absorption edge
generally increases as the radius of the cation decreases.261
Consequently, among the cations employed during such
experiments, Ni3+ and V5+ reduced the bandgap most
effectively. The electronic structures of 3d transition metal-
doped TiO2 were investigated based on ab initio calcula-
tions,262 which showed that the final band structure of the
doped TiO2 was reasonably well correlated with the t2g state of
the dopant. The localized level of the t2g state was found to
shift to lower energy values with increasing atomic number of
the dopant. Accordingly, the absorption was extended to the
visible light range, and this effect decreased along with
decreasing atomic number in the order of V > Cr > Mn >
Fe > Ni.256,263 Employing V, Cr, Mn, or Fe as the dopant, the
localized level of the t2g state was determined to be positioned
in the middle of the bandgap, while the addition of Ni
contributed electrons to the formation of a VB in conjunction
with O p and Ti 3d electrons. The concentration of the dopant
cation evidently also affected the extent of the absorption edge
red-shift.
Many other oxide semiconductors have also been examined
as host photocatalysts for metal cation doping, including
T DOI: 10.1021/acs.chemrev.9b00201
Review
InTaO4,163 and SrTiO3 (refs 167, 264, 265). As an example,
incorporating Ni into InTaO4 has been explored as an effective
means of obtaining an extended response under visible light
irradiation.163 The narrowed bandgap of Ni-doped InTaO4,
ascribed to internal transitions within the partially filled Ni d
shell, promotes the decomposition of water into stoichiometric
quantities of O2 and H2 under visible light with a QE of 0.66%.
Kudo et al. demonstrated that doping SrTiO3 with metal ions
such as Mn, Ru, Rh, and Ir results in intense absorption bands
in the visible light region.266 These bands are attributed to
excitation from discontinuous levels formed by the dopants to
the CB of the SrTiO3 host. Among the various doped
specimens, Rh-doped SrTiO3 exhibited the highest hydrogen
evolution rate in an aqueous methanol solution. The visible
light absorption bands in the diffuse reflectance spectroscopy
(DRS) data for Rh-doped SrTiO3 suggest the presence of both
Rh3+ and Rh4+. The Rh3+ ions are believed to create an
electron donor level, and transitions from this level to the CB
of SrTiO3 occur under visible light illumination. In contrast,
Rh4+ states contribute to optical absorption but deactivate
photogenerated electrons as an electron acceptor state and
provide recombination sites for photoexcited electron−hole
pairs.267,268 Research has also shown that codoping with Sb5+
at Ti4+ sites can ensure that Rh is in the trivalent state.167
Using this particular photocatalyst, water can be decomposed
under both visible light and simulated sunlight with an AQY of
0.1% at 420 nm.
Another approach to inducing visible-light-activated photo-
catalysis using oxides is to replace oxygen atoms with
nonmetals, including N, C, S, and X (F, Cl, Br), which causes
bandgap narrowing. Unlike oxynitrides, oxysulfides, and
oxyhalides, nonmetal ion dopants are generally added at
concentrations of less than 10 mol % when modifying
semiconductors. These dopants are less likely to establish
intrabandgap levels but rather elevate the VB edge. Many
studies continue to use TiO2 because this material is easy to
prepare, is relatively inexpensive, and is stable over long
periods of time. The calculated density of states data for
anatase TiO2 doped with C, N, F, P, or S demonstrate that,
among the dopants noted above, N for O is the most effective
because the p orbitals of these elements decrease the bandgap
by mixing with O 2p orbitals.269 Although doping with S also
reduces the bandgap, it is difficult to incorporate S into the
TiO2 lattice because of its large ionic radius, such that the
substitution of S requires a much larger energy input than the
substitution of N. The orbitals introduced by C and P doping
are too deep in the bandgap to overlap sufficiently with the
band states of TiO2. As an example, N-doped TiO2 obtained
by heating a mixture of urea and TiO2 exhibited an extended
absorption edge of 600 nm and showed photocatalytic activity
by producing hydrogen from an aqueous solution of Na2SO3
(as the SED) under visible light (λ > 400 nm).270 In contrast,
S- or N-doped anatase TiO2 reduced protons to H2 using
ethanol as an SED, whereas S- or N-doped rutile TiO2 oxidized
water to O2 when Fe3+ ions were added as SEAs under visible
light.271 The bandgap energies for S- or N-doped anatase TiO2
and S- or N-doped rutile TiO2 were estimated to be 2.28, 2.58,
2.34, and 2.94 eV, respectively. It is worth noting that X-ray
photoelectron spectroscopy (XPS) data have shown that S is
present as S6+ and S4+, indicating that cationic rather than
anionic sulfur is preferentially incorporated into the TiO2
lattice. In a study of TiO2 codoped with Br− or/and Cl−, the
bandgap of the TiO2 was narrowed to 2.85−2.95 eV151 and the
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Chemical Reviews
photocatalytic activity of this material during the cleavage of
water into H2 and O2 in an aqueous Na2CO3 solution under
UV light was enhanced compared to undoped TiO2.
N-Doped layered tantalates (KLaTa2O7 and RbLaTa2O7)272
and niobates (KCa2Nan−3NbnO3n+1 (n = 3 or 4))273 exhibit a
significant red-shift in their absorption spectra toward the
visible light region, similar to that of N-doped TiO2. In
addition, Pt loaded H+/RbLaTa2O7−xNy shows stable H2
generation in the presence of I− as the SED under visible
light illumination.272 The H2 evolution was observed at
wavelengths approximately 500 nm, in good agreement with
its absorption spectrum. This result indicates that the reaction
occurs photocatalytically through light absorption involving
excitation from a doping level consisting of N 2p orbitals to
empty Ta 5d orbitals. N-Doped KCa 2 Nb 3 O 10 and
KCa2NaNb4O13 specimens having a yellow coloration were
synthesized using an NH3 treatment process with the
assistance of a KCl flux.273 Heating the oxide precursors in
NH3 at a high temperature was expected to produce black-
colored samples due to the undesirable reduction of Nb5+ to
Nb, although, in practice, this was effectively prevented by the
addition of the KCl flux. Elemental analysis data and XRD
peak shifts both confirmed that the KCl flux treatment
increased the concentration of N3− anions in the sample and
thus enhanced absorption in the wavelength range from 350 to
550 nm.273 Consequently, O2 and H2 evolution rates under
visible light (λ > 400 nm) were markedly promoted in aqueous
solutions containing electron acceptors and donors, respec-
tively. The visible light sensitization of S-doped ZrW2O8 is
attributed to the S 3p orbitals in this compound, which
combine with O 2p orbitals in the VB and lower the bandgap
energy.274 This was confirmed by the evolution of O2 over this
material in response to irradiation up to 510 nm in the
presence of AgNO3 (as the SEA), suggesting that the
photocatalytic reaction proceeded in conjunction with
bandgap excitation. Other nonoxide semiconductors have
also been considered as host photocatalysts for nonmetal
doping. One example is the wide bandgap semiconductor ZnS,
which has bandgap energy values of 3.80 and 3.66 eV in the
hexagonal wurtzite and cubic zinc-blende phases, respectively.
C-doped ZnS was obtained by calcining a ZnS(en)0.5 (en =
ethylenediamine) complex precursor, prepared by a solvother-
mal route using ethylenediamine as the sole solvent.275 XPS
data confirmed the formation of Zn−C bonds in this material.
The C 2p orbitals in this catalyst participate in the formation of
the upper VB, thus narrowing the bandgap and providing a
visible light response such that this material produced H2 in
the presence of Na2S and Na2SO3 as SEDs under visible light
irradiation (λ ≥ 420 nm).
The self-doping of TiO2 with Ti3+ and/or oxygen vacancies
has been reported to result in a localized state with an energy
level of 0.75−1.18 eV, which lies below the CB of TiO2.276,277
Nonetheless, Ti3+ ions either on the surface or in the bulk of
the TiO2 are usually not stable because they are readily
oxidized, even by dissolved oxygen in water.278 In this prior
work, reduced TiO2 was synthesized through a facile one-step
combustion method and exhibited a high degree of stability in
air or water during irradiation.278 The presence of Ti3+ in the
bulk of the as-prepared sample was demonstrated by electron
paramagnetic resonance (EPR) spectra. Furthermore, the DRS
data for the reduced TiO2 showed that the presence of Ti3+
extended the photoresponse of the TiO2 from the UV to the
visible light region, allowing visible-light-driven photocatalytic
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hydrogen generation from water when using methanol as the
SED. The average QE values in the range of 400−455 nm and
at 420 nm were found to be 0.79% and 0.35%, respectively.
This Ti3+-doped TiO2 was stabilized by a carbon coating
process, during which both the Ti3+ and precursor for the
carbon coating were generated in situ via the hydrothermal
hydrolysis of titanium isopropoxide.276 The resulting Ti3+-
doped TiO2 coated with carbon had a yellow coloration and
exhibited excellent stability during photocatalytic hydrogen
production under visible light (λ ≥ 420 nm). This was possible
because the conductive carbon coating served as a barrier layer
to prevent H2O and O2 from diffusing into the surface of the
photocatalyst and thus inhibited the oxidization of the surface
O vacancies and Ti3+ in the TiO2. Self-doped NaTaO3 also
showed a shift in adsorption edge, from 315 to 730 nm.279 The
introduction of Ta4+ to bulk NaTaO3 accounts for the reduced
bandgap and the extension of the photocatalytic activity from
the UV to the visible light region.
Doping can both elevate the VB and alter the band structure
so as to fulfill the requirements for overall water splitting. A
good example is scheelite m-BiVO4, which is a well-
documented photocatalyst with a bandgap energy (2.4 eV)
suitable for absorbing visible light. Even so, this material is
incapable of evolving H2 from water because its CBM is
located at a more positive potential than the redox potential of
the H+/H2 pair. In an attempt to drive overall water splitting
under visible light using m-BiVO4, a BiVO4 variant having a
greenish coloration was developed by simultaneously sub-
stituting In3+ for Bi3+ and Mo6+ for V5+ in the m-BiVO4 host
lattice (Figure 14).161 A combined DFT and experimental
study indicated that dual doping with In3+ and Mo6+ triggered
a partial phase transformation from pure monoclinic BiVO4 to
a mixture of monoclinic and tetragonal phases. This
modification increased the unit cell volume and compressive
lattice strain while raising the CB edge and widening the
bandgap. The resulting material was capable of splitting water
into H2 and O2 via one-step photoexcitation, with an AQY of
3.2% under visible light (420−800 nm).
Even though dopants can produce catalysts active in the
visible light range, it should be noted that they can also serve as
recombination centers for photoexcited carriers, thus decreas-
ing photocatalytic activity.260 Both the level of doping and the
means by which doping is induced must therefore be precisely
controlled.
2.2.3. Solid Solutions. Solid solutions of isostructural
semiconductors are potentially advantageous in that these
mixtures readily undergo orbital hybridization between differ-
ent atoms and/or distortion of metal−oxygen octahedral/
tetrahedral units,34 leading to changes in band structures. The
bandgaps and energy levels of these materials can be
continuously tuned by varying the proportions of wide- and
narrow-bandgap semiconductors, as illustrated in Figure 9d.
Precise control over the bandgaps and band-edge positions of
semiconductors intended for single photoexcitation-based
water splitting has been achieved using the solid-solution
approach. Many materials have been studied in this regard,
including Sr2NbxTa2−xO7,280 YxIn2−xO3,101,102 ScxIn2−xO3,34
BiYWO6,159 (Ga1−xZnx)(N1−xOx),170,281−283 ZnO/GaN-P,172
(Zn1+xGe)(N2Ox),173,284 Li1−xCuxNb3O8,285 BaZr1−xSnxO3,133
BixY1−xMO4 (M = La, Eu, Sm, Y, Dy, Nd and Gd),157,158,160,286
and LaMgxTa1−xO1+3xN2−3x.176−178 In particular, our own
group reported work with GaN:ZnO solid solutions in 2005,
representing the first example of efficient and stable visible-
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Chemical Reviews
Figure 14. (a) A schematic showing the synthesis of greenish
Bi1−xInxV1−xMoxO4. (b) Time courses for photocatalytic overall water
splitting over Bi1−xInxV1−xMoxO4 under visible light (λ ≥ 420 nm).
Solid and dashed lines indicate evolved H2 and O2, respectively, while
the baseline represents a control experiment using pristine BiVO4.
Reprinted with permission from ref 161. Copyright 2015 CrossMark.
light-driven overall water splitting among semiconductors
having a bandgap smaller than 3 eV.170,281,282,287 The
absorption of light by both GaN and ZnO is restricted to
the UV region by their wide bandgaps (3.4 and 3.2 eV,
respectively). However, a solid solution of GaN and ZnO has a
bandgap smaller than those of either of the two, with an
estimated value of approximately 2.6 eV. DFT calculations
Figure 15. Time course of overall water splitting using Rh2−yCryO3/GaN:ZnO under visible light for 180 days, with evacuation several times (as
indicated by arrows). Red circles, H2; blue circles, O2. Reprinted with permission from ref 171. Copyright 2012 American Chemical Society.
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have revealed that the CBM for a GaN:ZnO solid solution is
primarily composed of Ga 4s and 4p orbitals, whereas the
VBM consists of N 2p and Zn 3d orbitals. The narrowed
bandgap results from the presence of Zn 3d and N 2p electrons
in the upper VB, which provides p−d repulsion for the
VBM.281,288 The addition of rhodium−chromium mixed oxide
(Rh2−yCryO3) NPs to the surface of this solid solution
remarkably enhances water cleavage under visible light (λ >
400 nm), leading to an AQY of 2.5% in the wavelength range
of 420−440 nm.170 The longest wavelength suitable for overall
water splitting by Rh2−yCryO3 loaded GaN:ZnO was found to
be approximately 500 nm, which coincides with the absorption
edge of the photocatalyst. The AQY was further improved to
5.9% within the range of 420−440 nm by an optimized
postcalcination treatment, attributed to reductions in the
densities of zinc- and/or oxygen-related defects in the
material.287 More importantly, the rate of visible-light-driven
water splitting over Rh2−yCryO3 modified GaN:ZnO remained
unchanged over a span of three months, during which time the
catalyst continuously produced a stoichiometric mixture of H2
and O2 (Figure 15), although six months of operation resulted
in a 50% loss of the initial activity.171 A (Zn1+xGe)(N2Ox)
solid solution was also developed and was demonstrated to
function as an effective photocatalyst for visible-light-
responsive overall water splitting.173,284,289 A (Zn1.44Ge)-
(N2.08O0.38) specimen was confirmed to be a solid solution
having a wurtzite-type structure in which oxygen atoms were
substituted for nitrogen atoms. This material had a bandgap of
approximately 2.7 eV and was active in response to visible
wavelengths. The energy difference between O 2p and N 2p
orbitals and the p−d repulsion between Zn 3d and (N 2p + O
2p) electrons in the upper VB resulted in significant band
dispersion, raising the VBM and shrinking the bandgap.284 An
optimized Rh2−yCryO3-loaded photocatalyst achieved an AQY
of 2.0% under irradiation at 420−440 nm.
The efficient harnessing of solar energy requires a photo-
catalyst capable of harvesting visible light with wavelengths
longer than 600 nm. In terms of light absorption properties, d0-
type (oxy)nitrides are more advantageous than d10-type
materials.176 Recently, our group reported the synthesis of a
LaMgxTa1−xO1+3xN2−3x (x = 1/3) solid solution from two
perovskite-type materials (the oxynitride LaTaON2 and the
complex oxide LaMg2/3Ta1/3O3) that represented the first-ever
example of overall water splitting operable at wavelengths as
high as 600 nm (Figure 16).176 In this material, Mg2+
selectively occupies Ta5+ sites, with the concurrent substitution
of O2− ions for N3− to maintain an overall charge balance as
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Chemical Reviews
Figure 16. (a) DRS of the LaMgxTa1−xO1+3xN2−3x series. “K.M.”
indicates Kubelka−Munk function. (b) Time course of overall water
splitting on TiOXH/SiOXH/RhCrOy/LaMg1/3Ta2/3O2N under UV/
vis irradiation (λ ≥ 300 nm; filled symbols) and visible-light
irradiation alone (λ ≥ 420 nm; open symbols). TiOXH and SiOXH
indicate TiO2−m(OH)2m·xH2O and SiO2−m(OH)2m·xH2O, respec-
tively. Reprinted with permission from ref 176. Copyright 2015
Wiley-VCH.
well as the original perovskite structure. It was found that this
dual substitution affected the band positions of the solid
solution and especially the VB position.178 The absorption
edge of LaMg2/3Ta1/3O3 was located at 270 nm, corresponding
to a bandgap of 4.59 eV, while LaTaON2 (having a bandgap of
1.93 eV) exhibited an optical response up to 640 nm.176
Accordingly, the absorption edge of LaMgxTa1−xO1+3xN2−3x
was blue-shifted monotonically from 640 to 525 nm as x was
increased from 0 to 0.6. An increase in the oxygen-to-nitrogen
ratio also shifted the VBM toward more positive potentials,
thus facilitating water oxidation and enabling overall water
splitting.178 Attempts at photocatalytic water splitting over this
series of solid solutions modified with RhCrOy indicated that
the material for which x = 1/3 was the most active.176 This
optimal x value results from a balance of various factors
affected by the solid solution composition, such as light
absorption, energy level positions, and defect formation. The
water splitting activity of this catalyst exhibited an onset
wavelength of 600 nm, in good agreement with the absorption
edge of the material. This result confirmed that bandgap
excitation of the LaMg1/3Ta2/3O2N was responsible for the
observed water splitting. The activity of this material was
dramatically increased by reducing the level of defects in
synthesized samples by employing reverse homogeneous
precipitation during preparation of the oxide precursors.177
The AQY values obtained from an optimized specimen were
0.18% at 440 ± 30 nm, 0.031% at 500 ± 30 nm, and 0.0048%
at 560 ± 30 nm. DFT calculations demonstrated that Mg2+
ions residing at Ta5+ sites in the LaMg1/3Ta2/3O2N do not
create a new energy level in the bandgap of the parent
compound. On this basis, it is possible that other foreign
W DOI: 10.1021/acs.chemrev.9b00201
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cations having ionic radii similar to that of Ta5+ (67 pm), such
as Sc3+ (74.5 pm), could also be used to modify the bandgap
energy and potential. In fact, similar bandgap tuning was
demonstrated in work using the LaSc x Ta 1−x O 1+2x N 2−2x
series.178 Concentration-dependent bandgap tuning of
LaScxTa1−xO1+2xN2−2x (0 < x < 0.75) was found to be
possible, with a range from 1.93 to 2.2 eV. As a result, this
series of materials were capable of overall water splitting in the
case of x values greater than 0.5, with an associated bandgap
energy of approximately 2.1 eV.
A series of photocatalysts comprising Bi-based solid
solutions that showed photocatalytic behavior under visible
light while cleaving water into H2 and O2 was developed, as
exemplified by BiYWO6.159 Investigations of the band
structures and photocatalytic properties of the series
Bi1−xMxVO4 (M = Dy, La, Sm, Nd, Gd, Eu, or Y)
demonstrated that the bandgap width of Bi0.5Y0.5VO4 was
located between those of BiVO4 and YVO4, suggesting the
incorporation of Y into BiVO4 increased the bandgap of
BiVO4. The authors pointed out that the introduction of M
cations not only made an indirect contribution by weakening
interactions between Bi and VO4 tetrahedra but also raised the
CBM of BiVO4, leading to a response to visible light up to 470
nm. On the other hand, Bi 6s orbitals in such solid solutions do
not create a new VBM but rather form energy levels due to
local distortion, as illustrated in Figure 17.157,158,160 Con-
sequently, these materials are capable of absorbing visible light
and exhibit a band structure that meets the requirement of
both water oxidation and proton reduction. Another series of
solid solution photocatalysts based on BiVO4 was developed
by combining BiVO4 with scheelite molybdates (CaMoO4 and
(NaBi) 0 . 5 MoO 4 ) to form Ca 1 − x Bi x V x Mo 1 − x O 4 and
Na0.5Bi1.5VMoO8 with tetragonal scheelite crystal struc-
tures.290,291 The resulting solid solutions had narrow bandgaps
of 2.4−2.5 eV and showed higher activity during photocatalytic
O2 evolution from an aqueous AgNO3 solution under visible
light irradiation as compared to pure BiVO4. DFT calculation
results demonstrated that, in both Ca1−xBixVxMo1−xO4 and
Na0.5Bi1.5VMoO8, the CB is principally composed of V 3d and
Mo 4d orbitals. In contrast, the VB is made of hybrid orbitals
comprising Bi 6s and O 2p orbitals, and the contribution of Bi
6s to the VB increases with increasing Bi ion content in the
solid solution.
Other solid solution based on sulfides are worth mentioning
due to their narrow bandgaps and extended absorption edges
(up to 600−800 nm), including (CuIn) xZn2(1−x)S2,292
(CuAg)xIn2xZn2(1−2x)S2,293 (CuxAg1−x)2ZnSnS4 (ref 294), and
La5Ti2Cu(S1−xSex)5O7.217 These materials are able to utilize
visible light at long wavelengths during photocatalytic H2
evolution in the presence of electron donors (such as Na2S/
Na2SO3). However, sulfides tend to undergo oxidative
photocorrosion unless particular reaction conditions are
applied, which limits their application to photocatalytic overall
water splitting.
2.2.4. Dye Sensitization. Inspired by dye-sensitized solar
cells, dye-sensitized photocatalytic water splitting systems have
recently been widely investigated in both PEC and photo-
catalytic systems as a means of utilizing light at longer
wavelengths.19,295 The dye sensitization of wide bandgap
photocatalysts has been demonstrated to expand the usable
wavelength range through excitation of the sensitizer, as
depicted in Figure 9e. During this sensitization process, the dye
molecules anchored on the semiconductor surface absorb
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Chemical Reviews
Figure 17. (a) Schematic band structures of YVO4, Bi0.5Y0.5VO4
(BYV(0.5)), zircon type BiVO4, and fergusonite BiVO4. (b) Time
courses of photocatalytic overall water splitting over Bi0.375Y0.625VO4
(BYV(0.375)) loaded with Rh−Cr2O3 cocatalyst under full arc-light
irradiation (λ > 300 nm). Reprinted with permission from ref 158.
Copyright 2011 The Royal Society of Chemistry.
visible light and subsequently excite electron−hole pairs. The
excited electrons are injected into the CB of the semi-
conductor, resulting in one-electron oxidized sensitizer
molecules. For this electron transfer cascade to proceed, the
CBM of the semiconductor must be positioned between the
oxidation energy level of the excited dye (ES+/S*) and the
reduction potential for the production of H2 from water. The
electrons injected into the semiconductor CB are consumed
via proton reduction to generate H2, while the oxidized
sensitizer is reduced to the ground state by accepting an
electron provided by a suitable electron donor.19,20,296 Thus,
the potential for dye regeneration (ES+/S) must be matched by
either a sacrificial electron donor or a water oxidation
photocatalyst. Efficient photocatalysis also requires intimate
contact between the sensitizer molecules and the semi-
conductor surface because the lifetime of the photosensitizer
excited state is typically too short to allow diffusion of the
molecule to the surface before charge recombination.297
Typical values for electron transfer kinetic parameters in
hybrid systems composed of a dye, semiconductor, and
cocatalyst are summarized in Figure 18. In these systems, the
forward electron transfer from the dye to the semiconductor
and from the semiconductor to the HEC must compete
effectively with back transfer to the oxidized dye as well as with
X DOI: 10.1021/acs.chemrev.9b00201
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Figure 18. Primary kinetic processes considered in the design of dye
sensitized photocatalytic systems. Photocatalysis-promoting (forward)
electron transfer processes are shown in blue (solid arrows), while
recombination pathways are in red (dashed arrows). Typical rates
determined for RuP|TiO2 modified with molecular catalysts are
indicated on the horizontal scale bar. The steps include: (1)
photoexcitation of the dye, (2) electron transfer from the photo-
excited dye to the semiconductor CB, (3) electron transfer from the
semiconductor to the catalyst, (4) catalytic reduction of protons to
H2, (5) regeneration of the oxidized dye by the sacrificial electron
donor, (6) direct electron transfer from the photoexcited dye to the
catalyst, (7) lifetime of the photoexcited state of the dye, and (8)
charge recombination between the semiconductor CB and the
oxidized dye. Reprinted with permission from ref 20. Copyright
2016 The Royal Society of Chemistry.
the recombination of photoexcited carriers.19,20 Electron
transfer across the dye−semiconductor interface has been
found to increase the charge carrier lifetime up to the hundreds
of microseconds time scale.20 The immobilization of dye
molecules on host surfaces can be achieved through covalent
bonding, electrostatic interactions, hydrogen bonding, hydro-
phobic interactions, van der Waals forces, and physical
entrapment.298 In many cases, functional groups such as
silanyl (−O−Si−), amide (−NH−(CO)−), carboxyl (−O−
(CO)−), and phosphonato (−O−(HPO2)−) moieties have
been shown to react spontaneously with hydroxyl groups on
oxide surfaces to form strong linkages even in aqueous
suspension.298 These anchor groups must exhibit significant
affinity for the semiconductor surface under the experimental
conditions, although the type of linkage also affects the rate of
interfacial electron transfer.20 The pH of the aqueous reaction
solution can affect the stability of these anchoring strategies,
thus limiting the use of a given system to a certain pH range.299
The sensitization of TiO2 by ruthenium(II) trisdiimine
complexes (such as Ru(bpy)32+, bpy = 2,2′-bipyridine) to
promote photocatalytic H2 production under visible light was
explored in 1981.300,301 Since then, this strategy has been
frequently applied to visible-light-driven water splitting, and
various dyes, including metal-based and organic dyes, have
been employed to sensitize wide bandgap semiconductors.
Metal-based dyes can absorb light via either metal-centered
(d−d), ligand-centered, π−π* ligand-to-ligand, metal-to-ligand
charge transfer, or ligand-to-metal charge transfer transi-
tions.302 Among the various metal-based dyes that exhibit
suitable redox characteristics and visible light sensitivity,
ruthenium complexes have been successfully employed as
sensitizers for TiO2 or SnO2 to obtain photocatalytic hydrogen
generation in the absence of sacrificial reagents. These
complexes include Ru(bpy) 3 2 + 3 0 0 , 3 0 1 , 3 0 3 and [Ru-
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Chemical Reviews Review

Figure 19. Time courses of H2 (closed symbols) and O2 (open symbols) evolution using a mixture of dye-treated [(a) NKX-2311 and NKX-2587,
(b) NKX-2677 and NKX-2697, and (c) MK-1 and MK-2] Pt/H4Nb6O17 and IrO2−Pt/WO3 suspended in a KI aqueous solution under visible
light. Arrows indicate evacuation of the gas phase. Reprinted with permission from ref 309. Copyright 2013 American Chemical Society.

(dcbpy)2(dpq)]2+ (where dcbpy = 4,4′-dicarboxy 2,2′-
bipyridine and dpq = 2,3-bis(2′-pyridyl)-quinoxaline).304
Organic dyes have been utilized for the spectral sensitization
of semiconductor photocatalysts because they are generally
made of more abundant and less expensive elements and often
have higher molar extinction coefficients than transition metal-
based dyes.20 Research has shown that highly efficient light
harvesting over a wide spectral range of sunlight is possible
using organic dyes, often due to π−π* transitions.20,305 As an
example, the photocatalytic splitting of water into H2 and O2
by KTa(Zr)O3 was greatly improved in the presence of various
porphyrinoids acting as long wavelength light harvester, such
as tetrakis(4-carboxyphenyl)porphine (TCPP), tetraphenyl-
porphine tetrasulfonic acid (TPPS), and cyanocobala-
min.306,307 Among the porphyrinoids examined, cyanocobala-
min showed the highest gas evolution rate and achieved an
AQY of 12.2% at 300 nm. The resulting photovoltaic potential
decay curve confirmed that the lifetimes of photoexcited
carriers in KTa(Zr)O3 were increased after coating with Cr−
tetraphenylporphyrin (Cr−TPP), suggesting that the addition
of such substances improved the charge separation efficiency.
The majority of dye molecules cannot oxidize water into O2 in
response to light irradiation, which has prevented demon-
strations of overall water splitting into H2 and O2 using dye
sensitized photocatalysts. For this reason, dye-treated Pt/
H4Nb6O17 was combined with a WO3 photocatalyst to obtain
H2 and O2 evolution, respectively, in a dual photoexcitation
system (that is, a Z-scheme system), as presented in Figure
19.308,309 The I3−/I− redox couple was used as a shuttle
mediator for electron relay between the HEP and OEP in this
system and simultaneous H2 and O2 evolution in an almost
stoichiometric ratio under visible light (λ > 400 nm) was
Y DOI: 10.1021/acs.chemrev.9b00201
achieved using coumarin dyes (NKX-2677, -2697, and
-2587)308 and carbazole dyes (MK-1 and -2)309 as sensitizers.
This study represents the first-ever example of overall water
splitting under visible light using an organic dye as a
photosensitizer for the HER. The results also demonstrated
that the oligothiophene moiety in the coumarin dyes played an
essential role in stabilizing the dye molecules during photo-
catalytic overall water splitting. The oxidized states of
coumarin dyes having an oligothiophene moiety (two or
more thiophene rings) in their structures showed long lifespans
and the ability to undergo reversible oxidation−reduction
cycles, while the carbazole dyes required a greater number of
thiophene rings to be well stabilized. An NKX-2677-sensitized
catalyst promoted the photocatalytic reaction for as long as 40
h without deactivation, although the associated AQY was less
than 0.1% at 500 nm. Co-Doped TiO2 on which rhodamine B
(Rh B) was adsorbed exhibited a strong absorbance peak in the
range of 500−600 nm and yielded the nearly stoichiometric
evolution of H2 and O2 under visible light (λ > 420 nm),310
and the synergic effect between the Rh B and Co was reported
to be crucial to the promotion of the water splitting reaction.
To date, various dyes, including Ru(bpy)32+ and its
derivatives,311,312 Eosin Y,313 Erythrosin B,314 zinc phthalo-
cyanine derivatives,315 diketopyrrolopyrrole,316 phenothiazine
derivatives,317,318 phenoxazine derivatives,319 carbazole deriv-
atives,319 and perylene monoimide,320 have been immobilized
on semiconductors such as TiO 2 , K 4 Nb 6 O 17 , C 3 N 4 ,
HCa2−xSrxNb3O10, and HCa2Nb3−yTayO10. These materials
have then been utilized as photosensitizers for the harvesting of
visible light. Such hybrid photocatalysts are able to generate
hydrogen from aqueous solutions containing electron donors
such as triethanolamine (TEOA), ethylenediaminetetraacetic
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Chemical Reviews
acid (EDTA), or ascorbic acid after loading HEC on the
surface. Nonetheless, most of the dye photosensitizers suffer
from a stability issue because the excited dye is unstable and
tends to deactivate in various ways, such as dissolution and
photocatalytic degradation.19,302 In addition, the stability of the
anchoring bonds between the semiconductor and dye varies in
an aqueous medium, and some of them can be only established
and stable within certain pH value range and certain
solvents.20,321 The development of strategies to stabilize the
dye sensitized photocatalysts is required for making a step-
change in the performance of these systems.
2.2.5. Localized Surface Plasmon Resonance Effect.
Taking advantage of the localized surface plasmon resonance
(LSPR) effect associated with metal NPs offers a potentially
useful approach to mitigating the limited visible light
absorption of wide bandgap photocatalysts. LSPR is an optical
phenomenon in which the electron cloud on a metal
nanocluster oscillates in resonance with the electric field of
the incident light. This effect results in a high degree of light
scattering and produces intense electric fields at the NP
surfaces, giving rise to sharp spectral absorption and scattering
peaks.322,323 The frequency of this resonance can be tuned by
varying the nanoparticle size and shape as well as modifying
the configuration of the metal nanoclusters, resulting in a
potentially wide absorption range within the visible light
spectrum.322,324 The proposed charge-transfer pathways in
metal/semiconductor hybrid systems under visible light
irradiation are shown in Figure 9f. In this mechanism, the
visible light is captured by metal NPs via LSPR rather than
through excitation of the semiconductor bandgap, which is
analogous to the dye sensitization described above. The excited
electrons in the NPs are subsequently injected into the CB of
the semiconductor, after which they migrate to the cocatalyst
on the surface and drive the reduction of protons to generate
H2. The positive holes remaining in the metal nanoparticles
can be removed by an electron donor.325 Direct plasmon-
induced electron transfer from gold nanodots to TiO2 has been
observed using femtosecond-scale transient absorption spec-
trometry (TAS).326,327 These studies demonstrated that the
electron injection was completed within 50 fs, with an electron
injection yield in the range of 20−50%. In addition,
photoinduced charge separation at the interface between Au
NPs and TiO2 has been investigated by means of Kelvin probe
force microscopy.328 The results suggest that the electron
transfer cascade from the plasmonic Au NPs to TiO2 proceeds
in response to visible and near-infrared (NIR) light, as
opposed to the injection of electrons from TiO2 to Au in the
case of excitation by UV light. The significant photo-
sensitization of TiO2 in this material is ascribed to the direct
injection of hot excited electrons in the Au NPs by quantum
tunneling.329 While the transfer process has been elucidated
experimentally, the source of excited charge carriers in the
metal is not yet fully understood. As an example, it has been
suggested that plasmonic charges at the Fermi energy of the
metal are not capable of driving the reduction and oxidation
half-reactions.322 A photocatalyst fabricated by immobilizing
Au NPs on SrTiO3 showed photocatalytic water oxidation
activity when illuminated with visible light having photon
energies well below the SrTiO3 bandgap.330 A theoretical
simulation of the optical excitation of Au NPs and the relative
band positions indicated that the hot electron transfer from the
NPs to the SrTiO3 primarily results from Au interband
transitions rather than from plasmon resonance. Interband
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transition generally requires higher photon energies (so as to
generate electrons from deeper bands) compared to plasmon
resonance, and the photoexcited holes are therefore situated far
from the Fermi surface.323 The electron transfer from Au NPs
to TiO2 was also monitored using in situ EPR spectroscopy.331
The results suggested that a combination of d−sp interband
transitions in the lower wavelength range of the visible
spectrum and the LSPR effect in the higher wavelength
contributes to the generation of electrons within Au.
In addition to light absorption and scattering on metal NPs,
as well as the hot electron transfer mechanism, local
electromagnetic field enhancement, and plasmon-induced
resonance energy transfer (PIRET) mechanisms have also
been suggested as contributors to the plasmonic effect during
light-driven water-splitting, and these mechanisms have been
summarized in previous reviews.322−324,332−334 Intense local
electric fields near the surfaces of metal NPs can be generated
by irradiating the NPs near their plasmon resonance frequency,
thus inducing charge separation in the semiconductor.322,324 In
the PIRET mechanism, electron−hole pairs can be created in
the semiconductors using energy levels either near or below
the bandgap as a consequence of the overlap of the metal NP
plasmon resonance with the semiconductor bandgap, thus
extending the absorption range.335,336
Several groups have added plasmonic metal NPs (primarily
Au and Ag, with particle sizes of tens to hundreds of
nanometers) to semiconductor surfaces and observed
improved photocatalytic performance during hydrogen pro-
duction under visible irradiation.337−341 Plots of photocatalytic
activity over such plasmonic metal modified photocatalysts as a
function of incident wavelength provide direct evidence that
LSPR plays a vital role in improving the photocatalytic
performance of the semiconductors. These data are obtained
from both oxygen- and hydrogen-evolution half-reactions on
various semiconductors and show that the largest improve-
ments in the gas evolution rates are obtained at wavelengths
corresponding to the metal LSPR. Because of their large
extinction coefficients in the visible region, Au NPs have been
widely applied as additives to semiconductors, including
TiO2,325−328,331,334,338,342−348 CdS,340 PbTiO3,349 and ZnS-
AgInS2 solid solutions,350 as a means of broadening the light
absorption range. In particular, the addition of plasmonic Au
NPs to TiO2 has been found to result in a visible-light-
responsive material capable of photocatalytic hydrogen
generation in the presence of sacrificial reagents. In one
study, hydrogen was produced from water over Au NPs
immobilized on P25 TiO2 under visible light (λ > 400 nm),
using EDTA as a SED.338 The authors have investigated the
hot electron injection mechanism and proposed that Au NPs
play a dual role as light harvesters injecting electrons into the
semiconductor CB and also as catalytic sites for gas generation.
Yoshida et al. also attributed photocatalytic hydrogen
production from aqueous ethanol solution over Au/TiO2
under visible light (510−740 nm) to the excitation of electrons
in the Au NPs.346 Hot electron injection from the Au NPs to
the TiO2 CB has been ascribed to quantum tunneling through
a Schottky barrier without overbarrier energy.329,342 Enhanced
optical absorption and the generation of electron−hole pairs
for photocatalysis during visible-light-driven hydrogen gen-
eration over noncentrosymmetric Janus Au/TiO2 photo-
catalysts345 was ascribed to highly localized plasmonic near-
fields close to the Au−TiO2 interface. The hydrogen
generation rates from such Au/TiO2 photocatalysts are
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Figure 20. (a) Schematics of the cross-section of an individual photosynthetic unit showing the inner gold nanorods, the TiO2 cap decorated with
platinum HEC, and the Co OEC deposited on the lower portion of the gold nanorods. (b) An energy level diagram superimposed on a schematic
of an individual unit of the plasmonic solar water splitter, showing the proposed processes occurring in its various parts and in energy space (CB =
conduction band; VB = valence band). (c) Hydrogen production rates with various illumination wavelengths. (d) O2 and H2 generation rates as
functions of time illuminated by AM 1.5. Reprinted with permission from ref 352. Copyright 2013 Macmillan Publishers Limited.

affected by numerous factors, including the Au NP shapes and
sizes338,345,346,348 as well as the TiO2 crystal phase and particle
size.338 It is worth noting that a distinct increase in the
interband transition intensity was exhibited after incorporating
Cu with Au to form Au−Cu alloys.351 NPs of this Au−Cu alloy
supported on SrTiO3 were also found to show photocatalytic
activity superior to that obtained from either Au/SrTiO3 or
Cu/SrTiO3 under visible light (λ > 400 nm) in aqueous
solutions containing methanol as the SED. In addition, an
increased oxygen evolution rate under visible light was
observed over Au supported on CeO2 and SrTiO3 in the
presence of AgNO3 as the SEA.330,339 Overall water splitting
using plasmonic TiO2 modified with Au NPs was reported in
2013.352 In this system, an array of aligned gold nanorods
serving as light harvesting antennae is capped with a crystalline
TiO2 layer. Additionally, a cobalt-based OEC is deposited on
the gold nanorods to facilitate oxygen evolution, while Pt NPs
acting as the HEC are loaded on the TiO2 to promote
hydrogen generation (Figure 20). Under simulated sunlight,
surface plasmons are excited in the gold nanorods, creating
electron−hole pairs with hot electrons. The hot electrons are
subsequently injected into the TiO2 and then captured by the
Pt nanoparticles, leading to proton reduction. This process
leaves holes in the gold nanorods, which are eventually
oxidized water to produce oxygen on the Co cocatalyst. As a
result, the simultaneous evolution of H2 and O2 was attained,
with an STH of approximately 0.1%.
In addition to Au NPs, Ag NPs have also been employed as
efficient plasmonic photosensitizers to drive photocatalytic
water splitting over TiO2 in an aqueous methanol solution
under visible light.353 In 2017, plasmonic W18O49 nanograss
AA
was applied to g-C3N4 nanosheets354 and the resulting
W18O49/g-C3N4 heterostructure was reported to harvest
photons with energies ranging from the UV to the NIR region
(Figure 21). During the irradiation of this composite with
visible−NIR light (450−900 nm), the LSPR-excited hot
electrons generated in the W18O49 were transferred to the
CB of the neighboring g-C3N4 nanosheets and promoted the
generation of H2 from water. Concurrently, the residual holes
in the W18O49 were filled by electrons from the SED (TEOA).
2.2.6. Quantum Confinement Effect. QDs are droplets
or nanocrystals of a material.355 The size of such droplets or
nanocrystals is very small compared to the wavelength of
visible light, and so QDs exhibit quantum confinement effects,
including the appearance of unique electronic characteristics
and large absorption coefficients.356 Massive changes in the
bandgap energy depending on size is one of the most striking
properties of QDs and allows tuning of the CB and VB
positions simply by modifying the dot size. Furthermore, the
threshold photon energy required for multiple electron
generation (MEG) in QDs can be in the visible or NIR
spectral region, thus allowing the creation of more than one
electron−hole pair per absorbed photon. This phenomenon
has been observed in PbS, PbSe, CdSe, PbTe, InAs, and Si
quantum dot arrays.357 The MEG effect has not yet been
demonstrated in conjunction with photocatalytic water
splitting reactions because it results in narrow bandgap
semiconductors able to capture only the upper wavelength
range of solar photons, and such bandgaps are insufficient for
splitting water.26 Nevertheless, this property could potentially
be applied to construct Z-scheme water splitting systems
composed of narrow bandgap light harvesters. For these
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Figure 21. (a) Energy band configuration and photoinduced charge
carrier transfer processes in a W18O49/g-C3N4 heterostructure under
UV−visible−NIR light. (b) Apparent quantum efficiency (AQE) for
the W18O49/g-C3N4 heterostructure as a function of the incident light
wavelength. Reprinted with permission from ref 354. Copyright 2017
WILEY-VCH.
reasons, QDs have attracted much attention during the past
several years due to the possibility of utilizing these materials
as light absorbers in the photocatalytic water splitting reaction.
Experimental confirmation of a direct relationship between
the degree of quantum confinement and the photocatalytic
water splitting activity of semiconductor nanocrystals was
provided by Osterloh et al. Specifically, the hydrogen evolution
rates from CdSe nanocrystals in an aqueous solution of
Na2SO3 (as an SED) were found to exhibit a dependence on
the crystal size (Figure 22).358,359 Efficient H2 evolution from
water over CdS, ZnSe nanocrystals and carbon QDs loading
with suitable cocatalysts and using electron donors has also
been reported in recent years.360−363 In particular, Reisner’s
group has demonstrated that ZnSe nanorods with a Ni-based
cocatalyst suspended in an aqueous ascorbic acid solution yield
H2 with a QE of 50 ± 4% at 400 nm.360 A multiband InGaN/
GaN nanowire heterostructure decorated with Rh/Cr2O3 NPs
as cocatalysts showed stable hydrogen generation from water
under light irradiation up to approximately 560 nm.364 The
associated QE was estimated to be approximately 13% at 440−
450 nm. Under both UV and visible light, electrons and holes
were produced in the GaN wire, InGaN ternary wire, and
InGaN QD components. The authors attributed the observed
photocatalytic activity during the overall water splitting
reaction to a collective effect from the reduction and oxidation
reactions driven by these photoexcited carriers. Overall water
splitting into H2 and O2 was also accomplished using N-doped
graphene oxide QDs without a sacrificial reagent under visible
light (420 < λ < 800 nm).365 In this case, the authors
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Figure 22. Relative H2 evolution rate (normalized with regard to
catalyst amount and absorbed photons) as a function of QD size.
Inset: schematic diagram of hydrogen evolution on a CdSe QD in the
presence of sodium sulfite. Reprinted with permission from ref 359.
Copyright 2013 American Chemical Society.
attributed the simultaneous H2 and O2 evolution to favorable
band bending in a diode system formed by the n-type N-doped
graphene oxide and p-type graphene oxide. These materials
promoted the evolution of O2 and H2, respectively, resulting in
a Z-scheme water-splitting system.
It is worth noting that graphene QDs have also been
investigated with regard to photocatalytic hydrogen production
under visible light (420−800 nm).366 The AQY values
obtained from graphene QD-1,1′-bis(2-naphthalene) during
hydrogen evolution in the presence of TEOA as an electron
donor were 11, 5.6, 3.0, and 2.7% at 420, 460, 500, and 550
nm, respectively. The authors suggested that the graphene QD
bandgap can be reduced by conjugating the dots with
polyaromatic moieties to enlarge the π conjugated sp2-carbon
systems and introducing intermediate n orbitals between π and
π* orbitals after conjugation, based on attaching electron-
donating functional groups.
Similar to the dye sensitized photocatalyst concept, hybrids
composed of QDs and semiconductors acting as photocatalysts
take advantage of the optical absorption of QDs in the visible
spectrum, as illustrated in Figure 9g. Upon photoexcitation, the
QDs inject electrons into the CB of a wide bandgap
semiconductor, providing charge carriers for the catalytic
energy conversion reactions. As described above, the main
advantage of applying QDs as light harvesters is that the
potential energy levels of the QD CB and VB can be controlled
by adjusting the QD size, and thus an appropriate size can be
selected to maximize the electron transfer efficiency. In
addition, the quantized nature of the energy levels in QDs
and the subsequent carrier confinement and enhanced
Coulomb interaction lead to relatively slow exciton relaxation
dynamics, possibly allowing hot charge transfer reactions.356,357
It has also been suggested that QDs are more amenable to
exciton creation and charge separation than organic dyes and
metal complexes.367 In one study, visible-light-responsive
photocatalytic H2 generation from an aqueous methanol
solution was observed over P25 TiO2 modified by carbon
QDs.368 The surface photovoltage (SPV) data and photo-
luminescence (PL) spectra acquired during this reaction show
that, under UV illumination (300−400 nm), carbon QDs acted
as electron reservoirs to receive electrons from the P25. In
contrast, under visible light (λ > 400 nm), the π-conjugated
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Figure 23. Z-Scheme overall water splitting system consisting of BiVO4 as the OEP, ZrO2-modified TaON as the HEP, and [Fe(CN)6]3−/
[Fe(CN)6]4− as a redox mediator. (a) Time course of Z-scheme overall water splitting under optimized conditions in response to visible light. (b)
AQY as a function of irradiation wavelength and DRS of the HEP and OEP. Reprinted with permission from ref 383. Copyright 2018 Elsevier Inc.
carbon QDs functioned as photosensitizers and injected
photoexcited electrons into the P25. Visible-light-driven
photocatalytic H2 production activity was also enhanced after
combining CdS QDs with g-C3N4.369 In this system, the
electrons in the CdS QDs, comprising those generated by the
material itself and those injected from the g-C3N4, eventually
accumulated on the Pt cocatalyst and subsequently partici-
pated in H2 evolution. Additionally, photogenerated holes in
the VB of the CdS QDs migrated to that of the g-C3N4 to drive
the oxidation reaction. Similarly, a Zn1−xCdxS solid solution
sensitized using CdS QDs showed enhanced photocatalytic
activity during H2 production in an aqueous solution
containing Na2SO3 and Na2S as sacrificial reagents under
visible light.370 Kang et al. reported that a carbon nanodot−
C3N4 composite could split water into H2 and O2 under
irradiation up to 650 nm with an STH of 2.0%.179 Unlike other
reported QDs photocatalytic systems, the authors claimed that
the carbon QD forms sub-band states in the bandgap rather
than functions as a photosensitizer. There is, however, no
robust evidence supporting this argument. The mechanism
underlying the high QE at long wavelength (e.g., 4.42% at 600
nm) is unclear and questionable. The performance has not yet
been reproduced.
2.2.7. Z-Scheme Configurations. An alternative ap-
proach to capturing sunlight efficiently is to construct a Z-
scheme system based on the two-step photoexcitation of an
HEP and an OEP, both having narrow bandgaps. The Z-
scheme pathway is exceptionally useful because the device
voltage is divided into several contributions, and thus the
bandgap of the photocatalytic material does not have to
straddle both the hydrogen and oxygen evolution potentials.
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Hence, narrow bandgap semiconductors that are active only
for proton reduction or water oxidation can be employed to
split water using solar energy. In such systems, visible light
irradiation generates electron−hole pairs in both the HEP and
OEP. The reduction of H+ to H2 is promoted by electrons in
the CB of the HEP, while O2 is produced as a result of water
oxidation by the holes in the VB of the OEP, as shown in
Figure 9h. Accordingly, four and eight photons are necessary to
produce a H2 molecule and an O2 molecule in the Z-scheme
system, respectively. This means that to achieve the same STH,
double QE is required for Z-scheme systems compared to one-
step photoexcitation systems. To complete the cycle, the
electrons in the CB of the OEP must pass through a relay/
shuttle to combine with holes in the VB of the HEP. A
comprehensive review of this topic was published by Tang and
Abe et al. in 2018.371
Redox couples, such as Fe3+/Fe2+,372−376 IO3−/I−,377−381
[Co(bpy)3]3+/2+,382 [Co(phen)3]3+/2+,382 [Fe(CN)6]3−/[Fe-
(CN) 6 ] 4 − , 3 8 3 , 3 8 4 and [SiW 1 1 O 3 9 Mn I I I (H 2 O)] 5 − /[Si-
W11O39MnII(H2O)]6− (ref 385), have been widely utilized to
mediate the electron transfer between the HEP and OEP. Very
recently, an AQY of 10.3% at 420 nm and an STH of 0.5%
were achieved in a Z-scheme system using [Fe(CN)6]3−/
[Fe(CN)6]4− as the redox mediator (Figure 23).383 In this
system, H2 and O2 are produced on facet-controlled BiVO4
and ZrO2-modified TaON, respectively. The electron migra-
tion from the BiVO4 to the [Fe(CN)6]3− was facilitated by
loading Au NPs onto the BiVO4. A numerical simulation
showed that a maximum STH efficiency of 34% could possibly
be achieved using a redox-mediator Z-scheme system with two
light absorbers having bandgaps of 1.53 and 0.75 eV.386
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Chemical Reviews Review

However, the presence of redox mediators also brings about

undesirable side reactions, including the reduction of oxidative
mediators on the HEP and the oxidation of reduced mediators
on the OEP and can result in shading of the photocatalysts
from incident light.
Kudo’s group has successfully developed redox-mediator-
free Z-schemes consisting of Rh-doped SrTrO3:Rh and BiVO4
as the HEP and OEP, respectively.267,387 In such systems,
interparticle electron transfer is achieved by adjusting the pH
of the reaction medium, which generates an attractive
electrostatic force between the respective photocatalyst
particles. The materials employed in such visible-light-driven
redox-mediator-free Z-schemes have been extended to include
various semiconductors, such as AgNbO3, Bi2MoO6, WO3,
Fe2O3, and Ta3N5.268,388,389
In a redox-mediator-free Z-scheme water splitting system, it
is of great importance to realize efficient electron transfer from
the OEP to the HEP. To this end, solid-state electron
mediators, including reduced graphene oxide,390,391 carbon,392
Au,393,394 and indium tin oxide (ITO),395 have been applied.
Our group has designed and developed photocatalyst sheets in
which the HEP and OEP particles are embedded in a
conductive layer. Distinct from the redox-mediator-free
powder suspension Z-scheme systems, the photocatalytic
activity of these photocatalyst sheets is almost independent
of the pH of the reaction solution, indicating that electron
transfer takes place preferentially through the conductive layer
rather than via aggregates of particles.393 The conductive layer
bridges the HEP and OEP, allowing efficient electron transfer
and in turn promoting the photocatalytic activity during overall
water splitting. Importantly, pH control, redox shuttles,
supporting electrolytes, buffering reagents, and circulation of
the reactants are not necessary for a photocatalyst sheet
system, in contrast to the conventional Z-scheme water-
splitting and PEC systems. Because hydrogen and oxygen
evolution occur in close proximity, H+ and OH− concentration
overpotentials and an IR drop between the HEP and OEP are
largely suppressed in such systems. The photocatalyst sheet
with high activity therefore is scalable as is. As an example, a
photocatalyst sheet composed of La,Rh-codoped SrTiO3
Figure 24. (a) Photographic image of a 3 cm × 3 cm Cr2O3/Ru
(SrTiO3:La,Rh) and Mo-doped BiVO4 (BiVO4:Mo) fixed on coloaded SrTiO3:Rh/C/BiVO4:Mo sheet illuminated with simulated
an Au or C layer attained an STH of above 1.0% with an AQY sunlight (AM 1.5G) in pure water for overall water splitting. (b)
of above 30% at 420 nm in pure water (Figure 24a).392,394 Z- Photographic image of a 30 cm × 30 cm printed SrTiO3:Rh/ITO
scheme overall water splitting has also been demonstrated over NPs/BiVO4:Mo sheet. (c) Time courses of the water splitting
various narrow bandgap photocatalysts (including reaction on Cr2O3/Ru coloaded SrTiO3:Rh/ITO NPs/BiVO4:Mo
LaMg1/3Ta2/3O2N (ref 396,397) and Ga-doped (red) and SrTiO3:La,Rh/Au NPs/BiVO4:Mo sheets (blue) under
La5Ti2Cu0.9Ag0.1S5O7 (ref 398)) using a photocatalyst sheet simulated sunlight (AM 1.5G). Hydrogen and oxygen are indicated by
configuration. It is also worth noting that printable photo- closed and open circles, respectively. Reprinted (b) and (c) with
permission from ref 395. Copyright 2018 Elsevier.
catalyst sheets composed of SrTiO3:La,Rh as the HEP,
BiVO4:Mo as the OEP, and nanoparticulate ITO as the
conductive mediator (SrTiO3:La,Rh/ITO NPs/BiVO4:Mo) need for vacuum processes during fabrication using readily
have been developed for efficient photocatalytic pure water accessible screen printing techniques.
splitting (Figure 24b and c).395 SrTiO3:La,Rh/ITO NPs/
BiVO4:Mo sheets having large active areas (30 cm × 30 cm) 3. CHARGE SEPARATION AND TRANSPORT
can be readily prepared via screen printing. Such photocatalyst Ultimately, the QE of the photocatalytic process is dictated by
sheets outperform analogous systems containing Au NPs as the the photoexcited carriers, which are involved in kinetic
conductive mediator owing to the unique properties of ITO competition between participation in the desired reactions
nanoparticles, such as high visible light transparency and low and recombination with one another. To promote the
electrochemical activity during oxygen reduction. Conse- photocatalytic reaction, photoexcited charge carriers must
quently, printable SrTiO3:La,Rh/ITO NPs/BiVO4:Mo sheets reach the redox-active sites on the photocatalyst surfaces and
decompose water with an STH of 0.4%, demonstrating that interfacial charge transfer must occur to extract and separate
efficient solar hydrogen production can be realized without the the charges. Typically, the excitons are in the Mott−Wannier
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Chemical Reviews
Figure 25. Electron energy profile for an n-type semiconductor in equilibrium with the electrolyte.403,405
mode in bulk semiconductors due to the large exciton radius,
whereas the Frenkel mode is dominant in organic molecules
and polymers. 399 These two exciton models involve
representative binding energies of less than 0.01 and 1 eV,
respectively, and efficient separation of excited electrons and
holes is only realized when the exciton binding energy is lower
than these values.399 The exciton binding energy, in turn, is
primarily determined by the effective masses and dielectric
constants, which are dependent on the electronic structures of
the semiconductors. Oxides tend to have extremely low exciton
binding energies due to their high dielectric constants.
Consequently, the dynamics of oxides is dominated by free
charges.
Once the photoinduced electrons and holes are separated,
these carriers must migrate from the bulk of the semiconductor
to the active sites on the surface to drive the catalytic reactions.
The average time required for the annihilation of the
photoexcited carriers is termed the carrier lifetime, τ, and is
an indicator of the extent to which a semiconductor can be an
effective photocatalyst. However, the carrier lifetimes of
semiconductor photocatalysts are typically short, ranging
from the picosecond to nanosecond scale and are similar to
the recombination time scale.400−404 The ability of photo-
generated carriers to diffuse through the semiconductor is
represented by their diffusion coefficient, D, which in turn is
related to their drift mobility, μ, through the Einstein relation:
kBT
D= μ electrolyte, the majority charges near the interface of the
q (3.1)
where kB is the Boltzmann constant, T is the absolute
temperature, and q is the electrical charge of a particle. The
average distance a carrier diffuses before it recombines with
another carrier is the diffusion length, L, and is given by
L = (Dτ )1/2 (3.2)
The electronic structure of the semiconductor determines not
only the absorption coefficient but also the charge carrier
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concentration, and these factors affect the carrier lifetime and
diffusion length.18
The equilibrium carrier momentum distribution is given by
the Fermi−Dirac distribution:22
1
f (E ) =
(
exp
E − EF
kBT )+1 (3.3)
where
ℏ2k 2
E = Ei +
2m* (3.4)
Here, f (E) is the probability that a carrier state having an
energy value E is occupied at equilibrium, m* is the effective
mass, ℏ is Planck’s constant divided by 2π, Ei is the band edge
energy, and EF is the Fermi energy. In the case of a
photocatalytic water splitting system without the application
of an external electric field, the occupation of a state with
momentum + ℏk is the same as that of a − ℏk state.
Consequently, there is net cancellation of momenta and no net
current flow. Thus, as a consequence of their random thermal
motion, free carriers tend to diffuse from regions of high
concentration to regions of low concentration. This diffusion is
evidently an inefficient form of carrier transport, and thus it is
vital to create potential gradients to accelerate the movement
of free charge carriers.
When a semiconductor is placed in contact with an
semiconductor will flow into the electrolyte until the EF of the
semiconductor equals the redox potential (E0) of the
electrolyte while preserving the band edge positions. This
mobility of the majority carrier generates an interfacial electric
field near the interface, known as the surface charge layer (or
depletion region). As illustrated in Figure 25, photogenerated
free minority charge carriers (that is, holes) in a typical n-type
semiconductor will migrate toward the electrolyte as a result of
upward band bending. This effect increases the carrier lifetime
within the surface charge layer compared to the bulk. In
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addition, electrons can be thermally activated over the entire
electric potential in the semiconductor surface charge layer,
thereby crossing the interface by catching acceptor species in
the electrolyte.405 The electrons can also tunnel through some
portion of the electric potential barrier and subsequently
proceed into the electrolyte.405 Notably, the degree of band
bending is usually less pronounced in the case of colloidal
nanoparticles, as shown in Figure 26. As the particle radius are
Figure 26. Space charge layer formation in large and small n-type
semiconductor particles in equilibrium with a solution redox system
for which the Fermi level is E0.399,406,409 W indicates the width of the
space charge layer. In the small particle, band bending is negligibly
small.
comparable to or smaller than the width of the space charge
region, the electric field will penetrate the whole particle and
will effectively minimize the band bending.26,406−408
3.1. Challenges
3.1.1. Recombination. In response to illumination,
electrons and holes pairs are generated in the CB and VB,
respectively. Electrons subsequently tend to fall from the CB to
the VB, thereby eliminating VB holes via recombination and
reducing the carrier concentrations back to their equilibrium
values. In semiconductor photocatalysts, this recombination
process can happen via radiative (band-to-band) recombina-
tion or, more commonly, recombination through traps (defects
or impurity states) in the forbidden gap (Figure 25). Different
materials can exhibit vastly different bulk recombination
kinetics. As an example, hematite exhibits a recombination
rate 100−1000 times faster than that of anatase TiO2 under
comparable conditions, as confirmed by TAS measurements,
possibly due to the localized Fe-centered d−d nature of the
optical transition in hematite.400,403 Band-to-band recombina-
tion is considered to be dominant in direct bandgap
semiconductors as a result of the density of available electrons
and holes. Conversely, in indirect bandgap semiconductors,
recombination predominantly occurs through a single level
trap located at an energy level within the forbidden gap, also
commonly referred to as Shockley−Read−Hall recombination,
and is facilitated by an energy exchange with a phonon.399
Electron−hole recombination can also occur via recombina-
tion at surface states, and this phenomenon plays an important
role in suspensions of NPs or colloids with high surface
areas.410,411 When photogenerated electrons are removed in
association with the reduction reaction more rapidly, holes are
left because they react more slowly with water to form oxygen.
If these holes are trapped in surface states, a change in the
potential drop across the Helmholtz layer will form, unpinning
the band edge. Such band edge unpinning will exacerbate the
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effects of surface recombination, leading to low QE during
light-driven water splitting.412 It has been suggested that, for
many semiconductor photocatalysts, improvements in charge
separation lifetimes by factors of 103−109 are required to
enable efficient utilization of the photogenerated charges
because electron−hole recombination proceeds so much more
rapidly than the interfacial reactions.413
3.1.2. Trapping. Injected electrons have been observed to
become trapped in energy levels distributed across the
forbidden gap on a time scale of picoseconds to nanoseconds
in a range of materials, including TiO2,414−416 BiVO4,401 g-
C3N4,417 GaN:ZnO,418 and Ta3N5.419 The trapping of a carrier
in a shallow energy level near the band edge may result in
spatial electron−hole separation and prolong the charge
lifetime into the microsecond time scale.415,420 Nonetheless,
charge trapping also decreases the carrier energetics and
mobility. As an example, a high concentration of deeply
trapped electrons was identified in g-C3N4 samples.417 These
carriers exhibited a long lifetime on the microsecond to second
time scale, but could not migrate to electron acceptors or
catalytic sites. Such electrons, therefore, were not only unable
to participate in H2 generation but also severely impeded the
accumulation of the holes required for water oxidation.
3.2. Strategies
3.2.1. Short Charge Carrier Migration Distances. The
most straightforward approach to reducing the charge carrier
migration distance is to decrease the photocatalyst particle size.
Ideal electron−hole collection is possible with suspended NPs
if their size is less than the electron and hole diffusion
lengths.26 The synthesis method and conditions as well as the
starting materials greatly affect the obtained particle size. A
good example of enhanced photocatalytic activity as a result of
a smaller particle size was provided in work with La-doped
NaTaO3 (NaTaO3:La). In this work, NiO-loaded NaTaO3:La
was developed as an effective photocatalyst for water splitting
to give H2 and O2 under UV irradiation, showing an AQY of
56% at 270 nm.85 The photocatalytic activity of this material
was nine times that obtained from a nondoped analogue,
presumably due to a decreased particle size with a high degree
of crystallinity being maintained (Figure 27). The photo-
Figure 27. Mechanism associated with highly efficient water splitting
over a NiO/NaTaO3:La photocatalyst. Reprinted with permission
from ref 3. Copyright 2009 The Royal Society of Chemistry.
generated carriers in this catalyst were able to efficiently
migrate over short distances to reach active sites on the surface
without recombination. Doping Ca, Sr, or Ba into the NaTaO3
had similar effects as the La doping, resulting in smaller particle
sizes and improved photocatalytic activity during overall water
splitting under UV light.421
An alternative strategy to combat poor carrier diffusion
lengths is to ensure that carriers are predominantly generated
at the surface. One means of achieving this is through the
construction of a core/shell structure in which the particle
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surface is enriched with a light responsive component. This
strategy has proven to be an effective approach to overcoming
short charge carrier diffusion lengths. As an example,
monodisperse Ta3N5 hollow spheres with a thickness of
approximately 40 nm have been obtained using transparent
spherical silica as a hard template, as shown in Figure 28.422
Figure 28. (a) Design principle for a core/shell Ta3N5 photocatalyst
loaded with two separate cocatalysts as effective charge collectors for
water splitting. (b) Time courses of H2 evolution on Ta3N5/Pt/SiO2
(TPS) core/shell particles, Ta3N5/Pt (TP) hollow spheres, and a bulk
Ta3N5 photocatalyst. Reprinted with permission from ref 422.
Copyright 2013 Wiley-VCH.
The carrier recombination probability in this material was
further diminished by modifying the photocatalyst with
spatially separated cocatalysts. Specifically, an HEC (Pt) was
loaded on the inner Ta3N5 shell surface as an electron collector
and an OEC (IrO2 or CoOx) was coated onto the outer shell
surface as a hole collector. This core/shell Ta3N5 photocatalyst
showed notably enhanced water reduction and oxidation
performance under visible light irradiation compared to bulk
Ta3N5.422 A two-step solid state reaction utilizing SrTiO3 as a
perovskite-type host produced a core/shell-structured La and
Rh codoped material (SrTiO3:La,Rh), the surface of which was
enriched with the dopants.268 Under visible light, the surface
layer over which the dopants were distributed absorbed light
via a transition from electron donor levels formed by the Rh3+
ions to the CB of the SrTiO3, whereas the SrTiO3 core was
inactive. Because the photoactive Rh3+ ions were densely
deposited over the surface of the core/shell structure,
photoexcited carriers were able to migrate to surface active
sites more readily and efficiently. As a result, compared to
samples with more homogeneous dopants, the core/shell-type
SrTiO3:La,Rh exhibited higher photocatalytic activity during
hydrogen evolution from an aqueous solution of methanol (as
the SED) under visible light. The effect of using nanoscale
particles on the extraction of short-lived minority carriers was
also evident in work with Fe2O3 NPs, which produce oxygen at
a higher rate than bulk Fe2O3 during the water oxidation
reaction with AgNO3 as the SEA.423 It is important to
emphasize that, even when aiming for a decreased carrier
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migration distance in such materials, the particle size in the
photocatalyst must still be carefully tuned. As discussed in
section 2, extremely small particles may suffer from insufficient
light absorption, which reduces the quantity of photogenerated
carriers. The highest possible degree of light absorption can be
achieved by optimizing the particle concentration and optical
path length of the reaction vessel.26 One or two-dimensional
(1D/2D) materials are emerging as attractive candidates for
applications in photosynthesis because of their larger specific
surface areas to provide more reactive sites and shorter carrier
diffusion lengths to restrain the recombination.424,425 As an
example, C3N4 nanosheets produced hydrogen from water
more efficiently compared to bulk C3N4 with or without
sacrificial reagents.426−428
3.2.2. Reduction of Defects. While some defects serve as
shallow trapping sites or active sites and thus improve charge
separation and overall performance,402,429−431 the reduction of
killer defects both in the bulk and at the surface of a
photocatalyst is still a major goal for particulate photocatalysts
used in solar water splitting.432,433 This is because many
defects have been shown to function as recombination centers
for photoexcited carriers and thus are detrimental to the
performance of photocatalytic systems.56,208,429,434−436 The
defect concentration and type are both greatly affected by the
synthesis process.173,437−443 The effect of structural defects on
the ability of a photocatalyst to generate a photovoltage and to
reduce protons has been investigated using g-C3N4.435 On the
basis of the results of SPV measurements, a monotonic
decrease in the photovoltage was observed as the synthesis
temperature was increased. These results were in agreement
with a loss of photoexcited charge carriers and a lowered quasi-
Fermi energy state in the illuminated sample. Both SPV and PL
results not only demonstrated two types of defect near the
CBM and VBM of g-C3N4, as presented in Figure 29, but also
afforded evidence that these defects served as e − /h +
recombination sites, thereby reducing the free carrier
concentration in the illuminated g-C3N4 and hindering
photocatalytic hydrogen production. The synthesis of poly-
meric C3N4 can be modified using a molten salt flux technique
to produce a more homogeneous product.442,444 The addition
of a salt mixture (ca. NaCl/KCl) has been shown to tailor the
crystallinity and grain boundary structure in the resulting
material as well as to limit the formation of defects. This
molten salt synthesis has been used to obtain a number of
photocatalysts with high degrees of crystallinity and fewer
defects, such as SrTiO3,445 (La-doped) NaTaO3,446,447
PbTiO 3 , 4 4 8 Sn 2 TiO 4 , 4 4 9 , 4 5 0 La 2 Ti 2 O 7 , 4 5 1 Ta 3 N 5 , 4 5 2
Na2Ca2Nb4O13,453 and BaNb1−xTaxO2N.454 This is possible
due to the ability of molten salts to accelerate the diffusion of
constituent ions and to control the crystal growth process
during the synthesis. Heptazine-based crystalline C3N4 with
fewer defects can also be synthesized by the ionothermal
method, resulting in a lower photogenerated electron−hole
recombination rate.443,455 In addition, optimized postsynthesis
calcination in an NH3 or H2S atmosphere was found to further
decrease the defect densities in (oxy)nitrides and sulfides,
respectively, thus increasing the photocatalytic activity.287,437
Ta3N5 has been considered to be a promising candidate for
photocatalytic water cleavage due to its simple chemical
composition, narrow bandgap energy of 2.1 eV, and suitable
band structure (Figure 11). However, obtaining simultaneous
H2 and O2 generation from water over this material in the
absence of sacrificial reagents had been highly challenging due
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Figure 29. (a) SPV spectra of g-C3N4 films (labeled as D52, D55,
D60, and D64, which correspond to processing temperatures of 520,
550, 600, and 640 °C) on ITO substrates along with the UV−visible
spectrum (dark-yellow line) of D52. The gray bar represents the
optical bandgap of the materials. (b) An energy diagram for g-C3N4,
showing the levels for defect 1 (at +0.97 V), defect 2 (−0.38 V), and
ITO (+0.76 V). Reprinted with permission from ref 435. Copyright
2014 The Royal Society of Chemistry.
to a significant degree of charge recombination at defects. Very
recently, Ta3N5 nanorod single crystals were grown on lattice-
matched cubic KTaO3 particles through a brief nitridation
process (Figure 30).182 Following the loading of Rh/Cr2O3 as
a cocatalyst, the single-crystal Ta3N5 nanorods yielded H2 and
O2 in a molar ratio close to the expected stoichiometric value
of 2:1 under visible light and simulated sunlight. The
associated AQE values were 2.2% at 320 nm (±25 nm),
0.22% at 420 nm (±25 nm), and 0.024% at 500 nm (±25 nm).
This achievement is ascribed to the minimized grain
boundaries and surface defect states in the Ta3N5 single
crystals. These results clearly demonstrate that semiconductors
can only operate at their full potential if impurities and killer
defects can be controlled.
It is noteworthy that Osterloh has proposed that the
deposition of layers made of conductive and diamagnetic
semiconductors on photocatalysts may passivate the surface
states that give rise to recombination, similar to the design of
photovoltaic devices.25
3.2.3. Junctions. Long carrier lifetime is an indispensable
requirement for photosynthetic devices driving the multi-
electron reactions associated with fuel synthesis, which
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Review
typically necessitates the spatial separation of charge carriers
across an interface. A simplified two-dimensional numerical
model developed by Takanabe et al. demonstrated that charge
separation potential gradients are only present in limited,
highly constrained regions near the semiconductor surface.
Consequently, the QE is exclusively governed by recombina-
tion in the bulk of the photocatalyst particles.456 To ensure the
extraction of majority carriers from the semiconductor, it is
essential to form a low-loss electronic contact (e.g., an Ohmic
or tunnel junction contact). Hence, the junctions generated
between metals and semiconductors, between semiconductors
with different gaps, and between the electrolyte and the
semiconductor have a significant effect on the properties of
PEC and photocatalytic devices because the motion of charge
carriers must be adequately guided by potential gradients.
Several parameters play decisive roles in the efficiency of such
junctions, including the built-in potential, the carrier
concentration, and the carrier mobility.26
The most common means of extracting charge carriers is
surface modification of the photocatalyst with metal NPs, such
as by loading a cocatalyst. The relative position of the work
function (ϕM) of the metal and EF of the semiconductor at the
metal−semiconductor interface determine whether a Schottky
barrier or Ohmic contact is generated. A ϕM value larger than
EF is typically required to form an Ohmic contact with a p-type
semiconductor. Gold (ϕM = 5.1 eV), platinum (ϕM = 5.7 eV),
and rhodium (ϕM = 5.0 eV) are thus candidates for the
formation of Ohmic contacts and therefore are widely
employed as HECs. Nonetheless, owing to the deep EF
position of typical p-type photocatalysts, a Schottky barrier is
normally generated even in contact with Pt. While there have
been claims that the Schottky barrier height is often
independent of the metal employed,22 the barrier height has
also been reported to be correlated with the electronegativity
of the metal and the nature of the semiconductor.18,457 In this
configuration, the electrons can only flow from the semi-
conductor to the metal via thermionic emission and tunneling
effects.22,399 As such, when using n-type materials, an Ohmic
contact can be created by employing a conductive metal with a
ϕM value smaller than EF, as depicted in Figure 31. This
strategy has been successfully employed to fabricate effective
photoanodes in which the metals function as contact layers and
withdraw electrons from semiconductors. These systems have
included Ti/BiVO4,458 Ta/SrTiO3,459 Ta/LaTiO2N,460 and
Ta/BaTaO2N.461
Another frequently applied strategy for the extraction of
photoexcited electrons from the semiconductor to diminish the
probability of charge carrier recombination is the construction
of composites with other semiconductors. A homojunction
refers to a phase junction that facilitates charge carrier transfer
and separation in the interface region between two different
phases in close contact, such as in the case of TiO2.462−464 The
phase junction formed between surface anatase NPs and
underlying rutile particles is believed to have improved the
photocatalytic performance of the TiO2. Carrier migration at
this rutile/anatase phase junction was assessed using Kelvin
probe force microscopy (KPFM) and spatially resolved surface
photovoltage spectroscopy (SRSPS), as illustrated in Figure
32.465 In this system, a built-in electric field of up to 1 kV/cm
was generated at the phase junction interface, pointed toward
the rutile material, and so photoexcited electrons flowed from
the rutile to anatase phase under UV irradiation. The effect of a
Ga2O3 phase junction on photocatalytic performance was also
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Figure 30. (a−d) Annular dark-field scanning transmission electron microscopy (ADF-STEM) images of Ta3N5/KTaO3. (e) Crystal structures of
Ta3N5 and KTaO3 (d indicates the interplanar distance). (f−i) Colorized and magnified ADF-STEM of Ta3N5/KTaO3 with different nitridation
time. (j) Time courses of gas evolution during overall water splitting over Rh/Cr2O3-modified Ta3N5/KTaO3 under simulated sunlight. The dashed
lines represent the evacuation of the reaction system (evac). (k) AQE as a function of the incident light wavelength for overall water splitting over
Rh/Cr2O3-modified Ta3N5/KTaO3. Reprinted with permission from ref 182. Copyright 2018 Springer Nature Publishing AG.

Figure 32. Schematic showing the application of cross-sectional

KPFM to gain the transfer direction of photogenerated electrons and
holes at the interface of a TiO2 phase junction. Reprinted with
permission from ref 465. Copyright 2017 American Chemical Society.

Depending on the two semiconductors employed, the

Figure 31. Energy band diagrams of metal and n-type semiconductor
contacts. (Evac = vacuum energy, Ec = energy of CB minimum, Ev =
energy of VB maximum, ϕm = metal work function, ϕs =
semiconductor work function, χs = electron affinity of the semi-
conductor). Reprinted with permission from ref 409. Copyright 2012
American Chemical Society.
investigated using an α−β phase junction with Ga2O3.46 A
drastically enhanced photocatalytic overall water-splitting rate
was observed on Ga2O3 in conjunction with an α−β phase
junction compared to specimens having solely α or β phase
structures. Upon irradiation, photoexcited electrons were
transferred from the α phase to the β phase, while holes
flowed in the opposite direction.
AI
resulting heterojunction can be classified as a p−n junction
(Figure 33) or either a n−n or p−p junction. Descriptions of
typical n-type and p-type photocatalysts are provided in Figure
34. In prior work, a photocatalytic nanodiode consisting of p-
type CaFe2O4 and n-type PbBi2Nb1.9W0.1O9 was developed by
Lee et al.466 A nanodimensional p−n junction was created by
dispersing CaFe2O4 nanoislands over a highly crystalline
layered perovskite base lattice made of PbBi2Nb1.9W0.1O9
(Figure 35).467 The operation of this photocatalytic nanodiode
was initiated by the absorption of light, which generated
electron−hole pairs in both the n- and p-type semiconductors.
The resulting photoelectrons are believed to migrate across the
p−n junction from the CaFe2O4 to the PbBi2Nb1.9W0.1O9,
while the holes move in the opposite direction. Consequently,
the carriers are efficiently separated, resulting in high activity
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Figure 33. Forming a p−n junction. (a) Both p- and n-type regions before junction formation. (b) Schematic of the junction and the band profile
showing the semiconductor bands. ECB,n, EVB,n, and EF,n indicate the CBM, VBM, and Fermi level of a n-type semiconductor. ECB,p, EVB,p, and EF,p
indicate the CBM, VBM, and Fermi level of a p-type semiconductor.

Figure 34. Bandgaps and band positions of (a) n-type semiconductors and (b) p-type semiconductors used for composite photocatalyst
heterojunctions.470,471 Data were respectively obtained from ref 472 and ref 473 for CuNb3O8 and MnV2O6.

with a QE of 38% during the production of oxygen in the
presence of AgNO3 as an SEA. Notably, this p−n junction is
distinct from Z-scheme systems consisting of a p-type HEP
and an n-type OEP.387 In this configuration, the electrons
transfer from the CB of the p-type material to the CB of the n-
AJ
type material, whereas electrons flow from the CB of the n-
type material to the VB of p-type material (i.e., recombine) in a
Z-scheme system. Lee et al. have also reported a photocatalytic
diode composed of n-CdS/p-AgGaS2 that exhibits a higher
hydrogen evolution rate than CdS or AgGaS2 single composite
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Chemical Reviews
Figure 35. (a) High-resolution transmission electron microscopy image showing nanocrystalline p-CaFe2O4 islands decorating a large n-
PbBi2Nb1.9W0.1O9 particle. (b) Schematic of the p−n heterojunction driving water oxidation. (c) Energy band model of a p−n heterojunction.
Reprinted with permission from ref 467. Copyright 2012 Elsevier BV.
from water containing the S 2−/SO32− pair as a hole
scavenger.468 Very recently, n-CdS/p-Cu7S4 heterostructured
nanocrystals with p−n junctions were found to promote
photocatalytic hydrogen production in an aqueous solution
containing Na2S and Na2SO3 under near- to shortwave-IR light
(up to 2500 nm), with an AQY of 3.8% at 1100 nm (Figure
36).469 TAS data have demonstrated that the hot carriers
generated in the Cu7S4 LSPR band are injected into the CB of
Figure 36. (a) Hot electron injection at a plasmonic p−n
heterojunction upon infrared light plasmon excitation. (b) The
AQY for the HER over CdS/Cu7S4 heterostructured nanocrystals
under monochromic light and the absorption spectrum of this
material. Reprinted with permission from ref 469. Copyright 2019
American Chemical Society.
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Review
the CdS in response to femtosecond laser pulses, indicating
efficient hot electron injection and charge separation over a
long time span (>273 μs) at the p−n heterojunction. The
electrons in the CB of the CdS phase drive the reduction of
protons to produce H2, while holes remaining in the Cu7S4 are
consumed by sacrificial agents.
There have been many applications of n−n junctions to the
promotion of charge separation and photocatalytic perform-
ance, whereas photocatalytic composites based on p−p
junctions have rarely been examined. The n-CdS/n-TiO2
system was one of the first photocatalyst composites based
on n−n junctions and has been intensively investigated.474−476
This composite was found to generate H2 much faster than a
CdS single photocatalyst from water containing the S2−/SO32−
pair as the SED under visible light.474 TAS data demonstrated
that the charge injection process from the CB of CdS to the
CB of TiO2 is very rapid (within 18 ps),475 and this rapid
electron transfer across the junction is believed to be the most
important factor reducing recombination. Electron movement
in a CdS/TiO2 composite was also investigated using time-
resolved microwave conductivity.477 The results showed that
the photoexcitation of CdS grown on TiO2 leads to efficient
electron injection into the TiO2, generating long-lived charge
carriers. The QE for electron injection into TiO2 per photon
absorbed by the CdS was reported to be close to unity. Well-
defined heterojunctions have also been established in La, Cr-
codoped Sr2TiO4 (n-Sr2TiO4:La,Cr) and La, Cr-codoped
SrTiO3 (n-SrTiO3:La,Cr) by matching the lattice fringes of
SrTiO 3 :La,Cr and Sr 2 TiO 4 :La,Cr. 478 The Sr 2 TiO 4 /
SrTiO3:La,Cr photocatalyst exhibited photocatalytic activity
up to 6.4 and 3.0 times those obtained from SrTiO3:La,Cr and
Sr2TiO4:La,Cr, respectively. In this composite, the CBM of
SrTiO3:La,Cr is more negative than that of Sr2TiO4:La,Cr,
while the VBM of Sr2TiO4:La,Cr is more positive than that of
SrTiO3:La,Cr. Upon light irradiation, photoexcited electrons
readily flow from the SrTiO3:La,Cr to the Sr2TiO4:La,Cr, while
holes move in the opposite direction. An important
consequence of this process is the efficient separation of
charge carriers, which has been confirmed by the observation
of long-lived electrons during studies with time-resolved
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Figure 37. (a) Synthesis of SrTiO3@TiO2 hollow multishelled structures via a hydrothermal reaction. (b) Durability of the composite during
overall water splitting based on reuse after each 5 h trial. (c) Proposed band structure diagram. Reprinted with permission from ref 479. Copyright
2019 Wiley-VCH.
Fourier transform infrared spectroscopy. Promising results
have been obtained from photocatalytic water splitting with
SrTiO3/TiO2 heterojunctions having a hollow multishelled
structure.479 These SrTiO3/TiO2 junctions were constructed
by applying a coating of SrTiO3 onto a TiO2 surface via a facile
hydrothermal method. This material exhibits an improved
water splitting rate compared to that of SrTiO3 NPs, with an
AQY gain of 8.6% at 365 nm. Two possible transfer paths for
the photogenerated carriers have been proposed to occur in
SrTiO3/TiO2 junctions (Figure 37). On the surfaces of the
shells, electrons generated in the SrTiO3 directly reduce
protons to generate H2 on the Pt cocatalyst, while holes
participate in the water oxidation reaction to produce O2.
Conversely, in the interiors of the shells, the photoexcited
electrons and holes move from the CB of the SrTiO3 to the CB
of the TiO2 and from the VB of the TiO2 to the VB of the
SrTiO3, respectively, thus providing electron−hole pair
separation. In addition to the limited degree of carrier
recombination in this material, its light absorption ability was
also increased owing to the hierarchal shell structure, which
enabled multiple reflections of incident light. For all these
reasons, the photocatalytic water splitting performance of this
catalyst was enhanced. An analogous junction was employed to
obtain efficient charge separation in (oxy)nitride combina-
tions.480−482 In particular, a simple ammonia thermal synthesis
resulted in intimate interfaces between one-dimensional n-
Ta3N5 nanorods and n-BaTaO2N NPs, which originated from
the similar Ta-based octahedral Ta3N5 and BaTaO2N units.480
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KPFM and electrochemical impedance spectroscopy analyses
provided evidence for effective interface charge separation in
the Ta3N5/BaTaO2N heterostructure (Figure 38). The authors
suggested that photogenerated electrons migrated along the
1D nanorod orientation direction, while the holes moved in
the lateral direction and thus had a very short transfer distance.
A redox-mediated Z-scheme configuration combining this
Ta3N5/BaTaO2N heterostructure as the HEP and PtOx/WO3
as the OEP yielded H2 and O2 in the stoichiometric molar ratio
of 2:1 under visible light. The synergistically accelerated charge
separation process attributable to the heterostructure and 1D
nanorod structure improved the photocatalytic water splitting
activity by an order of magnitude in such Z-scheme systems
relative to systems utilizing solely Ta3N5 or BaTaO2N or a
mixture of Ta3N5 and BaTaO2N as the HEP.
The incorporation of photocatalysts into graphene-based
conductors has also been explored as an attractive strategy for
hindering electron−hole recombination. Time-resolved fluo-
rescence spectroscopy has demonstrated ultrafast electron
transfer (on the picosecond scale) from excited CdS to a
graphene sheet in graphene/CdS QD nanocomposites.483 This
result indicates that graphene acts as an electron sink/reservoir,
thereby significantly diminishing the recombination of the
photoexcited electrons and holes in the CdS QDs. A
graphene/CdS nanosheet produced H2 at a rate approximately
five times higher than that obtained from CdS alone when
lactic acid was used as the SED, with an AQE of 22.5% at 420
nm.484 The authors ascribed this high photocatalytic perform-
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Figure 38. (a) Schematic illustration of the spatial separation of
photogenerated charge carriers between the 1D Ta3N5 nanorods and
BTON nanoparticles (Red., the reduction reaction; Oxd., the
oxidation reaction; BTON, BaTaO2N). (b) Effect of cutoff wave-
length on performance (blue circles) and UV−vis DRS data (black
line) for a Ta3N5/BTON sample. (c) Z-Scheme overall water splitting
activities of a Ta3N5/BTON heterostructure. Reprinted with
permission from ref 480. Copyright 2019 Wiley-VCH.
ance to the presence of graphene, which provides conductive
channels to efficiently separate photogenerated charge carriers
in the CdS NPs (Figure 39). A review summarizing the
application of graphene/CdS nanocomposites to photo-
catalytic reactions was published in 2015.485 An analogous
promotional effect was observed in work with graphene/
TiO2,486,487 graphene/Bi2WO6,488 graphene/C3N4,489 and
graphene/Sr2Ta2O7−xNx composites490 with regard to photo-
catalytic hydrogen generation, attributed to the prolonged
lifetimes of charge carriers.
The junction formation pathway greatly enhances the
photocatalytic activity of the catalyst, and numerous
composites for light-driven hydrogen production have been
fabricated based on this principle, including ZnO/CdS,491
ZnO/ZnS,492 CdS/CeO x,493 TiO2 /MoS2/CdS,494 CdS/
CdSe,361 CdS/g-C3N4,495,496 and Co9S8/ZnIn2S4.497 The
reader is referred to several reviews discussing photocatalytic
heterojunctions in more detail and providing further
examples.432,467,470,498−502
3.2.4. Facet Control. The photocatalytic performance of
particulate semiconductors is also dictated by their crystal
planes because the reactions taking place at the surfaces or
interfaces of the materials are quite sensitive to the exposed
surface atomic structures and the corresponding physicochem-
ical properties. Spatial charge separation has been observed in a
number of single crystals between different exposed facets. As
an example, Pt serving as HECs will selectively photodeposit
on rutile TiO2 {110} facets, while PbO2 particles acting as
OECs will be loaded on {011} facets preferentially, implying
that these facets provide reduction and oxidation sites,
respectively.503 The separation of electron−hole pairs on
faceted rutile crystals is attributed to the lower electronic
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Review
Figure 39. (a) Schematic illustration of charge separation and transfer
in the graphene/CdS system under visible light. (b) Comparison of
the visible light photocatalytic activities of samples with various
graphene amounts during H2 production using an aqueous lactic acid
solution as a sacrificial reagent and Pt as a cocatalyst. Reprinted with
permission from ref 484. Copyright 2011 American Chemical Society.
energy levels of the {110} face compared to those of the {011}
face.
An analogous effect has been observed in the case of
BiVO4.504,505 Here, reduction reactions involving electrons and
oxidation reactions involving holes occur separately on the
{010} and {110} facets upon photoirradiation, as shown in
Figure 40. A Pt/MnOx/BiVO4 sample with metallic Pt and
MnOx particles selectively photodeposited on the {010} and
{110} facets, respectively, exhibited much higher oxygen
production from an aqueous solution of NaIO3 (as the SEA)
during photocatalytic water oxidation compared to materials in
which the cocatalyst was loaded at random sites using
impregnation. This result suggests that photocatalytic perform-
ance can be enhanced to the greatest extent only if the
reduction/oxidation cocatalysts are selectively deposited on
their preferred reaction facets, in agreement with simulation
results from Takanabe and co-workers.456 SRSPS data have
provided direct evidence for highly anisotropic photogenerated
charge separation on different facets of a single BiVO4
crystal.506 The SPV signal intensity on the {011} facet was
70 times stronger than that on the {010} facet, demonstrating
that much greater band bending was induced by the built-in
electric field in the surface charge region of the {110} facet
than that in the vicinity of the {010} facet. This observation is
consistent with the fact that photogenerated holes tended to
accumulate on {110} facets. A DFT simulation using a small
polaron model also supported these results.507 The outcome
suggested that the mobility of electrons along the {010}
direction was 5 orders of magnitude larger than that along the
{110} direction, while the mobility of holes along the {110}
direction was 2 orders of magnitude greater than that along the
{010} direction. On the basis of these results, precise tuning of
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Figure 40. SEM images of (a) BiVO4, (b) Au/BiVO4, (c) Pt/BiVO4, (d) Ag/BiVO4, (e) MnOx/BiVO4, and (f) PbO2/BiVO4. Scale bar = 500 nm.
(g) Photocatalytic water oxidation performance of BiVO4. Reprinted with permission from ref 504. Copyright 2013 Macmillan Publishers Limited.

Figure 41. Schematic showing the driving force for charge separation in (a) PEC and photocatalyst particles, and in particles with (b) symmetric
built-in electric fields, (c) anisotropic built-in electric fields on different facets, and (d) asymmetric cocatalyst assembly. Reprinted with permission
from ref 509. Copyright 2018 The Royal Society of Chemistry.

the crystalline phase and morphology of monoclinic BiVO4
crystals was achieved through regulating the acidity of the
reaction solution in conjunction with hydrothermal synthesis.
The photocatalytic activity during water oxidation over a
BiVO4 crystal having a specific configuration of {010} and
{011} exposed facets was 50 times that obtained from
tetragonal BiVO4 particles.508
The SRSPS technique has confirmed that anisotropic
photoinduced charge transfer depends strongly on the built-
in electric fields in the space charge regions of different facets.
On this basis, Li et al. proposed a nanocrystal morphology
tailoring strategy to accelerate spatial carrier separation and
improve photocatalytic performance (Figure 41).509 By tuning
the morphology of the photocatalyst particles, the difference
between built-in electric fields at different facets can be
accentuated, creating a net driving force for charge separation
(Figure 41c). In addition, the symmetry of the surface built-in
electric fields can be increased by the asymmetric assembly of
AN
cocatalysts (Figure 41d). The facet engineering of cubic
SrTiO3 nanocrystals has validated this prediction.510 The
spatial separation of reduction and oxidation sites on SrTiO3
was observed in work with 18-facet nanocrystals after forming
{110} facets at the intersections of {001} facets. After the
optimized loading of Pt at the reduction sites (that is, the
{001} facets) and Co3O4 at the oxidation sites ({110} facets)
on the 18-facet SrTiO3, a 5-fold improvement in the AQY for
photocatalytic water splitting was achieved compared to that
obtained from 6-facet SrTiO3 with isotropic facets.
To date, photocatalysts enclosed by well-defined facets have
been widely explored, including anatase TiO2,511−514 rutile
TiO2,515 Cu2O,516 CdS,517 Ag3PO4,518 and WO3,519 with the
aim of achieving photocatalytic hydrogen or oxygen evolution
in aqueous solutions containing scavengers. It appears that the
separation of reduction and oxidation sites on different crystal
facets is a common phenomenon in such semiconductor
nanocrystals, and a comprehensive review summarizing
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progress in the facet engineering of photocatalysts for water The HER via hydronium ion reduction in acidic conditions
splitting was published very recently.520 is believed to proceed via either the Volmer−Tafel or Volmer−
Charge separation in such materials driven by asymmetric Heyrovsky mechanisms, written as526,530,531
light irradiation has also been reported.521 Using a high-
symmetry Cu2O photocatalyst particle as a prototype, one (Volmer) H3O+ + e− + ∗ F H* + H 2O(l) (4.5)
study demonstrates that asymmetric light illumination (based and
on the photo-Dember effect) produces a charge mobility
difference to generate a driving force for charge separation. (Heyrovsky) H* + H3O+ + e− F H 2(g) + H 2O(l) + ∗
This driving force is equal to or even stronger than that (4.6)
provided by conventional built-in electric fields, thereby
allowing the photogenerated carriers to be efficiently separated together with
during solar-driven chemical reactions. (Tafel) 2H* F H 2 + 2∗ (4.7)

4. SURFACE CHEMICAL REACTIONS
The water splitting reaction ends with the consumption of
photoexcited carriers that reach the surface, via the HER and
OER, as discussed in section 1. It is evident that the kinetics of
the OER and HER processes significantly affect the perform-
ance of a photocatalyst. The thermodynamically uphill water
splitting reaction, which involves a high activation energy or
overpotential, generally suffers from low activity. In particular,
the multistep proton-coupled electron transfer process in the
OER is kinetically sluggish. TA data shows that O2 generation
on TiO2 proceeds on the seconds time scale and so is much
slower than H2 production, which takes place on the hundreds
of microseconds time scale.522 The mechanism for the
electrochemical OER in an acidic environment involves the
four electron reaction paths:523−528
H 2O(l) + ∗ F HO* + H+ + e− (4.1)
In the case of the HER, the strength of the M−H bond (where
M is a transition metal) is employed as an atomic-level activity
descriptor.532 The free energy diagram for two pairs of
reversible reactions involving oxygen and hydrogen demon-
strates that the rate-determining step for the OER is the
formation of the OOH* state, while the formation of the H*
state is the potential-determining step for the HER when the
Volmer−Heyrovsky mechanism (eqs 4.5 and 4.6) is assumed
(Figure 42).529 However, the literature contains conflicting
reports regarding the rate-determining step in the HER
process.533 The current view appears to be that different
facets of the metal catalysts allow different reaction

HO* F O* + H+ + e− (4.2)

O* + H 2O F HOO* + H+ + e− (4.3)

and
HOO* F ∗ + O2 (g) + H+ + e− (4.4)

Here, the * symbol represents a catalytically active surface

site, and OH*, O*, and OOH* denote the surfaces with the
corresponding chemisorbed species residing at an active site.
Each oxidation step creates a proton that is ejected into the
electrolyte, balancing the protons consumed at reduction sites.
First-principles periodic DFT calculations have demonstrated
that the lowest possible theoretical overpotential for the OER
on a wide variety of oxides is defined by an approximately
constant difference between the binding energies of HOO*
and HO*.523 The origin of the scaling relationship between
HOO* and HO* is attributed to the binding of both to the
surface through an oxygen atom via a single bond. In contrast,
the linear relation between the binding energy of O* and HO*
commonly shows a slope of 2 because O* forms two bonds
with the surface. Rarely, some catalysts have been found to Figure 42. Plots of Gibbs free energies of reactive species and of the
operate at this minimum theoretical overpotential. However, chemisorptions of intermediates (horizontal lines) versus the reaction
various catalyst materials, including rutile, perovskite, spinel, coordinate of (a) the HER and (b) OER. Blue lines and red lines
rock salt, and bixbyite oxides, are further burdened with an indicate energetics of a typical (real) catalyst and ideal catalyst at
three different electrode potentials (E1, E2, E3), respectively. Dashed
additional overpotential generated by a suboptimal O* binding lines indicate energetics at the electrode potential at which all
energy, indicating that the overpotential is dictated by the O* thermochemical barriers disappear. ΔGi denotes the free reaction
adsorption energy such that either eqs 4.2 or 4.3 is the energy of the two elementary reaction steps. The red case corresponds
potential-determining reaction. Consequently, it has been to an overpotential-free catalyst. E° denotes the standard reversible
suggested that the OER overpotential is equal to ΔGO* − electrode potential of the HER, η is the overpotential. Reprinted with
ΔGHO*.523,529 permission from ref 529. Copyright 2010 Wiley-VCH.

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mechanisms for the HER.534−537 Additionally, it has been

proposed that hydronium ions (that is, protons) and hydroxyl
ions are more easily reduced and oxidized, respectively, than
water molecules due to the strong O−H bonds in water
molecules.18,530
Despite much work on the electrocatalytic OER and HER,
investigations regarding the connection between the surface
adsorbate binding strength and the electronic band structure of
the catalyst have remained scarce. In the case of metals, metal
oxides, and metal alloys, the d-band model was developed to
predict trends in the chemisorption energies for various
adsorbates, including simple gaseous atoms of H, C, N, and
O.538 The activation barriers and chemisorption energies were
found to depend strongly on the degree of filling of the
antibonding states on adsorption as well as the extent of orbital
overlap with the adsorbate. Repulsive coupling will occur
between an atom or molecule with a filled one-electron level
below the noble metal d bands and d states as long as the
coupling matrix element is not strong enough to push the
antibonding peak above the Fermi level. A deeper d band,
corresponding to increased filling of the antibonding states,
tends to destabilize the metal−adsorbate interaction and thus
produce weaker binding. As a result, the hydrogen adsorption
energy on an Au surface is low because Au has a filled
antibonding adsorbate-metal d state. In contrast, the energy
level of the antibonding state formed by a H 1s orbital and a Ni
d orbital is high, thus producing strong hydrogen adsorption.
In addition, based on Trasatti’s theory, the work function of
the metal substrate determines the exchange current for
electrolytic hydrogen evolution.532 The discharge at typical
overvoltages and the hydrogen removal rate close to
equilibrium is slow for sp metals, whereas hydrogen removal
is the rate-determining step for systems involving transition
metals. In perovskite oxides, occupancy of the eg/t2g orbitals of
surface transition metal cations has been demonstrated to
determine the oxygen binding energy and thus the intrinsic Figure 43. (a) Relationship between the OER catalytic activity and
the occupancy of the eg-symmetry electron of the transition metal (B
OER activity.539,540 A perovskite oxide with an eg occupancy in ABO3). Reprinted with permission from ref 539. Copyright 2011
close to unity and highly covalent transition metal−oxygen American Association for the Advancement of Science. (b) Relation-
bonds was predicted to exhibit the maximum possible OER ship between the total number of occupied states and t2g symmetry
activity, as shown in Figure 43. An analysis of graphene-based occupation. Reprinted with permission from ref 540. Copyright 2011
catalysts has suggested that the VB (v) of the graphene active American Association for the Advancement of Science.
sites hybridizes with the bonding (σ) orbital of the adsorbed
species to form bonding (v−σ) and antibonding (v−σ)* A simulated selectivity diagram (Figure 44) indicates that
states.541 It has been suggested that a higher valence orbital some typical OEPs, such as WO 3 and BiVO 4 , are
energy favors decreased filling of the antibonding (v−σ)* state, thermodynamically located in the selectivity region for H2O2
leading to stronger adsorption of OOH* and OH* production.542 Moreover, issues with stability continue to
intermediates. plague (oxy)nitrides,543 metal chalcogenide,544 and some oxide
4.1. Challenges photocatalysts, as typified by Cu2O,545 which often undergoes
severe photocorrosion. A major cause of such stability issues is
4.1.1. Side and Back Reactions. Because the evolution of that the water-splitting reaction competes with reactions
oxygen during water oxidation requires four electrons to involving lattice ions. As an example, S2− anions in CdS are
simultaneously transfer from at least two adsorbed water more susceptible to oxidation by photogenerated holes than
molecules to the semiconductor, this process is normally water in the absence of an SED, according to the reaction:
hindered in the absence of cocatalysts, in which charges can be
accumulated. Water can also be photocatalytically oxidized to CdS + 2h+ → Cd2 + + S (4.10)
form OH radicals or H2O2 through single-electron or two- Aside from the side reactions discussed above, back
electron processes, proceeding via the reactions: reactions involving molecular oxygen, such as the oxygen
reduction reaction (ORR) (eq 4.11) and water formation from
H 2O → •OH + H+ + e− E° = 2.73 V (4.8) the evolved hydrogen and oxygen (eq 4.12), are a common
problem during the simultaneous stoichiometric generation of
and H2 and O2 in the overall water splitting reaction and must be
inhibited. Many HER cocatalysts, especially noble metals,
2H 2O → H 2O2 + 2H+ + 2e− E° = 1.76 V (4.9) catalyze the ORR either thermally or electrocatalytically
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Figure 44. Phase diagram in terms of the binding energies of O*
versus OH*. The black solid line indicates the scaling line between
O* and OH* on different oxides. Reprinted with permission from ref
542. Copyright 2017 American Chemical Society.
because the hydrogen/metal-surface interaction can also
involve oxygen, and this competes with the proton reduction
process according to the reactions.538,546
O2 + 4H+ + 4e− → 2H 2O (4.11)
and
H 2 + O2 → H 2O (4.12)
This theory has been supported by experimental PEC data
for various photocatalysts, including TiO2, NaTaO3, Cr, and Sb
codoped TiO2 and SrTiO3 without cocatalysts.547 The ORR
and hydrogen oxidation reaction (HOR) preferentially proceed
in O2 and H2 saturated electrolytes, respectively, compared to
those saturated with N2. Therefore, in the case of powder
suspension systems, it is necessary to remove H2 and O2 to
drive the water-splitting reaction continuously. A notable
reduction in the photocatalytic water splitting activity is also
often observed as the pressure in the reactor increases because
these reverse reactions (eqs 4.11 and 4.12) more readily
compete at increased pressures. The overall water splitting
rates over a Ru-loaded SrTiO3:La,Rh/Au/BiVO4:Mo photo-
catalyst sheet and RuO2-loaded (Ga1−xZnx)(N1−xOx) powders
dropped to 10−40% of the original value when increasing the
background pressure from 5 to 20−30 kPa.394,548 The
suppression of these side and back reactions is thus essential
to achieving efficient overall water splitting.
4.2. Strategies
4.2.1. Cocatalysts. Cocatalysts are capable of not only
facilitating charge separation and transport through creating
junctions, as discussed in section 3.2.3., but also serve as
reaction sites and catalyze the reactions.418,549−551 The 2-fold
functioning of IrO2 on TiO2 is illustrated in Figure 45.552 Hole
transfer from TiO2 to IrO2 was estimated to occur with a rate
constant of 6 × 105 s−1, indicating that the IrO2 intercepted the
photoexcited holes coming from the TiO2 and mediated the
hole transfer process. The presence of O2 during UV
irradiation has been shown to indirectly scavenge holes in
the IrO2, whereas the electrons and holes are accumulated
without O2. Additionally, reduced oxygen scavenges trapped
holes but only in the presence of IrO2. These results indicate
that the IrO2 also catalyzes the combination of trapped holes
AQ
Review
Figure 45. Charge transfer events that follow the UV excitation of
TiO2/IrO2 containing trapped holes (left) in the presence of nitrogen
and oxygen. Reprinted with permission from ref 552. Copyright 2011
American Chemical Society.
with reduced oxygen species. Few semiconductors have been
shown to possess catalytic ability for the water oxidation and/
or proton reduction reactions, and most function primarily as
light absorbers. For this reason, cocatalysts are deposited on
the semiconductor surfaces to drive the reactions because the
surface reactions on these semiconductors are too slow to
consume the charges efficiently. Cocatalysts on the semi-
conductor also reduce the activation energy of the reactions,
thereby promoting the photocatalytic performance, as
illustrated in Figure 46.
Figure 46. Schematic of the energy diagram for photocatalytic water
splitting.
Generally, superior electrocatalysts also act as efficient
cocatalysts.18 Tafel slopes are often used to evaluate the
intrinsic properties of an electrocatalyst, as they provide the
exchange current density obtained from the material,553,554 and
a volcano plot of the exchange current density during the HER,
j0, allows a quantitative evaluation of catalyst performance
(Figure 47a). The common volcano plots for the HER result
from Langmuir-type adsorption, with the maximum located
near ΔGH* = 0.555 Specifically, the closer the position of the
ΔGH* and j0 values to the peak of the plot, the better the
catalyst. Consequently, noble metals such as Pt and Rh, which
show moderate adsorption−desorption behavior (that is,
|ΔGH* | → 0), exhibit lower activation energy values during
H2 evolution and thus accelerate the HER kinetics. An ideal
catalyst should allow the moderately strong adsorption of
reaction intermediates.555 This is required because the
discharge reaction in the Volmer step will be slow if the H*
binding energy is too low, while overly strong binding of H*
will limit H atom removal in the Heyrovsky or Tafel steps. Pt is
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commonly considered to be the most suitable HEC because

Figure 47. (a) The HER j0 value as a function of the hydrogen
adsorption free energy for the surfaces of various metals, alloys, and
nonmetallic materials. Reproduced with permission from ref 614.
Copyright 2014 Macmillan Publishers Limited. (b) Activity trends for
the OER as a function of (ΔGO* − ΔGHO*). Reproduced with
permission from ref 523. Copyright 2011 Wiley-VCH.
both its catalytic and electronic properties are well-suited to
this role. This metal also has a large work function that assists
in establishing an effective junction while retarding electron−
hole recombination as well as a suitable metal d-band center
energy value.546 For these reasons, greatly enhanced hydrogen
evolution rates have been obtained after loading Pt on the
surfaces of many nanostructured materials, including ox-
ides,556,557 (oxy)nitrides,558−560 (oxy)sulfides,209,561−563 and
polymeric photocatalysts.564 Nonetheless, Pt exhibits a low
overpotential for the ORR and also catalyzes back reactions
and hence is not suitable for use during overall water splitting
on single particles.374,565 This issue is largely avoided by using
Ru374,394 or Rh,282,565 both of which have been widely applied
to promote water cleavage into H2 and O2. In recent years, a
wide range of noble-metal-free materials have also been found
to work as effective HER catalysts, including NiS,566−569
MoS2,570,571 CoMoSx,572 WCx,573,574 Ti3C2,575 Co2C,576
Ni2P,577,578 and FeP,579 as have been summarized else-
where.531,554,580−582 In particular, NiSx-modified Cd0.5Zn0.5S
has been reported to exhibit a QE approaching 100% at 425
nm while generating H2 from water with the assistance of
Na2S/Na2SO3 as the SED (Figure 48).567 The underlying
principle leading to this high level of performance is a collision-
contact mechanism. In contrast to a traditional heterojunction
that relies on intimate interconnections between the photo-
catalyst and cocatalyst, the NiSx cocatalyst is present in the
reaction solution as freestanding subnanometer clusters rather
than anchored on the Cd0.5Zn0.5S surface. The authors
reported that frequent collisions between the Cd0.5Zn0.5S

Figure 48. (a) Initial rates of hydrogen evolution over Cd0.5Zn0.5S (CZS) twinned photocatalysts with different Ni contents during the first 5 h of
the test. (b) UV−visible absorbance spectrum and AQY values for the composite. (c) Schematic illustration of a proposed mechanism in which
NiSx and CZS nanorods undergo collisions to transfer photogenerated electrons. The NiSx clusters are believed to serve as reaction centers for H2
evolution. (d) Band alignment around a twin boundary in CZS and the photocatalytic process involving charge separation and surface redox
reactions. In both panels, red indicates wurtzite and blue indicates zinc blende crystal phases. Reproduced with permission from ref 567. Copyright
2016 Macmillan Publishers Limited.

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nanorods and NiSx clusters facilitated electron transfer to the

cocatalyst and diminished the back reaction.
Among OECs loaded on semiconductors to promote
photocatalytic oxidation reactions, metal oxides such as
RuO2, IrO2, and CoOx are the most active,142,381,422,552,583−588
in good agreement with the volcano plot for the OER in Figure
47b. The introduction of OECs to photocatalytic systems not
only accelerates oxygen production but also inhibits photo-
corrosion of the host light absorber. An example is RuO2-
loaded CdS, in which holes generated in the CdS are trapped
by RuO2 sites on the surface and subsequently generate oxygen
from water.589 The stabilization of the CdS in this system is
attributed to the presence of the RuO2 catalyst, which provides
a driving force for water oxidation in excess of 600 mV. This
results in a suitably rapid water oxidation process that is able to
compete with surface corrosion. An analogous phenomenon
was also observed during works with (oxy)nitrides and
oxysulfides.586−588,590 In these works, the production of N2
by the oxidation of N3− species near the surface of
(oxy)nitrides, such as LaTiO2N, was largely suppressed after
loading CoOx on the surface.
It is worth mentioning that molecular complexes and
enzymes are alternatives to NPs as cocatalysts in semi-
conductor-based photocatalytic reactions.316,591−597 Such
homogeneous cocatalysts, which do not have issues related
to limited contact with the reactants, have been found to
present more active sites for catalysis than nanoparticulate
cocatalysts.593 An excellent example is the hydrogenases
(H2ases), a family of H2-cycling enzymes representing one of Figure 49. (a) Schematic representation of solar H2 production using
the most efficient noble-metal-free electrocatalysts for H2 the hybrid carbon QD (CQD)−NiP system. (b) Optimized H2
production. Hybrid systems based on H2ases as HECs and generation using CQD and NiP in an aqueous EDTA solution
semiconductors (include dye sensitized TiO2,598 CNx,599 and under 1 sun irradiation in the absence (λ > 300 nm) and presence of a
CdTe QDs600 ) as light absorbers have demonstrated 400 nm UV filter. Control experiments without EDTA, CQD, and
promising photocatalytic activity during hydrogen production NiP, as well as with the heterogeneous catalyst precursors NiCl2 and
in sacrificial schemes. Furthermore, a noble-metal-free Ni- K2PtCl4, are also shown. Reproduced with permission from ref 362.
Copyright 2015 American Chemical Society.
bis(diphosphine) catalyst (NiP) serving as an HEC immobi-
lized on carbon QDs has shown an AQY of 1.4% at 360 ± 10
nm when using EDTA as the SED (Figure 49).362 A hybrid
system comprising BiVO4 as the photosensitizer and a cubic
Co complex as the OEC resulted in a dramatically improved
O2 generation rate during the OER, up to nine times that
obtained without the molecular cocatalyst, in conjunction with
an AQY of 4.5% at 420 nm in the presence of NaIO3 as the
SEA.595 A comprehensive review discussing hybrid photo-
catalytic systems combining molecular complexes and semi-
conductors has been published very recently.601
The activities of OECs and HECs in the aforementioned
photocatalytic systems is affected by many factors, such as the
cocatalyst loading, the particle size,602−604 the structure and
composition of the cocatalyst,419,561,605−609 and the interface
between the cocatalyst and semiconductor.610,611 Regardless of
the photocatalyst and cocatalyst employed, a volcano-type
relationship is typically observed between the cocatalyst
loading and the photocatalytic activity (Figure 50).581 The Figure 50. Volcano-type relationship between the loading amount of
loading of a cocatalyst onto a semiconductor results in a cocatalyst and the photocatalytic activity of the cocatalyst-loaded
semiconductor photocatalyst. Reproduced with permission from ref
diminished charge recombination and enhanced reaction 581. Copyright 2014 The Royal Society of Chemistry.
kinetics, thereby improving the photocatalytic activity.
However, excessive loading of the cocatalyst will lead to a
drastic drop in the photocatalytic activity because the electron−hole recombination across the space charge layer but
cocatalyst shields the photocatalyst surface from incident not to contribute significantly to the overall water oxidation
light and introduces charge recombination centers. It is worth flux owing to its relatively slow water oxidation kinetics.612,613
noting that some materials, as exemplified by cobalt phosphate Such materials are considered as surface modification rather
(CoPi) loaded on BiVO4, have been found to retard the back than cocatalyst.
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4.2.2. Surface Modification. Successful inhibition of back
reactions on noble metal HECs without interfering with
hydrogen evolution has been accomplished using a surface
modification strategy. In this approach, amorphous (oxy)-
hydroxides, such as Cr2O3,565,615 TiO2,616 Nb2O5,616 Ta2O5,616
lanthanoid(III) oxide,617 SiO2,618 and MoOx619 cover the
noble metal HEC or the entire surface of the photocatalyst
particles, creating a core/shell structure. A well-known example
is the Cr2O3/Rh core/shell HEC, in which a Cr2O3 layer (ca. 2
nm) is formed around metallic Rh HEC NPs through a
photodeposition process.565 This Cr2O3 layer was demon-
strated to provide active sites to reduce adsorbed protons to
H2 rather than to serve as a promoter to extract electrons from
the bulk to the surface. More importantly, the Cr2O3 layer is
permeable to protons and the resulting hydrogen molecules
but not to oxygen, thereby diminishing the back reactions that
involve O2 molecules on the noble metal. In addition to the
successful demonstration of water cleavage into stoichiometric
H2 and O2 by this material (see Table 1), the negative effect of
increasing ambient pressure on the photocatalytic activity
during overall water splitting was effectively suppressed
following this surface modification.392,394 An extension of the
surface modification approach was the deposition of
amorphous Ti, Ta, or Nb oxy(hydroxides) onto Sc-doped
SrTiO3 (SrTiO3:Sc) modified with Rh2O3.616 These thin shells
act as selective membranes because their amorphous structure
is composed of very small hydrated clusters.619,620 As shown in
Figure 51, the deposited oxy(hydroxide) layer does not retard
Figure 51. Schematic of the function of (a) a Cr2O3 shell and (b)
amorphous Ti, Ta, or Nb oxy(hydroxide) layers. Reproduced with
permission from ref 616. Copyright 2015 American Chemical Society.
the release of O2 molecules from the photocatalysts due to the
high O2 partial pressure and the lattice flexibility of the
amorphous layer. On the contrary, O2 permeation in the
opposite direction is unlikely to occur because the partial
pressure of O2 in the outer region is lower than that in the
coating layer. Consequently, O2 is selectively blocked from
accessing the HER, thereby suppressing the back reaction and
promoting the efficiency of the overall water splitting. On the
AT
Review
basis of this approach, stable H2 and O2 evolution from water
was achieved over a TiO2−m(OH)2m·xH2O (TiOXH) and
SiO2−m(OH)2m·xH2O (SiOXH)-coated RhCrOy/
LaMg1/3Ta2/3O2N photocatalyst under visible light irradi-
ation.176,177
5. CONCLUSION AND PERSPECTIVES
For solar hydrogen to compete with fossil fuels, photocatalytic
systems must undergo dramatic increases in both efficiency
and durability, which is a challenging but achievable goal. This
review demonstrates that it is feasible to employ the
fundamental principles underlying photocatalytic water split-
ting to design and build artificial photocatalytic systems. The
multistep processes that take place during photocatalytic water
splitting are sequentially and coherently connected, and the
efficiency of the device is therefore dictated by that of each
elemental step. This review examines the common principles
that govern the photocatalytic water-splitting reaction and
describes the primary frameworks in which the simultaneous
control of each step could pave the way for future
improvements, as summarized in Figure 52, serving as a
guide to the development of new photocatalytic systems while
highlighting the key gaps that require to be addressed.
First, it should be noted that a sufficient body of knowledge
regarding the intrinsic properties of proposed materials,
including the absorption coefficients, carrier lifetimes, and
carrier diffusion lengths, is necessary to assess whether such
compounds are suitable for efficient photocatalysis. These
factors identified to affect the efficiency of the water-splitting
process include (i) absorption coefficient (absorption depth),
(ii) width of the space charge region, (iii) diffusion length of
the charge carriers that depends on the diffusion coefficient
and on the lifetimes of the charge carriers, (iv) mobility of
photoexcited charge carriers, (v) recombination rate of charge
carriers, (vi) distribution of charge carriers, (vii) concentration
of defects in the bulk and on the surface, and (viii) amount of
active sites on the surface. Such information should guide the
design decisions for photocatalytic devices, such as spectral
absorption enhancements, particle size decreases or junction
formation.
It is worth mentioning that the combination of theory and
experiment can elucidate the challenges in developing and
further improving the materials for photocatalytic reactions,
serving as an initial platform to design strategies to circumvent
technical hindrances.621−624 Takanabe’s simulation for 2D
particulate photocatalytic systems revealed that the QE was
exclusively governed by the low charge separation efficiency
and severe charge recombination in the bulk of the
photocatalyst particles.456 Hence, to achieve a breakthrough,
the design of particulate photocatalysts was suggested to create
a path for transporting the photogenerated carriers to their
respective active sites efficiently. Our simulation of the
relationship between defect density and QE indicates that
the QE is extremely sensitive to the defect density and
increases by 2 orders of magnitude as defect densities decrease
from 1 × 1018 to 1 × 1016 cm−3.625 The efficiency of water-
splitting reactions is expected to improve dramatically by
increasing crystallinity and reducing defect density. Further-
more, the modeling for (oxy)nitrides concludes two factors
preventing the application of (oxy)nitrides for overall water
splitting: short lifetimes of photoexcited holes and an
insufficient driving force for the OER. Moderating n-type
semiconductivity, enhancing OEC kinetics, and generating an
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Figure 52. Summarization of the functions and disadvantages of the design strategies for enhancing the efficiency of particulate photocatalysts for
light-driven water splitting.
asymmetric electric field inside the photocatalyst particles are
therefore suggested to overcome these problems. On the basis
of the combined experimental and simulation studies on
photocatalysts consisting of Si and III−V semiconductors, Hu
and co-workers, on the other hand, proposed to introduce a
carrier-selective layer between the cocatalyst and photocatalyst
because the energetics of photocatalyst/cocatalyst interfaces
may induce charge recombination at the interface.408 In such
three-component conjuration, the carrier-selective layer
induces band bending and passivates the surface recombina-
tion sites on the photocatalyst, while cocatalysts accelerate the
reactions. In addition, high-throughput computational screen-
ing of materials is considered as a powerful tool to rapidly and
efficiently predict and discover promising candidates for overall
water splitting.626,627 The integrated computational and
experimental approach has estimated a variety of new materials
AU
Review
as possible photocatalysts for one-photon water splitting,
including oxides Ca2PbO4, Cu2PbO2, AgGaO2, AgInO2, and
NaBiO3 as well as a range of single or 2D layered nitrides and
chalcogenides. Cooper et al. recently integrated robotic
experimentation with high-throughput computation for the
screening of linear polymers, allowing rapidly investigate and
identify high-activity photocatalysts for hydrogen evolution.628
For any material to be viable in a photocatalytic device, it
must first and foremost be a good absorber of sunlight. It has
been suggested that photocatalytic characterization can
commence if the material possesses a bandgap that lies in
the range of 1.5−2.5 eV.629 Otherwise, a photon collection
approach must be implemented to effectively harvest visible
light without compromising the charge separation probability.
Modulation of the bandgap and band-edge positions can be
achieved by doping and the formation of a solid solution. The
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Figure 53. (a) SEM image and (b) spatial distribution of the SPV signals for BiVO4 coated with MnOx and Pt. (c) Summary of the SPV signals
acquired at the {011} and {010} facets on a bare single BiVO4 photocatalyst particle and for single BiVO4 photocatalyst particles with differently
deposited cocatalysts. The orange and black arrows mark the direction of built-in electric fields toward the external surfaces of {011} and {010}
facets, respectively. Schematic band diagrams across the border between the {011} and {010} facets of (b) a bare single BiVO4 photocatalyst
particle and (c) a single BiVO4 photocatalyst particle with a MnOx cocatalyst selectively deposited on {011} facets (green line) and with MnOx and
Pt NPs selectively deposited on {011} and {010} facets (dashed pink line). Reproduced with permission from ref 550. Copyright 2017 American
Chemical Society.

doping level and the ratio of the two isostructural materials,
however, require precise control to avoid inducing deep
trapping and recombination sites for the photoexcited carriers.
In photosensitizer-based or Z-scheme systems, the forward
electron transfer must be designed so as to be kinetically
competitive or dominant. As an example, the electron transfer
rates for dye sensitized systems are strongly distance-
AV
dependent,19 and so the arrangement of the molecules in
space can possibly promote forward electron transfer. One of
the major obstacles in realizing the overall water splitting over
the materials other than oxides, including (oxy)nitrides,
(oxy)sulfides, metal chalcogenides, oxyhalides, conjugated
polymers, and hybrid organic−inorganic materials, is the self-
photocorrosion, resulting in low stability during the photo-
DOI: 10.1021/acs.chemrev.9b00201
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

catalytic reaction. As examples of (oxy)nitrides and (oxy)- Present Address

sulfides, loading with OEC on the surface might be necessary §
Department of Chemistry, University of Cambridge, Lensfield
in order to suppress the oxidation of lattice nitrogen and sulfur Road, Cambridge CB2 1EW, UK.
ions and stably oxidize water to O2.
Notes
Enhanced charge separation would allow exploitation of the
built-in electric fields of nanoscale and microscale junctions. The authors declare no competing financial interest.
Nonetheless, this charge separation is typically insufficient in
Biographies
the case of photocatalysts with submicrometer particle sizes
because the potential gradients near the semiconductor surface Qian Wang obtained her Ph.D. in 2014 at the University of Tokyo,
and constrained space regions are limited.456 Therefore, certain Japan, under the supervision of Prof. Kazunari Domen, working on
material strategies, such as the enhancement of crystallinity and the development of perovskite-type oxide photocatalysts for visible-
the reduction of defects, that result in long-lived charge light-driven water splitting. She then joined the Japan Technological
separation states are a priority, along with facet engineering for Research Association of Artificial Photosynthetic Chemical Process
the spatial separation of reduction and oxidation sites. In (ARPChem) for postdoctoral work with a focus on the development
addition, nanotechnology gains an outstanding control on the of standalone photocatalyst devices for overall water splitting. Since
architecture of functional materials. The application of 1D/2D September 2018, she has joined the group of Prof. Erwin Reisner at
materials and multicomponent materials assembled in the the University of Cambridge as a Marie Sklodowska-Curie Research
Fellow. Her current research is focused on the development of
nanoscale are becoming common. The development of
photocatalysts for the reduction of CO2 to fuels and higher-value
nanostructured photocatalysts has led to promising photo-
chemicals.
catalytic performance attributable to the reduced carrier
diffusional path and the precise combination of materials on Kazunari Domen is currently a University Professor at The University
a nanometric scale. of Tokyo and a Special Contracted Professor at Shinshu University
In spite of the numerous electrochemical catalysts developed and the team leader of Japan Technological Research Association of
for the HER and OER, only a few cocatalysts have been found Artificial Photosynthetic Chemical Process (ARPChem). He received
to decompose water into H2 and O2, including RuOx, NiOx, a B.Sc. (1976), M.Sc. (1979), and Ph.D. (1982) honors in chemistry
from the University of Tokyo. He joined the Tokyo Institute of
and RhCrOx, as presented in Table 1. The majority of
Technology as an assistant professor in the Chemical Resources
photocatalysts require cocatalysts to drive these reactions
Laboratory and was promoted to an associate professor in 1990 and a
efficiently because the reactions on semiconductors otherwise
professor in 1996. He became a professor at the University of Tokyo
proceed slowly. This implies that it may be essential to load in 2004 and was appointed to a University Professor in 2019. He was
both the OEC and HEC on one single particle. In such cases, cross-appointed as a Special Contracted Professor at Shinshu
synergistic interactions and the spatial separation of the HEC University in 2017. His research focuses on the development of
and OEC will be vital factors. Increased overall water splitting photocatalysts and devices for efficient solar hydrogen generation via
rates were observed upon coloading of the HEC and OEC in water splitting.
systems composed of GaN:ZnO, 630,631 ZrO 2 -modified
TaON,174 TiO 2 ,632 Bi0.5 Y 0.5 VO 4 ,633 SrTiO3 ,634 and g-
C3N4,635 compared to those obtained solely using the OEC ACKNOWLEDGMENTS
or HEC. Even in the case that both OECs and HECs are This work was financially supported by the Artificial Photo-
loaded on particle surfaces, promoting simultaneous H2 and O2 synthesis Project of the New Energy and Industrial
generation remains challenging, such that overall water Technology Development Organization (NEDO) and a
splitting has only been demonstrated over a limited number Grant-in-Aid for Scientific Research(A) (no. 16H02417)
of materials. Facet engineering to transport the OEC and HEC from the Japan Society for the Promotion of Science.
to their respective sites is an elegant means of controlling the
spatial separation of cocatalysts and could allow the develop- ABBREVIATIONS USED
ment of more materials for overall water splitting. A prototype AQE apparent quantum efficiency
based on BiVO4 modified with a MnOx and Pt dual cocatalyst AQY apparent quantum yield
is presented in Figure 53.550 HEC hydrogen evolution cocatalyst
It is hoped that the current review will provide guidelines to CB conduction band
assist in developing future design strategies for the enhance- CBM conduction band minimum
ment of specific properties of photocatalytic devices, eventually D diffusion coefficient
leading to efficient and durable solar hydrogen production via DFT density functional theory
photocatalytic water splitting. DRS diffuse reflectance spectroscopy
e− electron
AUTHOR INFORMATION EDTA ethylenediaminetetraacetic acid
E photon energy
Corresponding Author E0 redox potential
*Phone: +81-3-5841-1148; +81-26-269-5225. Fax: +81-3- EF Fermi energy
5841-8838; +81-26-269-5550. E-mail: domen@chemsys.t.u- Eg bandgap energy
tokyo.ac.jp; domen@shinshu-u.ac.jp. Ei band edge energy
ES+/S* oxidation energy level of the excited dye
ORCID
ES+/S potential for dye regeneration
Kazunari Domen: 0000-0001-7995-4832 EPR electron paramagnetic resonance
AW DOI: 10.1021/acs.chemrev.9b00201
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

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BO DOI: 10.1021/acs.chemrev.9b00201
Chem. Rev. XXXX, XXX, XXX−XXX