Photochemical Splitting of Water For Hydrogen Production

Review
Photochemical splitting of water for hydrogen production

by photocatalysis: A review
Adel A. Ismail
a,b,c,n
, Detlef W. Bahnemann
c
a
Advanced Materials Department, Central Metallurgical R&D Institute, CMRDI, P.O. Box 87, Helwan 11421, Cairo, Egypt
b
Advanced Materials and NanoResearch Center, Najran University, P.O. Box: 1988, Najran 11001, Saudi Arabia
c
Institute fr Technische Chemie, Leibniz Universitt Hannover, Callinstrasse 3, D-30167 Hannover, Germany
a r t i c l e i n f o
Article history:
Received 26 January 2014
Received in revised form
21 April 2014
Accepted 27 April 2014
Available online 2 June 2014
Keywords:
Water splitting
Hydrogen production
Photocatalysts
UV and visible illumination
a b s t r a c t
Hydrogen production from water using a catalyst and solar energy is an ideal future fuel source. The search
for suitable semiconductors as photocatalysts for water splitting into molecular hydrogen and oxygen has
been considered to be an urgent subject for our daily life. In this review, we aim to focus on the research
efforts that have been made so far for H
2
generation from water splitting by UV and visible light-driven
photocatalysis. A number of synthetic modication methods for adapting the electronic structure to enhance
the charge separation in the photocatalyst materials are discussed. Sacricial reagents and electron
mediators for the overall water splitting are also reviewed. The quantum efciency of photocatalyst
materials upon visible and UV illumination will be reviewed, summarized and discussed.
& 2014 Elsevier B.V. All rights reserved.
Contents
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
1.1. Basic principles of photocatalytic hydrogen generation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
1.2. Main processes of photocatalytic hydrogen generation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
1.3. Evaluation of photocatalytic water splitting systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2. Photocatalysts for water splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.1. UV photocatalysts for water splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.1.1. TiO
2
and titanates as photocatalysts for H
2
production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.1.2. Nb- and Ta-based oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
2.1.3. W-, Mo-, and V-based oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2.1.4. d
10
Metal oxide photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2.1.5. f
0
Metal oxide photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2.1.6. Nonoxide photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2.2. Visible light active photocatalysts for H
2
production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2.2.1. Efcient separation of photogenerated charge carriers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
2.2.2. Cocatalyst loading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
2.2.3. Z-scheme photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
2.2.4. Metal suldes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
2.2.5. GaN:ZnO solid solution photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
2.2.6. Overall water splitting employing dye-sensitized solar cells to harvest visible light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
2.2.7. Electron mediators for overall water splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
3. Main challenges and opportunities. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4. Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Contents lists available at ScienceDirect
journal homepage: www.elsevier.com/locate/solmat
Solar Energy Materials & Solar Cells
http://dx.doi.org/10.1016/j.solmat.2014.04.037
0927-0248/& 2014 Elsevier B.V. All rights reserved.
n
Corresponding author.
E-mail address: adelali141@yahoo.com (A.A. Ismail).
Solar Energy Materials & Solar Cells 128 (2014) 85101
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
1. Introduction
Photocatalytic water splitting into H
2
and O
2
using semiconduct-
ing catalysts has received much attention due to the potential of
this technology, as well as the great economic and environmental
interest for the production of the clean fuel H
2
from water using
solar energy. Fujishima and Honda demonstrated the potential of
TiO
2
semiconductor materials to split water into H
2
and O
2
[1,2].
Their work triggered the development of semiconductor photo-
catalysis for a wide range of environmental and energy applications
[1,2]. The photocatalytic activity of conventional metal-oxide photo-
catalysts for the overall water splitting is known to be heavily
dependent on the crystallinity and the particle size of the material,
as determined by the preparation conditions [35]. During the past
40 years, various photocatalyst materials have been developed to
split water into H
2
and O
2
under UV and visible light illumination.
The direct splitting of water using a particulate photocatalyst would
be a good way to produce clean and recyclable H
2
on a large
scale [69]. A number of photocatalysts have been proposed and
achieved high quantum efciencies under UV illumination. At
present, there is a lack of suitable materials with sufciently band
gap positions for overall water splitting, and the stability necessary
for practical applications. In general, efcient photocatalytic materi-
als contain either transition-metal cations with a d
0
electronic
conguration (e.g., Ta
5
, Ti
4
, Zr
4
, Nb
5
, Ta
5
, W
6
, and
Mo
6
) or typical metal cations with d
10
electronic conguration
(e.g., In
3
and Sn
4
, Ga
3
, Ge
4
, Sb
5
) as principal cation
components, the empty d or sp orbitals of which form the bottom
of the respective conduction bands [69]. The tops of the valence
bands of metal oxide photocatalysts with d
0
- or d
10
-metal cations
usually consist of O2p orbitals, which are located at about 3 eV or
higher versus normal hydrogen electrode (NHE) and, as such,
produce a band gap too wide to absorb visible light [9]. Also,
(oxy) nitrides containing d
0
transition-metal cations, such as Ta
3
N
5
,
TaON, and LaTiO
2
N, are potential photocatalytic materials to achieve
water splitting [10]. The highest quantum efciencies (QEs) have
been reported for NiO-modied La/KTaO
3
(QE56%) using water
under UV light [11], QE90% has been obtained for H
2
generation
employing ZnS as photocatalysts in the presence of aqueous Na
2
S/
Na
2
SO
3
as sacricial reductant under UV illumination [12] and for
Cr/Rh-modied GaN/ZnO (QE2.5%), in pure water under visible
light illumination [1315]. So far, no material capable of catalyzing
reaction (Eq. (1)) with visible light and a QE larger than 10% has
been found [15]. Therefore, investigating the physical factors that
govern the photocatalytic activity for H
2
production is an important
and indispensable issue in the development of highly active photo-
catalysts. While a number of visible-light-driven photocatalysts
have been proposed as potential candidates for the overall water
splitting, a satisfactory material has yet to be devised [1619]. At a
power level of 1000 W/m
2
the solar energy incident on the earth's
surface by far exceeds all human energy needs [20,21]. Photovoltaic
and electrochemical solar cells that convert solar energy into
electricity can reach up to 5577% efciency [2225] but remain
uneconomical because of high fabrication costs, insufcient light
absorption [26], and inefcient charge transfer [22]. In a process
that mimics photosynthesis; solar energy can also be used to
convert water into H
2
and O
2
, the fuels of a H
2
-based energy
economy (Eq. (1))
H
2
O-1=2 O
2
H
2
g; G 237 kJ=mol1:3 eV=e;
min
1100 nm
1
The development of a photocatalytic system that functions
efciently under visible light, representing almost half of the
available solar energy on the surface of the earth, is therefore
essential for the practical utilization of solar energy. In this review,
we aim to summarize the research efforts having been made so far,
for H
2
generation from water splitting employing UV and visible
light-driven photocatalysts in combination with the view on
inspiring new ideas to tackle this important challenge. A number
of synthetic and modication techniques for adjusting the band
structure of the photocatalyst to harvest visible light and to
improve the charge separation in photocatalysis are discussed.
Sacricial reagents and electron mediators for the overall water
splitting are also reviewed.
1.1. Basic principles of photocatalytic hydrogen generation
Fig. 1a shows a schematic diagram of water splitting into H
2
and
O
2
over photocatalysts. Photocatalysis on semiconductor particles
involves three main steps: (i) absorption of photons with energies
exceeding the semiconductor bandgap, leading to the generation of
electron (e
) and hole (h
) pairs in the semiconductor particles;

(ii) charge separation followed by migration of these photogener-
ated carriers in the semiconductor particles; (iii) surface chemical
Fig. 1. Schematic illustration of water splitting over semiconductor photocatalysts.
Source: Ref. [103].
A.A. Ismail, D.W. Bahnemann / Solar Energy Materials & Solar Cells 128 (2014) 85101 86
reactions between these carriers with various compounds (e.g.,
H
2
O); electrons and holes may also recombine with each other
without participating in any chemical reactions [3,7]. When a
photocatalyst is used for water splitting, the energetic position of
the bottom of the conduction band must be more negative than the
reduction potential of water to produce H
2
, and that of the top of
the valence band must be more positive than the oxidation
potential of water to produce O
2
, as shown in Fig. 1b. Furthermore,
the photocatalyst must be stable in aqueous solutions under
photoirradiation. Scaife noted in 1980 that it is intrinsically difcult
to develop an oxide semiconductor photocatalyst that has both,
a sufciently negative conduction band for H
2
production and a
sufciently narrow band gap (i.e., o3.0 eV) for visible light absorp-
tion because of the highly positive position of the valence band
(at ca. 3.0V vs. NHE) formed by the O2p orbitals [27]. To facilitate
water oxidation, the potential of the valence band edge must exceed
the oxidation potential of water of 1.23 V vs NHE at pH0
(0.82 V at pH7). Based on these parameters, a theoretical
semiconductor band-gap energy of 1.23 eV is required to drive
the water-splitting reaction according to Eq. (1). The smallest band
gap achieved so far in a functional catalyst is 2.30 eV in NiO/RuO
2
Ni:InTaO
4
[28,29].
Semiconductors with smaller band gaps or lower at-band
potentials require a bias voltage or external redox reagents to drive
the reaction. Alternatively, two or more small band-gap semicon-
ductors can be combined to drive water oxidation/reduction pro-
cesses separately via multiphoton processes. It is well known that
at-band potentials strongly depend on ion absorption (protonation
of surface hydroxyl groups), crystallographic orientation of the
exposed surface, surface defects, and surface oxidation processes
[30,31]. These factors are rarely considered in the preparation and
testing of photochemical water-splitting catalysts [3234].
1.2. Main processes of photocatalytic hydrogen generation
The individual processes involved in the photocatalytic gen-
eration of H
2
are illustrated in Fig. 1. They include light absorption
of the semiconductor photocatalyst, generation of excited charge
carriers (electrons and holes), recombination of these charge
carriers, separation of the excited charge carriers, migration of
electrons and holes, charge carrier trapping, and transfer of the
charge carriers to water or other molecules [3,7]. All of these
processes affect the nal generation of H
2
from the semiconductor
photocatalyst system. The total amount of H
2
generated is deter-
mined by the amount of excited electrons at the water/photo-
catalyst interface capable of reducing water. After the electron/
hole pairs are created, charge recombination and separation/
migration processes are two important competitive processes
inside the semiconductor photocatalyst that largely affect the
efciency of the photocatalytic reaction for water splitting [35].
Charge recombination reduces the number of e
/h
pairs by
emitting light or generating phonons. This includes both, surface
and bulk recombination, and is classied as a deactivation process,
and it is ineffective for water splitting. Efcient charge separation
and fast charge carrier transport, avoiding any bulk/surface charge
recombination, are thus fundamentally important for the photo-
catalytic H
2
generation through water splitting. The reaction of
photogenerated H
2
and O
2
to form H
2
O on the photocatalyst
surface is normally called surface backreaction (SBR). There are
two main approaches to suppress the SBR: one involves the
addition of sacricial reagents into the photocatalytic reaction
environment and the second creates a separation of the photo-
active sites on the surface of the photocatalysts. In general,
sacricial reagents acting as electron donors or acceptors, respec-
tively, drive the reaction into alternative pathways as they are
reduced or oxidized, respectively. Taking into consideration the
basic mechanism and the individual processes of photocatalytic
water splitting, there are two keys for the development of a
suitable high-efciency semiconductor for the visible-light-
driven photocatalytic splitting of water into H
2
and/or O
2
: (1) a
photocatalyst should have a sufciently narrow band gap
(1.23 eVoEgo3.0 eV) to both harvest visible light and possess
the correct band structure; and (2) photoinduced charges in the
photocatalyst should be separated efciently in order to avoid
bulk/surface electron/hole recombination. In addition, both charge
carriers must migrate to the photocatalyst surface for H
2
and/or O
2
evolution at the respective photocatalytic active sites [36]. It is
important that economical, highly efcient photocatalytic systems
for light-to-H
2
energy conversion, in which aqueous solutions
containing sacricial reagents can be used to minimize the back-
ward reaction of H
2
and O
2
to water on the surface of photo-
catalysts, can be constructed.
1.3. Evaluation of photocatalytic water splitting systems
The rate of gas (O
2
and H
2
) evolution with units such as mol h
1
is used to enable a measurable comparison between different
photocatalysts under similar experimental conditions. The quantum
yield, as an extension from the overall quantum yield dened in a
homogeneous photochemical system, becomes important and accep-
table to evaluate the photocatalytic activity for water splitting.
The overall quantum yield is dened for H
2
and O
2
formation by
Eqs. (2) and (3), respectively [37]. The quantum yield is estimated to
be smaller than the overall quantum yield because the number of
absorbed photons is usually smaller than the number of photons
available in the incident light. Activities of photochemical water-
splitting catalysts are usually assessed by the rates of evolved gases
[mol/h] per catalyst amount [g] under the specied irradiation
conditions. From the measured evolution rate [H
2
], the apparent
QE2[H
2
]/I of the catalyst can be calculated using the known photon
ux [mol/s] incident on the reaction mixture.
Overall quantum yield%
2 Number of evolved H
2
molecules
Number of incident photons
100for H
2
evolution

2
Overall quantum yield%
4 Number of evolvedO
2
molecules
Number of incident photons
100for O
2
evolution

3
2. Photocatalysts for water splitting
2.1. UV photocatalysts for water splitting
A wide range of semiconducting materials have been devel-
oped as photocatalysts under UV irradiation. On the basis of their
electronic conguration properties, these UV-active photocatalysts
can be typically classied into four groups: (1) d
0
metal (Ti
4
,
Zr
4
, Nb
5
, Ta
5
, W
6
, and Mo
6
) oxide photocatalysts, (2) d
10
metal (In
3
, Ga
3
, Ge
4
, Sn
4
, and Sb
5
) oxide photocatalysts,
(3) f
0
metal (Ce
4
) oxide photocatalysts, and (4) a small group of
nonoxide photocatalysts.
2.1.1. TiO
2
and titanates as photocatalysts for H
2
production
TiO
2
was the rst material described as a photochemical water-
splitting catalyst (Fig. 2). It crystallizes in three structure types:
Rutile, Anatase, and Brookite. All modications contain TiO
6
octahedra that are interconnected via two (Rutile), three (Broo-
kite), or four (Anatase) common edges and via shared corners, and
as a result, the band gaps (3.0 eV for Rutile and 3.15 eV for
Anatase) differ slightly [38]. In their 1971/72 papers, Fujishima
and Honda described an electrochemical cell consisting of a n-type
TiO
2
(Rutile) anode and a Pt black cathode [1,2]. When the cell was
irradiated with UV light (o415 nm) from a 500 W Xe lamp, O
2
evolution was observed at the anode with a current owing to the
Pt counter electrode. Based on the current, a photoelectrochemical
efciency of approx. 10% was estimated.
Under UV irradiation, PtTiO
2
was found to catalyze the water
reduction with iodide as the sacricial electron donor, whereas
TiO
2
was observed to be the water oxidation catalyst itself in the
presence of IO
3
as the electron acceptor. After both catalysts were
combined, H
2
and O
2
were formed stoichiometrically from a basic
(pH11) solution, with iodide serving as a redox shuttle. A similar
system was realized with PtTiO
2
and PtWO
3
, giving QE4%
upon irradiation with UV light [39]. Other recent efforts have
sought to improve the optical response of TiO
2
-based catalysts via
doping with C or N, and S [4043]. Pt-modied catalysts evolve O
2
from aqueous AgNO
3
as the sacricial electron acceptor and traces
of H
2
from aqueous methanol as the sacricial electron donor
under visible light [44]. Newly synthesized tailored anatase/
brookite mixtures as well as pure brookite TiO
2
nanorods were
also employed for H
2
production. The results achieved so far
revealed that anatase/brookite mixtures and brookite nanorods
exhibit higher photocatalytic activity than anatase nanoparticles
and even higher efciencies than TiO
2
P25 for the photocatalytic
H
2
evolution from aqueous methanol solution [45,46]. Further-
more, mesoporous TiO
2
nanostructures have been studied as a
route to minimize Pt loading on TiO
2
photocatalysts for H
2
production. The results indicated that the amount of H
2
evolved
on 0.2 wt% Pt/TiO
2
calcined at 450 1C is three times higher than
that evolved on Pt/TiO
2
-P25 and twelve times higher than that
evolved on Pt/TiO
2
calcined at 350 1C [47]. Also, a series of TiO
2
and graphene sheet(GSs) composites were synthesized [48]. The
photocatalytic activity of these samples was evaluated by H
2
evolution from water photo-splitting under UVvis illumination.
On the other hand, when TiO
2
is fused with metal oxides (SrO,
PbO, etc.) metal titanates with intermediate band gaps can be
obtained. Of these, SrTiO
3
crystallizes in the Perovskite structure
type and has a band gap of 3.2 eV, slightly larger than that of TiO
2
.
It was rst employed in 1976 as a photocatalyst in a water-splitting
electrochemical cell together with p-CdTe or p-GaP photocathodes
[49]. An optimized version of this system was reported in 1977 by
Ohashi and co-workers to be the rst self-supported photoelec-
trochemical cell [50] with a photon to-electron conversion ef-
ciency of 0.0440.67%. In 1980, it was shown that NiO-modied
SrTiO
3
powder splits water vapor stoichiometrically under UV
irradiation, while SrTiO
3
alone did not show any activity [51]. The
conditions of the NiO deposition had a strong effect on the
catalytic activity [52]. Abe et al. used Cr/Ta-doped Pt/SrTiO
3
together with PtWO
3
in a two-particle catalyst system for overall
water splitting with visible light. Cr/Ta:SrTiO
3
Pt produced H
2
and
PtWO
3
produced O
2
, with an iodide/iodate redox couple serving
as the redox mediator between the two catalysts [53]. The effect of
metal cocatalysts (Ru, Ir, Pd, Pt, Os, Re, Co) on the water-splitting
activity of SrTiO
3
was also studied [54,55]. From pure water, H
2
and O
2
were evolved stoichiometrically, with the activity decreas-
ing in the order Rh4Ru4Re4Pt4Ir4Pd4Os4Co. SrTiO
3
alone produced H
2
but no O
2
. A series of layered Perovskites as
photochemical water-splitting catalysts was investigated [56,57].
The NiO-modied catalyst is active for H
2
/O
2
evolution with a QE
up to 12% [5658]. By doping with BaO and upon addition of NaOH
to the catalyst suspension, this activity could be further increased
to QE50% [56], only slightly below that of the best catalyst, i.e.,
La-doped NaTaO
3
with QE56% [59,60].
2.1.2. Nb- and Ta-based oxides
Nb
2
O
5
has a band gap of 3.4 eV and it is not active for pure
water splitting under UV irradiation. After modication with Pt as
a cocatalyst, however, it can efciently produce H
2
from aqueous
solutions containing methanol as an electron donor [61]. Meso-
porous Nb
2
O
5
, demonstrated a photocatalytic activity 20 times
higher for H
2
evolution than a bulk Nb
2
O
5
without any porosity.
Intercalation of In
2
O
3
into the mesoporous structure further
increased the photoactivity of mesoporous Nb
2
O
5
by 2.7 times
[62]. Besides Nb
2
O
5
, a large number of niobates can produce H
2
and O
2
via water splitting upon UV irradiation. K
4
Nb
6
O
17
was
developed as the rst example of a niobate photocatalyst that
showed high and stable activity for H
2
evolution from aqueous
methanol solution without any assistance from other materials
such as the noble metals [63,64]. There are various nanocompo-
sites of SrNb
2
O
6
, Sr
2
Nb
2
O
7
, and Sr
5
Nb
4
O
15
that exhibited efcient
photocatalytic activities for H
2
and O
2
production under UV
irradiation [6567]. In particular, Sr
2
Nb
2
O
7
with a highly donor-
doped layered perovskite structure gave quantum yields as high as
23%. The activity of Sr
2
Nb
2
O
7
was further enhanced achieving
quantum yields up to 32% [65]. Kudo and co-workers reported
Ba
5
Nb
4
O
15
with a layered perovskite structure for water splitting
loaded with NiO cocatalysts and reported 17% quantum yield upon
270 nm illumination [66,67]. Partial substitution of Nb
5
with
Zn
2
to obtain BaZn
1/3
Nb
2/3
O
3
with a distorted perovskite struc-
ture showed favorable photocatalytic activities under UV irradia-
tion [68,69]. The photocatalytic activity of ZnNb
2
O
6
was negligible,
whereas NiO-loaded ZnNb
2
O
6
revealed a high photoactivity [70].
Chen and coworkers prepared ABi
2
Nb
2
O
9
(ACa, Sr, Ba) perovs-
kite photocatalysts for both H
2
and O
2
evolution from aqueous
solutions containing sacricial reagents [71]. The photocatalytic
performance decreased in the order of SrBi
2
Nb
2
O
9
4BaBi
2
N-
b
2
O
9
4CaBi
2
Nb
2
O
9
. M
2
BiNbO
7
(MIn
3
,Ga
3
) with pyrochlore
structures were sensitive to UV irradiation and had the ability to
split water [72]. Sabio et al. studied the photocatalytic water
splitting activities of suspended KCa
2
Nb
3
O
10
nanoscale and bulk
particles and compared them using a kinetic model [73]. Their
model showed that the higher activity of the nanoniobate can be
rationalized by shortened transport paths for electrons and holes
to the reactive surface, which reduce the lattice recombination.
This effect apparently outweighs the increase in surface recombi-
nation that is to be expected for the nanomaterial, due to its
increased specic surface area.
Fig. 2. Schematic representation of a photoelectrochemical cell (PEC).
Source: Reprinted with permission from Ref. [1].
2.1.3. W-, Mo-, and V-based oxides
PbWO
4
incorporating a WO
4
tetrahedron showed high and
stable photocatalytic activity for the overall splitting of water
[74,75]. H
2
and O
2
was produced under UV irradiation when RuO
2
was loaded onto the metal oxide. The photocatalytic performance
was attributed to large dispersions in both the valence and
conduction bands. PbMoO
4
catalyzed the H
2
evolution from
aqueous methanol solution. It also exhibited photocatalytic O
2
evolution from aqueous AgNO
3
solution under UV irradiation with
its O
2
evolution activity being comparable to that observed for
TiO
2
[76]. Na
2
W
4
O
13
and Bi
2
W
2
O
9
, with layered structures, were
active for photocatalytic H
2
and O
2
evolution under UV irradiation
[77,78]. However, Bi
2
MoO
6
with a similar structure evolved only
O
2
from aqueous AgNO
3
solution at a low rate [79]. A new crystal
structure of VO
2
, with a body centered-cubic structure (bcc) and a
large optical band gap of 2.7 eV, surprisingly showed excellent
photocatalytic activity for H
2
production under UV irradiation [80].
The bcc VO
2
phase exhibited a high quantum efciency of 38.7%
when synthesized as nanorods. Also, Bi
2
GaVO
7
and Bi
2
YVO
8
with
tetragonal structures were studied. These two compounds
initiated both, H
2
and O
2
evolution, from water under UV irradia-
tion. This is in spite of the fact that both of them showed strong
optical absorption in the visible region (4420 nm) [81,82].
2.1.4. d
10
Metal oxide photocatalysts
Various typical metal oxides (In
3
, Ga
3
, Ge
4
, Sn
4
, Sb
5
)
with d
10
were shown to be effective photochemical water-splitting
catalysts under UV irradiation. Ni-loaded Ga
2
O
3
appears to be one
of the promising photocatalysts for overall water splitting [83]. Its
photocatalytic activity could be effectively improved by the addition
of Ca, Cr, Zn, Sr, Ba, and Ta ions [84]. Zn ion doping remarkably
improved the photocatalytic activity, with an apparent quantum
yield for Ni/ZnGa
2
O
3
of QE20%. By combining with Lu
2
O
3
, the
resulting Zn-doped Lu
2
O
3
/Ga
2
O
3
proved to be a novel composite
photocatalyst for stoichiometric water splitting under UV irradia-
tion. NiO was loaded as the cocatalyst, the quantumyield at 320 nm
amounted to 6.81%. Ga
1.14
In
0.86
O
3
showed the highest photocataly-
tic activity for H
2
and O
2
evolution [85]. In comparison, Y
1.3
In
0.7
O
3
,
showed the highest photocatalytic activity for the overall water
splitting when combined with RuO
2
as a promoter [86].
2.1.5. f
0
Metal oxide photocatalysts
CeO
2
was reported to show a consistent activity towards O
2
production in aqueous solutions containing Fe
3
and Ce
4
as
electron acceptors [87]. Sr
2
-doped CeO
2
was an active photo-
catalyst for overall water splitting when RuO
2
was loaded as a
promoter [88]. Ce
3
supported zeolites showed higher photoca-
talytic activity for water splitting [89]. H
2
and O
2
evolution was
observed. Photoirradiation of Ce
3
species generated electrons
(Ce
3
h-Ce
4
e
) that were captured effectively by water

molecules resulting the formation of molecular hydrogen. Yuan
et al. [90] reported that BaCeO
3
produced H
2
and O
2
from aqueous
solutions containing CH
3
OH and AgNO
3
as sacricial reagents,
respectively.
2.1.6. Nonoxide photocatalysts
ZnS in SO
3
2
solutions were used for H
2
production under UV
irradiation exhibiting 90% quantum yield at 313 nm [91]. CdSe
nanoribbons in Na
2
S/Na
2
SO
3
solution showed photocatalytic activ-
ity for H
2
evolution under both, UV and visible light illumination.
The quantum efciency for this process has been reported to be
0.09% [92]. The photocatalytic water-splitting activity of GaN was
found to be strongly dependent on the crystallinity of the material
and on the cocatalyst employed [93]. Modication of well-
crystallized GaN with Rh
2y
Cr
y
O
3
nanoparticles as a cocatalyst
for H
2
evolution resulted in the stable stoichiometric decomposi-
tion of H
2
O into H
2
and O
2
under UV irradiation. RuO
2
modica-
tion, on the other hand, did not bring about appreciable H
2
and O
2
evolution. However, Zn
2
, Mg
2
, and Be
2
doping of GaN con-
verted it into a remarkably active and stable photocatalyst. Again,
the presence of RuO
2
as a cocatalyst was required [94]. -Ge
3
N
4
was another effective nitride photocatalyst to show efcient
activity for splitting water into H
2
and O
2
when combined with
RuO
2
nanoparticles as reported by Domen's group [95,96]. The
photocatalytic activity of RuO
2
-loaded -Ge
3
N
4
was strongly
dependent on the reaction conditions employed. The highest
activity was obtained when the reaction was carried out in 1 M
aqueous H
2
SO
4
solution. Moreover, treatment of as-prepared
-Ge
3
N
4
powder under high-pressure ammonia effectively increased
the photocatalytic activity by up to 4 times. This was attributed to
a decrease in the density of anion defects in the bulk and at the
surface [97]. A AgBr/SiO
2
catalyst showed a stable and high
2
generation from CH
3
OH/H
2
O solution
under UV irradiation. The high activity of this AgBr/SiO
2
catalyst has
been related to photogenerated Ag species acting as sites for H
2
formation [98]. Very recently, metal-free polymeric photocatalysts
have attracted much attention. Wang et al. demonstrated that
graphitic carbon nitrides (g-C
3
N
4
) can be photocatalytically active
for H
2
evolution from water under visible light irradiation [99].
By introducing a mesoporous structure into polymeric C
3
N
4
, the
efciency of H
2
production from the photochemical reduction of
water is increased by one order of magnitude and the quantum
efciency (QE) is 1.4% [100,101].
2.2. Visible light active photocatalysts for H
2
production
Although, more than 100 photocatalytic systems based on
metal oxides have been reported to be active for the water
splitting, most of them require ultraviolet (UV) light (o400
nm) due to the large bandgap of these semiconductor materials
[16101]. Since nearly half of the solar energy incident to the
earth's surface lies in the visible region (400 nmoo800 nm)
(see Fig. 3), it is essential to use visible light efciently to realize H
2
production on a large scale by photocatalytic water splitting.
A maximum solar conversion efciency for photocatalytic water
splitting with a quantum efciency of 100% can be calculated using
the standard solar spectrum. Even if all UV light up to 400 nm
were utilized, the solar conversion efciency would be only 2%,
which is similar to the maximum conversion efciencies of
photosynthesis in green plants under normal environmental
Fig. 3. Solar spectrum and maximum solar light conversion efciencies for water
splitting reaction with 100% of quantum efciency.
Source: Ref. [103].
conditions (12%) [102]. However, if it was possible to utilize
visible light up to 600 nm, the efciency would drastically improve
to 16%; a further extension up to 800 nm would give a conversion
efciency of 32%. Therefore, achieving water splitting under visible
light has been a challenging goal since the discovery of the
HondaFujishima effect in 1972 [1,2]. Despite many years of
intensive efforts by researchers around the world, the rst repro-
ducible demonstration of water splitting under visible light
irradiation was reported only a decade ago [11,39,103].
2.2.1. Efcient separation of photogenerated charge carriers
While visible-light-driven photocatalysts with proper band
structures are currently being developed using some modication
technologies or band engineering approaches, the issue of photo-
generated charge carrier separation is another key factor strongly
affecting the efciency of the photocatalytic water-splitting pro-
cess [3,103]. The energy band conguration of a semiconductor
plays a signicant role in the absorption of light and in determin-
ing the redox potentials [3]. In order to narrow the bandgap of
semiconductors to extend the absorption of light into the visible
region, three approaches have been widely used: (I) modication
of the VB, (II) adjustment of the CB, and (III) continuous modula-
tion of the VB and/or CB [104] (Fig. 4).
2.2.2. Cocatalyst loading
Transition metals, especially noble metals, are widely used as
effective cocatalysts for photocatalytic readtions [54,55]. The
processes of charge transfer between cocatalyst and host photo-
catalyst are described in Fig. 5 [7]. When the noble metal is loaded
onto the surface of the photocatalyst, the photogenerated elec-
trons migrating to the surface of the host photocatalyst are
entrapped by the noble metal cocatalyst, because the Fermi energy
level of noble metal is always lower than that of the semiconduc-
tor photocatalyst [46,47]. Meanwhile, the photogenerated holes
stay at the host photocatalyst and also migrate to its surface.
Subsequently, the separately localized electrons and holes will be
involved as reducing and oxidizing agents, respectively. The
importance of cocatalysts as follows: It improves the overall
photocatalytic activity of the water splitting and it accelerates
the surface chemical reaction by inhibiting the backward reaction.
To date, the most widely used co-catalysts are noble metals (Pt, Ru,
Rh, Pd) and metal oxides (NiO, RuO
2
) [105]. Compared to the
investigation of photocatalysts, efforts in developing co-catalysts
are quite rare. However, the design and discovery of new types of
co-catalyst may play an equally important role in the development
of photocatalysts themselves by nally enabling a high H
2
evolu-
tion efciency for practical applications. For example, a rhodium
chromium mixed oxide as co-catalyst led to coupled GaN:ZnO
photocatalysts with 2.5% quantum efciency for water splitting
under visible light irradiation [15]. Au as a cocatalyst was
improved the photocatalytic water splitting over La-doped NaTaO
3
[106]. Besides noble metals and metal oxides, metal suldes have
also been explored as active cocatalysts. MoS
2
as a co-catalyst has
been reported to be even more effective than Pt for CdS water
splitting systems [107].
2.2.3. Z-scheme photocatalysts
There are two main approaches for achieving water splitting
using visible light. One approach is to apply a two-step photo-
excitation mechanism between two photocatalysts (a two-step
system; Fig. 6a) [11,39,53,78,108112]. This process was inspired
by natural photosynthesis in green plants and is known as the
photocatalytic Z-scheme. In two-step systems, the water splitting
reaction is broken up into two stages: one for H
2
evolution and the
other for O
2
evolution; these are combined by using a shuttle
redox couple (Red/Ox) in the solution. At the H
2
evolution
photocatalyst, the photoexcited electrons reduce water to H
2
while
the holes in the valence band oxidize the reductant (Red) to its
oxidized form (Ox). This system lowers the energy required for
photocatalysis, allowing visible light to be utilized more efciently
than in conventional water-splitting systems (Fig. 6b) [103].
Visible-light responsive oxides such as WO
3
can be used as O
2
photocatalysts if they can reduce the oxidant to a reductant.
Indeed, different semiconductor materials can be used in the
Fig. 4. Three strategies to narrow the bandgap of semiconductor photocatalysts to
match the solar spectrum.
Source: Ref. [3,104].
Fig. 5. Processes of charge transfer between host photocatalyst and cocatalyst.
Source: Ref. [35].
Fig. 6. Schematic energy diagrams of photocatalytic water splitting systems:
(a) two-step photoexcitation system and (b) conventional one-step system.
Source: Ref. [103].
Z-scheme even if they do not satisfy all the stringent requirements
for a one-step system. Z-scheme systems has ability to separate
the production of H
2
and O
2
by employing a separator. The
disadvantage of Z-scheme systems. it requires the number of
photons to be twice as large as the one-step system to achieve
water splitting. The other approach is a single visible-light
responsive photocatalyst, as illustrated in Fig. 6b. Because only a
few semiconductor materials can absorb visible light and have a
sufciently high potential for water splitting, band engineering of
semiconductors is required to nd out new photocatalysts that
satisfy the following requirements for water splitting upon visible
light illumination [103]: exhibit a narrow band gap, be stable
under photoirradiation, and have suitable conduction and valence
band levels for H
2
and O
2
production, respectively. Various band
engineering methods have been employed, including the intro-
duction of midgap electron donor levels [113117], hybridization
of the O2p orbital with other orbitals (oxides [118,119], oxynitrides
[120,121] and oxysuldes[18,122]), and the formation of solid
solutions [15,123,124]. However, there are still few reliable photo-
catalysts for the one-step water splitting under visible light
[123,124] due to the stringent requirements. An effective one-
step water-splitting system that uses a solid solution photocata-
lyst, i.e., (Ga
1x
Zn
x
)(N
1x
O
x
) or (Zn
1x
Ge)(N
2
O
x
), [123,124] has
been described recently.
Water splitting under visible light illumination was demon-
strated for the rst time in 2001 using a Z-scheme photocatalytic
system consisting of SrTiO
3
doped with Cr and Ta (denoted as
SrTiO
3
:Cr/Ta) for H
2
evolution, WO
3
for O
2
evolution, and an
iodate/iodide (IO
3
/I
) redox couple as electron mediator (Fig. 7)

[11,39]. Prior to that, Z-scheme photocatalytic water splitting had
been demonstrated using a combination of Pt-loaded anatase TiO
2
and bare rutile TiO
2
photocatalysts in the presence of an iodate/
iodide (IO
3
/I
) shuttle redox mediator [125]. Although this

system operates only upon UV light irradiation (o400 nm) due
to the large band gap of the TiO
2
photocatalysts, it eventually
opened the way to achieve water splitting under visible light. The
key was controlling the reactivity of electrons and holes with the
redox mediator (IO
3
/I
anions) and the water molecules, respec-

tively. It is quite difcult to achieve the simultaneous evolution of
H
2
and O
2
in two-step water-splitting systems (Z-scheme) because
the backward reactions of the redox mediator usually proceed
readily over both photocatalysts thus suppressing the forward
reactions (H
2
and O
2
evolutions) (Fig. 7). Highly efcient and
selective O
2
evolution was found to proceed over rutile TiO
2
and
Pt-loaded WO
3
(Pt/WO
3
) photocatalysts in an aqueous solution
containing IO
3
anions as electron acceptors (Ox) according to the

following reactions (Eqs. (4)(6)):
h-e
CB
h
VB
(4)
IO
3
3H
2
O6e
CB
-I
6OH
(5)
2H
2
O4h
VB
-O
2
4H
(6)
Z-scheme systems consisting of a modied BaZrO
3
BaTaO
2
N
solid solution and a reversible donor/acceptor pair (i.e., IO
3
/I
and
Fe
3
/Fe
2
) were constructed [126]. BaZrO
3
BaTaO
2
N having a
band gap of 1.8 eV has sufcient potential to reduce and oxidize
water by absorbing visible photons of up to 660 nm (Fig.8). SrTiO
3
was selected as the mother structure and was doped with either
vanadium (and sodium) or rhodium to introduce visible light
sensitivity. By utilizing these two types of SrTiO
3
-based photo-
catalysts, the simultaneous liberation of H
2
and O
2
in the presence
of (IO
3
)/I
as a redox mediator under irradiation with only visible

light (4420 nm) could be realized. QE values under irradiation
with 360 nm UV light and 420 and 480 nm visible light were 0.33,
0.056, and 0.039%, respectively [127].
A fully integrated system of nanoscale photoelectrodes
assembled from inorganic nanowires for direct solar water split-
ting has been described [128]. The articial photosynthetic system
comprises two semiconductor light absorbers with large surface
area, an interfacial layer for charge transport, and spatially
separated cocatalysts to facilitate the water reduction and oxida-
tion. Under simulated sunlight, a 0.12% solar-to-fuel conversion
efciency is achieved, which is comparable to that of natural
photosynthesis. A model Z-scheme system with two light-
absorbing materials is chosen here to demonstrate the capability
of an integrated nanostructure to use sunlight to split water [129].
Earth abundant and stable semiconductors, silicon (Si) and TiO
2
,
were chosen as the H
2
-generating photocathode and O
2
-generat-
ing photoanode, respectively (Fig. 9). Upon illumination photo-
excited electronhole pairs are generated in Si and TiO
2
, which
absorb different regions of the solar spectrum (Fig. 9b), the
photogenerated electrons in the Si nanowires migrate to the
surface and reduce protons to generate H
2
; meanwhile the photo-
generated holes in the TiO
2
nanowires oxidize water to evolve O
2
.
The holes from Si and electrons from TiO
2
recombine at the ohmic
contact, completing the relay of the Z-scheme [129,130], similar
to that of natural photosynthesis.
A visible light responsive plasmonic photocatalytic composite
material has been designed by rationally selecting Au nanocrystals
and assembling them with TiO
2
-based photonic crystal substrates
[131]. The design of the composite material was expected to
signicantly increase the Au surface plasmonic resonance (SPR)
intensity and consequently boost the hot electron injection from
the Au nanocrystals into the conduction band of TiO
2
, leading to a
considerably enhanced water splitting performance of the
Fig. 7. Overview of water splitting on Z-scheme photocatalysis system with an
iodate (IO
3
) and iodide (I
) ion redox couple.

Source: Ref. [103].
Fig. 8. Schematic illustration of spontaneous H
2
and O
2
evolution by Ru/Na,V-STO
and Ru/Rh-STO under irradiation with visible light in the presence of IO
3
/I
redox
mediator.
Source: Ref. [127].
material under visible light. The results showed that under entire
solar light irradiation both, H
2
and O
2
were evolved at the
expected stoichiometric ratio with generation rates of
27.9 mol h
1
for H
2
and 13.6 mol h
1
for O
2
within a 120 min
testing period.
2.2.4. Metal suldes
CdS is probably the best studied metal sulde photocatalyst
due to its relatively narrow band gap (2.4 eV), it absorbs visible
light at wavelengths of o510 nm [132]. The at-band potential of
CdS (0.87 V) [30] is sufciently high to reduce H
2
O, and the top
of its valence band (1.5 V vs NHE) is theoretically suitable to allow
the oxidation of water. For 4 nm CdS nanoparticles, the lifetime of
photogenerated charge carriers is on the order of 50 ps. However,
prolonged irradiation of CdS suspensions leads to photocorrosion
of CdS into Cd
2
and S [31,133]. This reaction can be suppressed
by the addition of reducing agents to the aqueous phase. Under
visible light irradiation, PtCdS powder evolved H
2
from aqueous
EDTA solutions with QE4%, but without Pt, the activity was
reduced by a factor of 10. Prolonged irradiation (44 h) leads to the
decomposition of the catalyst [134]. In 1984, Reber and co-workers
published the most comprehensive study concerning photocata-
lysis with CdSPt microcrystalline powders [135]. The best cata-
lysts evolved H
2
at 2.9 mmol h
1
(QE25%) under irradiation with
light of 4300 nm in the presence of either S
2
, SO
3
2
, or S
2
/
HPO
2
as reducing agents. The activity dropped by 21% over the
course of 6 days, likely because of the deactivitation of Pt due to
formation of PtS species. Under solar irradiation, 50 mL/h of H
2
were produced with 0.4 g of catalyst suspension equal to an
energy efciency of 2%. In a follow-up study, the activity of CdS
could be increased up to 357 mL/h
1
(QE37%) of H
2
in aqueous
Na
2
S/Na
2
SO
3
suspensions by doping CdS with 15 mol% ZnS and by
the addition of a Pt cocatalyst [136,137]. ZnS has a band gap of
3.66 eV, which restricts light absorption to the UV (o340 nm).
Similar to CdS, it undergoes photochemical decomposition into its
components when irradiated in the absence of sacricial electron
donors. The rst report on water splitting with ZnS was published
by Yanagida in 1983 [138], who synthesized ZnS from ZnSO
4
or
ZnCl
2
and Na
2
S in water. With tetrahydrofuran or alcohols as the
sacricial donor, this catalyst produced H
2
gas under UV irradia-
tion. The most comprehensive study on photocatalytic reactions of
ZnS and ZnSPt was carried out by Reber et al. [133]. Under
irradiation with 4300 nm light and at 60 1C, ZnSPt catalyzed H
2
evolution with quantum yields of up to 90% from aqueous
solutions of sulde and sulte. To improve the visible light
absorption of ZnS, Kudo's group has tested metal dopants (Cu,
Ni, and Pb [139141]). Doping can move the absorption edge to
500 nm in the case of Ni
2
ions and to 550 nm in the case of Pb
2
ions. Under visible light irradiation, a Ni
2
-doped catalyst pro-
duced H
2
from aqueous K
2
SO
3
/Na
2
S with QEs of up to 1.3% [140].
Cu-doped ZnS gave QE3.7% under visible light irradiation for the
molecular hydrogen formation from aqueous Na
2
SO
3
[139]. Dop-
ing of ZnS with variable amounts of AgInS
2
or CuInS
2
produces a
series of solid solutions that crystallize in the cubic zinc blende or
hexagonal Wurtzite structure [142145]. Visible light irradiation of
the respective Pt- or Ru-derivatized catalysts produced H
2
with
a QE of up to 7.5% from aqueous Na
2
S/Ka
2
SO
3
[143]. For the
Pt-loaded Ag
0.22
In
0.22
Zn
1.56
S
2
photocatalyst, a QE of 20% was
measured at 420 nm under solar irradiation conditions [145].
Na
14
In
17
Cu
3
S
35
xH
2
O evolved small quantities of H
2
under visible
light irradiation using Na
2
S as the sacricial electron donor, equal
to QE3.7% at 420 nm with SO
3
2
, the QE dropped to 0.37%. Under
visible light irradiation, the Pt-modied catalyst showed good
2
evolution from aqueous K
2
SO
3
solutions [146]. When supported on SiO
2
and using uorescein
as a sensitizer, the catalyst produced H
2
from aqueous EDTA
solutions under visible light illumination [147]. Bi
2
S
3
has a band
gap of 1.28 eV; it produces H
2
at intermediate rates from an
aqueous sulde solution. Rates decline after 100 min, probably
because of disulde formation. Platinization improves the activity
by 25% [148].
2.2.5. GaN:ZnO solid solution photocatalysts
Domen et al. demonstrated water splitting into H
2
and O
2
under visible light irradiation using a single (Ga
1x
Zn
x
)(N
1x
O
x
)
photocatalyst material with an average quantum yield of ca.
0.14% [123]. Although (Ga
1x
Zn
x
)(N
1x
O
x
) with a ZnO concen-
tration above 75% can absorb long-wavelengths visible light
[149,150], only GaN-rich (Ga
1x
Zn
x
)(N
1x
O
x
) with a ZnO con-
centration below 22% exhibited activity for overall water split-
ting [151]. In the rst report, the origin of the visible light
absorption was explained by band gap narrowing due to pd
repulsion between Zn 3d and N 2p electrons in the upper
valence band [123]. A solid solution of ZnO and Ge
3
N
4
Fig. 9. Schematics of the asymmetric nanoscale tree-like heterostructures used for solar-driven water splitting. (a) Structural schematics of the nanotree heterostructure.
The small diameter TiO
2
nanowires (blue) were grown on the upper half of a Si nanowire (gray), and the two semiconductors absorb different regions of the solar spectrum.
The two insets display the photoexcited electronhole pairs that are separated at the semiconductorelectrolyte interface to carry out water splitting with the help of
cocatalysts (yellow and gray dots on the surface). (b) Energy band diagram of the nanotree heterostructure for solar-driven water splitting. The photogenerated electrons in
Si and holes in TiO
2
move to the surface to perform water splitting, while the holes in Si and electrons in TiO
2
recombine at the ohmic contact between the two
semiconductors. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
Source: Ref. [130].
(Zn
1x
Ge)(N
2
O
x
) was also demonstrated to be an active photo-
catalyst for the one-step overall water splitting under visible
light irradiation [124].
2.2.5.1. Co-catalysts for efcient H
2
production over GaN:ZnO. Most
semiconductor photocatalysts that have been developed to date
need to be loaded with suitable co-catalyst particles to promote H
2
production, whereas some photocatalysts with wide bandgaps can
decompose water even without co-catalyst loading. To prevent the
backward reaction, transition metal oxides such as NiO
x
or RuO
2
have mainly been used as effective co-catalysts to decompose
water into H
2
and O
2
. In NiO
x
co-catalysts, the Ni core functions as
an electron pool that accepts photoexcited electrons from the bulk
of the semiconductor and the NiO shell effectively suppresses the
backward reaction, while reduction of water to H
2
can occur on
the surface [51]. However, the application of NiO
x
has been limited
to thermally stable materials such as metal oxides because loading
of NiO
x
co-catalysts requires relatively high temperatures for
activation. Therefore, NiO
x
cocatalysts appear to be unsuitable for
non-oxide photocatalysts. RhCr mixed oxide (Rh
2y
Cr
y
O
3
)
nanoparticles as co-catalyst was investigated, which signicantly
enhances H
2
production (Fig. 10) [14,15]. Dispersion of Rh
2y
Cr
y
O
3
nanoparticles on (Ga
1x
Zn
x
)(N
1x
O
x
) produced an effective
catalyst for H
2
evolution exhibiting a quantum efciency of ca.
2.5%, which was the highest quantum efciency reported for
photocatalytic water splitting under visible light irradiation [15].
The Rh
2y
Cr
y
O
3
revealed the important role of co-catalysts in
achieving highly efcient water splitting over semiconductor
photocatalysts. Since the report of these Rh
2y
Cr
y
O
3
co-catalysts,
other researchers have reported various new co-catalyst materials
that are effective for H
2
evolution [152155].
Noble metal (core)/Cr
2
O
3
(shell) nanoparticles were developed
as a cocatalyst for water splitting. [156159] Noble metals such as
Rh and Pt were deposited on the surface of the photocatalyst by
conventional photodeposition. The surfaces of the noble metal
particles were therefore coated with thin Cr
2
O
3
layers, forming
noble metal (core)/Cr
2
O
3
(shell) nanoparticles. Such core/shell
nanoparticles can be readily prepared by the photoreduction of
Cr(VI) ions using noble metal or metal oxide loaded photocatalyst
powders in the absence of air [160]. Rh-loaded GaN:ZnO photo-
catalysts exhibit little photocatalytic activity for water splitting
due to the rapid water formation from the evolved H
2
and O
2
on
the Rh nanoparticles. However, GaN:ZnO loaded with a Rh/Cr
2
O
3
core/shell co-catalyst particles yielded H
2
and O
2
evolution from
water. Electrochemical measurement on model electrodes with a
core/shell structure revealed that the thin Cr
2
O
3
layers do not
interfere with the proton reduction to H
2
and that the proton
reduction occurred at the Cr
2
O
3
/Pt interface [161]. On the other
hand, Cr
2
O
3
layers effectively suppressed the reduction of O
2
to
water as illustrated in Fig. 11.
The co-loading of Rh (core)/Cr
2
O
3
(shell) and Mn
3
O
4
nanopar-
ticles as H
2
and O
2
evolution promoters, respectively, on GaN:ZnO
resulted in higher photocatalytic activities as compared with
Mn
3
O
4
nanoparticles modied with either Rh/Cr
2
O
3
or Mn
3
O
4
[162]. A gradual size control of poly(N-vinyl-2-pyrrolidone)-pro-
tected Rh nanoparticles was applied for the use as cocatalysts on
the photocatalyst (Ga
1x
Zn
x
)(N
1x
O
x
) achieving overall water
splitting under visible light illumination. Moreover, it was illu-
strated that smaller Rh cores yielded higher activities than larger
ones. These results indicate that Rh loaded on GaN:ZnO, additional
modied with Cr
2
O
3
, achieve the functionality as cocatalysts to
promote the water splitting by GaN:ZnO [163].
Fig. 10. Photocatalytic performance of the photocatalyst (Ga
1x
Zn
x
)(N
1x
O
x
) loaded with mixed oxides of rhodium and chromium in overall water splitting.
Source: Ref.[15].
Fig. 11. Schematic illustration of H
2
evolution on core/shell-structured nanoparti-
cles (with a noble metal or metal oxide core and a Cr
2
O
3
shell) as a cocatalyst for
photocatalytic overall water splitting.
Source: Ref. [160].
2.2.5.2. Mechanism of photocatalytic water splitting. Many studies
have focused on the development of materials that are suitable for
the visible-light-driven overall water splitting by addressing light
absorption properties, band edge position, crystallographic quality,
particle morphology, and phase purity [160]. However, it is difcult
to understand what factor(s) dominate(s) the net photocatalytic
activity based on the above physical properties because the
photocatalytic reactions proceed through a complicated sequence
of competing multistep processes. Aspects of the photocatalytic
water splitting mechanism on GaN:ZnO powder modied with a
RhCr mixed oxide cocatalyst were investigated with respect to the
effects of cocatalyst loading, light intensity, hydrogen/deuterium
isotopes, and reaction temperature on the photocatalytic activity
[162]. The water splitting rate with the optimally modied
photocatalyst was found to be proportional to the light intensity
under solar-equivalent or weaker irradiation, indicating that the
accumulation of photoexcited electrons and holes was negligible.
The HD isotope effect on the overall water splitting was signi-
cantly lower than previously reported values for photocatalytic and
electrochemical H
2
evolution reactions. The apparent activation
energy for the overall water splitting was as low as 8 kJ mol
1
and
was unchanged by the addition of electron donors or acceptors [160].
These results reect a shortage of photoexcited carriers available for
surface redox reactions under steady light irradiation. In summary,
the experimental results indicate that the balance between the rates
of redox reactions on the photocatalyst surface and the carrier
generation/recombination in the photocatalyst bulk determines the
steady state charge concentration in the photocatalyst, that is,
developing both, the photocatalyst and the cocatalyst is important.
The proposed kinetic model of photocatalytic water splitting also
suggests that the reaction probability of photoexcited holes for O
2
evolution versus their recombination with intrinsic electrons in the
photocatalyst determines the water splitting activity of GaN:ZnO. It
would be natural to expect that loading both, H
2
and O
2
evolution
cocatalysts, onto the same photocatalyst would improve the water
splitting activity, compared to that for photocatalysts modied with
either an H
2
or an O
2
evolution cocatalyst.
It is easy to imagine that the two different cocatalysts would
separately facilitate H
2
and O
2
evolution, thereby promoting the
overall water splitting in harmony. Recently, GaN:ZnO loaded with
Rh/Cr
2
O
3
(core/shell) and Mn
3
O
4
nanoparticles was demonstrated
as H
2
and O
2
evolution promoters, respectively, under visible light
irradiation [164]. The goal of the respective study was to generate
both, H
2
and O
2
evolution sites, separately on the same photo-
catalyst surface. The preparation method developed by Domen's
group is a stepwise deposition involving the adsorption of MnO
nanoparticles followed by calcination to obtain crystallized Mn
3
O
4
nanoparticles and a subsequent photodeposition of Rh/Cr
2
O
3
(core/shell) nanoparticles, as shown schematically in Fig. 12a.
As mentioned earlier, core/shell structured Rh/Cr
2
O
3
nanoparticles
provide active sites for H
2
evolution [164]. On the other hand,
photoelectrochemical analysis revealed that Mn
3
O
4
nanoparticles
on GaN:ZnO promote the photooxidation of water. Finally, overall
water splitting was attempted using the as-prepared samples
under visible light irradiation. As expected, the activity of GaN:
ZnO modied with both Rh/Cr
2
O
3
and Mn
3
O
4
provided a higher
activity than modication with either Rh/Cr
2
O
3
or Mn
3
O
4
, as
shown in Fig. 12b. The proposed reaction scheme of overall water
splitting on GaN:ZnO modied with Rh/Cr
2
O
3
and Mn
3
O
4
is
depicted in Fig. 12c [160].
Fig. 12. (a) Scheme for the preparation of GaN:ZnO loaded with both Mn
3
O
4
and core/shell-structured Rh/Cr
2
O
3
. (b) Photocatalytic activity of GaN:ZnO modied with
different cocatalysts under visible light (4420 nm). (c) Illustration of the reaction scheme for overall water splitting on GaN:ZnO modied with Mn
3
O
4
and core/shell-
structured Rh/Cr
2
O
3
.
Source: Ref. [160].
2.2.6. Overall water splitting employing dye-sensitized solar cells to
harvest visible light
The basic principle of the dye-sensitized photocatalytic H
2
production from water is shown in Fig. 13. Photoexcitation of the
dye adsorbed onto a semiconductor leads to the injection of
electrons into the conduction band of this semiconductor. The
electrons are consumed by the reduction of water to produce H
2
.
The oxidized dye molecules are subsequently reduced and thus
regenerated by accepting electrons from a suitable electron donor
[165,166]. Photocatalytic H
2
production systems in which ruthe-
nium(II) complex dyes sensitize wide band gap semiconductors to
visible light have been the focus of intensive research for many
years. In the early 1980s, Gra tzel and co-workers [167,168]
succeeded in decomposing water by visible light using tris(2,2'-
bipyridine)ruthenium(2)ion (Ru(bpy)
3
2
) and its amphiphilic
derivatives as sensitizers. Pt/RuO
2
-loaded TiO
2
particles proved
particularly effective in these systems, acting as electron mediators
and catalysts for H
2
formation process. Nakahira et al. found that
Pt/TiO
2
sensitized with a polymer-pendant Ru(bpy)
3
2
complex
was effective in H
2
evolution in the presence of the sacricial
donor (EDTA) under visible-light irradiation [169]. Hirano et al.
found that, when tris(bipyrimidine)ruthenium(II) (Ru(bpym)
3
2
)
was used as the visible-light sensitizer, Pt/TiO
2
showed much
higher efciency for H
2
production than with Ru(bpy)
3
2
[170].
Pt/TiO
2
/p-Ru(bpy)
3
2
anchored through phosphonate groups exhi-
bited higher photocatalytic activity for H
2
production from water
than Pt/TiO
2
/c-Ru(bpy)
3
2
anchored through carboxylate groups
[171]. Because of the more rapid regeneration of p-Ru(bpy)
3
2
as
compared with c-Ru(bpy)
3
2
, the phosphonate group seemed to be
better than the carboxylate group as a ruthenium sensitizer
linkage to the TiO
2
surface in an aqueous environment. The effect
of the energy gap between the I
3
/I
redox potential and the

highest occupied molecular orbital (HOMO) level of the dyes on
the photocatalytic activity of Ru complex dye-sensitized Pt/TiO
2
in
water/acetonitrile solutions was studied [172]. The inuence of
different ruthenium(II)bipyridyl complexes on the photocatalytic
H
2
evolution rate on TiO
2
under visible light illumination was
investigated [173,174]. When compared to Ru(bpy)
2
(him)
2
-NO
3
-
and Ru(dcbpy)
2
(NCS)
2
-sensitized Pt/TiO
2
, Ru
2
(bpy)
4
L1-PF6-
sensitized Pt/TiO
2
displayed higher photocatalytic efciency for
H
2
evolution. This may be related to the dynamic equilibrium
between the linkage of the ground-state dye to TiO
2
and the
separation of the oxidized dye from TiO
2
. The addition of Al
2
O
3
overlayer on Ru(bpy)
3
2
-sensitized TiO
2
was signicantly increased
the visible-light-sensitized activity for H
2
production [175]. This
resulted in an enhanced photocatalytic H
2
production rate upon
visible light irradiation [176]. Reisner et al. constructed a special
system consisting of [NiFeSe]-hydrogenase attached to Ru dye-
sensitized TiO
2
, with triethanolamine (TEA) being the sacricial
electron donor [177]. This system showed a high and stable
2
generation under visible light illu-
mination. Also, the photocatalytic efciency of SnO
2
could be
greatly improved using Ru(bpy)
3
2
sensitization [178]. The highest
2
evolution, with a quantum yield of
2.40% upon illumination was observed for a Pt/SnO
2
/RuO
2
Ru
(bpy)
3
2
MV
2
EDTA system. The dynamics of photoexcited Ru
(bpy)
3
2
intercalated into K
4
Nb
6
O
17
interlayers was investigated
[179]. Because of the fast and efcient electron transfer between
Ru(bpy)
3
2
and K
4
Nb
6
O
17
, the transient bleaching of the Ru(bpy)
3
2
band showed a fast and non-exponential decay. This differed
from the behavior of Ru(bpy)
3
2
in water, and thus explained the
photocatalytic H
2
evolution over Ru(bpy)
3
2
intercalated K
4
Nb
6
O
17
from aqueous solutions containing appropriate electron donors
[180]. Moreover, different layered oxide semiconductors were
studied as building blocks for the visible-light induced H
2
produc-
tion from water using ruthenium complexes as photosensitizers
[164,181185]. Ru(bpy)
3
2
-sensitized K
4
Nb
6
O
17
nanoscrolls were
found to exhibit higher photocatalytic activity than Ru(bpy)
3
2
-
sensitized lamellar K
4
Nb
6
O
17
and TiO
2
. This was primarily
explained by the high surface area of the nanoscrolls and by their
excellent ability to bind Ru(bpy)
3
2
thus leading to the facile
transfer of electrons from the sensitizer to the Pt catalyst islands
via the single-crystalline nanoscrolls. The authors claimed that the
platinized K
4
Nb
6
O
17
nanoscrolls were slightly better electron
transfer mediators than acid-restacked HCa
2
Nb
3
O
10
nanosheets.
The apparent quantum yield of visible-light photocatalytic H
2
production over Pt/H
4
Nb
6
O
17
nanoscrolls was reported to be 25%
upon 450 nm excitation, when sensitized by Ru(bpy)
3
2
complexes
[182,183]. The simplest system for exploring the idea of visible
light water splitting with a sensitized oxide semiconductor is a
photoelectrochemical cell [181] thus avoiding possible complica-
tions through the undesired H
2
O
2
recombination by generating
Fig. 13. Basic principle of dye-sensitized photocatalytic H
2
production from water.
Source: Ref. [165].
Fig. 14. (top) Schematic diagram of a water-splitting dye sensitized solar cell. The
inset illustrates a sensitizer-capped IrO
2
nH
2
O catalyst particle in the mesopores of
the TiO
2
electrode lm. (bottom left) Current transient obtained upon visible light
illumination. (bottom right) Energy level diagram showing the rates of forward and
back electron transfer from and to the sensitizer molecule.
Source: Ref. [181].
H
2
in a physically separated cathode compartment. A scheme of
such a cell is shown in Fig. 14with the photoanode being a
mesoporous TiO
2
electrode [186], like in a dye-sensitized solar
cell [187]. The dye is a monolayer of sensitizer capped IrO
2
nH
2
O
particles. The [Ru(bpy)
3
]
2
sensitizer is modied with both
phosphonate and malonate ligands in the 4-positions of the 2,2
0
-
bipyridyl ligands in order to adsorb strongly to TiO
2
and on
IrO
2
nH
2
O, respectively. The cathode is a Pt wire electrode.
Because the potential of electrons in trap states below the anatase
conduction band is not sufciently negative to reduce water, a bias
voltage (330 mV) must be applied for water splitting to occur in
this cell. In a conventional DSSC, the anode and cathode are
connected by a I
/I
3
redox couple, which very rapidly regenerates

the Ru(II) state of the sensitizer following electron injection into
the TiO
2
anode lm. The observed low quantum efciencies can be
understood in terms of three problems that can, in principle, be
addressed by an improved design at the molecular level [181].
The simplest of these problems is to make catalyst particles that
are connected to only one sensitizer molecule, so that each
sensitizer can bind both TiO
2
and IrO
2
nH
2
O. A second problem
is to slow down the back electron transfer reaction by changing
the distance between redox partners, and a third is to speed up the
electron transfer from Ir(IV) to Ru(III). The photocurrent transients
in this system (Fig. 14) show an initial spike that decays over a
timescale of seconds, indicating a certain degree of polarization of
the mesoporous TiO
2
electrode. Because the O
2
evolution reaction
generates protons, the current decay may result from a local pH
drop in the TiO
2
lm, which decreases the overpotential for water
oxidation. A simple solution to this problem would be to nd more
effective buffers that can penetrate into the porous lm.
Recently, a molecular water oxidation (Fig.15) Ru catalyst (1)
(silane group, Ru(II)(bda)(4-picoline) L (H
2
bdabipyridine-dicar-
boxylic acid; LN-(3-(triethoxysilyl) propyl) isonicotinamide)(2))
has been synthesized and immobilized together with a molecular
photosensitizer [Ru(bpy)
2
(4,4-(PO
3
H
2
)
2
bpy)]Br
2
(2) on nanostruc-
tured TiO
2
particles xed on conducting FTO glass, forming a
photoactive anode (TiO
2
(12))[184]. By using TiO
2
(12) as the
working electrode in a three-electrode photoelectrochemical cell
(PEC), visible light driven water splitting has been successfully
demonstrated in an aqueous phosphate buffer solution, with O
2
and H
2
bubbles evolved from the working and the counter
electrode, respectively. A high photocurrent density of more than
1.7 mA cm
2
has been achieved in this set-up.
2.2.7. Electron mediators for overall water splitting
Water splitting using photocatalysts has a serious problem in that
the obtained gas will be a mixture of H
2
and O
2
. However, it would be
possible to generate H
2
separately from O
2
using electron mediators.
It is therefore important to nd new electron mediators for the
improvement of the efciency of Z-scheme systems as well as for
the development of new systems. Kudo's group has reported a novel
Z-scheme water splitting system without an electron mediator [188].
Fujihara et al. have succeeded in the overall water splitting under UV
light irradiation by the Z scheme photocatalyst system using two
compartments connected by a Pt wire with bromide and iron ions
acting as electron mediators [189]. The separation of molecular H
2
and
O
2
is achieved under visible light irradiation by O
2
evolution on WO
3
from a ltered aqueous solution containing iron ions following H
2
evolution on Pt/SrTiO
3
:Rh [190]. Many transition metal complexes
have been reported as electron mediators in dye-sensitized solar cells
[191193]. Gratzel et al. have found that the Co-complexes with
imine-group ligands are comparable electron mediators to the well-
known I
3
/I
redox couple in dye-sensitized solar cells or on inorganic

photocatalysts [53,191,193]. In addition, Elliot et al. have reported Co-
complexes to be effective mediators when combined with other
ligands [192]. There are some analogies between an electron mediator
of the Z-scheme photocatalyst system and that of a dye-sensitized
solar cell, the required redox potential, the reversibility, and the
electron transfer between the solid and the liquid phase (Fig.16). [Co
(bpy)
3
]
3/2
and [Co(phen)
3
]
3/2
redox couples were reported to
act as electron mediators for the overall water splitting under
Fig. 15. Schematic illustration of a molecular device employing a photoanode co-
adsorbed with a photosensitizer [Ru(bpy)
2
(4,4-(PO
3
H
2
)
2
bpy)]Br
2
(1) and a mole-
cular Ru catalyst (2) on nanostructured TiO
2
(TiO
2
(12)), and a passive Pt cathode,
for visible light driven water splitting in aqueous solution.
Source: Ref. [184].
Fig. 16. Overall water splitting using a Z-scheme photocatalyst system.
Source: Ref. [194].
visible light irradiation in Z-scheme photocatalyst systems com-
posed of Ru/SrTiO
3
:Rh and BiVO
4
powders. [194]
3. Main challenges and opportunities
Signicant progress has been made in recent years for the develop-
ment of novel nano- and photocatalysts [3,195199]. Nevertheless, the
efciency of photocatalysis under visible light, must be improved in
order to meet engineering requirements. Furthermore, the stability
and cost of these materials should also be carefully considered. It is
thus a challenge of great importance to identify and design new
semiconductor materials that are efcient, stable, and abundant [3].
The rst property relevant to the photocatalytic activity of a semi-
conductor is its energy band conguration, which determines the
absorption of incident photons, the photoexcitation of electron-hole
pairs, the migration of the charge carriers, and the redox capabilities
of excited-state electrons and holes [27]. Therefore, energy band
engineering is a fundamental aspect for the design and fabrication
of semiconductor photocatalysts. Regarding optical absorption, direct
and narrow band gap semiconductors are more likely to exhibit high
absorbance and is suitable for the efcient harvesting of low energy
photons. However, the recombination probability for photo-excited
electron-hole pairs is rather high in these types of semiconductors,
and the band-edge positions are frequently incompatible with the
electrochemical potential that is necessary to trigger specic redox
reactions [3]. Some renowned photocatalysts such as TiO
2
and WO
3
are in fact indirect band gap semiconductors, which, however, exhibit
a rather abrupt absorption onset similar to direct band gap semi-
conductors. In order to modulate the band gap and band-edge
positions in a precise manner, both, doping with different elements
and solid-solution strategies have been extensively investigated and
applied [200204]. Furthermore, the inter-particle electronic coupling
of semiconductor nanocrystals has been found to be effective for
energy band reconstruction and for band gap narrowing [205]. The
utilization efciency of incident photons in photocatalytic semicon-
ductor materials can be improved by methods other than energy band
engineering, such as the improvement of light sensitization by the
inclusion of quantum dots [206], the plasmonexciton coupling
between anchored noble metal nanoparticle co-catalysts and the host
semiconductor [207], and the photon coupling in photonic semicon-
ductor crystals [208]. Another key issue inuencing the photocatalytic
capability of a semiconductor is the nature of its surface/interfacial
chemistry. The surface energy as well as the chemisorption properties
play crucial roles in the transfer of electrons and energy between
substances at the interface, in governing the selectivity, the rate and
the overpotential of redox reactions on the photocatalyst surface, and
in determining the susceptibility of the photocatalyst toward photo-
corrosion [209]. In general, a higher surface energy should yield higher
catalytic activity. Recently, much interest has been focused on research
into semiconductor crystals with morphologies providing large per-
centages of highly reactive facets [210]. Attempts to deliberately
fabricate such materials are usually challenged by the thermodynamic
growth mechanisms of the crystals. In this way, it is possible to grow
specic nanostructured materials with surfaces comprising nearly
100% high-energy facets with the examples including ultra-thin sheets
and highly symmetric polyhedral particles.
During the search for visible-light responsive photocatalysts,
signicant efforts have been devoted to the development of active
sites on the photocatalysts and to the elucidation of the underlying
reaction mechanisms, leading to signicant progress in the eld of
heterogeneous photocatalysis for water splitting, especially during
the last 5 years [15,153161]. Several promising systems, including
Rh
2y
Cr
y
O
3
-loaded GaN:ZnO (a one-step water splitting system)
and a two-step system consisting of Pt/ZrO
2
/TaON and Pt/WO
3
have been developed employing IO
3
/I
shuttle redox mediators,

with respective apparent quantum yields of about 5.1% upon
illumination at 410 nm and 6.3% upon illumination at 420 nm,
respectively. However, research continues to pursue more active
photocatalytic systems capable of harvesting more visible photons.
As shown in Fig. 17, the solar energy conversion efciency
increases once the overall water splitting can be achieved upon
longer wavelengths irradiation. Needless to say, this is because the
number of available photons in the solar spectrum increases with
increasing wavelength. To provide one-third of the projected
energy needs of the human society in 2050 from solar energy,
preliminary estimation by Doman et al. suggest that approxi-
mately 10,000 solar plants need to be built with each plant being
5 km5 km in area and a solar energy conversion efciency of
10%. The total required area for these constructions, 250,000 km
2
,
corresponds to 1% of the earth's desert area; 570 t of H
2
gas would
be produced per day, assuming an integrated solar energy of AM
1.5G irradiation for a day with correction for sunlight angle. This
H
2
would be available for use as a recyclable reactant in fuel cells
and as a raw material for the production of important chemicals
such as methanol and so on. Of course, a technology to separate
simultaneously produced H
2
and O
2
will also be required.
4. Conclusions and outlook
Over 140 metal oxides, Perovskites and oxynitrides are known to
catalyze the photochemical water-splitting reaction. Even though the
principle activity controlling factors in the employed semiconductor-
heterostructures have been identied, many aspects of the function of
inorganic photocatalysts are still unclear. Metal compounds with d
0
ions (Ti, Zr, Nb, and Ta) and d
10
ions (Ga, In, Ge, Sn, and Sb) both
exhibit activities for the overall photochemical splitting of water.
Oxides are dominant, but nitrides and oxynitrides have also been
shown to catalyze the reaction. Most importantly, the molecular
mechanism of water reduction and oxidation on the semiconductor
surface has not yet been elucidated in sufcient details. Many
questions concerning the charge transfer between semiconductors
and cocatalysts, and its dependence on the structural and electronic
features of the interface still remain unanswered. The effects of
variable material preparations and surface impurities on the catalytic
activity of semiconductors have not been fully considered. These R&D
areas represent signicant opportunities for improving water splitting
photocatalysts. The development of better photocatalysts is also going
Fig. 17. Calculated solar energy conversion efciency as a function of wavelength
for the overall water splitting using photocatalysts with various quantum efcien-
cies. The solar irradiance used for these calculations is taken from AM 1.5G data.
Source: Ref. [160].
to benet from the recent progress in nanoscience. Quantum size
effects can now be used to tailor both, the electronic structure and the
reactivity of nanostructures while synthetic methods can be employed
for controlling the morphology of catalysts down to the nanoscale to
further raise the efciency of photochemical water splitting systems.
Further efforts concerning the development of novel co-catalysts may
furthermore provide additional breakthroughs in obtaining highly
efcient photocatalysts. Such progress in the research is currently
under way along with new synthetic directions for the photocatalyst
preparation and novel system development processes.
Acknowledgment
A.A. Ismail acknowledges the Alexander von Humboldt Foundation
(AvH) for granting hima research fellowship (Renewed Research Stay).
D.W. Bahnemann acknowledges a megagrant from the Russian
Ministry of Science supporting the work for this publication.
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Photochemical Splitting of Water For Hydrogen Production

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Photochemical Splitting of Water For Hydrogen Production

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Review

Photochemical splitting of water for hydrogen production

) pairs in the semiconductor particles;

) that were captured effectively by water

) redox couple as electron mediator (Fig. 7)

) shuttle redox mediator [125]. Although this

anions) and the water molecules, respec-

anions as electron acceptors (Ox) according to the

as a redox mediator under irradiation with only visible

) ion redox couple.

redox potential and the

redox couple, which very rapidly regenerates

redox couple in dye-sensitized solar cells or on inorganic

shuttle redox mediators,

, J. Phys. Chem. B 109 (2005) 1605216061.

shuttle redox mediator under visible light irradiation, Chem.

shuttle redox mediator, Chem. Phys. Lett. 344 (2001) 339344.

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