Roadmap On Solar Water Splitting

VERUSCRIPT FUNCTIONAL NANOMATERIALS
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Photoelectrochemical solar water splitting: From

basic principles to advanced devices
Bandar Y. Alfaifi1,*, Habib Ullah1, Sulaiman Alfaifi2, Asif A. Tahir1,
Review
Tapas K. Mallick1
Article history: 1
Environment and Sustainability Institute (ESI), University of Exeter,
Received: 20 September 2017
Penryn Campus, Penryn, Cornwall, TR10 9FE, United Kingdom
Accepted: 29 October 2017 2
Department of Chemistry, King Abdulaziz University, Jeddah 21589,
Published: 12 February 2018
Saudi Arabia
*Correspondence: Abstract
BYA: ba283@exeter.ac.uk
Photoelectrochemical water splitting (PEC) offers a promising
Peer review:
path for sustainable generation of hydrogen fuel. However,
Double blind
improving solar fuel water splitting efficiency facing tremendous
Copyright: challenges, due to the energy loss related to fast recombination
© 2018 Alfaifi et al. c This is an open access of the photogenerated charge carriers, electrode degradation,
article distributed under the Creative as well as limited light harvesting. This review focuses on the
Commons Attribution License (CC‑BY 4.0), brief introduction of basic fundamental of PEC water splitting
which permits unrestricted use, distribution, and the concept of various types of water splitting approaches.
and reproduction in any medium, provided Numerous engineering strategies for the investgating of the
the original work is properly cited and its higher efficiency of the PEC, including charge separation, light
authors credited. harvesting, and co-catalysts doping, have been discussed.
Moreover, recent remarkable progress and developments for
Keywords: PEC water splitting with some promising materials are discussed.
photoelectrode; metal oxide; water splitting Recent advanced applications of PEC are also reviewed. Finally,
the review concludes with a summary and future outlook of this
Citation: hot field.
Alfaifi B. Y., Ullah H., Alfaifi S., Tahir A. A., and
Mallick T. K. Photoelectrochemical solar
water splitting: From basic principles to
Introduction
advanced devices. Veruscript Functional
Nanomaterials. 2018; 2: #BDJOC3.
The traditional sources of energy such as coal, oil and nat-
https://doi.org/10.22261/FNAN.BDJOC3 ural gas have supplied the world with energy that drives
society for long decades. But the energy consumption
around the world is incredibly increased and is estimated to
be double by 2050 [1]. Since the fossil fuel resources are
limited and concentrated in certain region around the world,
while global demand is increasing; subsequently, a secure
supply is increasingly challenging to assure [2]. Furthermore,
pollution created from fossil fuel plants has significant
impact on our health. Moreover, the emissions of green-
house gas and Carbon dioxide have negative impact on our
planet.
Renewable energy resources such as wind, biomass and solar
fuel have been investigated for years to help in the replace-
ment of fossil fuels. Extensive research and development are
required to produce such a technology that can compete the
fossil fuel and commercially available everywhere. However,
Veruscript Funct. Nanomater. | 2018 | 2: #BDJOC3 | https://doi.org/10.22261/FNAN.BDJOC3 1

Alfaifi et al. | Photoelectrochemical solar water splitting https://www.veruscript.com/a/BDJOC3/
the most developed renewable energy sources are based on electricity generation, producing trans-
portable and storable fuel, which is remains a challenge.
Among these energy resources, solar energy is considered a primary carrier that may hold potential
promise for a sustainable and clean energy future [3]. Solar energy focused on direct conversion of sun
light into chemical fuels in the form of hydrogen gas (H2) [4]. The advantages and attractiveness of
solar water splitting, include sufficient water resources, small reaction potential required (1.23 eV), and
zero CO2 emission [5].
In this review, we are aiming to briefly introduce the basic principles of PEC. An overview of the
common used materials that have been investigated for photoelctrochemical water splitting will be
presented. In addition, the current state of the technology is discussed. Finally, the review concluded
with a summary and future viewpoint in this hot topic of research.
Basic principles of photocatalytic water splitting
Generating Hydrogen fuel directly from sunlight, comes from natural phenomena called natural
photosynthesis (NP), exist in plants [6,7], where sunlight is used to convert water and carbon dioxide
into oxygen and carbohydrates. The potential technology that converts water into H2 and O2 using
sunlight for generation of solar fuel is called artificial photosynthesis (AP), which aims to mimic NP
using man-made materials [7,8].
The water splitting reactions (see reactions 1–3) is an uphill reaction with a net Gibbs free energy of
238 kj/mol or 1.23 eV, as shown in Equation (1),
O2 + 4H+ + 4e - U 2H2O Water Oxidation (1)
+ -
4H + 4e U 2H2 Water Reduction (2)
2H2O → 2H2 + O2 Water Splitting (3)
The basic mechanism of photocatalysis water splitting in general is based on the generation of photo-
excited charge carriers. Generally, photocatalytic water splitting reaction on semiconductor particles
involves three main steps: (1) absorption of light irradiation with energies exceeding the semiconductor
bandgap, generate electrons (e−) and holes (h+) pairs inside the semiconductor particles; (2) the
generated electrons and holes are separated followed by migration of these charges to the interface of
the semiconductor particles; (iii) surface chemical reactions between these carriers with various
compounds (e.g., H2O); electrons and holes to produce H2 and O2, respectively as it shown in
Figure 1 [9,10]. Recombination of electrons and holes may also occurs on a very fast timescale without
participating in any chemical reactions [5,9,11,12].
General approaches for water splitting
Production of Hydrogen, using water splitting technique mainly fall into three categories; pho-
tocatalyst system (PC), photoelectrochemical system (PEC), and photovoltaic-photoelectrochemical
system (PV-PEC) [13,14]. In photocatalytic system (PC), which is considered as the simplest,
cheapest, and for potential scalable method for water splitting. Photocatalyst which form as
powders are dispersed in water for water splitting under light irradiation (Figure 2). Photocatalysts
possess the advantage that the water splitting can occur in the homogeneous phase without the
need of transparent electrodes and without the need of directional illumination [10]. Whereas, PC
have many disadvantages that limit its use for water splitting. (1) Separation of the generated
hydrogen and oxygen immediately when formed are required, which will consume additional
energy, causing low efficiency of water splitting process. (2) The illumination of PC systems
without fast removal of the catalysts will eventually cause a photostationary state, where all forward
and backward reactions have identical rates, and no more water splitting can take place. (3)
Implementing PC system at high scale still challenging. Due to these limitation, PC system will not
be covered in this review.

Figure 1. Fundamental principle of photocatalytic water splitting on semiconductor.
Adapted with permission from ref [8]. Copyright 2011 Materials Research Society.
Photoelectochemical water splitting has been reported for the first time early 1968 by illumination a
conductive electrode made from TiO2 in aqueous solution [15]. The interaction of incident light with
TiO2, generate electron hole pairs, where the holes oxidize water at the TiO2 surface to generate
oxygen, and the electrons travel to the Pt counter electrode to reduce water to produce hydrogen
(Figure 3a)[11–14]. In PEC technique, the photocatalysts initially prepared on conductive substrates
as electrodes and additional small bias applied for water splitting.
To make this cell, one or both electrodes should be a photoactive semiconductor, where the charge
separation forms at the semiconductor/liquid interface (Figure 3b and 3c). When the cell is exposed
to sun-light, photogenerated carriers are separated by the space-charge field and the minority charges
(holes for an n-type photoanode and electrons for a p-type photocathode) travel to the semi-
conductor electrode-liquid interface for reaction [17]. Compared to photocatalyst system (PC), PEC
have advantage that there is no need for gas separation in PEC systems because the generation of H2
and O2 is spatially separated at different electrode sides [17,18]. PEC will be described in this review
with focus on different semiconductor materials used to fabricate both photoanode and photo-
cathode.
Photocathode for hydrogen evolution
Water splitting photocathodes are generally p-type semiconductors and must generate the required
cathodic current to reduce water to hydrogen and need to have high stability in aqueous environments.
The optimal photocathode material, need to have the conduction band edge potential to be more
negative than the hydrogen redox potential. Many earlier studies on electrochemical photocathodes
mainly focused on p-type silicon and III–V semiconductor such as InP and GaP. Recently, p-type
semiconductor including oxides and sulphide have received lots of attention. In this section, the review
is focused on various photocathodes materials, which include monometallic and bimetallic oxides,
chalcopyrites, silicon, and III–V semiconductors.

Figure 2. Schematic diagram for solar hydrogen via photocatalytic water splitting system (PC).
Adapted with permission from ref [8]. Copyright 2011 Materials Research Society.
Figure 3. General Illustration of photoelectrochemical water splitting (PEC).
(a) A single photoelectrode PEC configuration powered by a photovoltaic (PV) cell to allow water reduction at the
cathode. (b) A two photoelectrodes PEC configuration connected in parallel. (c) A two photoelectrodes connected in
series. Adapted with permission from ref [16]. Copyright 2010 Royal Society of Chemistry.
Single metallic
Cuprous oxide (Cu2O), cupric oxide (CuO), and nickel oxide (NiO) are among the forefront p-type
semiconductors oxide that have been investigated for solar water splitting. They are favourable
photocathodes having low cost, earth abundance, and ideal band-gap energies that allow for the
absorption of visible light.

Cu2O
Cuprous oxide is one of the most investigated p-type semiconductors, used for solar water splitting.
Cu2O has a direct band gap of 1.9–2.2 eV [19], which makes it an excellent solar absorber; however
the photocorrosion is the major limitation of Cu2O [19,20]. Recent studies show that there is a
possibility to suppress the photocorrosion of Cu2O by adding a passivation layer on the surface of
Cu2O (Figure 4a). This layer prevent the direct contact between the Cu2O surface and the sur-
rounding electrolyte [21]. The best performance of Cu2O was demonstrated from cathodic reduction
of Cu2+ ions in aqueous solution with pH 12, where TiO2 was as a protective layer with photocurrent
of −7.6 mA/cm2 at 0V vs RHE as shown in Figure 4c [22].
CuO
Cupric oxide (CuO) is another p-type copper oxide with an indirect band gap of 1.2–1.8 eV [23,24],
where its small band gap allows CuO to achieve more photocurrent than Cu2O. However, CuO as a
photocathode for water splitting has received less attention than Cu2O, due to its conduction band,
more positive than that of the Cu2O [25–27]. Though, recent studies on hydrogen evolution by CuO
Figure 4. (a) Schematic diagram of Cu2O photocathodes deposited with ZnO:Al and TiO2 as a protective
layer and (b) SEM image of deposited Cu2O, (c) J-V plot of the FTO/Cu2O/TiO2 photocathodes.
Adapted with permission from ref [22]. Copyright 2011 Macmillan Publishers Ltd.

Figure 5. (a) Photocurrent response of NiO/CdSe/CdSe:NiO electrodes under dark and visible light.
(b) UV/Vis absorption spectra of NiO/CdSe/CdSe:NiO electrodes.
Adapted with permission from ref [38]. Copyright 2015 Wiley and Sons.
with composites photocatalysts, confirm the possibility of CuO to reduce water to hydrogen [28–31].
Similar to Cu2O, photocorrosion is another major drawback with CuO as photocathode in water
splitting. However, some recent studies show that a reduction in photocorrosion of Cu2O may apply
to CuO [31–33].
NiO
Nickel oxide (NiO) is a semi-transparent p-type semiconductor with direct band gap of 3.6–4.0 eV
[34]. This wide band gap NiO possess low resistance, high p-type concentration, high hole mobility,
and low lattice mismatch with ZnO, which are favourable for formation of p-n heterojunction [34–37].
On the other hand, the photocurrents obtained by NiO photocathode are low due to low potential of
its valence band (0.3V vs RHE) [38]. However, sensitizing NiO photocathodes with quantum dots (e.
g., CdSe) possess high photocurrent and photopotential as shown in Figure 5a and 5b [37,39].
Bimetallic
CuFeO2
CuFeO2 has a ABO2-type semiconductor delafossite structure with bandgap of 1.5–1.6 eV, which can
absorb the entire range of visible light [40]. In addition to its small band gap, CuFeO2 is an earth
abundant material with high onset potential and good stability in aqueous solution [40,41]. However,
the lack of poor charge transfer, limit its performance for PEC water splitting. Recent studies show that
the fabrication techniques, involving post treatment in air with hybrid microwave annealing, enhanced
the activity of the electrode which make the CuFeO2 attractive candidate for PEC water splitting as
shown in Figure 6a [42]. In Figure 6b and 6c, photocurrent activity of CuFeO2 possess enhancement
after modifying with electrocatalyst such as nickel-iron (NiFe) and reduced graphene oxide (RGO) [42].
LaFeO3
Perovskite oxides are quite encouraging materials for PEC water splitting due to their high efficiency
and stability in water. LaFeO3 with ABO3 perovskite structure is a promising candidate to be used for
water splitting due to its high stability, optoelectronic properties and small band gap energy [43–46].
However, failure to improve their photoresponse limit their use as photocathode which is because of
the lack of preparative technique for LaFeO3 photocathode with effective quality [46]. Recent effort

Figure 6. (a) J-V plot of untreated CuFeO2 electrode (CFO) and post treated at different annealing time
with using hybrid microwave annealing (HMA) comparing to the conventional thermal annealing (CTA).
(b) Chronoamperemetry of CuFeO2 treated with CTA, HMA, and HMA-NiFe/RGO. (c) J-V plot of HMA,
HMA-NiFe, and HMA-NiFe/RGO simulated in 1 sun irradiation in 1 M NaOH electrolyte.
Adapted with permission from ref [42]. Copyright 2014 American Chemical Society.
show that the efficiency of LaFeO3 as photocathode can be improved via doping with metals which
have 2+ oxidation state similar to that of Fe3+, such as Mg2+ and Zn2+. These dopant agents lead to
change the structure and electrical properties of the photocathode which enhanced the overall pho-
toelectrochemical response of LaFeO3 (Figure 7a and 7b) [47].
CaFe2O4
Calcium iron Oxide (CaFe2O4) has been discovered for the first time as a p-type semiconductor oxide
for use of electrolyse of water [48]. It has band gap of 1.9 eV with suitable conduction and valance
band edges of −0.6 and +1.3 V vs RHE, respectively, which is suitable for splitting water [49].
However, the photoresponse of CaFe2O4 is relatively low, because of its poor charge separation and
charge carrier mobility [50,51]. Moreover, CaFe2O4 photocathode with metal doping such as, CuO
and Au shows a higher photocurrent response due to the increase absorption wavelength range [52].
Furthermore, CaFe2O4 doped with Ag, exhibited 23 times higher photocurrent response than
undoped CaFe2O4 as shown in Figure 8 [53].
Chalcogenides
To date, some p-type chalcogenides have been studied as a photocathode for solar water splitting.
Semiconductors with chalcopyrite structure (e.g., CuInS2, CuGaS2), have recently shown significant
photocathode performance for solar water splitting due to their excellent photovoltaic properties.

Figure 7. (a) FE-SEM images of pristine LaFeO3 comparing to doped LaFeO3 electrodes. (b) Photocurrent
transients for pristine LaFeO3, Mg, and Zn doped LaFeO3 electrodes at −0.25 V.
Figure 8. J-V curves for the; Ag- CaFe2O4 (red line), Cuo- CaFe2O4 (blue line), Au- CaFe2O4 (green line),
and undoped CaFe2O4 (black line).
CuInS2
Copper indium disulphide (CuInS2) is considered as a promising candidate to be used in thin film
solar cells due to its direct bandgap (1.5 eV) and large absorption coefficient (105 cm−1) in the visible
spectral range [54–56]. Moreover, it is environmentally friendly [56], but the fabrication of CuInS2
thin film is expensive. Fabrication techniques such as chemical deposition, especially spray pyrolysis
possess an attraction solution to this issue where the large area of thin film can easily be coated [57].

Spray pyrolysis at low temperature (about 150–200°C) shows the possibility of CuInS2 thin film on
cheap and flexible substrates [57].
CuGaS2
Copper gallium disulphide (CuGaS2) is less interesting to be used as photocathode in solar cell than
CuInS2 due to its wide direct band gap of 2.4 eV [58]. However, CuGaS2 has conduction band
located at more negative potential than that of CuInS2 which make it a possible photocathode for solar
water splitting [21,59,60]. In addition to its wide band gap, gallium deposition requires more cathodic
potential than that of indium metal, where the fabrication of uniform film remain is challenging [21].
Recent studies suggested that doping CuGaS2 film with co-catalyst such as Zn and Ti enhanced the
morphology and phase structure of Cu-Ga photocathode film [61].
III-V Semiconductors
GaP
Gallium phosphide (GaP) has an indirect band gap (2.2−2.3 eV) and band edges above the reduction
potential of hydrogen which is make it suitable material for water splitting [62,63]. The n-type of GaP
is unstable in water, but the p-type form has more stability for longer periods of time in electrolytes
under cathodic conditions [62]. Despite the wide bandgap of GaP, still it does not show the expected
photocurrent [64,65]. Recent investigation show that the influence of the interface structure region
between the semiconductor and the electrolyte, depositing of platinum particles on top of GaP notable
increased the efficiency of the photoelectrochemical cell [63].
InP
Indium phosphide (InP) has a direct band gap of 1.35 eV, which makes it well-matched to the solar
spectrum [66–69]. Moreover, its conduction band edge is slightly above the water reduction potential
[69]. For these reasons, InP is considered as a promising photocathode for water splitting. Although
p-type InP is suffer from photocorrosion in acidic solution [70,71], but the stability and efficiency of
InP electrode can be enhanced with protective coat-layer of TiO2 [72]. Despite its efficiency, high cost
of bulk materials and fabrication process, InP photocathode limits its scalable application [72]. Latest
studies demonstrated a low-cost and high efficiency solar device, implemented using the thin-film
vapour–liquid–solid (TF-VLS) growth technique that decreases usage of feedstock materials [73].
Figure 9. (a) Current-voltage curve of Si coated with various STO thicknesses as protective layer.
(b) Voltage versus time curve.
Adapted with permission from ref [77]. Copyright 2015 Macmillan Publishers Ltd.

Silicon
Silicon (Si) has been extensively used for water reduction over the past few decades due to its narrow
band gap (1.1 eV) [74,75]. In addition to its small band gap energy, silicon is one of the most
promising materials for photoelectrodes in a PEC due to its natural abundance, environmental
friendly and ability for large-scale production [76–78]. The practical use of Si as photocathode
electrode in water splitting was originally limited due to its instability in water [75]. However,
several approaches have been developed to protect its surface from corrosion using protective layers
(e.g., ALD of TiO2, Al2O3, and different catalysts layers) to enable more stable PEC performances
of Si electrodes in different aqueous environments [70,79–83]. Latest study indicated that Si
photocathode deposited with strontium titanate, SrTiO3 (STO), as protective layer achieved pho-
tocurrent density of (35 mA/cm2) and long-term stability as illustrated in Figure 9 [77].
Photoanode for water splitting
Photoanode materials, responsible for oxygen evolution must be; an n-type semiconductor, band gap
that are suitable for absorb wide range of spectrum, and efficient charge collection and charge carriers’
motilities. In addition to that, the materials must be stable in aqueous solution, low cost, and
environmental friendly. This section will focus on the n-type semiconductors that have been inves-
tigated as a photoanodic electrode in PEC water splitting. Examples of these materials are mono-
metallic and bimetallic oxides, chalcogenide, and nitride.
Monometallic
TiO2
Titanium dioxide (TiO2), which is an n-type semiconductor having band gap of ~3.2 eV, is con-
sidered to be the most promising oxides used in PEC [84–87]. It’s reported for the first PEC water
splitting as photoanode under UV irradiation by Honda and Fujishima in 1972 [11]. Due to its
excellent stability in aqueous solution, it has been implemented as protection layers for photo-
electrodes (e.g., Cu2O, Si, InP, etc.) that are not stable in water [72,81,82]. However, the applications
of TiO2 photoanode in PEC water splitting is limited due to its wide band gap. Several techniques
have been explored to improve the light absorption and charge carries transport of TiO2 such as
doping with cocatalyst (e.g., Co and Ag) (Figure 10). For example, N-modified TiO2 photoanode,
Figure 10. (a) Linear sweep voltammetry of, TiO2 nanowire arrays (blue), Cobalt doped TiO2. (b) Chro-
noamperometry measurement of TiO2 nanowire arrays and the same film after treated with cobalt and
silver.

which were synthesized via the nitridation of hydrothermally synthesized TiO2 nanowire arrays in
NH3 atmosphere, obtained a band gap of 2.4 eV [88]. Additionally, TiO2 nanotubes treated with heat
and chemical reduction demonstrated enhanced photocatalytic activity, with a photocurrent of
2.0 mA/cm2 at 1.23 V [89].
ZnO
Zinc oxide (ZnO) is also an n-type semiconductor which is environmentally friendly and inexpensive
[90–92]. It has band gap of 3.2 eV, similar to TiO2 but higher carrier mobility [91–96]. Nevertheless,
the effective applications of ZnO as photoanode for water splitting still requires the improved design
and synthesis technique to overcome the limitations of ZnO [97]. Recent studies revealed that by
controlling the morphology of ZnO, the light harvesting ability can be enhanced by thermal evapo-
ration approaches and a photocurrent of ~0.4 mA/cm2 at applied potential of 0.8 VAg/AgCl is achieved
[97,98].
WO3
Tungsten oxide (WO3), an n-type semiconductor has been well studied as photoanode for water
splitting compared to their other metal oxides. It has an indirect band gap of 2.5–2.8 eV which can
harvest about 12% of the solar spectrum [99]. WO3 is an inexpensive, nontoxic, and possess high
stability in acidic aqueous solution [99–101]. However, this material can only absorb a limited
portion of visible light due to its wide band gap [99]. Moreover, its conduction band is too low
(0.3 V vs RHE) comparing to Hydrogen evolution reaction redox potential [102]. Recent studies
have demonstrated that morphological control and hydrothermal treatment can significantly affect
the morphology of the synthesized electrode and may exhibit a far higher enhancing photocurrent of
WO3 [103,104]. In particular, it was shown that fabricated WO3 nanospheres by removing the top
platelets of WO3 via a hydrothermal method exhibited a photocurrent of 2.6 mA/cm2 at 1.2 V
[104].
α-Fe2O3
Alpha-Hematite (α-Fe2O3) is undoubtedly the most extensively studied n-type semiconductor to be
used in water splitting. It has band gap of 2.0–2.2 eV which absorb a significant portion of visible
light with efficiency exceeds 12% [17,105–107]. It is also stable in most of the aqueous media, and
has high resistance towards photocorrosion [17,108,109]. In addition, it is environmental friendly
and inexpensive but it has low absorption efficiency, low electrical conductivity, short diffusion
length (2–4 nm), and facile surface recombination are serious challenges for its used in practical
application as a photoanode [110]. To overcome these limitations, several synthesis techniques and
strategies have been developed, which include surface modification and composition [108,111,112].
Surface modification with catalysts such as IrO2, aim to reduce the overpotential and thus enhanced
the efficiency [113,114], while composition aims to increase charge mobility [114]. Recent study
reported that preparing α-Fe2O3 film by electrodeposition method followed by surface decorating
with Co-Pi catalyst showed a stable photocurrent of ~1.89 mA/cm2 at 1.23 V vs RHE as presented
in Figure 11 [115].
Bimetallic
BiVO4
Another n-type semiconductor is Bismuth vanadate (BiVO4), which is recently emerged as a viable
candidate for photocatalytic water splitting. It has band gap of 2.4 eV and can absorb a significant
portion of the visible spectrum [116,117]. It has a suitable conduction band position very near to the
H2 evolution potential, and relatively low onset potential for O2 evolution [118,119]. However,
BiVO4 lacks low photocurrent efficiency under solar radiation, fast electron–hole recombination, slow
charge transfer, and low water oxidation kinetics [120–122]. To overcome these drawbacks, several

Figure 11. (a) J-V measurements with chopped light for Co-Pi/α-Fe2O3 films at different deposition times
(300 s, 600 s, and 1,200 s). (b) Photocurrent versus time curve of α-Fe2O3 and 600s Co-Pi/α-Fe2O3
photoanode.
Adapted with permission from ref [115]. Copyright 2015 Royal Society of Chemistry.
Figure 12. (a) PEC photocurrent potential (J-V) curves of five photoanodes (i.e., BVO = BiVO4, B/W =
BiVO4/WO3, B/S = BiVO4/SnO2, B/S/W = BiVO4/SnO2/WO3, B/W/S = BiVO4/WO3/SnO2). (b) Photocurrent
density and solar to hydrogen conversion efficiency as a function of time for the BiVO4/WO3/SnO2
photoanode tandem cell.
techniques has be applied such as construction of heterojunction structures, morphology control, and
doping. Previous works have demonstrated that BiVO4 heterojunction WO3/BiVO4 less than
1.0 mA/cm2 at 1.0 V vs RHE [123,124]. A significant enhancement has been achieved using a
double-heterojunction photoanode based on BiVO4/WO3/SnO2 triple layers prepared by spin
coating, which has an increased the PEC photocurrent to 3.1 mA/cm2 at 1.23 V vs RHE as presented
in Figure 12 [125].
CuWO4
Copper tungstate, also known as copper tungsten oxide (CuWO4) is an n-type semiconductor with
indirect optical band gap of 2.3 eV [126–128]. It has been widely studied for different applications
such as detector, lasers, and optical sensor [127–129]. Due its small band gap, it is very close to ideal

Figure 13. (a) Photocurrent versus voltage (j-v) curve of Current vs time curve for CuWO4 electrode
before and after decorating with TiO2-coated Au NPs. (b) Photocurrent versus time (j-t) curves at
1.23 V vs RHE under AM 1.5 irradiation.
potential for PEC water spiting as promising photoanode material [128,130]. In addition, single
crystal of this materials have maximum conversion efficiency of 0.52% [127]. The PEC of CuWO4 is
significantly low due to its low absorption light and high bulk charge transfer resistance [130–133].
Several approaches such as surface modification and construction of heterojunction structures can help
to mitigate some of its PEC water splitting limitations. Recent studies demonstrated that modification
of the CuWO4 photoanode surface with TiO2-coated Au NPs can significantly increase the PEC
water-splitting performance and increased the water splitting photocurrent from 0.03 to 0.1 mA/cm2
(Figure 13) [134]. Coupling CuWO4 with WO3, to form heterojunction photoanode can enhanced
the absorbed photon density and charge mobility [135,136].
Nitride and Oxynitride

TaON
Tantalum oxynitride (TaON) with band gap of 2.5 eV is another n-type semiconductor, suitable for
solar water splitting [137–139]. It has achieved a maximum quantum efficiency of 34% [140].
Moreover, TaON shows reasonably alignment of its CB and VB edges relative to the OH-/O2
oxidation and H+/H2 reduction potentials, generate H2 and O2 [137]. However, the activities for H2
production is lower than those for O2 evolution, which is sufficiently negative for H2 production
[141]. TaON suffer from low stability due to the introduction of N 2p orbitals in the valence band
[137]. Recent studies has demonstrated that the photocatalytic activity of TaON for water splitting
can be enhanced through photo-deposition with noble nanoparticles such as Ru [142]. Also, a sig-
nificant enhancement to the photocurrent in TaON photoanode by heat treatment of the surface with
TiCl4 has been reported (Figure 14) [143].
Ta3N5
Tantalum nitride (Ta3N5) has received significant attention over the past years due to its small band
gap (2.1 eV) and stability [139,144–147]. It has CB lies at ca.−0.4 V vs. RHE, and VB lies at ca.
+1.6 V vs. RHE, which possibly allow Ta3N5 to perform unassisted solar water splitting [144,148].
Due to these band energies, Ta3N5 can theoretically split water spontaneously as a single photoanode
with maximum solar to hydrogen efficiency of about ~15% [148–150]. However, Ta3N5 suffer from
the poor charge transport, low photocurrent efficiency and insufficient light absorption [151–153].
Effective strategies have been developed to enhance the PEC performance of Ta3N5 photoanode, such

Figure 14. Current–bias dependence over the TaON electrodes before and after the TiCl4 treatment
under chopped visible light irradiation.
Adapted with permission from ref [143]. Copyright 2005 The Chemical Society of Japan
as nanostructuring and morphology control [154,155]. Particularly, Ta3N5 photoanode with a 1D

configuration, such as nanotubes (NTs), nanorodes (NRs), have been considerably investigated
[151,152,156–160]. These 1D nanostructure offer advances of charge transfer to the solid-liquid
interface without recombination and high absorption of incident light. Ta3N5 nanorod arrays
modified by Co(OH)x co-catalyst yields a stable photocurrent density of 2.8 mA/cm2 at 1.23 V vs
RHE as illustrated in Figure 15 [157].
Chalcogenides
CdS
Cadmium sulphide (CdS) is the most investigated metal chalcogenide materials for water splitting
under visible light irradiation due to its favourable direct band gap (2.4 eV). Furthermore, its band
edge positions are suitable for water splitting to produce hydrogen and oxygen [161,162]. Despite
these advantages, the photocurrent activity of CdS is not sufficient due to the photpgenrated
charges (electrons and holes) which cannot be efficiently separated and transferred [162–164].
Additionally, CdS suffer from photocorrosion in aqueous media which hampers their long term
stability in solar water splitting [161,165]. To overcome these drawbacks, extensive studies have
been investigated to improve the stability and efficiency of CdS photoanode. Recent studies
demonstrated that, formation of CdS 2D-nanostructer offer significant advantages such as, reduc-
tion of the scattering rate which increase the carrier collection efficiency and increase the absorption
of incident light [166].

Figure 15. (a) Photocurrent vs applied potential bias curve of Ta3N5 photoanode before and after loading
of the Co (OH)x co-catalyst. (b) Photocurrent vs time (j-t) curve.
ZnS
Zinc sulphide (ZnS) is a promising candidate for photocatalysis of hydrogen production due to its
ability, generation of mobile photo excited charge carriers, and high conduction band potential which
ensures fast electron transfer [167–170]. Moreover, it has active sites for hydrogen evolution without
the need to deposit expensive charge transfer co-catalyst like Pt or RuO2 [171]. But due to its large
band gap (≈3.6 eV), the performance in photocatalysis is limited, which means that pure ZnS are only
active under UV irradiation [172,173]. Therefore, several studies have been investigated to improve
the light absorption behaviour of ZnS photoanode. For instance, it has been reported that doping ZnS
with transition metal ions such as Ni, Sn, and Cu has improved the H2 production under visible light
irradiation [174–176]. An alternative approach to doping is the defect engineering, which also increase
the overall efficiency of ZnS [177]. Moreover, the modification of the fabrication conditions can lead
to defect states in ZnS thin films which also enhance visible-light absorption, charge separation, and
photocurrent up to 1.6 mA/cm2 [177].
Current state of the art for water splitting
Tandem approach
Photoelectrochemical (PEC) water splitting is considered as a promising technology to convert solar
energy into storable and transportable fuel. Potential energy greater than 1.23 eV should be sufficient
to split water. However, the actual required energy is considerably greater due to the different kinetic
and thermodynamic non-idealities in the oxidation and reduction reactions. Therefore, using a single
semiconductor absorber, requires a semiconductor with large energy bandgap to absorb a maximum
portion of the solar spectrum [178]. This drawback, can be solved by dual-absorber-four photon (D4)
tandem approach (Figure 16) [179]. In PEC tandem device, the cell configuration is composed of two
sided light absorption electrodes, a p-type photoanode and a n-type photocathode, where hydrogen
evolution (water oxidization) and oxygen reduction (water reduction) reactions take place on the
photocathode and photoanode, respectively [179].
Tandem cell has an improved overall efficiency due to the two different band gaps used and the high
portion of the light absorbed. It show a theoretical estimated light conversion efficiency of 18% [180].
Tandem cell used a III–V semiconducting materials have been shown to perform with efficiencies of
12.4% under concentrated sun light [181]. Though, their commercial applications still far to achieve

Figure 16. Schematic diagram of PEC water splitting approach using a dual-absorber tandem cell.
Figure 17. Photovoltaic-integrated photoelectrochemical cells.
due to poor stability, high cost and complexity of their fabrication [182]. To reduce the cost, increase
stability, and enhanced the efficiency, several methods have been proposed [179,183–188]. Recently,
Graetzel et al. reported a perovskite tandem solar cell based on CH3NH3PbI3 and achieved solar-
to-hydrogen efficiency of 12.3% [189].
PEC/PV approach
Due to the difficulties in designing PEC tandem cell with sufficient bandgap energies and band edge
positions of photocathodes and photoanodes; photovoltaic-integrated photoelectrochemical cells are
attractive approach for mitigating this aspect. In this configuration, the bandgap energy levels in
PEC cells have no role with the water redox due to PV cells could play the direct role of potential
supply; therefore, there are no limitations on selecting the material type (Figure 17) [184]. PV-PEC
systems possess many advantages for water splitting compared with PEC systems, excluding major
cost. PV-PEC device has been developed for the first time for hydrogen production via water

splitting in 1998, using a GaInP2/GaAs tandem cell which has achieved more than 10% efficiency
[181].
Moreover, coupling a WO3/BiVO4 photoanode with a double junction GaAs/InGaAsP solar cell, to
build a self-operating integrated PEC device, generated solar to hydrogen efficiency of up to 8.1%
[118]. The highest efficiency of PV-PEC approach was recently achieved through fabrication of an
integrated system with Ni electrodes and multi-junction GaInP/GaAs/Ge solar cell, delivered solar
water splitting efficiency of about 22.4% [190]. Despite this high efficiency, the fabrication of PV-
PEC solar cells is complicated and expensive. Without considering the cost factor, PV-PEC systems are
the most viable hydrogen production method for the practical applications. PV-PEC system based
hydrogen production is expected to be primarily used in navigation, military, and aerospace appli-
cations to provide fuel for these special situations.
Conclusion and outlook
Significant increase in research activity around the solar hydrogen production via direct water splitting
under sunlight has been achieved in the last decade.
• In this review, we present the fundamental mechanisms and basic principle of water splitting.
• We investigated the common engineering strategies of hydrogen production via solar water
splitting.
• Many semiconducting materials such as p-type, n-type, nitride, and chalcogenide have been
successfully developed as a photocathode and photoanode for PEC.
• Advanced PEC applications such as tandem cell and PV-PEC hybrid system have possessed
significant solar to hydrogen efficiency.
• The solar to hydrogen efficiency of different approaches has been improved to more than 12.3%
and 22.4% for PEC and PV-PEC water splitting systems, respectively.
• Solar driven hydrogen production is ideal pathway to produce green energy but it faces many
challenges to achieve this goal.
• Significantly, several factors such as stability, electronic properties, structure, surface states and
morphology of catalysts, cost, and toxicity need to be carefully considered to drastically improve
the hydrogen production efficiency through solar water splitting in practical applications.
Acknowledgements
We would like to acknowledge The Saudi Arabian Cultural Bureau (SACB) for providing PhD
fellowship to Bandar Y. Alfaifi.
Funding sources
The partial financial support was provided by Engineering and Physical Science Research Council
(EPSRC), UK, under research grant No. EP/P510956/1.
Competing interests
All authors including Bandar Alfaifi, Habib Ullah, Sulaiman Alfaifi, Asif Tahir and Tapas Mallick
declare that they have no conflict of interest.

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Roadmap On Solar Water Splitting

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VERUSCRIPT FUNCTIONAL NANOMATERIALS

Photoelectrochemical solar water splitting: From

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Basic principles of photocatalytic water splitting

General approaches for water splitting

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Figure 1. Fundamental principle of photocatalytic water splitting on semiconductor.

Photocathode for hydrogen evolution

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Figure 3. General Illustration of photoelectrochemical water splitting (PEC).

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Photoanode for water splitting

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Nitride and Oxynitride

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as nanostructuring and morphology control [154,155]. Particularly, Ta3N5 photoanode with a 1D

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Current state of the art for water splitting

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Figure 17. Photovoltaic-integrated photoelectrochemical cells.

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Conclusion and outlook

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