Nano-Micro Lett.

(2016) 8(1):112
DOI 10.1007/s40820-015-0063-3

REVIEW

Recent Advances in Visible-Light-Driven Photoelectrochemical

Water Splitting: Catalyst Nanostructures and Reaction Systems
Xiaoping Chen1,2 . Zhixiang Zhang1,2 . Lina Chi2,3 . Aathira Krishnadas Nair2 .
Wenfeng Shangguan1 . Zheng Jiang2

Received: 17 August 2015 / Accepted: 31 August 2015 / Published online: 28 October 2015
The Author(s) 2015. This article is published with open access at Springerlink.com

Abstract Photoelectrochemical (PEC) water splitting using solar energy has attracted great attention for generation of
renewable hydrogen with less carbon footprint, while there are enormous challenges that still remain for improving solar
energy water splitting efficiency, due to limited light harvesting, energy loss associated to fast recombination of photo-
generated charge carriers, as well as electrode degradation. This overview focuses on the recent development about catalyst
nanomaterials and nanostructures in different PEC water splitting systems. As photoanode, Au nanoparticle-decorated TiO2
nanowire electrodes exhibited enhanced photoactivity in both the UV and the visible regions due to surface plasmon
resonance of Au and showed the largest photocurrent generation of up to 710 nm. Pt/CdS/CGSe electrodes were developed as
photocathode. With the role of pn heterojunction, the photoelectrode showed high stability and evolved hydrogen contin-
uously for more than 10 days. Further, in the Z-scheme system (Bi2S3/TNA as photoanode and Pt/SiPVC as photocathode at
the same time), a self-bias (open-circuit voltage Voc = 0.766 V) was formed between two photoelectrodes, which could
facilitate photogenerated charge transfers and enhance the photoelectrochemical performance, and which might provide new
hints for PEC water splitting. Meanwhile, the existing problems and prospective solutions have also been reviewed.

Keywords Photoelectrochemical water splitting
Nanostructures
Reaction system
Heterojuction
Hybrid systems

1 Introduction fuels are suffering from accelerated depletion and

bringing about serious environmental issues and threats
The energy consumption nowadays to maintain modern to global climate. It is a mission of international scale to
lifestyle of mankind mainly relies on primary fossil fuels explore and utilize alternative energy to compensate for
such as oil, coal, natural gas, etc. However, the fossil the consumption of fossil fuels and mitigate the corre-
sponding climate changes. Among various alternative
energies, hydrogen has been considered as a promising
& Wenfeng Shangguan candidate to solve aforementioned problems because it is
shangguang@sjtu.edu.cn a source of green and renewable energy. There are a
& Zheng Jiang variety of strategies for hydrogen production, such as
Z.Jiang@soton.ac.uk electrolysis, thermal water splitting, cracking of petro-
1
leum, hydrocarbon reforming, etc. However, these tech-
Research Center for Combustion and Environment
Technology, Shanghai Jiao Tong University,
niques are either costly or rely on fossil fuels. In 1972,
Shanghai 200240, Peoples Republic of China Fukushima and Honda discovered photoelectrochemical
2
Faculty of Engineering and the Environment, University of
(PEC) water splitting in which hydrogen and oxygen
Southampton, Highfield, Southampton SO17 1BJ, UK were released, respectively, from titanium dioxide (TiO2)
3 photoelectrode and Platinum (Pt) counter electrode under
School of Environmental Science and Technology, Shanghai
Jiao Tong University, Shanghai 200240, ultraviolet (UV) light irradiation [1], revealing the
Peoples Republic of China potential of solar energy water splitting to produce

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2 Nano-Micro Lett. (2016) 8(1):112

sustainable hydrogen. This discovery stimulated great 2 Working Principle of Photoelectrochemical

interest to explore effective photoelectrode materials for Water Splitting
solar energy hydrogen generation via solar energy water
splitting which is not only a clean process but also stores Loaded with semiconductor photocatalysts, the conductive
solar energy in hydrogen [24]. However, the widespread electrode substrates can be metal plates, silicon substrates, or
application of PEC water splitting still demands great glass coated with conductive layers, such as fluorine-doped
efforts in the discovery of effective photocatalysts and tin oxide (FTO) and indium tin oxide (ITO) [1619]. In PEC
coating process. water splitting system, the free energy change (DG) is
In comparison with photocatalytic water splitting using 237.2 kJ mol-1 for converting one molecule of H2OH2 and
heterogeneous powder semiconductors, PEC water splitting 1/2 O2 under standard condition. When a photoelectrode is
possesses great advantages in (i) the external or self-bias immersed in an electrolyte solution, electron transfer takes
voltage can suppress recombination of photogenerated place between the semiconductor and the electrolyte solution
charge carriers and thus improve the separation and so that the Fermi level is equilibrated with the redox potential
transfer of excited electronhole pairs of the photocata- of electrolyte solution [15]. With n-type semiconductors as
lysts; (ii) hydrogen and oxygen can be easily separated via working photoanodes, for example, as shown in Fig. 1,
collection at different photoelectrodes; (iii) semiconductor photoexcited holes on the semiconductors would oxidize
films are coated on the conductive substrates, which favors water and produce oxygen, while electrons are transferred to
scale up for industrial application in the future; and (iv) the counter electrode to generate hydrogen. Sometimes, an
last, but not the least, it does not need stirring, so it con- external voltage is needed to compensate for the potential
sumes less power relative to powder photocatalytic water deficiency, which can also accelerate the separation of
splitting systems [2, 5]. In practice, the performance of excited charges. The electrolytes are essential in the PEC
PEC water splitting system is dominated by the properties system for charge transfers, which usually are NaOH, Na2-
of the semiconductor photocatalysts that harvest solar SO4, etc. [20, 21]. Some sulfides and organic agents can also
energy for hydrogen generation. serve as electrolytes [19, 22]; where there is no oxygen
Various effective UV-light-responsive photocatalysts evolution, as water oxidation potential is more positive than
have been well established [6, 7], although most of them the oxidation potential of these materials.
suffer from photocorrosion and are not active under
visible light which accounts for 45 % energy of solar
spectrum, nearly an order of solar energy in UV region. 3 Semiconductors Systems for PEC Water
In the recent decades, designing visible-light-driven Splitting
photocatalysts for water splitting represents a major
mission for photocatalytic water splitting to maximize the Different semiconductor systems for PEC water splitting
solar energy conversion and storage. For instance, the and their PEC performance are shown as in Table 1. They
metal sulfides have been found as a class of efficient can be classified into three groups: (1) photoanode, (2)
photocatalysts but require sacrificial agents to reduce photocathode, and (3) Z-scheme system for PEC water
photocorrosion [812]. (Oxy) nitride semiconductors splitting.
recently emerged as new type of phototcatalysts for
visible-light-responsive photocatalytic water splitting [13 Bias
15], whereas they can respond to short-wavelength visi-
ble light with rather low solar energy conversion effi-
e
ciency. Fortunately, the hybrid photocatalyst systems H2O
have demonstrated enhanced water splitting efficiency, CB
e
which, however, require dedicated design and alignment hv H2
of the corresponding photocatalytic materials [6].
In this study, we briefly overviewed the recent
research advances in the field of hydrogen evolution from VB H 2O
PEC water splitting, addressing the different PEC water h+ O2
splitting systems and corresponding electrode materials.
Key issues and challenges involved in PEC water split- Electrolyte
ting systems and potential solutions were highlighted via Photoelectrode Counter electrode
the comparison of various photoelectrode materials and
nanostructures. Fig. 1 The schematic setup of PEC water splitting system

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Nano-Micro Lett. (2016) 8(1):112 3

Table 1 Different photoelectrodes and their photoelectrochemical performance

Photoelectrode Photocurrent Experimental condition Reference
(mA cm-2)

TiO2-xCx nanotube array 1.0 0 V versus Ag/AgCl, 1 M KOH(aq), 2500 W Xe lamp (100 mw cm-2), 35
[420 nm
N-doped TiO2 nanotube arrays 0.182 0 V versus calomel electrode, 0.01 M Na2SO4 (aq), 250 W halogen lamp, 36
[400 nm
S-doped TiO2 nanotube arrays 0.41 0.1 V versus SCE, 0.1 M Na2SO4 (aq), 50 W fiber optic illuninator, 37
[400 nm
Au nanoparticle-decorated TiO2 1.49 0 V versus Ag/AgCl, 1 M NaOH(aq), white-light illumination (100 mW 40
nanowire electrodes cm-2)
Au decorated ZnO nanowire 1.5 1 V versus RHE, 0.5 M Na2SO4 (aq), 300 W Xe lamp (100 mW cm-2), 42
arrays [420 nm
CdTe/TiO2 0.44 0 V versus Ag/AgCl, 0.6 M Na2S (aq), 300 W Xe arc lamp 43
(6.0 W cm-2 [400 nm
CdS/TiO2 5.6 0 V versus Ag/AgCl, 0.1 M Na2S (aq), 300 W Oriel solar simulator (100 46
mW cm-2)
Bi2WO6/TiO2 0.014 1 V versus Ag/AgCl, 0.5 M Na2SO4 (aq), 300 W Xe lamp, [420 nm 47
CdS/TiO2/WO3 1.6 0 V versus Ag/AgCl, 0.05 M Na2S (aq), 300 W Xe lamp, [495 nm 50
Hydrogen-treated TiO2 1.97 -0.6 V versus Ag/AgCl, 1 M NaOH(aq), 150 W Xe lamp (100 mW 52
nanowire arrays cm-2)
N-doped ZnO nanowire arrays *0.15 0.5 V versus NHE, 0.5 M NaClO4 (aq), white light source (100 mW 56
cm-2)
WO3/BiVO4 0.8 0.5 V versus NHE, 0.5 M Na2SO4 (aq), chopped white light (100 mW 58
cm-2)
FeOOH 10 0.55 V versus RHE, 1 M Na2CO3 (aq), 150 W Xe arc lamp (100 mW 60
cm-2), [400 nm
IrO2
nH2O/TaON *3.75 0.6 V versus Ag/AgCl,, 0.1 M Na2SO4 (aq), chopped visible light 65
IrO2-loaded Ta3N5 3.6 0.6 V versus Ag/AgCl, 0.1 M Na2SO4 (aq), 300 W Xe lamp, [400 nm 67
-2
TiO2 nanoarrays sensitized with 3.98 0 V versus Ag/AgCl, 1.0 M KOH (aq), 300 W Xe lamp (100 mW cm ), 68
CdS quantum dots [420 nm
PtIn2S3/CuInS2 -17.5 to -7.0 0 V versus RHE, 0.1 M Na2SO4 (aq), 300 W Xe lamp 74
PtCdS/CuGaSe2 -3.2 0 V versus RHE, 0.05 M Na2HPO4(aq) ? 0.05 M NaH2PO4(aq), 150 W 18
Xe lamp
pn Cu2O homojuction -0.2 0 V versus NHE, 0.5 M Na2SO4 (aq), 500 W Xe lamp 79
Pt/ZnO, Al2O3, TiO2/Cu2O -7.6 0 V versus RHE, 1 M Na2SO4 (aq), 500 W Xe lamp (100 mW cm-2), 80
visible light
Photoanode: TiO2 0.2 0 V versus Ag/AgCl, 1 M NaOH(aq), 500 W Xe lamp 83
Photocathode: CaFe2O4
Photoanode: WO3 0.02 3 M H2SO4(aq), 250 W Oriel tungstenhalogen quartz lamp (200 mW 84
Photocathode: GaInP2 cm-2)
Photoanode: Bi2S3/TNA 1.6 0 V versus Ag/AgCl, 0.25 M Na2S ? 0.125 M Na2SO3, Xe lamp (100 19
Photocathode: Pt/SiPVC mW cm-2), [400 nm

3.1 Photoanode and Anodic Semiconductors electrochemical potential point of view, the valence band
edge of the photocatalysts should be more positive than the
In the PEC water splitting setup, photoanode usually oxygen evolution potential enabling the photoanode to
comprises n-type semiconductors coated on conductive generate oxygen. As one of the significant advantages of
substrates [15, 19]. Under light illumination, photoexcited PEC, external voltage bias may be applied to compensate
holes accumulate on the surface of the photoanode semi- for the potential deficiency and accelerate the separation of
conductors and are consumed in oxidation reactions, while excited charge carriers, although zero bias is desirable once
electrons are transferred to a counter electrode via an the PEC systems become well aligned with suitable semi-
external circuit as shown in Fig. 2 [15]. From the conductor materials. Starting with traditional TiO2

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4 Nano-Micro Lett. (2016) 8(1):112

e construction of heterojunction, and hydrogenation, or cre-

ation of structural vacancies [3133]. Doping with metal
or/and non-metal (C, N, S, B, etc.) was started in the early-
e e
twenty-first century as an effective solution to narrow the
CB bandgap of TiO2 for enhancing PEC efficiency [6, 3439].
H+/H 2
Metal doping and non-metal doping can lead to the conduct

1.23V
band and the valence band increases of acceptor, respec-
O2/H2O tively, which narrowed the bandgap of the photocatalysts
VB
and make the photocatalysts respond to visible light. Park
h+
et al. prepared carbon-doped TiO2 nanotube arrays with
high aspect ratios. The total photocurrent was more than 20
Photoanode Counter electrode times higher than that with a P-25 nanoparticulate film
under white-light illumination [35]. Recently, surface
Fig. 2 Semiconductors coated on substrate as photoanode for PEC plasmon resonance has been applied in PEC water splitting
water splitting [15]
with extend light absorbance in the entire UVVisible
region [4042]. Surface plasmon resonance is an intrinsic
photoanode, this section highlights the recent advances in property of metal nanoparticles, in which the oscillation
photoanodes composed of one-dimensional (1D) TiO2 and frequency is highly sensitive to the metal size and shape as
various hybrid photoanode systems (Fig. 3). well as the dielectric constant of the surrounding environ-
Titanium dioxide (TiO2) is the most attempted n-type ment. For instance, Au nanoparticle-decorated TiO2
semiconductor for PEC water splitting due to its low cost, nanowire electrodes showed the largest photocurrent gen-
and better chemical and optical stability [2326]. Among eration at 710 nm and enhanced photoactivity across the
various nanostructured TiO2, 1D titanium dioxide nanotube entire UVVisible region, which is due to the excitation of
arrays (TNAs) have gained much attention due to their surface plasmon resonance of Au [40].
intrinsic large surface area and unidirectional flow of Modifying TiO2 nano-semiconductor with second nano-
charges [24, 27]. TNA can be easily fabricated via semiconductor of lower bandgap to form heterojunction
anodization of metal titanium foil or plate with great represents another promising route to harvest visible light.
potential for large-scale application [24, 2729]. 1D TiO2 The second nano-semiconductor serves as a photosensitizer
nanowire arrays were also coated on transparent conduct- and builder for internal electric field across the interface.
ing oxide (TCO)-coated glass through a mild hydrothermal The internal potential bias significantly promotes the
reaction [30]. The photoconversion efficiencies of N719 excited electrons and holes separation and transportation
dye-sensitized solar cells fabricated with the 1D nanowire across the interface of the dual photocatalysts, leading to
arrays can be up to 5.02 %, which is much higher than reducing recombination. For instance, TiO2 nanotube
those fabricated with the simple TiO2 powders. Titanium arrays (TNAs) were always modified with p-type CdTe and
dioxide itself shows low photoelectrochemical activity Cu2O semiconductors [4345]. TiO2 is n-type semicon-
since it is not responsive to visible light due to wide ductor. CdTe and Cu2O are p-type semiconductors. Thus,
bandgap (*3.2 eV). In order to enhance the visible light pn junctions can be formed between them, respectively,
absorption, researchers have developed various strategies which facilitate the separation of the excited electrons and
including doping TiO2 with metal or non-metal, holes. Some heterojunctions can enhance the

Fig. 3 SEM images of titanium dioxide arrays [29, 34]

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Nano-Micro Lett. (2016) 8(1):112 5

Substrate conduction bands. The maximum photocurrent density of

Catalyst B the ternary hybrid is up to 1.6 mA cm-2 (at 0 V Ag/AgCl)
under visible light irradiation, which is much higher than
e CB
those of bare CdS and any binary hybrids.
e
Oxygen vacancy technique has often been applied to
CB enhance the performance of TiO2 for PEC water splitting in
recent years [51]. Oxygen vacancies can be produced
through hydrogen treatment [51, 52]. It can also be gen-
erated by annealing metal oxide under oxygen-deficient
VB
VB h+
conditions [53]. In comparison with the hydrogen treatment
h+
method, this approach eliminates the potential influence of
hydrogen impurities. The PEC performance of TiO2 elec-
trodes can be enhanced by controlling the introduction of
Catalyst A
oxygen vacancies, which as shallow donors can signifi-
Fig. 4 The overlapping in band gaps between two different photo- cantly improve electrical conductivities of TiO2 nano-
catalysts and the electron-trap mechanism semiconductors.
Besides TiO2, many other metal-oxide photocatalysts
Bi2WO6 TiO2
such as BiVO4, WO3, ZnO, etc. have invariably been
attempted to be coated on substrate as photoanodes for
PEC water splitting [17, 5457]. External voltage is needed
reduction e CB
when BiVO4 or/and WO3 photoanodes are applied for PEC
water splitting. This is because their conduct bands are
hv more positive than the potential of hydrogen evolution.
Heterojunction can be applied to improve their photo-
electrochemical performance. For example, nanostructured
oxidation
h+ WO3/BiVO4 heterojunction is prepared for PEC water
h+ VB
splitting as shown in Fig. 6 [58]. BiVO4 layer was coated
on WO3 nanorod array by spin coating. The charges can be
Fig. 5 Schematic interfacial electron transfer between TiO2 and
quickly separated and transferred due to the energy dia-
Bi2WO6 [47]
gram of WO3/BiVO4 heterojunction. Because of excellent
photoelectrochemical properties because of the overlap- properties of graphene oxides for electron transfer, they
ping in band gaps between two different photocatalysts, have often been used to improve the photoelectrochemical
which could favor the charge carrier transfer and separa- properties of semiconductors in recent years [59]. And
tion. Typical examples are the ones illustrated in Figs. 4, 5. some metal hydroxides such as FeOOH (Fig. 7), NiOOH,
The conduction band (CB) of catalyst A (Bi2WO6) is more and layered double hydroxide (LDH) have been reported as
negative than the one of catalyst B (TiO2); therefore, the effective photoanode materials for PEC water splitting
excited electrons from catalyst B (TiO2) can be quickly because the alignment reduced interface recombination at
transferred to catalyst A (Bi2WO6). The valance band (VB) the junction between them and semiconductors, and created
of catalyst A (Bi2WO6) is more positive than the one of a more favorable Helmholtz layer potential drop at the
catalyst B (TiO2), and the excited holes from catalyst A semiconductor/electrolyte junction [16, 60, 61], which
(Bi2WO6) can be quickly transferred to catalyst B (TiO2). provides a hint for searching new materials in the field of
As a result, the excited electrons and holes can be separated PEC water splitting.
and transferred quickly for efficient water splitting. This Owing to their narrow bandgap, some n-type metal sulfide
technique has been extensively applied in enhancing the [6264] and oxynitride [6567] photocatalysts can respond
photoelectrochemical performance of TiO2 through modi- to visible light with long wavelength and appropriate band
fication using visible-light responsive semiconductors such levels for water splitting, and therefore are chosen as pho-
as CdS, Bi2WO6, Rh-doped SrTiO3, etc. [4649]. toanode materials for PEC water splitting in order to make
The above examples are related to binary hybrid systems better use of solar energy. CdS (Fig. 8) and other sulfides are
for PEC water splitting. It should be noted that the CdS often used in photoanodes as sensitizer for PEC water
TiO2WO3 ternary hybrid system for PEC water splitting splitting [68]. However, the sulfides are not stable because of
has also been reported recently [50]. The cascaded elec- photocorrosion, which can be reduced by adding sacrificial
trons are transferred from CdS to TiO2 to WO3 through the agents [69]. Tantalum oxynitrides also show visible light
interfacial potential gradient in the ternary hybrid absorption with long wavelengthyet they are not

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6 Nano-Micro Lett. (2016) 8(1):112

hv

e CB
e CB
h e
h

FTO
e

h e
VB h
e h
VB BiVO4
h WO3
e

Fig. 6 The diagram of BiVO4/WO3 heterojunction and electron transport process [58]

0
No catalyst

Current density (mA cm2)

1
a-FeOOH catalyst
Light absorber

2
Back contact

4OH 3
With a-FeOOH
4
O2 + 2H2O + 4e
5
1.2 1.0 0.8 0.6 0.4 0.2 0
Potential (V vs RHE)

Fig. 7 FeOOH as photoanode for photoelectrochemical water splitting [60]

e e e
e e H2 e e
Pt e H2O
e
e
h+ e
e hv
e e
e E0(H+/H2) e
h+ O2 e 0V
e
e e CdS
H2O E0(O2/H2O)
e TiO2
e
1.23V h+
e
FTO e h+

Fig. 8 The scheme of the nanostructure of the CdS/TiO2 nanoarrays and charge-transfer mechanism [68]

stable and the intensity of absorption is low. Therefore, shown in Fig. 9, under light illumination, water is reduced on
different techniques such as modification with cocatalysts, the surface of semiconductor, while water is oxidized on the
heterojunction, etc., have been developed to reduce the counter photoelectrode. From the electrochemical potential
photocorrosion and enhance the PEC properties [6668]. point of view, the conduction band edge of the photocatalysts
should be more negative than the hydrogen evolution potential
3.2 Photocathode and Cathodic Semiconductors enabling the photocathode to generate hydrogen. Compared
with the reports of n-type semiconductor photoanodes, there
Photocathode usually comprises p-type semiconductor coated are fewer reports based on p-type semiconductor as photo-
on conductive substrates in the PEC water splitting system. As cathodes for PEC water splitting [7077].

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Nano-Micro Lett. (2016) 8(1):112 7

e TiO2
ZnO:Al Pt

e
Cu2O
H+/H2 CB Au
FTO

1.23 V
VB

O2/H2O Fig. 11 Schematic representation of the electrode structure of the

e h+ surface-protected Cu2O electrode [80]

82], and Pt-modified Si photovoltaic cell (Pt/SiPVC) based

on pn radial junctions with a p-type Si substrate has also
Counter electrode Photocathode
been reported as an effective photocathode for PEC water
Fig. 9 Semiconductors coated on substrates as photocathode for PEC splitting [19]. Si-based photoelectrodes for PEC water
water splitting [15] splitting has a potential prospect because of low-cost and
abundant Si resource, while the efficiency should be further
improved.
Recently, copper sulfides or selenides (CuInS2, Cu2-
ZnSnS4, Cu(In, Ga)Se2, etc.) have been reported as effi-
cient p-type photocathodes for PEC water splitting under
visible light [74, 75]. However, they suffered from serious
photocorrosion. Moriy et al. deposited CdS on Cu(In,
Ga)Se2 through chemical bath deposition (CBD) as shown
in Fig. 12 [18]. The photocurrent increased due to the pn
junctions formed between them, which accelerated the
charge separation. Further, the Pt/CdS/CuGaSe2 electrode
showed a stable photocurrent (about 4 mA cm-2, 0.05 M
Fig. 10 SEM image of a pn Cu2O homojunction [78]
Na2HPO4(aq) ? 0.05 M NaH2PO4(aq), pH 7, 150 W Xe
Cu2O is a typical p-type semiconductor used as photo- lamp, 0 Vvs RHE) under reductive conditions for more
electrode for PEC water splitting, while it readily gets than 10 days under visible-light irradiation.
degraded due to self-reduction by photogenerated elec-
trons. WO3/Cu2O pn junctions have been synthesized to 3.3 Z-scheme System for PEC Water Splitting
reduce the self-reduction of Cu2O and enhance the PEC
properties [77]. In addition, pn homojunctions have also With suitable band structure, n-type semiconductors are
been prepared to improve their PEC performance [78, 79]. usually used as photoanode and p-type semiconductors as
Colleen et al. [78] fabricated pn Cu2O homojunction solar photocathode for PEC water splitting. It is known that
cells by electrochemically depositing an n-Cu2O layer on a n-type semiconductor has a Fermi level near the conductor
p-Cu2O layer as shown as in Fig. 10. The intrinsic doping band (CB) edge and p-type semiconductor has a Fermi
levels of the prepared p-Cu2O and n-Cu2O layers were very level near the valance band (VB) edge [19]. When n-type
low, and they made Ohmic junctions with Cu metal. The and p-type semiconductors are simultaneously used as
best cell performance (an n of 1.06 %, a VOC of 0.621 V, photoanode and photocathode, respectively, (Z-scheme) as
an ISC of 4.07 mA cm-2, and a fill factor of 42 %) was shown in Fig. 13, the mismatching Fermi levels could
obtained, which was better than other pn Cu2O homo- produce self-bias which can drive the excited electrons
junctions. Paracchino et al. reported that Cu2O photocath- from photoanode to combine with the excited holes from
ode, as shown in Fig. 11, which was protected against photocathode. Meanwhile, water oxidation and reduction
photocathodic decomposition in water by nanolayer of Al- take place over the photoanode and photocathode, respec-
doped zinc oxide and titanium dioxide and activated for tively. In the Z-scheme systems, the self-bias would act as
hydrogen evolution with electrodeposited Pt nanoparticu- an extra driving force for carriers charge transfers and
lates, showed photocurrents of up to -7.6 mA cm-2 at a transportation while their performance is still governed by
potential of 0 V versus the reversible hydrogen electrode at the materials and the competition between chemical reac-
mild pH [80]. tion and recombination.
B-doped Si with the decoration of Pt, has often been Ida et al. constructed a PEC water splitting using p-type
used as a p-type photocathode for PEC water splitting [81, CaFe2O4 as photocathode and n-type TiO2 as photoanode

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8 Nano-Micro Lett. (2016) 8(1):112

A
I
vs. NHE TiO2 Bi2S3 Pt-black n-Si p-Si

1 CB e H+ e CB
CB
0 hvOX. self-biasH2 hv hv EF
EF
1
VB h+ S2,SO32 h+ VB
2
3
VB
Photoanode: Bi2S3/TNA Photocathode: Pt/SiPVC
Fig. 12 EDX mapping of CdS/CuGaSe2 sample with chemical bath
deposition for 1 min [18] Fig. 15 The energy-level diagram of the self-biasing PEC cell
assembled with Bi2S3/TNA photoanode and Pt/SiPVC photocathode
under short-circuit situation [19]
e

short-circuit current of about 200 lA cm-2. However, this

system is not responsive to visible light because TiO2 only
e
responds to ultraviolet light. A PEC cell [84] made up of
e CB WO3 photoanode and p-GaInP2 photocathode has been
H+/H2
reported, both of which are responsive to visible light.
CB Self-bias VB
1.23 V

However, the conduct band edge of WO3 (about 0.25 V vs.

h+ NHE) is more positive than the valance band of p-GaInP2
VB O2/H2O (about 0 V vs. NHE), which restricts the charge transfer
from photoanode to photocathode via external circuit.
h+
Furthermore, the WO3 films show relatively poor charge
separation properties and weak visible-light absorbance.
Photoanode Photocathode
Thus, this PEC cell cannot split water till enough light
intensity is applied. TiO2 itself could not respond to visible
Fig. 13 n-type and p-type semiconductors coated on substrates as light. Zeng et al. used Bi2S3-decorated TiO2 nanotube
photoanode and photocathode, respectively, for PEC water splitting arrays as photoanode and Pt-modified Si photovoltaic cell
(Z-scheme) [15]
(Pt/SiPVC) as photocathode [19]. Both of them could
respond to visible light. As shown in Fig. 15, the conduc-
e tion band edge of TiO2 (about -0.05 V vs. NHE) is more
Cathode Anode
negative than the valance band edge of Pt/SiPVC (about
2
hv hv 0.8 V vs. NHE). A self-bias of about 0.85 V is formed
CB e between two photoelectrodes for efficient spontaneous
1 e
H2 hydrogen evolution and electricity generation under visible
E/V vs. NHE

light irradiation. However, this system for PEC water

0 H2O
H2O/H2
OCV
splitting needs to be added with sacrificial agents. Thus, an
efficient Z-scheme system consisting visible-light respon-
1 FL
sive photocatalysts for PEC water splitting without addi-
O2/H2O h+ O2
tion of sacrificial agents needs to be developed.
2
VB h+
H2O
p-type n-type
CaFe2O4 etc. TiO2 etc. 4 Conclusions and Future Perspective
Fig. 14 Reaction and band model in photovoltaic cell using p-type Photoelectrochemical devices comprising of visible-light-
CaFe2O4 and n-type TiO2 semiconductor electrodes [83]
responsive semiconductors have attracted great efforts in
water splitting processes to obtain sustainable hydrogen, in
[83]. As shown in Fig. 14, under illumination without search of a promising technique to combat the challenges
external voltage, hydrogen and oxygen were produced from global climate change. The prospect of the PEC water
from photocathode and photoanode, respectively, with a splitting systems were highly limited by the nanostructured

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Nano-Micro Lett. (2016) 8(1):112 9

photocatalysts and their device configurations. The most (in)stability (due to photodegradation) of the semiconduc-
important issues associated with the PEC devices lay on the tors employed in the photoelectrodes.
sunlight absorbance, energy loss due to undesirable charge Resistance photocorrosion is pivotal to realizing long-
carrier recombination and photodegradation of the photo- term application of PEC water splitting. Although intro-
electrodes. Along with the rapid and great development of duction of sacrificial agents may somehow resist photo-
nanomaterial science and semiconductor engineering, sig- corrosion of the photoelectrodes, configurations of
nificant advances have been observed, which shed light on semiconductor heterojunctions have proven to be more
resolving the aforementioned challenges in the PEC water promising because of their broader manufacturing possi-
splitting in the recent decades, since the discovery of PEC bility and low cost. In terms of the heterojunction principle,
water splitting by Honda and Fujisma in the 1970s. the Z-scheme systems may be stable due to the closed
Starting from brief introduction of the working mecha- electric circuit involved; however, limited information can
nism and history of PEC system, this article overviewed the be found from the literature regarding their stability, sug-
greatest progress in PEC water splitting systems compris- gesting greater efforts are still required in this area.
ing visible-light-responsive photocatalysts. The advantages Apparently, there is a significant step to apply PEC water
and disadvantages of the emerging photoanodes and pho- splitting in hydrogen generation on industrial scale in the
tocathodes were assessed with typical examples, to disclose near future. However, spurred by global energy and envi-
the potentially effective strategies to promote the efficiency ronmental challenge, PEC water splitting is an ideal route
and stability of various PEC systems. Special attention was to generate hydrogen with less-adverse impact on climate
paid to the TiO2 nanotube arrays and modified TiO2 pho- change, and hence, industrial-scale application of PEC
toelectrodes, which can be responsive to visible light via water splitting would be the next-door event once the
doping with metal and/or nonmetal elements, creating lat- highly efficient and stable photoelectrodes with visible-
tice vacancies, and designing heterojunction or Schottky light-response could be developed, where the most
junctions by means of combining other semiconductors or promising PEC system might emerge from the break-
nanoscaled metal particles. Such modifications would not through on Z-scheme system.
only revise the band structures and energy alignment of
TiO2 photoelectrodes in the PEC electrolyte solution but Acknowledgments This work was supported by the EU-China Eco-
Fuel project (FP7, 246772) from the European Commission.
also introduce additional drivers that influence photogen-
erated charge carriers separation and transfer. On the basis Open Access This article is distributed under the terms of the
of advances in TiO2 photoelectrodes and PEC systems, Creative Commons Attribution 4.0 International License (http://crea
other visible-light-responsive semiconductor photoelec- tivecommons.org/licenses/by/4.0/), which permits unrestricted use,
distribution, and reproduction in any medium, provided you give
trodes and Z-scheme systems were addressed. Among appropriate credit to the original author(s) and the source, provide a
those strategies, heterojunctions and homojunctions were link to the Creative Commons license, and indicate if changes were
found to be more attractive for single photoelectrode due to made.
the low cost and broad room to align the energy gradient
across the semiconductor interface.
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