Afroz 2018

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Materials Chemistry A
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A heterojunction strategy to improve the visible

light sensitive water splitting performance of
Published on 28 June 2018. Downloaded by Iowa State University on 1/25/2019 12:43:55 PM.
Cite this: J. Mater. Chem. A, 2018, 6,

21696 photocatalytic materials
Khurshida Afroz,a Md Moniruddin,a Nurlan Bakranov,a Sarkyt Kudaibergenovbc
and Nurxat Nuraje *a
Photocatalytic water splitting is a promising path for generating hydrogen which will decrease the dependency
on conventional fossil fuels to generate power and provides an environmentally benign way to store solar
energy. Designing photocatalysts is one of the key challenges in making photocatalytic water splitting
efficient and economically viable. Heterojunction formation using different functional materials in a single
photo-catalyst has the potential of broadening light harvesting properties, improving chemical stability,
enhancing the photoexcited charge separation, and thus boosting water splitting efficiency. This article gives
an overview on the heterojunction strategy for improving photocatalytic water splitting performance. Recent
developments in different visible light-responsive heterojunction systems are discussed for metal oxide–
Received 5th May 2018
Accepted 28th June 2018
metal oxide and metal oxide–non-metal oxide heterojunctions. Along with experimental observation and
the proposed charge separation mechanism, synthesis techniques of heterojunction materials are also
DOI: 10.1039/c8ta04165b
included in this article. In addition to recent progress in the heterojunction-based photocatalytic system, this
rsc.li/materials-a review article also provides future directions for photocatalytic water splitting.
1 Introduction
a
Department of Chemical Engineering, Texas Tech University, Lubbock, TX79409, USA.
Researchers have meticulously researched solar energy conversion
E-mail: nurxat.nuraje@ttu.edu
b
Department of Physics and Engineering Prole, Kazakh National Technical University,
and storage processes to efficiently utilize the tremendous amount
Almaty, Kazakhstan (4.3 1020 J h1) of energy hitting the earth's surface as sunlight.1
c
Institute of Polymer Materials and Technology, Kazakhstan It is stated that the amount of solar energy reaching the earth's
surface in one hour is sufficient to meet the global annual energy
consumption (4.1 1020 J).2 Solar energy can be converted directly
Nurxat Nuraje received his PhD into electricity or stored in as a chemical bond.3 Photocatalytic
from CUNY in 2008. He was water splitting is a promising, ecofriendly way to store untapped
a postdoctoral associate at MIT solar energy via chemical bonding as a form of hydrogen fuel.
from 2008 to 2013 and a research Hydrogen is a green energy source when it is used in fuel cells for
scientist at MIT from 2013 to power generation because water is the only byproduct.4 In addi-
2015. Then, he joined Texas Tech tion, hydrogen also offers high energy density and it can be easily
University as an Assistant stored and transported using existing technology.5
Professor in January of 2015. For In the photocatalytic water splitting process, a photoactive
his PhD research, he has been material is used in aqueous solution to harness the photonic
awarded the ‘‘Graduate Student energy from light, which then drives the thermodynamically
Silver Medal’’ by the MRS and unfavorable water splitting reaction.3 Researchers have devoted
the ‘‘Rose Kfar Rose’’ award by their efforts to exploring different photoactive materials which
CUNY. In 2015, because of his meet kinetic and thermodynamic criteria for efficient photo-
outstanding research, he has been selected as the winner of the conversion of solar energy through water splitting.6 An effi-
“Joseph Wang Award” by Cognizure Publishing. He was the recip- cient photocatalyst will have characteristics including a suitable
ient of both 2017 and 2018 US Airforce Faculty Summer Fellowship band gap, favorable conduction band (CB) and valence band
and recognized as the most inuential faculty member by the (VB) edge positions, high photo-corrosion resistivity, and
college of engineering of Texas Tech University. Dr Nuraje's a suitable structure for charge transfer.7 Many research studies
research interests are primarily in nanomaterials and biomaterials have been conducted on photocatalytic water splitting using
and their applications in renewable energy. a single photocatalyst material.3 However, most single
21696 | J. Mater. Chem. A, 2018, 6, 21696–21718 This journal is © The Royal Society of Chemistry 2018
View Article Online
Review Journal of Materials Chemistry A
photocatalyst materials are either UV-active or suffer from which are both considered critical issues for overall water
signicant photo-corrosion. Photoexcited charge recombination splitting efficiency. Recently Co–P,34 a heterojunction photo-
is another major drawback of the single photocatalyst based catalyst, showed the highest efficiency (STH efficiency 5.4%) in
water splitting system.8 Forming heterostructures with different overall water splitting, which is the champion photocatalyst so
functional materials in a single photocatalyst shows great far for a heterojunction-based particulate system.
promise in overcoming the single photocatalyst material draw- This review article starts with the fundamentals of various
backs. The heterojunction approach allows different favorable heterojunction strategies applied in water splitting. Recent
properties from each participating compound to be combined, progress of different visible light-active heterojunction photo-
extending the absorption range of the visible spectrum,9 catalysts, including metal oxide–metal oxide and metal oxide–
reducing photoexcited electron hole recombination,10 and non-metal oxide groups, in photocatalytic water splitting
increasing the photo-corrosion stability, thus improving water systems is discussed. In the Metal oxide–metal oxide section,
splitting efficiency.11 metal oxy nitrides along with metal oxides are included. Metal
Design strategies and the fabrication of heterostructures with suldes and phosphides are included in the non-metal oxide
different functional materials are the key challenges to achieving group. The synthesis of heterojunctions is an important step in
the desired characteristics for a water splitting photocatalyst. In investigating their performance in water splitting. The synthesis
designing a heterojunction, the energy level of each coupling of heterojunction materials is included in a separate section.
material needs to have nearly matched overlapping band struc- Recently reported visible light sensitive heterojunction systems
tures.12 At the heterojunction interface, when photo-generated along with their corresponding synthesis method, hydrogen/
charges migrate from one material to another material, the oxygen evolution rate, apparent quantum yield, current
oxidation and the reduction ability of these transported holes density, incident photon to current conversion efficiency and
and electrons decrease respectively.13 Especially in type I heter- measurement conditions are summarized and tabulated
ojunctions (Fig. 6), holes transfer to the less positive valence [Tables 1 and 2] in this article. Especially, Table 1 provides
band of a material while the electrons transfer to the less a recent update on the photocatalytic performances of
negative conduction band position.14 As a result, the photoex- particulate-based heterojunction photocatalysts, whereas Table
cited charge separation improves but the redox ability of 2 summarizes the performances of electrode-based hetero-
photoexcited charges decreases aer transfer through the het- junction photocatalysts for water splitting. Finally, the
erojunction. In a heterojunction structure for water splitting, the Summary and outlook section provides some future directions
participating materials need to meet strict conditions, such as to improve the performances of heterojunction photocatalysts.
a narrow band gap that facilitates visible light absorption and
proper energy level matching, which facilitates good charge
transfer along with improved oxidation and reduction ability.13 1.1 Photocatalytic water splitting principles
The fabrication of heterojunctions with the proper combination Thermodynamically, water splitting is an unfavorable reaction
of one H2 evolving and one O2 evolving photocatalyst is impor- and requires more than 1.23 eV energy to drive the reaction
tant for overall water splitting under visible light irradiation.15 forward.16,35 In an articial technique, water oxidation is ve
There are several excellent review papers on different types of times slower than the hydrogen evolution process17 because
photocatalysts for particulate and photoelectrochemical water every oxygen molecule requires four holes, making water
splitting systems. We refer readers to early published tutorial oxidation more challenging than H2 reduction.36 Photocatalytic
review articles.16,17 These review articles provide very nice water splitting consists of several key steps. In designing pho-
explanations on water splitting spanning the fundamentals to tocatalysts for this process, it is of the utmost importance to
specic material applications. Some review articles focus on understand the mechanism of each step and identify the key
specic metal oxide-based nanomaterials such as TiO2,18 parameters inuencing the process efficacy. Some review arti-
Fe2O3,19 or general metal oxide-based systems.20,21 Also several cles nicely describe the fundamental steps of water splitting and
review articles22–24 nicely summarize non-metal oxide-based discuss the key parameters that determine the efficiency of this
photocatalytic systems. Particulate photocatalytic systems4,25–27 process.37,38 The major steps involved in the photocatalytic
are summarized by Chen,4 Kudo,16 and Moniz.17 Moniruddin water splitting process are: (a) photon absorption, (b) photoex-
et al.28 discussed perovskite-based material applications in cited charge separation, (c) charge diffusion and transport, (d)
water splitting. There are also some review articles on Z scheme- catalytic reaction on the catalyst's active site, and (e) mass
based14,29 water splitting. Some review articles focus solely on transfer (Fig. 1).39 The water splitting reaction initiates with
the photoelectrochemical-based30–32 water splitting system. photon absorption via a photocatalyst, where numerous
Hisatomi et al.33 discussed the catalytic and kinetic aspects of photoexcited electrons and holes are generated in the CB and
photocatalytic water splitting. In this review article, we VB, respectively. These photoexcitation processes occur when
summarize recent developments in heterojunction visible light- the photonic energy is higher or equivalent to the band gap
active photocatalytic systems based on our literature search of energy of the photocatalyst materials and happen on the
research progress of the past 10 years since the heterojunction femtosecond time scale.40,41 The photoexcited charges relax
system is a promising strategy to improve overall water splitting quickly at their respective band edge positions on the femto- to
efficiency. The heterojunction strategy not only improves light the pico-second time scale and then transport to the catalytic
harnessing capability but also enhances charge separation, active site on the nano- to the micro-second time scale to
This journal is © The Royal Society of Chemistry 2018 J. Mater. Chem. A, 2018, 6, 21696–21718 | 21697
Table 1 Photocatalytic performance of heterojunction particles
Apparent quantum
Material Synthesis method Hydrogen evolution Oxygen evolution yield Sacricial agent Stability Ref.
ZnIn2S4/g-C3N4 g-C3N4 by thermal 14.1 mmol h1 with 15 wt% — — Triethanolamine- Stable for a 24 h run 106
polymerization, ZnIn2S4 ZnIn2S4 mine (TEOA)
hydrothermal deposition
Cu2ZnSnS4–Pt/ Cu2ZnSnS4– Solvothermal method 1.02 mmol h1 g1 catalyst — — 0.1 M Na2S and Stable within a 12 h 107
Au Na2SO3 run
Journal of Materials Chemistry A
NiO/NaTaO3 doped with Solid state reaction 19.5 mmol h1 9.7 mmol h1 56% at 270 nm — Stable for more than 108
lanthanum 400 h
g-C3N4/InVO4 Hydrothermal process 212 mmol h1 g1 with 20% — 4.9% at 420 nm Methanol Stable during 13
InVO4 a 200 h run
21698 | J. Mater. Chem. A, 2018, 6, 21696–21718

MsTa2O6XNY/TaON — 1.25 mol h1 — 6.8% at 420 nm 20 vol% CH3OH — 109
buffered with 0.15 g
La2O3
In0.9Ni0.1TaO4 with NiOy Solid state reaction 16.6 mmol h1 with NiOy 8.3 mmol h1 with 0.66% at 420 nm Pure water Stable during 71
and with RuO2 and 8.7 mmol h1 with NiOy and 4.3 mmol a 400 h run
RuO2 h1 with RuO2
ZnRh2O4/Ag/s-BiV2O11 Melting-slow cooling to row s- 0.02 mmol h1 under 0.01 mmol h1 under 0.036% at 500 nm Pure water Stable during 80
BiVO11, ZnRh2O4 by a solid 545 nm irradiation 545 nm 29 a 120 h run
state reaction irradiation-n
ZnRh2O4/Ag/Ag1XSbO3Y Solid state reaction 0.1682 mmol aer 24 h 0.0841 mmol aer 24 — Pure water Stable during 90
h a 144 h run
Ta2O5/g-C3N4, Pt cocatalyst Solid state reaction method 36.4 mmol h1 g1 with — — 20 vol% methanol Stable during a 20 h 92
7.5% TO/CN run
ZnO/TiO2 nanotube TiO2 by anodizing titanium 44 mL cm2 240 min1 — — 1 M NaOH (pH ¼ — 110
foil, ZnO by chemical bath 13.6)
deposition
NiS2/CdLa2S4 Hydrothermal method 2.5 mmol h1 g1 with — 1.6% at 420 nm 0.35 M Na2S and Constant activity in 89
2 wt% NiS2 0.25 M Na2SO3 an up to 20 h run
Gd2Ti2O7/In2O3 Solid state reaction 869.7 mmol in 3 h — — 10 vol% methanol Stable during a 9 h 63
run
g-C3N4/CdS quantum dot Heterojunction by the 17.27 mmol h1 with — — 25 vol% methanol No decrease in 104
with Pt co catalyst chemical impregnation 30 wt% CdS QD activity during
method a 28 h run
CaFe2O4/TiO2 TiO2 nanosphere by the 2100 mmol h1 g1 in 1 wt% — — Both for 10 wt% Stable during a 25 h 111
solvothermal method, CaFe2O4 with 10 wt% methanol and pure run
CaFe2O4 by the polymerizable methanol (solar light), for water
complex method, pure water 92 mmol h1 g1
heterojunction by solid state with 2 wt% CFTO
dispersion
Fe2O3/TiO2 Sol–gel and calcination route 217.6 mmol h1 with 2 wt% — 0.94% at 447 nm 0.35 M Na2S/0.25 M Stable during a 7 h 112
using Papilio paris buttery TiO2 Na2SO3 run
wings as the template
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This journal is © The Royal Society of Chemistry 2018

Review
Table 1 (Contd. )
Review
Apparent quantum
Material Synthesis method Hydrogen evolution Oxygen evolution yield Sacricial agent Stability Ref.
ZnO/ZnS/g-C3N4 g-C3N4 by direct solid state 1205 mmol g1 H2 at 4 h — — 0.25 M Na2S/0.25 M — 105
thermal decomposition, ZnO Na2SO3
by chemical precipitation,
ZnO/ZnS by adding ZnO on
Na2S and then heating and
drying
N doped TiO2/SrTiO3 Sol–gel method 136 mmol g1 h1 — — 25% methanol — 73
SrTiO3 : La, Rh/Au/ Particle transfer method. 80 mmol cm2 at 331 K and 40 mmol cm2 aer 33% at 419 nm at Pure water Without surface 75
BiVO4 : Mo particulate SrTiO3 : La, Rh and BiVO4 : Mo 10 kPa aer 4 h 4 h at 331 K and 10 331 K temperature modication water
sheet were embedded on a gold layer kPa and 10 kPa pressure splitting decreased
with time, and aer
surface

modication with
Cr2O3 the same
activity was
maintained for 10 h
SrTiO3 : La, Rh/C/ SrTiO3 : La, Rh and BiVO4 : Mo 8.6 mmol h1 cm2 at 288 K 4.4 mmol h1 cm2 26% at 419 nm Pure water High activity for at 76
BiVO4 : Mo particulate were produced by a solid state and 5 kPa at 288 K and 5 kPa least 6 h
sheet reaction and then SrTiO3 : La,
Rh/C/BiVO4 : Mo by the
particle transfer method
NiS/C3N4 NiS was deposited on C3N4 by 48.2 mmol h1 — 1.9% at 440 nm 15 vol% H2 evolution 103
the hydrothermal method triethanolamine decreased gradually
over time
NiS nanoparticle/CdS CdS by the solvothermal 1131 mmol h1 g1 — 6.9% at 420 nm 0.35 M Na2S and No decrease in 113
nanorod method and NiS by the 0.25 M Na2SO3 activity aer 9 h
hydrothermal method
Co/P Solvothermal method 131.6 mmol h1 at 353 K — 42.55% at 430 nm Pure water No decrease in 34
and at 353 K activity aer a 40 h
run
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J. Mater. Chem. A, 2018, 6, 21696–21718 | 21699

Table 2 Photocatalytic performance of heterojunction films
Apparent quantum
Hydrogen or oxygen yield/IPCE/photo-
Material Synthesis method evolution conversion efficiency System Current density Stability Ref.
WO3/BiVO4 Solvothermal deposition of — Nanorod WO3/BiVO4 0.5 M sodium sulfate 0.8 mA cm2 at +1 V for Nanorod 48
WO3 nanorods on glass, and showed 31% IPCE solution the planar heterojunction more
then spin coating of BiVO4 where planar WO3/ heterojunction and 1.6 stable than the planar
BiVO4 showed 9.3% mA cm2 for the WO3/BiVO4 lm
IPCE at 420 nm nanorod
CuO/CdS/TiO2/Pt CuO by electrodeposition, CdS 100% faradaic Less than 5% IPCE at 1 M phosphate-ate 1.68 mA cm2 at 0 V Highly stable over a 30 3
by chemical bath deposition, efficiency (hydrogen) a 500 nm wavelength buffer (K2HPO4/ (RHE) minute run
TiO2 by atomic layer KH2PO4)
deposition, Pt by
photoelectron deposition
21700 | J. Mater. Chem. A, 2018, 6, 21696–21718

WO3/W$BiVO4 Flame vapor deposition and 79% faradaic efficiency IPCE 60% at 300–450 0.5 M potassium 3.1 mA cm2 at 1.23 V Stable within a 1 h run 69
nanowire drop casting with 0.5 M Na2SO4 nm phosphate electrolyte
(oxygen)
a Fe2O3/graphene/ a Fe2O3 by the hydrothermal 95% faradaic efficiency Photo-conversion 0.01 M Na2SO4 1.97 mA cm2 at 1 V vs. Stable during a 12 h run 10
BiV1xMoxO4 method, GO synthesized by (oxygen) efficiency 0.53% Ag/AgCl
chemical exfoliation deposited a 0.4 V vs. Ag/AgCl
by spin coating, BiV1xMoxO4
by spin coating
ZnO/TiO2/CuO tree-like ZnO electrochemical 0.8 mmol cm2 h1 — 0.1 M KH2PO 1.4 mA cm2 at 0.3 V vs. Stable during a 4 h run 114
structure deposition, TiO2 and CuO by (hydrogen) Ag/AgCl
the hydrothermal method
Se/BiVO4 Se deposition galvanostatic- — — 0.5 M Na2SO4 2.2 mA cm2 at 1.3 V Stable current density 56
ally, BiVO4 by chemical vapor in an up to 40 minute
deposition run
Rutile TiO2/a-Fe2O3 a-Fe2O3 by the solvothermal — — 1 M NaOH (pH ¼ 13.6) 0.3 mA cm2 at 0.4 V — 65
method, rutile TiO2 by the
hydrothermal method
BiVO4/WO3/SnO2 Sol–gel process, BiVO4 by spin — Internal quantum yield 0.5 M phosphate buffer 3.1 mA cm2 at 1.23 V Stable for a 20 minute 64
coating 80% solution with H2O2 as (RHE) run
a hole scavenger
g-C3N4/WS2 Gas–solid reaction method 101 mmol h1 g1 with — 0.5 M Na2SO4 for the 0.11 mA cm2 (lm) No decrease in activity 115
0.01 wt% WS2 from lm during a 9 h run
25 vol% methanol
solution (hydrogen)
WO3/BiVO4 Combination of glancing angle 102 mmol h1 cm2 (1 IPCE more than 90% pH 7 6.72 mA cm2 under 1 Stable 68
deposition (GLAD) of WO3 and sun, 25 C), 281 mmol across 300–500 nm sun at 1.23 V (RHE)
electrochemical deposition of h1 cm2 (3 sun, 50 C) wavelengths
BiVO4 for hydrogen; 51 mmol
h1 cm2 (1 sun, 25 C),
140.5 mmol h1 cm2 (3
sun, 50 C) for oxygen
GaTe/ZnO Two step chemical vapor 1.5 mmol h1 cm2 — 0.1 mol L1 Na2SO4 2.5 mA cm2 at Constant activity for 57
deposition (hydrogen) (pH ¼ 7) 0.39 V vs. RHE a 50 minute run
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Review
Table 2 (Contd. )
Review
Apparent quantum
Hydrogen or oxygen yield/IPCE/photo-
Material Synthesis method evolution conversion efficiency System Current density Stability Ref.
Si/ZnO nanowire (NW) Metal assisted chemical — — 0.25 M Na2SO4 buffered 8 mA cm2 at 1.5 V vs. Stable for a 200 second 9
etching to grow Si NW and with PBS with pH ¼ 7.2 Ag/AgCl RE run
hydrothermal growth of ZnO
NW
Ag3PO4/TiO2 TiO2 array by anodizing Ti foil — — 1 M KOH solution 2.34 mA cm2 at 0 V — 84
in ethylene glycol and Ag3PO4
was deposited by the
sequential chemical bath
deposition method
CdS/Au/TiO2 TiO2 on FTO by the — IPCE 85% at 375 nm. 0.25 M Na2S and 0.35 M 4.07 mA cm2 at 0 V (Ag/ — 98
hydrothermal method, Au by Photoconversion Na2SO3 (pH 12) AgCl)

photo-reduction, CdS efficiency 2.8% at
quantum dot by chemical bath 0.56 V vs. Ag/AgCl
deposition
Pt/In2S3/CdS/ Cu2ZnSnS4 by 0.477 mmol min1 H2 at IPCE 45–50% from 400 0.2 mol dm3 Na2HPO4/ 9.3 mA cm2 at 0 V — 99
Cu2ZnSnS4 electrodeposition of Cu, Sn, 0 V for 20 minutes. 96% to 700 nm NaH2PO4
and Zn followed by faradaic efficiency for
sulfurization, CdS and In2S3 by hydrogen evolution
chemical bath deposition, Pt
by photoelectro-deposition
WO3/Bi2S3 WO3 on FTO by the — IPCE 68.8% and photo- 0.1 M Na2S and 0.1 M 5.95 mA cm2 at 0.9 Photocurrent density 100
hydrothermal process, Bi2S3 conversion efficiency of Na2SO3 (pH 12) VRHE decreased slowly during
seed layer by the SILAR 1.7% a 600 s stability test
method, Bi2S3 by chemical
bath deposition
ZnO/Fe2O3 nanosheet ZnO by electrochemical — — 0.01 M KCl solution 1.5 mA cm2 — 66
fabrication, Fe2O3 by spin
coating
ZnO/ZnS/CdS/CuInS2 Ion exchange and — IPCE 57.7% at 480 nm 0.5 mol L1 Na2S and 10.5 mA cm2 at 0 V — 93
hydrothermal process 0.5 mol L1 Na2SO3 versus Ag/AgCl
CaFe2O4/TaON Both materials were deposited No H2 or O2 evolution IPCE 30% at 400 nm 0.5 M NaOH solution 1.26 mA cm2 at 1.23 V Photocurrent density 5
by electrophoretic deposition without co-catalysts vs. RHE decreased to half aer 3
h
p-GaInP2/TiO2/(OOCpy) p-GaInP2 was grown on a GaAs Faradaic efficiency close IPCE up to 80% across Argon purged 0.1 M 9 mA cm2 at 0 V versus During a 20 h run 96
Co(dmgH)2-(Cl)/TiO2 substrate by an atmospheric to 100% for hydrogen 470 to 680 nm NaOH solution (pH 13) RHE a decrease in activity
pressure organometallic vapor evolution. Turn over from 10 to 5 mA cm2 in
phase epitaxy process. number (TON) was over the rst 4 h and then no
Electron beam deposition of 139000 and turn over change for 16 h
a Ti layer, and then dipping the frequency (TOF) was
electrode in 5 103 M greater than 1.9 s1 for
(HOOCpy)Co(dmgH)2(Cl) 20 h
ethanol solution for 24 h, and
then atomic layer deposition of
a TiO2 layer
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J. Mater. Chem. A, 2018, 6, 21696–21718 | 21701

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Journal of Materials Chemistry A Review
perform the water redox reaction.41 For the hydrogen evolution
Ref.
101
67
Retention of 80% of the 95

reaction (HER) and the oxygen evolution reaction (OER) to occur
the initial photocurrent

on the catalyst's active sites, the energy level of the CB needs to
Highest 2.3 mA cm2 at 41.67% decrease from

be more negative than the hydrogen evolution potential (EH2/H2O,
for a 10 minute run
initial photocurrent
during a 20 h run
0 V vs. NHE) and the VB energy level has to be more positive
than the water oxidation potential (EO2/H2O, 1.23 V vs. NHE),
respectively.42 Theoretically, the minimum band gap of a mate-
Stability
rial for water splitting is 1.23 eV. However, in practice relatively

high energy is required due to overpotential involved in the
0.82 mA cm2 at 1.23 V —

water splitting reaction.43 The suitable band alignment and
vs. RHE from the type II

high stability of the photocatalytic material in an aqueous
11 mA cm2 at 0 V vs.
solution are also important for the water splitting reaction. The
Current density
low activation barrier of the catalyst surface is preferable for the
heterojunction
1.23 V vs. RHE
water splitting reaction.44 Sometimes cocatalysts can be added

to the photocatalyst materials which catalyze the water redox
reaction faster than the photocatalyst itself. The photon
RHE
absorption, charge separation, and charge transportation

signicantly depend on the crystal structure as well as elec-
Ar purged 0.5 M H2SO4
tronic conguration of the photocatalytic material.45 The phys-

iochemical properties of a photocatalyst also have a strong
effect on the photocatalytic water splitting reaction.26
0.5 M Na2SO4
IPCE 55% at around 400 1 M NaOH
The photocatalytic performance of a material is determined

electrolyte
(pH 0.3)
by the solar to hydrogen (STH) energy conversion for overall

System
water splitting. The STH efficiency is dened as:

Output energy rH2 DG
STH ¼ ¼ (1)
for hydrogen evolution across the visible light
Incident solar light energy PSun AGeometric

conversion efficiency
33% IPCE at 330 nm

Apparent quantum
94% faradaic efficiency IPCE around 70%

yield/IPCE/photo-
where rH2 is the hydrogen production rate, DG is the Gibbs free

energy, PSun is the energy ux of sunlight, and AGeometric is the
area of the reactor. Theoretical rH2 can be calculated from the
photon's number in the solar spectrum at a different quantum
aer 6 h, aer 20 h TON range
nm
efficiency (QE).
2 rH 2
367000 and TOF 5.7 s1
QEðhnÞ ¼ (2)
Io ðhnÞ
Hydrogen or oxygen
were obtained
Thus, theoretical STH at a different quantum efficiency can

evolution
be estimated using eqn (1) and (2).

For sacricial agent-assisted water splitting, incident photon
—
to current conversion efficiency (IPCE) and photo-conversion

efficiency are used which are dened by the following two
vapor phase epitaxy, a-TiO2 by
atomic layer deposition, MoS2
hydrothermal method, g-C3N4

by electrophoretic deposition
450 C form an intermediate
annealing at 300 C form an
equations:
by electrochemical cathodic
hydrothermal method, wet-
p-GaInP2 by metal–organic
chemical route to form an
deposition, annealing at
1240 J
IPCE ¼
Fe2O3 shell layer, PH3
(3)
l Ilight
WO3 on FTO by the
ZnO on FTO by the
Synthesis method
where J is the photocurrent density at 0 V at a certain wave-

Fe2PO5 layer
length (l), and Ilight represents irradiance intensity at l

MoOx layer

jV j
Photo conversion efficiency ¼ jp 1:23 (4)
Io
where jp denotes the photocurrent density at the measured

ZnO/a-Fe2O3 core–shell
Fe2PO5 protective layer
g-MoSx/MoOx/c-TiO2–p
potential, V is the bias potential vs. RHE, and Io is the power

(Contd. )
nanowire with an
density of incident light.

Fig. 2 shows the solar to hydrogen efficiency and photon
WO3/g-C3N4
number as a function of wavelength according to the data from

Material
Table 2
the standard AM 1.5G spectrum.39 The maximum theoretically

GaInP2
attainable STH efficiency is 48% at the integrated wavelength
View Article Online

Fig. 1 Schematic of the major steps in the photocatalytic water splitting process. Reprinted with permission from ref. 39.
from UV to 1000 nm, whereas STH efficiency in the UV region A large portion of reported photocatalysts are not suitable for
(up to 400 nm) is only 3.3% at a QE of 100%. According to DOE, the overall water splitting reaction and only a few of them are
the targeted baseline of STH efficiency is set to 10% based on visible light sensitive.17,47 The photocatalytic performance of the
the economic feasibility of the existing hydrogen market. At this materials is limited due to the quick recombination of photo-
efficiency, a photoelectrode needs to produce hydrogen at a rate generated charges, photo-corrosion, and a lack of appropriate
of 154 mmol cm2 h1 and a photoelectrochemical current of band gap energy for absorbing visible light.48 In Fig. 3, the band
8.3 mA cm2, which corresponds to a photon consumption positions of different materials are shown. The band gap of the
rate of 260 nm2 s1 on a at surface.46 A large reactor surface material should be less than 2.8 eV to effectively absorb visible
area is required at low STH (UV region) to meet these criteria, light (l > 420 nm).49 Band engineering is one of the strategies
but a large reactor area increases the cost of hydrogen produc- used to develop the visible light sensitivity of water splitting
tion. Therefore, designing photocatalysts that can absorb solar materials. Low band gap photocatalytic materials are usually
light up to the 600–700 nm (1.8–2.0 eV) wavelength is the key more susceptible to photo-corrosion than larger band gap
to achieving the targeted efficiency. materials, but higher band gap materials are not capable of
harnessing visible light.48 Heterojunction based composite
materials can be optimized to get appropriate band gap align-
ment for visible light sensitive water splitting. These hetero-
junction based photocatalysts are advantageous over single
material-based photocatalysts since they harness more visible
light than the individual materials. In addition, heterojunction
formation with suitable band alignment also facilitates an
enhanced charge separation. The heterojunction combines
different favorable properties from different materials and can
be used to achieve the targeted STH efficiency.
1.2 Photoelectrochemical and particulate heterojunction

systems for water splitting
In photoelectrochemical water splitting, photoexcited electron–
hole pairs are generated before electrons transfer from the
anode to the cathode through an external circuit.51 At the
interface of the electrode and electrolyte, electron transfer
continues until the Fermi level of the semiconducting electrode
is in the same position as the electrolyte redox potential.52
Sometimes an external bias voltage is also applied to overcome
the potential difference between the two electrodes.21
Fig. 2 Theoretical STH and photon number of AM 1.5G solar light
Generally, photoelectrochemical (PEC) cells consist of either
integrated from a low to the respective wavelength at different QEs a single photoelectrode (photoanode or photocathode) along
(30%, 60% and 100%) as a function of wavelength.39 with a counter electrode or two photoelectrodes (photoanode
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Fig. 3 Band position of different photocatalytic materials. Reprinted with permission from ref. 50.
and photocathode).53 Fig. 4(a) and (b) present single photo- of light harvesting with improved stability.52 The application of
electrochemical cell systems and Fig. 4(c) depicts a dual pho- narrow band gap semiconductors is preferred for designing
toelectrochemical cell system. In Fig. 4(a), aer light heterojunction-based PEC cells since they can harness a large
illumination the photoexcited electron from the conduction portion of the solar spectrum. In the design strategy of hetero-
band of a n-type photoanode transfers to the counter electrode junction PEC cells, relative band edge alignment is critical to
through an external circuit for the HER whereas the respective improving charge transfer for overall water splitting.54 When
photogenerated hole is consumed in the OER.21 In a p-type a photoanode is constructed with an n–n type heterojunction
photocathode (Fig. 4(b)), the photoexcited electrons are (Fig. 5(a) and (b)), photoexcited electrons go to the counter
directly utilized to produce hydrogen from the electrolyte and electrode for water reduction through an external circuit. For
the OER occurs at the counter electrode. this type of design, the conduction band position of the semi-
For this type of construction, the conduction band position conductor attached with the conductive layer needs to be lower
of the electrode needs to be more negative than the water than the conduction band position of the semiconductor on the
reduction potential. Instead of using a counter electrode, both electrolyte side. In the electrolyte side semiconductor, holes
a photoanode and photocathode are applied to construct a dual accumulate to oxidize water and generate oxygen. However, p–p
band photoelectrochemical cell (Fig. 4(c)).21 type heterojunctions (Fig. 5(c)) work as a photocathode when
Unlike the particulate photocatalytic system, photo- photoexcited electrons transfer to the electrolyte side semi-
electrochemical water splitting is dependent on efficient light conductor and reduce water to hydrogen. Finally, p–n type
absorption, band gap, and band edge position of semi heterojunctions can be used as a photoanode (Fig. 5(d)) or
conductive materials. Heterojunction-based photoelectrodes photocathode (Fig. 5(e)). In both cases, electrons and holes
provide improved charge separation and a broader wavelength
Fig. 4 Different types of photoelectrochemical cells, (a) the semiconductor photoanode with the counter electrode, (b) the semiconductor
photocathode with the counter electrode, and (c) both the photoanode and the photocathode used in a dual band PEC cell. Reprinted with
permission from ref. 21.
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Fig. 5 Different types of heterojunctions in photoelectrodes with band alignment and the mechanism of possible charge transfer. Reprinted with
permission from ref. 52.
transfer in opposite directions and better change separation Based on band alignment, there are three main types of hetero-
occurs compared to a single semiconductor electrode. junction structures between binary dissimilar particulates. In type
One of the most important advantages of a heterojunction I heterojunctions, material A has a smaller band gap than material
structure is that it allows for preferential band alignment to B.56 Holes and electrons transfer from material B to material A due
achieve visible light responsive photocatalytic water splitting.55 to a more negative CB and a more positive VB of material B.17 An
Fig. 6 Band alignment for three different types of heterojunctions. Redrawn with permission from ref. 56.
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example of a type I heterojunction is shown in Fig. 6, and photo- transportation is possible by connecting dissimilar materials
generated hole and electron ow occurs from TiO2 to Fe2O3. via a heterojunction.64
In type II heterojunctions, the CB position of material B is Hematite (Fe2O3) has a suitable band gap (2–2.2 eV) for
more negative than that of material A, but material A has a more visible light absorption and offers several benets including
positive VB position. As a result, holes and electrons transfer in high photocurrent density, good aqueous stability and photo-
opposite directions. When an electron transfers from material B corrosion resistance, naturally abundant, and less expensive
to A, the hole transfers from A to B. The WO3–BiVO4 hetero- than other commonly used photo active materials.65 In spite of
junction is one example of this type of system. This kind of these advantages, its limitations include a short excited-state
charge ow results in effective charge separation and therefore lifetime, low pH instability, low carrier mobility, and a weak
improves photocatalytic activity.17 In this type of band align- absorption coefficient for high utility of Fe2O3.65 To improve its
ment, the Z scheme can also be established when electrons water splitting efficiency, surface modication, nanostructure
from the CB of material A combine with the holes from the VB control, elemental doping, and forming heterojunctions with
of material B. Water oxidation occurs in material A, where other photocatalysts with a suitable energy band structure were
photo-excited electrons from material B contribute to hydrogen investigated thoroughly. The heterojunction strategy shows
production. In Fig. 6, BiVO4-g-C3N4 represents this type of Z favorable effects to improve photocatalytic water splitting
scheme heterojunction.56 performance.65 Other materials with a lower conduction band
Type III heterojunctions have a similar band structure to type II position than Fe2O3 will thermodynamically drive photo-
heterojunctions. The difference between the VB and CB of two generated electrons in space and work well for charge separa-
materials is larger in type III heterojunctions, however, which tion when coupled with Fe2O3.65 Unusual electron transfer from
increases photocatalytic performance by providing a higher the CB of Fe2O3 to the higher position CB of rutile and anatase
driving force for charge transfer.57 The photogenerated electron TiO2 was reported by Luan et al.65 Because of the slightly less
from material A combines with the hole of material B, and the negative CB position of rutile TiO2 (0.05 eV) compared to
electron from material B and the hole from material A participate anatase TiO2 (0.16 eV), better electron transfer was obtained in
in the reduction and oxidation of water respectively. The FeS2 and the rutile TiO2–Fe2O3 heterojunction. Because of increased
Sb2Se3 system represents this type of heterojunction in Fig. 6.17 charge transfer, under the same operating conditions rutile
In spite of several challenges, various effective, viable, and TiO2–Fe2O3 showed 1.6 times higher photocurrent density than
visible light-responsive sulde, oxide, and oxynitride photo- anatase TiO2–Fe2O3. The highest reported photocurrent density
catalysts have been synthesized for photocatalytic water split- for rutile TiO2–Fe2O3 was 0.3 mA cm2 at 0.4 V vs. the Ag/AgCl
ting applications.11 electrode from 1 M NaOH aqueous solution. Hou et al. used
graphene as a fast electron transfer mediator in the hetero-
junction of an a-Fe2O3 nanorod/BiV1XMoXO4 system and
1.3 Metal oxide–metal oxide heterojunction compared its photocatalytic activity with and without graphene
Inspired by the pioneering work of Fujishima and Honda in (Fig. 7). Graphene inserted into the heterojunction showed a 1.4
1972, who used titania for photocatalytic water splitting with UV times higher photocurrent density than the system without
irradiation,58 many materials have been studied to improve graphene. Improved photoelectrochemical properties as
photocatalytic water splitting efficiency.59,60 Developing a highly a result of window effect was observed within a-Fe2O3 cores and
efficient and sturdy photoanode in aqueous solution is one of a BiV1XMoXO4 shell where an effective photo excited carrier
the main challenges for photoelectrochemical (PEC) water separation in a-Fe2O3 nanorod/graphene/BiV1XMoXO4 inter-
splitting. Good resistance against corrosion, low electric resis- face occurred.10 Nanorod array (NA) geometry showed some
tance, at band potential, and suitable band gap of metal oxides special advantages over other various structures. When these
make them a potential highly efficient photoanode for PEC NAs were aligned vertically (e.g., TiO2, ZnO, and Fe2O3) they
cells.61 Photocatalytic materials need to absorb a large portion provided a large surface area and contributed to a small diffu-
of visible light to become highly efficient. Lower cost, higher sion length which was perpendicular to the charge-collecting
stability, and good visible light sensitivity make simple metal substrate. This is an effective structure for a smaller amount
oxides (Fe2O3, Al2O3, Ga2O3, Ta2O5, CoO, Co3O4, WO3, Cu2O, of loss due to charge recombination.10 Its outstanding charge
BiVO4, Bi2O3, PbO, SnO, CuO, and ZrO2) an attractive option for carrier mobility enables graphene to act as an electron mediator
photocatalytic water splitting.62 Oxynitrides like TaON and for photo-excited electrons which leads to effective charge
LaTiO2N also perform efficiently as oxidation photocatalysts for separation in this system.10 In the core/shell heterojunction
water splitting.5 Some binary and ternary metal oxides with structure of an a-Fe2O3 nanorod array (NA) with graphene
complex structures are also suitable photocatalysts for water sheets, graphene played a role of an electron mediator for the
splitting. Many perovskite-based materials like NaTaO3, SrTiO3, photocatalytic water splitting application.10 Reduced graphene
PbTiO3, KTaO3, and CaTa2O6 have shown good performance in oxide (RGO) sheets developed a bridge-like connection and
water splitting.28 Layered perovskite materials (Sr2Nb2O7, cover the a-Fe2O3 NA.10 This special structural feature provided
Sr2Ta2O7, and La2Ti2O7) perform better than bulk perovskite an intimate interface connecting the nanorod array and the
materials (SrTiO3 and LaTiO3) as they have inter-layer space that reduced graphene oxide which played a role in improving the
can be used for reaction sites.63 Further improvement of optical transportation of photo-excited electrons. Both a-Fe2O3 NA and
and interfacial properties as well as charge separation and BiV1XMoXO4 simultaneously absorbed photons which
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Fig. 7 Mechanism for charge transfer through an a-Fe2O3-NA/RGO/BiV1XMoXO4 heterojunction. Reprinted with permission from ref. 10.
contributes to an increase in light absorption ability. It could be density (2.3 mA cm2 at 1.23 V) than untreated ZnO/a-Fe2O3 (1
said that the ‘window effect’ was exhibited by the a-Fe2O3-NA/ mA cm2 at 1.23 V) by suppressing surface recombination and
RGO/BiV1XMoXO4 heterojunction.10 This system showed 0.53% protecting the ZnO from photo-corrosion. In addition, the
photo-conversion efficiency at 0.04 V and good stability during average transport time of photoexcited electrons to diffuse to
a photocurrent density test in 0.01 M Na2SO4 solution. However, the electrode was reduced from 0.9 ms to 0.38 ms aer PH3
this system suffered from the low conduction band position of treatment, which indicated the signicant reduction of charge
Fe2O3 in the visible light region. An external bias was applied to recombination in the treated electrode. An incident photon to
obtain oxygen evolution. Fe2O3-coated ZnO heterojunction current conversion efficiency (IPCE) of 55% was reported for the
systems also showed visible light photoactivity and high PH3-treated system in 0.1 M NaOH solution. The major limita-
photocurrent density due to improved charge separation. tion of this system is ascribed to the low conduction band
Johnson et al. recently reported the effect of the morphology of position of Fe2O3. Another heterojunction system, In2O3/
ZnO and the polarization eld in the ZnO/Fe2O3 system.66 ZnO Gd2Ti2O7, demonstrated high photocatalytic activity compared
nanorods and nanosheets were prepared with different to pure In2O3 or Gd2Ti2O7 under visible light. A 60% Gd2Ti2O7
precursor concentrations and different electrochemical depo- loaded In2O3/Gd2Ti2O7 sample produced 869.7 mmol H2 from
sition times. On top of the ZnO structure, Fe2O3 was deposited 10 vol% methanol solution aer 3 h where pure In2O3 evolved
by spin coating. Along with favorable Fermi level alignment, the only 98.6 mmol H2 under the same operating conditions.63 The
spontaneous polarization eld built in the ZnO nanosheets reason for the improved photocatalytic activity was the well-
contributed to improved charge separation and increased matched band alignment between In2O3 and Gd2Ti2O7 which
current density.66 The non-centrosymmetric structure of the reduced charge recombination at the In2O3/Gd2Ti2O7 hetero-
ZnO nanosheets with a polar direction along the c-axis resulted junction interface.63 Although the heterojunction strategy was
in an opposite direction xed induced polarization charge.66 applied to improve hydrogen evolution over single particle
ZnO nanorods did not show this type of polarization effect and systems (In2O3 and Gd2Ti2O7), this system has limited light
showed a photocurrent density 4 times lower than that of the absorption due to large band gaps (2.6 and 3.2 eV for In2O3 and
ZnO nanosheets because of quick charge recombination.66 The Gd2Ti2O7, respectively).
ZnO/Fe2O3 heterojunction photocatalytic performance can be Although BiVO4 has a small band gap (2.4 eV) which facili-
further improved by applying a Fe2PO5 protective layer. tates visible light absorption, the high rate of recombination of
Recently, Qin et al. applied a protective layer of Fe2PO5 using photoexcited charges has decreased its electron transport
PH3 gas on a ZnO/a-Fe2O3 core–shell nanowire.67 In this system, properties.68 This high charge recombination rate results from
the Fe2PO5 layer helped to activate the hematite. Thus, the PH3- the small diffusion length (Ld around 70 nm), which is ulti-
treated ZnO/a-Fe2O3 electrode showed higher photocurrent mately responsible for the poor photocurrent density of BiVO4.
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Co-catalysts, such as Co, RhO2, and NiOOH/FeOOH, help to improve the attachment of the catalyst layer on the substrate.
improve its performance. Doping with Mo and W helps to The catalyst seed layer over ITO or FTO is also effective for
develop the transport properties and increase the photocurrent providing better contact between the catalyst and the substrate.
density of BiVO4. Rao et al. reported natural doping of W in The interaction between the seed and the catalyst layer also
a thin BiVO4 shell which facilitated efficient light absorption in needs to be considered for effective charge transfer and better
a WO3/W–BiVO4 heterojunction photoanode.69 This doping performance. The structure of the BiVO4/WO3/SnO2 double
occurred naturally during the annealing process because of the heterojunction and its performance are shown in Fig. 8. A
close contact between WO3 and the BiVO4 layers, and the further improvement in photo-catalytic performance was ach-
doping concentration decreased gradually from the contact ieved by CoOx deposition and by performing an etching treat-
surface to the outer BiVO4 layer. This gradient W doping ment with a reactive ion.64 The Co3O4/BiVO4 heterojunction
introduced an electric eld, which is the reason for efficient system was reported to increase photocurrent density with
radial electron transfer from the W : BiVO4 shell to the improved charge separation because of the formation of an
conductive WO3 core. The long length (average length 2.5 mm) of internal electric eld inside the p–n junction.70 It is possible to
WO3 nanowires provided a higher surface area of the BiVO4 drive photogenerated electrons from a small band gap-
shell which introduced efficient light absorption.69 Among light containing material to a large band gap-containing material
absorption (habs), charge separation (hsep), and charge transfer by making a couple with large and small band gap semi-
(htrans) efficiencies, hsep was especially improved in that system conductors with a more negative CB position.48 The hetero-
compared to other WO3/W : BiVO4 structures. High hsep (77%) junction formation of BiVO4, a small band gap photocatalyst,
resulted from a thin (60 nm) W : BiVO4 layer because photo- with WO3 (which has a relatively less negative CB and decent
generated holes needed to travel a shorter path than their corrosion resistivity) showed good photoactivity under visible
diffusion length (70–100 nm).69 For this system, the obtained light irradiation.48 The WO3/BiVO4 nanorod heterojunction
current density was 3.1 mA cm2 in 0.5 M potassium phosphate showed 1.6 mA cm2 photocurrent density in 0.5 M sodium
electrolyte solution with 60% IPCE across the 300–450 nm sulfate solution with 31% IPCE at a 420 nm wavelength.48
range.69 Triple planar heterojunctions (TPHs) fabricated with Another strategy was applied to construct a layer of WO3 as an
BiVO4/WO3/SnO2 were able to improve photocurrent density extremely thin layer absorber (ETA), thinner than the diffusion
(3.1 mA cm2 at 1.23 V vs. RHE) in 0.5 M phosphate buffer length (Ld) of BiVO4 in the heterojunction of BiVO4/WO3 to
solution and had an internal quantum efficiency (IQE) of enhance the photocatalytic performance. This ETA layer
around 80%.64 The bottom layer of WO3/SnO2 helped the effi- resolved the negative effect of the short Ld of BiVO4 and
ciency of charge transfer, decreased interfacial resistance, and improved the charge collection probability. Photon absorption
developed close contact by forming a disordered heterojunction was also enhanced by this ETA, because of improved light
layer. The top BiVO4/WO3 heterojunction layer increased carrier scattering through the optical path. Pihosh et al. were able to get
density by improving photon absorption and charge separation. nearly 90% (6.72 mA cm2) of maximum theoretical photocur-
The construction of a SnO2 seed layer over ITO and FTO can rent (7.5 mA cm2) density from pure water by tuning the
Fig. 8 (a) Structure of the BiVO4/WO3/SnO2 double heterojunction and (b) its performance in water splitting. Reprinted with permission from
ref. 64.
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electronic thickness and optical optimization of ETA.68 Insert- layer were reported to split pure water under visible light in the
ing a thinner absorber layer than the diffusion length is an presence of a RuCl3 co-catalyst.75 RuCl3 was deposited as a co-
effective strategy to improve the performance of materials with catalyst, with an optimum addition efficiency of 0.2 mmol.75
a large diffusion length. RuCl3 provided more active sites for the reaction, but further
Sometimes doping one material and making a hetero- loading blocked the light absorption site for the catalyst. Fig. 9
junction with another material improves photocatalytic effi- illustrates the synthesis method and the pure water splitting
ciency. Zou et al. reported a RuO2 heterojunction with mechanism for the SrTiO3 : La, Rh/Au/BiVO4 : Mo catalyst.
In0.9Ni0.1TaO4 as a visible light-sensitive material able to evolve Here, the thick gold layer did not act as a surface plasmonic
8.7 mmol h1 H2 and 4.3 mmol h1 O2.71 When NiOy was material, but acted as a conductive medium to facilitate the
inserted instead of RuO2, an increased hydrogen and oxygen charge transfer in this system.75 This system decomposed pure
evolution of 16.6 mmol h1 and 8.3 mmol h1, respectively, water at a 2 : 1 ratio (H2 : O2) under ambient conditions, but the
were obtained from pure water.71 The reported apparent photocatalytic activity of this system drastically dropped at
quantum yield was 0.66% at 420 nm for this system.71 STH for elevated pressure due to the undesirable backward reaction. To
this system was not reported. Ni-doping narrowed the band gap address this issue, the SrTiO3 : La, Rh/Au/BiVO4 : Mo particu-
energy, which increases the photocatalytic activity by facili- late sheet was modied with a Cr2O3 and TiO2 layer that helped
tating electron excitation from the valence to the conduction to maintain catalyst activity and negate the pressure effect to
band position. No gas was formed when the light was turned a certain extent by reducing the backward reaction. Aer this
off, which indicates that the production of gas was conducted modication, this catalyst showed a 33% apparent quantum
with visible light absorption.71 Under visible light irradiation, yield at 419 nm and reached 1.1% STH efficiency at an elevated
metal-doped strontium titanate SrTiO3 (dopant: Ta, Rh or Ni) temperature and pressure of 331 K and 10 KPa, respectively.
and metal oxides like RbPb2Nb3O10 and SnNb2O6 can split water Furthermore, as part of the interface modication, a less
with the aid of a sacricial agent.72 TiO2 and SrTiO3 are both UV- expensive carbon lm was introduced instead of Au to form
responsive materials. However, doping TiO2 with nitrogen and SrTiO3 : La, Rh/C/BiVO4 : Mo particulate photocatalyst sheets.76
making a heterojunction with SrTiO3 makes it an efficient solar This system demonstrated an enhanced STH efficiency of 1.2%
light responsive photocatalyst.73 Along with particle agglomer- at a temperature of 331 K and a pressure of 10 kPa with an AQY
ation prevention, ner crystals and a larger specic surface area of 26% at 419 nm for unassisted pure water splitting. In addi-
in this heterojunction73 improved reduction by favorably shi- tion, activated carbon is also less prone to facilitate the oxygen
ing the Fermi level of the catalyst system. Up to 5 wt% SrTiO3, reducing backward reaction than Au and results in higher
photocatalytic ability increased, but a further increase in SrTiO3 photocatalytic performances than SrTiO3 : La, Rh/Au/BiVO4 : Mo
caused the material to behave more like SrTiO3. Since SrTiO3 is particulate sheets. The effects of varying pH, temperature,
only responsive in the UV region, photocatalytic efficiency and pressure on the water splitting activity of the SrTiO3 : La,
decreased.73 This system showed 136 mmol g1 h1 H2 evolution Rh/C/BiVO4 : Mo system were investigated.76 Applying a partic-
from 25% methanol solution.73 SrTiO3 can also be modied as ulate sheet to generate hydrogen from water is a scalable pho-
a visible light-responsive material by doping with appropriate tocatalytic water splitting process. Here, the main challenge is
materials. For example, Rh-doped SrTiO3 reduced its band gap to reduce the reverse reaction at elevated pressure. Inserting
and gave a response in the visible light range.74 Rh and La- a membrane in this type of system to separate evolved hydrogen
doped SrTiO3 and Mo-doped BiVO4 embedded into a gold and oxygen could be an effective way to improve the
Fig. 9 (a) Synthesis of a SrTiO3 : La, Rh/Au/BiVO4 : Mo particulate sheet by the particle transfer method. (b) Overall water splitting mechanism
with the synthesized material. Reprinted with permission from ref. 75.
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photocatalytic performances.77 More studies regarding surface Moreover, this single crystalline Bi4V2O11 mediated ZnRh2O4/
modication are required to prevent the backward reaction and Ag/s-Bi4V2O11 was able to utilize the visible spectrum up to
make this process scalable. 740 nm.80 The scarcity of the Rh component is a huge drawback
Oxynitrides of transition metals and lanthanides such as for utilizing the favorable properties of ZnRh2O4/Ag/s-Bi4V2O11
TaON,78 LaTiO2N, and CaTaO2N79 are good hydrogen evolving on a large scale. Excess Ag in the system created another
photocatalysts under visible light irradiation. Environmentally drawback in ZnRh2O4/Ag/s-Bi4V2O11 mediated pure water
toxic heavy metals (Pb) and rare and expensive transition metals splitting because excess Ag worked as a sacricial agent for
(Rh, Nb, Ta or La) have limited the practical utility of these oxygen evolution. To remove excess Ag, a nitric acid treatment is
oxynitrides and transition metal oxides for being used in large- required which might damage ZnRh2O4 and s-Bi4V2O11. The
scale photocatalytic water splitting.72 Kim et al. reported an damage of ZnRh2O4 and s-Bi4V2O11 leads to reduced photo-
improvement in photocurrent with a TaON/CaFe2O4 hetero- catalytic activity.80 This problem can be solved by replacing Ag
junction.5 Bare TaON showed a very small amount of photo- with Au, which does not act as a sacricial agent and is highly
current density (4 mA cm2 at 1.23 V vs. RHE) which was caused stable. Thus Au inserted in the ZnRh2O4/Au/s-Bi4V2O11 system
by the poor contact of the electrode and particles. Photocurrent was capable of splitting pure water.80 This system demonstrated
density improved with TaCl5 treatment, which contributed to a hydrogen production rate of 0.02 mmol h1 and an oxygen
ll the void between the electrode and particles. Photocurrent production rate of 0.01 mmol h1 with an AQY of 0.036% at
density was also improved by extending the electrophoretic a 545 nm wavelength. Although this system was able to split
deposition time from 1 to 2 minutes, since it increased the pure water up to 720 nm, no STH value was reported for this
agglomeration of TaON particles on the FTO substrate and system. Au and Ag have another unique property of surface
simultaneously helped to rearrange them.5 It was also found plasmonic resonance that improves photocatalytic efficiency.
that heterojunction formation with CaFe2O4 enhanced the The surface plasmon resonance (SPR) of noble metals like Au
photocurrent density by 5 times (1.24 mA cm2) compared with and Ag can be utilized for increasing the photocatalytic activity
that of bare TaON.5 The IPCE of bare TaON was 5% at 500 nm, of different materials.2 Plasmon resonance is conned within
whereas for the TaON/CaFe2O4 heterojunction it was 30% at an interface which is actually a charge density wave.2 Surface
400 nm.5 The maximum STH efficiency for the heterojunction plasmon resonance is developed by the collective oscillation of
system was 0.053% at 1 V. This system is still subject to self- free conductive electrons which is induced by photons.83
oxidation of TaON and the backward reaction between Surface electrons naturally oscillate against the restoring posi-
hydrogen and oxygen. These ndings indicated that the inti- tive force exerted by the nucleus, and SPR is observed when this
mate contact of TaON and CaFe2O4 was essential for increased frequency is matched with the frequency of incident photons.44
photocatalytic performance.5 The CaFe2O4 layer not only Different metals exhibit this resonance at different photon
improved the separation of photo-generated electrons and wavelengths. With the addition of the metal, the intensity of the
holes, but also increased the charge carrier density by absorbing plasmonic resonance is also dependent on the size and shape of
photons from visible light.5 the nanoparticle. Manipulating the size, shape, and composi-
Two photocatalytic materials can be coupled to form ‘Z- tion of plasmonic metals, it is possible to fabricate a photo-
scheme’ heterojunction structures for water splitting applica- catalytic system which can absorb any wavelength of the solar
tions.80 Sayama and coworkers rst reported heterojunctions of spectrum.44 The utilization of the plasmonic resonance char-
a hydrogen evolution photocatalyst strontium titanate co-doped acteristics of novel metals is a good strategy for fabricating
with chromium and tantalum, and an oxygen evolution photo- visible light-responsive photocatalysts. For large nanoparticles
catalyst tungsten trioxide with Pt co-catalyst deposited.81 This Z- (Ag > 50 nm) the plasmonic resonance decays by scattering
scheme arrangement was capable of overall water splitting in resonant photons radiatively while for comparatively small
NaI aqueous solution. In the Z scheme system, Ag may work as nanostructures (Ag < 30 nm) the resonance decreases with the
a mediator to transfer photo-excited electrons from the formation of energetic charge carriers.44 SPR is capable of
conduction band of the oxygen evolution catalyst to the valence converting photonic energy with heat energy, amplifying the
band of the hydrogen evolution catalyst.80 A ZnRh2O4/Ag/ electromagnetic eld and scattering electromagnetic radiation.
Ag1XSbO3Y system was able to utilize visible light up to These mechanisms are elaborately discussed in various review
545 nm while a ZnRh2O4/Ag/Bi4V2O11 system was able to func- papers.85–87
tion up to 700 nm irradiation. Mainly Ag1XSbO3Y and SPR improves the local electric eld close to the photo-
Bi4V2O11 determine the absorption properties in their respec- catalyst which ultimately enhances the electron hole pair
tive systems.82 Normal solid-state reactions can be used for the generation rate.2 The exciton diffusion length can be increased
synthesis of polycrystalline Bi4V2O11 (p-Bi4V2O11) powder to by improving the electron and hole lifetime on the metal–pho-
make a heterojunction with ZnRh2O4/Ag/p-Bi4V2O11.82 Kobaya- tocatalyst interaction surface. Along with an efficient charge
shi et al. synthesized a single crystal of Bi4V2O11 (s-Bi4V2O11) transfer mechanism, these noble metals enhance the absorp-
using a pulverization technique which resulted in a powdered tion of visible light with their SPR.62 Cao et al. reported an
ZnRh2O4/Ag/s-Bi4V2O11 photocatalyst system.80 This single improved photocatalytic activity of m-BiVO4 combined with Au
crystal Bi4V2O11 had higher crystallinity and anisotropy than nanoparticles. In 5.33 mM Na2S2O8 solution, Au incorporated
polycrystalline Bi4V2O11, which improved the mobility and on m-BiVO4 nanosheets showed 5862 mmol h1 g1 O2 evolution
separation of the photogenerated electrons and holes. while bare m-BiVO4 evolved only 1579 mmol h1 g1 of O2.62 m-
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BiVO4 showed low photocatalytic activity because of poor charge the catalyst systems some sacricial agents are used. Some
separation.62 But, the charge separation was dramatically photocatalysts like bismuth-yttrium-tungsten ternary oxide
enhanced with the addition of Au, which prevented charge (BiYWO6), zinc-germanium oxynitride ((Zn1.44Ge) (N2O0.44)),
recombination before taking part in the reaction.62 This system and niobium-substituted silver-tantalum oxide (AgTa0.7Nb0.3-
is still at the half reaction stage and the conduction band O0.3) are capable of splitting pure water under visible light
position of BiVO4 is not favorable for H2 evolution. Ingram et al. illumination.90 The ZnRh2O4/Ag/Ag1XSbO3Y system showed
reported an increased photocatalytic activity of N-doped TiO2 0.1682 mmol H2 and 0.0841 mmol O2 evolution from pure water
under visible light irradiation when it was combined with plas- aer 24 h of visible light irradiation.90 No AQY or STH was re-
monic Ag particles.88 Luchao et al. thoroughly investigated the ported for this system. Nanoparticulated CoO was reported to
TiO2 particle size dependence for plasmon-induced charge split water under visible light irradiation without the help of any
separation and the recombination dynamics in a plasmonic Au– co-catalyst or sacricial agents.91 This CoO catalyst showed 5%
TiO2 system.83 Within 50 fs, the electron injection from gold STH efficiency but suffered from quick deactivation (active for
nanoparticles to the conduction band of TiO2 happened and around 1 h).91 Making suitable heterojunctions with other
charge recombination reduced.83 This decrease in charge materials may improve the stability of nanocrystalline CoO.
recombination was a strong function of the TiO2 particle
diameter.83 A time-resolved IR probe technique was used to
1.4 Metal oxide–non-metal oxide heterojunction
investigate charge transfer and charge recombination processes.
TiO2 particles with a larger diameter needed longer diffusion The applications of noble metal co-catalysts for H2 evolution are
lengths and resulted in a longer charge recombination time becoming infeasible because they are expensive and not readily
compared with smaller diameter particles.83 Yu et al. reported available in nature.89 As an alternative to using noble metals,
a promising TiO2/Ag3PO4 electrode where Ag3PO4 reduced to people have been using transition metal sulde co-catalysts like
a Ag particle under visible light irradiation and facilitated elec- MoS2, NiS, CdIn2S4, CdLa2S4, and ZnIn2S4 for H2 evolution
tron and hole transport by surface plasmonic resonance.84 because they are cheap and highly abundant in nature.89 These
Fig. 10 shows that electrons generated in the Ag3PO4 layer are co-catalysts are great candidates for H2 evolution.89 Different
transferred to the CB of TiO2 through the Ag particle layer. In types of heterojunctions between metallic and non-metallic
1 M KOH solution, the photocurrent density was 5 times higher components were reported which improve photocatalytic
(2.34 mA cm2 at 0 V) than that for a pure TiO2 electrode.84 This activity and increase the hydrogen production rate from water
type of in situ generated layer provides a strong connection splitting.92 Some of them include Se/BiVO4,56 g-C3N4/TiO2, g-
between the two different catalyst layers and thus facilitates C3N4/CdS, g-C3N4/MoS2, g-C3N4/Cu2O, g-C3N4/WO3, g-C3N4/
charge transfer. An in situ generated conductive layer is widely Ni(OH)2, g-C3N4/ZnIn2S4, g-C3N4/Cd0.5Zn0.5S7, g-C3N4/SrTiO3, g-
utilized in the solid state Z scheme system. C3N4/Sr2Nb2O7, and g-C3N4/ZnFe2O4.92
Co-catalyst loading is another effective strategy to improve Se is a non-metallic photo-responsive material and when
water splitting efficiency. Loading an appropriate co-catalyst used to make a heterojunction with a comparatively large band
onto a catalyst surface provides an electron sink-like support gap-containing material, the combined effect is benecial for
that improves photo-induced charge separation and also acts as both reducing photo-generated electron hole recombination
a catalytic active site for generating hydrogen and oxygen and suppressing photo-corrosion of the Se layer.56 Se is
molecules.89 Co-catalysts can also be inserted into the hetero- a promising alternative as a photo-absorber in place of the
junction to further improve the oxidation or reduction effi- traditional semiconducting Si component.56 Various advantages
ciency of photocatalysts. Besides co-catalyst loading, in most of like small grain size, higher surface area, and increased
roughness have heightened its preference as a good
Fig. 10 (a) Illustration of electron and hole flow in the TiO2/Ag3PO4 electrode and (b) charge separation mechanism with band alignment.
Reprinted with permission from ref. 84.
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photocatalyst. A Se layer played a vital role in trapping photo- visible light absorption of CuInS2 and CdS, excellent charge
generated hole, absorbing light, and improving charge separa- carrier supply from CdS, charge recombination prevention
tion in the Se/BiVO4 lm (Fig. 11).56 Nasir et al. reported a Se/ within the metal oxide and CuInS2 interface by the ZnS buffer
BiVO4 lm where both Se and BiVO4 worked as a dual absorp- layer, and action of ZnO as a pathway for photogenerated
tion layer which signicantly increased the density of photoelectron transfer.93 ZnO underwent photo-corrosion by self-
induced charges.56 Maximum reported current density was 2.2 oxidation; an atomic layer deposition of a very thin TiO2 layer
mA cm2 at 1.3 V from a 0.5 M Na2SO4 solution.56 Sun et al. can protect it from photo-corrosion.94 GaInP2 has excellent
fabricated nanowire heterojunctions of a Si backbone and ZnO electronic and diffusion properties but suffers from poor
branches which were capable of enhancing light absorption and corrosion resistance. Gu et al. described graded MoSx, MoOySz,
photocurrent generation (Nanoscale, 2012, 4, 1515–1521). This MoOx, and TiO2 layers to protect the GaInP2 electrode in highly
fabrication drastically increased the surface area and reduced acidic environments.95 A MoOx–MoSx hybrid improved the
the radius of curvature which contributed to effective charge conductive and diffusive properties of the MoSx layer. Moreover,
separation and improved gas evolution from the water splitting MoOx–TiO2 mixed metal oxides provided strong acid resistance
reaction. Si-based materials usually face high charge recombi- because of their Bronsted acidity properties.95 Here, annealing
nation on the electrolyte surface and have a low hydrogen the MoSx/a-TiO2–GaInP2 catalyst at 400 C helped form a MoOx
evolution rate. The gas evolution performances of one Si-based layer and transformed TiO2 from amorphous to a crystalline
material was improved through the fabrication of a two step state. This system exhibited an IPCE efficiency of 70% and
solution phase integration of ZnO branches on a Si core to a faradaic efficiency of 94% in the presence of 0.5 M H2SO4
create an effective p–n junction for water splitting (Nanoscale, aqueous solution (pH 0.3). GaInP2 also showed high photo-
2012, 4, 1515–1521). In a Si/ZnO heterojunction, ZnO had current density under strongly basic conditions (pH 13).96 A
a lower CB position than Si, which drove photo-excited electrons covalently attached molecular cobalt catalyst and an amor-
towards the ZnO layer to the reduction level of water, where phous TiO2 protective layer were used in the p-GaInP2 electro-
photo-generated holes proceed toward Si in the opposite lyte interface in a highly basic environment. At pH 13 it showed
direction. Different etching times were used to grow different an enhanced IPCE efficiency of 80% and 100% faradaic effi-
lengths of nanowires. Longer Si nanowires obtained from 15 ciency in a 0.1 M NaOH aqueous solution. The truancy of oxide
minutes of etching produced 50–100% higher photocurrent and surface hydride layers made it difficult to attach a molec-
than shorter Si nanowires obtained with 5 minutes of etching. ular (HOOCpy)Co(dmgH)2(Cl) catalyst onto the p-GaInP2
Longer wires resulted in better light absorption and provided an surface. The insertion of an amorphous TiO2 layer by atomic
increased surface area for ZnO branches (Nanoscale, 2012, 4, layer deposition helped to form covalent bonding with the
1515–1521). carboxylic group of the molecular cobalt catalyst.96 The cova-
Yu et al. reported a system fabricated with ZnO/ZnS/CdS/ lently attached molecular cobalt reduced the kinetic barrier for
CuInS2, which exhibited a photocurrent density of 10.5 mA the HER and worked as a highly active HER catalyst. CdS is used
cm2 and an IPCE efficiency of 57.7% at 480 nm in the presence in different photocatalysts as a quantum dot (QD). Some other
of 0.5 M Na2S and 0.5 M Na2SO3 aqueous solutions.93 This high semiconductor QDs such as CdTe, CdSe, PbS, and CuInS2 can
photocurrent density resulted from the combined effect of large be used in photocatalysts to improve their photoactivity. Sun
et al. reported that CdS QDs attached to a TiO2 photocatalyst
showed a H2 evolution rate of 2200 mmol h1 W1 within the
visible light spectrum.97 Moreover, the addition of a plasmonic
metal at the CdS/TiO2 interface can improve photocatalytic
activity. Li et al. incorporated Au, as a plasmonic photosensi-
tizer, at the interface of the CdS/TiO2 heterojunction. This
system showed an improved photocurrent density of 4.07 mA
cm2 without applying any bias voltage in a 0.25 M Na2S and
0.35 M Na2SO3 aqueous solution. Here, Au not only acted as
a photo-sensitizer but also worked as a conductive bridge that
facilitated the charge transfer.98 The addition of a CdS-
decorated In2S3 layer in the Pt/Cu2ZnSnS4 electrode system
also enhanced its photocatalytic activity.99 The Pt/In2S3/CdS/
Cu2ZnSnS4 electrode demonstrated 1.63% HC-STH at 0.31 VRHE,
which was the highest reported STH efficiency for Cu2ZnSnS4-
based heterojunction systems.99 CdS-based heterojunctions still
suffer from poor stability.
Recently a WO3-based photoelectrochemical system was re-
ported by Wang et al.100 Aer the deposition of WO3 on FTO via
hydrothermal methods, they deposited a seed layer of Bi2S3 via
Fig. 11 Charge flow within the Se–BiVO4 heterojunction structure. a successive ionic layer adsorption and reaction (SILAR) method
Reprinted with permission from ref. 56. before chemical bath deposition of a Bi2S3 layer.100 This seed layer
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increased contact between the WO3 and Bi2S3 layers. For the higher temperatures, Ni2+ ions work as a catalyst to decompose
same synthesis conditions (Bi2S3 deposited for 4 h), increased C3N4.103 Optimum NiS loading in that system was found to be
photocurrent density (4.3 mA cm2 at 0.9 V vs. RHE) was 1.25 wt%. Higher loading decreased photocatalytic efficiency by
observed compared to the WO3/Bi2S3 electrode without the seed blocking pores of the C3N4 catalyst.103 A g-C3N4 sheet also
layer (3.1 mA cm2 at 0.9 V vs. RHE).100 This system had a good worked as a promising support for the in situ growth of other
photocurrent density but suffered from poor corrosion resistance nanomaterials.13 For example, Hu et al. conrmed the uniform
in 0.1 M Na2S and 0.1 M Na2SO3 aqueous solution.100 Wang et al. dispersion of InVO4 nanoparticles (20 nm) on g-C3N4 sheets via
reported two different electron transfer mechanisms by either SEM and TEM imaging.13 This uniformly dispersed surface
WO3 or g-C3N4 initial deposition on FTO.101 When WO3 was rst helped to get intimate contact, which improved photocatalytic
deposited, a type II (rst charge transfer mechanism of the type II activity by accelerating charge transfer and reducing the
heterojunction in Fig. 6) heterojunction was formed. Initially g- photoinduced electron hole recombination rate.13 The opti-
C3N4 deposition formed a Z scheme (second charge transfer mized InVO4 nanoparticle dispersed (20 wt%) g-C3N4/InVO4
mechanism of the type II heterojunction in Fig. 6) charge transfer heterojunction showed an enhanced hydrogen production
mechanism. The initial WO3 deposition showed better photo- compared to pure g-C3N4 at 212 mmol g1 h1 and had an AQY
current density (0.82 mA cm2 at 1.23 V vs. RHE) than the initial of 4.9% at 420 nm in 20 vol% methanol solution. Here, g-C3N4
g-C3N4 deposited sample (0.22 mA cm2 at 1.23 V vs. RHE).101 acted very signicantly to form g-C3N4/InVO4 nanocomposites.
Developing a g-C3N4-based heterojunction is a good The probable growth mechanism of g-C3N4/InVO4 depending
approach for improving the photocatalytic activity of other on various g-C3N4 mass fractions was discussed.13 Sometimes,
materials since g-C3N4 alone can split pure water.102 The large quantum dots are introduced into g-C3N4 to increase its pho-
band gap of Ta2O5 has conned its function within the UV toactivity.104 A g-C3N4-based heterojunction showed an
range; coupling with small band gap g-C3N4 initiates the enhanced charge separation but its applications are limited to
absorbance of visible light.92 The more negative conduction sacricial agent-assisted water splitting systems.
band potential of g-C3N4 helped to transfer photogenerated Ternary heterojunctions including g-C3N4 are also useful for
electrons to the conduction band of Ta2O5 through the heter- getting higher photocatalytic hydrogen generation from water
ojunction interface. These gathered electrons in the CB of Ta2O5 splitting. Dong et al. reported a double Z-scheme ZnO/ZnS/g-
then participated in photocatalytic hydrogen production via C3N4 ternary heterojunction which was able to produce
water reduction. Methanol worked as a sacricial agent to tap hydrogen at a rate of 301.25 mmol g1 h1 in a 0.25 M Na2S and
photo-generated holes from the valence band of g-C3N4.92 This 0.25 M Na2SO3 aqueous solution.105 High surface area and
Ta2O5/g-C3N4 heterojunction thus simultaneously improved multi-stage charge transfer contributed to better electron hole
visible light absorption and reduced photoinduced electron transfer and separation which resulted in better photocatalytic
hole pair recombination, which resulted in increased hydrogen activity. The charge transfer mechanism through the ZnO/ZnS/
evolution compared to pure Ta2O5 or g-C3N4 alone.92 NiS-loaded g-C3N4 system and hydrogen evolution using different systems
C3N4 was reported to efficiently evolve H2 under visible light are shown in Fig. 12. In the proposed mechanism [Fig. 12(b)]
irradiation.103 This system produced H2 at a rate of 48.2 mmol a double Z-scheme is established when electrons from the CB of
h1 with an AQY of 1.9% in 15 vol% triethanolamine aqueous ZnO transfer to the VB of ZnS, and electrons from the CB of ZnS
solution. During the H2 evolution reaction, water passed accumulate in the VB of g-C3N4. These electron transfers ulti-
through a reactor outside to maintain low temperatures since at mately increase the electron density in the CB of g-C3N4.105
Fig. 12 (a) Performance of the synthesized material for water splitting and (b) the proposed mechanism for hydrogen production using
ZnO/ZnS/g-C3N4. Reprinted with permission from ref. 105.
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2 Synthesis method photoinduced e/h+ recombination. The combination of the

electrospinning method with the hydrothermal method opens
The fabrication of photoelectrodes for PEC water splitting up opportunities for growing nanoobjects directly onto micro/
involves synthetic, etching, and cutting processes. In this nanobers. For example, SrTiO3 nanocubes can be grown
section we briey introduce the synthesis techniques of hydrothermally onto electrospun long TiO2 bers to form
composites for photocatalyst preparation. Some of the synthesis SrTiO3/TiO2 nanober heterostructures. This fabricated heter-
methods consist of complicated steps, such as lithography or e- ostructure provided fast separation of photogenerated charge
beam evaporation116 while others employ only simple and carriers due to direct contact between SrTiO3 and TiO2, thus
versatile forms such as hydrothermal, sol–gel,117 layer by layer dramatically enhancing photocatalytic activity.131 Despite the
(LBL),118 and dip coatings.46 Each system has its own short- many advantages of the electrospinning process, it has some
comings and advantages. For example, in contrast to the high challenges, including the production of low dimensional bers
vacuum lm deposition method, the sol–gel technique has in c axes.132 The ability to produce aligned nanobers is more
a number of advantages such as low-temperature processing, interesting in PEC terms because vertically aligned nanoobjects
easy large surface coating, and possible formation of homoge- provide a high area of interfacial contact and highly efficient
neous multicomponent lms.119 But the use of this method is pathways for generated charges.133 It is essential to increase the
limited by the list of certain materials.120 To produce complex speed of the electrospinning process without affecting nano-
composites which are not feasible by a single synthesis method, ber properties for an effective manufacturing process.
a combination of several synthetic techniques into one fabri-
cation process is being exploited. Proceeding from the fact that
different methods allow obtaining various structures, it 2.2 Hydrothermal
becomes possible to tune the architecture of coatings using The hydrothermal synthesis of nanomaterials proceeds at high
a wide range of materials. In the literature,121 authors synthe- temperature, where solid materials react in aqueous solutions
sized a TiO2/TiSi2 core/shell heterojunction nanostructure by or vapors.134 Due to its simplicity, hydrothermal synthesis has
combining both chemical vapor deposition (CVD)122 and atomic become very popular in the development of photoelectrodes as
layer deposition (ALD) routes. Various nanoarchitectures of an easy route to obtain nanostructures in relatively large
multicomponent systems were also produced by using several amounts.135 Active layers of inorganic materials are hydrother-
methods or steps. As an example,123 four separate steps were mally deposited on electrodes by many researchers working in
utilized to obtain a system of a platinum-tipped cadmium the eld of photocatalysis. Various structures with a high
sulde rod with an embedded cadmium selenide seed, surface area such as nanotubes of titanium dioxide,136 ZnO
improving the catalytic performance in the visible range. Some nanorods,137 crystalline powders of BiVO4,138 and TiO2 nano-
of the common methods for the synthesis of nanostructured wires can be obtained in one hydrothermal step without further
materials are discussed in more detail below. treatment.139 Through multiple hydrothermal synthesis steps,
more complex hierarchical structures can be obtained. The
hydrothermal fabrication of 3D hierarchical architectures with
2.1 Electrospinning a core of TiO2 nanobelts and a shell of MoS2 nanosheets has
Electrospinning is a technique used for the fabrication of been demonstrated in ref. 140. The obtained TiO2/MoS2 heter-
continuous nanobers124 by applying an electric eld to create ostructure performed well and demonstrated stable hydrogen
a charged jet of polymer solution.125 This method creates a 1D production. Limin Song and co-workers141 applied the hydro-
material with a diameter ranging from a few micrometers to thermal method without any surfactants or templates to
a few nanometers.126 For example, hierarchical structures of produce Fe2O3 nanotubes, which act as a good visible light
Bi2WO6/TiO2 (BWO/TiO2)127 and CuO/SnO2 have been produced photocatalyst and are also suitable for other electronic nano-
by combining electrospinning and other techniques.128 devices.142 The broadening of the spectral sensitivity of wide
Controllable fabrication of nanostructures via electrospinning bandgap photocatalysts obtained by hydrothermal synthesis is
can be realized by changing several parameters:129 also feasible by depositing narrow bandgap semiconductor
(1) Intrinsic properties of the solution: type of polymer, materials over them with other methods. Plasmonic hetero-
polymer chain, and viscosity. structures as the photoanode for a water splitting system were
(2) Strength of the applied electric eld. prepared by the photoreduction of Au3+ to Au0 directly onto
(3) Temperature. hydrothermally obtained wide bandgap semiconductors.137
(4) Humidity. Wang X. W. and Cheng H. M. synthesized ZnO/CdS core–shell
In addition to the above parameters, the ratio of polymer, nanorods, which exhibit highly stable and efficient photo-
precursor, and solvent involved in the synthetic process inu- catalytic hydrogen evolution by two step hydrothermal routes.
ences the morphology and diameter of low dimensional bers. First, ZnO nanorods were obtained by a modied hydrothermal
Furthermore, authors130 fabricated core–shell heterojunction method, where 0.1 M zinc acetate and 0.6 M hexamethylene
structures of (CdS)1/(ZnO)1, (CdS)0.5/(ZnO)1, and (CdS)1/(ZnO)0.5 tetramine dissolved in 50 mL DI water was treated for 10 h in an
by optimal design of the above parameters in electrospinning autoclave at 95 C. The CdS shell was deposited onto the
and compared their photocatalytic performance. The best result hydrothermally obtained ZnO nanorods by suspending them in
was obtained from (CdS)1/(ZnO)1 and explained by reduced 20 mL cadmium acetate solution under ultrasonic conditions
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for 1 h, followed by heating in H2S gas at different tempera- components in heterojunction systems, and making conductive
tures.143 Despite its simplicity, hydrothermal synthesis bridges with appropriate materials help to improve the effi-
possesses some disadvantages, such as a long reaction duration ciency of photocatalytic water splitting. Some recent studies,
and difficulty in obtaining a uniform photocatalyst size.136 including those on the polarization eld effect and particulate
sheets in heterojunction systems, have opened the door to
2.3 Sol–gel further improvements in the photocatalytic system. Particulate
photocatalyst sheet-based systems have shown promising
The sol–gel process includes two steps, which are hydrolyzation
results for designing a scalable water splitting system. Various
and condensation. Reactive species are initially hydrolyzed to
types of materials could be explored to design particulate pho-
become colloidal sol. With the assistance of a catalyst, the sol
tocatalyst sheets for obtaining a higher performance from this
solution further reacts to form an innite network of gel parti-

type of system. Light harnessing capability, effective charge
cles through the condensation process. The gel can be further
separation, and improvements in the stability of photocatalysts
treated to obtain the desired material by a heating treatment.144
remain as the key challenges to enhancing photocatalytic water
For example, nanocrystalline ZnO, CdS, and SnO2 particles have
splitting efficiency.
been synthesized by a simple sol–gel method.145
In future studies, we believe the overall pure water splitting
efficiency using photoelectrochemical cells still needs to be
2.4 Solid state reactions
improved. Designing heterojunction nanostructured materials
Solid state reactions offer a good opportunity to synthesize leveraging the advantages of different material properties will
unique nanostructured materials which are usually difficult to lead to the achievement of a high overall pure water splitting
obtain by conventional synthesis techniques.146 During solid efficiency. In heterojunction design, the inclusion of conductive
state reactions, a phase change occurs aer mixing necessary bridging (Au, Ag, graphene, and carbon) and an internal elec-
component substances. The powder mixture is further treated trical eld (ferroelectric materials and polarized materials) still
at a high temperature. For obtaining an AI2O3–TiO2 composi- needs to be extensively studied for effective charge separation
tion via a solid state reaction, the powder mixture of small and efficient charge transportation. Instead of two-component
particle size was isothermally treated at around 1580 K.147 To heterojunction systems, some multicomponent heterojunction
synthesize CaFe2O4, powders of Fe2O3 and CaCO3 were mixed systems show better activity towards the visible light driven
and then heated to 1100 C for 2 h.148 water splitting process. A proper understanding of the interac-
tions between different layers is necessary to successfully design
3 Summary and outlook more effective multicomponent heterojunction systems. The
stability issue of single photocatalysts can be further improved
One decade ago, photocatalytic pure water splitting under in the future through designing new heterojunction systems.
visible light irradiation was a dream reaction. Tremendous The excellent electronic and diffusion properties of metal
research into photocatalytic and photoelectrochemical water suldes and phosphides can be utilized more by forming
splitting has turned that dream into reality. To compete with effective heterojunctions with a protective layer around them.
conventional fuel prices, the efficiency of photocatalytic water Different inexpensive molecular catalysts can be investigated
splitting needs to improve now. According to the US Depart- more to fabricate the protective layer. Finding the optimal co-
ment of Energy, photocatalytic water splitting can compete with catalyst for a heterojunction photocatalyst system needs to be
conventional fuel if the water splitting efficiency (STH) reaches fully understood. The elimination of expensive and rare co-
around 10%.149 To attain this efficiency, photocatalysts are catalysts is necessary to obtain an economically feasible pho-
required to absorb wavelengths between 600 and 700 nm with tocatalytic system. Mixed metal oxide co-catalysts with different
a 40–60% apparent quantum yield. The heterojunction strategy compositions should be further investigated for improved
helps to synthesize highly efficient photocatalytic materials at photocatalyst system performance. The fabrication of photo-
low cost. Deep insight into the heterojunction interface is electrodes still needs to be improved to obtain stable photo-
needed to build up new, efficient photocatalysts. To create electrochemical systems.
heterojunctions, one needs to proceed strategically. First, band
alignment should be investigated to determine which hetero-
junction system will give a thermodynamically favorable charge Conflicts of interest
transfer. Then, a study of charge transfer dynamics with
appropriate characterization tools can provide a fundamental There are no conicts to declare.
understanding of the performance of the heterojunction system
and help to design an efficient photocatalyst system. Thus,
various research studies are going on to improve the efficiency Acknowledgements
of photocatalytic water splitting. The improvement of the
stability of different photocatalysts in aqueous medium is still The authors greatly acknowledge nancial support from Texas
one of the main concerns in photocatalytic water splitting. Tech University. This work was supported by ACS PRF (57095-
Surface modications of different catalysts, crystal structure DNI7). The authors want to thank Robin Dupre for her contri-
study, utilization of plasmonic resonance of metallic bution to xing grammatical errors in the manuscript.
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References 28 M. Moniruddin, B. Ilyassov, X. Zhao, E. Smith, T. Serikov,

N. Ibrayev, R. Asmatulu and N. Nuraje, Materials Today
1 M. Moniruddin, K. Afroz, Y. Shabdan, B. Bizri and Energy, 2018, 7, 246–259.
N. Nuraje, Appl. Surf. Sci., 2017, 419, 886–892. 29 K. Maeda, ACS Catal., 2013, 3, 1486–1503.
2 Z. Liu, W. Hou, P. Pavaskar, M. Aykol and S. B. Cronin, Nano 30 S. Chen, S. S. Thind and A. Chen, Electrochem. Commun.,
Lett., 2011, 11, 1111–1116. 2016, 63, 10–17.
3 W. Septina, R. R. Prabhakar, R. Wick, T. Moehl and 31 G. Wang, Y. Ling, H. Wang, L. Xihong and Y. Li, J.
S. D. Tilley, Chem. Mater., 2017, 29, 1735–1743. Photochem. Photobiol., C, 2014, 19, 35–51.
4 X. Chen, S. Shen, L. Guo and S. S. Mao, Chem. Rev., 2010, 32 M. G. Walter, E. L. Warren, J. R. McKone, S. W. Boettcher,
110, 6503–6570. Q. Mi, E. A. Santori and N. S. Lewis, Chem. Rev., 2010,
5 E. S. Kim, N. Nishimura, G. Magesh, J. Y. Kim, J.-W. Jang, 110, 6446–6473.

H. Jun, J. Kubota, K. Domen and J. S. Lee, J. Am. Chem. 33 T. Hisatomi, K. Takanabe and K. Domen, Catal. Lett., 2015,
Soc., 2013, 135, 5375–5383. 145, 95–108.
6 J. Su, X.-X. Zou, G.-D. Li, X. Wei, C. Yan, Y.-N. Wang, J. Zhao, 34 B. Tian, B. Tian, B. Smith, M. Scott, R. Hua, Q. Lei and
L.-J. Zhou and J.-S. Chen, J. Phys. Chem. C, 2011, 115, 8064– Y. Tian, Nat. Commun., 2018, 9, 1397.
8071. 35 J. Tang, J. R. Durrant and D. R. Klug, J. Am. Chem. Soc., 2008,
7 A. Paracchino, V. Laporte, K. Sivula, M. Grätzel and 130, 13885–13891.
E. Thimsen, Nat. Mater., 2011, 10, 456–461. 36 M. Graetzel, Acc. Chem. Res., 1981, 14, 376–384.
8 S. Y. Reece, J. A. Hamel, K. Sung, T. D. Jarvi, A. J. Esswein, 37 K. Takanabe, ACS Catal., 2017, 7, 8006–8022.
J. J. Pijpers and D. G. Nocera, Science, 2011, 334, 645–648. 38 Z. Hu, B. J. Deibert and J. Li, Chem. Soc. Rev., 2014, 43, 5815–
9 K. Sun, Y. Jing, C. Li, X. Zhang, R. Aguinaldo, A. Kargar, 5840.
K. Madsen, K. Banu, Y. Zhou and Y. Bando, Nanoscale, 39 K. Takanabe, in Solar Energy for Fuels, Springer, 2015, pp.
2012, 4, 1515–1521. 73–103.
10 Y. Hou, F. Zuo, A. Dagg and P. Feng, Nano Lett., 2012, 12, 40 H. Wang, L. Zhang, Z. Chen, J. Hu, S. Li, Z. Wang, J. Liu
6464–6473. and X. Wang, Chem. Soc. Rev., 2014, 43, 5234–
11 Q. Xiang, J. Yu and M. Jaroniec, J. Phys. Chem. C, 2011, 115, 5244.
7355–7363. 41 N. J. Turro, V. Ramamurthy and J. C. Scaiano, Photochem.
12 Y. Tian, B. Chang, J. Lu, J. Fu, F. Xi and X. Dong, ACS Appl. Photobiol., 2012, 88, 1033.
Mater. Interfaces, 2013, 5, 7079–7085. 42 T. Jafari, E. Moharreri, A. S. Amin, R. Miao, W. Song and
13 B. Hu, F. Cai, T. Chen, M. Fan, C. Song, X. Yan and W. Shi, S. L. Suib, Molecules, 2016, 21, 900.
ACS Appl. Mater. Interfaces, 2015, 7, 18247–18256. 43 J. Liao, B. Sa, J. Zhou, R. Ahuja and Z. Sun, J. Phys. Chem. C,
14 P. Zhou, J. Yu and M. Jaroniec, Adv. Mater., 2014, 26, 4920– 2014, 118, 17594–17599.
4935. 44 S. Linic, P. Christopher and D. B. Ingram, Nat. Mater., 2011,
15 S. Tanigawa and H. Irie, Appl. Catal., B, 2016, 180, 1–5. 10, 911.
16 A. Kudo and Y. Miseki, Chem. Soc. Rev., 2009, 38, 253– 45 Y. Yuan, J. Lv, X. Jiang, Z. Li, T. Yu, Z. Zou and J. Ye, Appl.
278. Phys. Lett., 2007, 91, 094107.
17 S. J. Moniz, S. A. Shevlin, D. J. Martin, Z.-X. Guo and J. Tang, 46 K. Kato, Y. Torii, H. Taoda, T. Kato, Y. Butsugan and
Energy Environ. Sci., 2015, 8, 731–759. K. Niihara, J. Mater. Sci. Lett., 1996, 15, 913–915.
18 M. Ni, M. K. Leung, D. Y. Leung and K. Sumathy, Renewable 47 Z.-K. Tang, W.-J. Yin, L. Zhang, B. Wen, D.-Y. Zhang,
Sustainable Energy Rev., 2007, 11, 401–425. L.-M. Liu and W.-M. Lau, Sci. Rep., 2016, 6, 32764.
19 K. Sivula, F. Le Formal and M. Grätzel, ChemSusChem, 2011, 48 J. Su, L. Guo, N. Bao and C. A. Grimes, Nano Lett., 2011, 11,
4, 432–449. 1928–1933.
20 N. Nuraje, R. Asmatulu and S. Kudaibergenov, Curr. Inorg. 49 A. Kudo, H. Kato and I. Tsuji, Chem. Lett., 2004, 33, 1534–
Chem., 2012, 2, 124–146. 1539.
21 T. Hisatomi, J. Kubota and K. Domen, Chem. Soc. Rev., 2014, 50 X. Li, J. Yu and M. Jaroniec, Chem. Soc. Rev., 2016, 45, 2603–
43, 7520–7535. 2636.
22 S. Ye, R. Wang, M.-Z. Wu and Y.-P. Yuan, Appl. Surf. Sci., 51 Z. Shi, X. Wen, Z. Guan, D. Cao, W. Luo and Z. Zou, Ann.
2015, 358, 15–27. Phys., 2015, 358, 236–247.
23 S. Cao and J. Yu, J. Phys. Chem. Lett., 2014, 5, 2101–2107. 52 S. Choudhary, S. Upadhyay, P. Kumar, N. Singh,
24 J. Wen, J. Xie, X. Chen and X. Li, Appl. Surf. Sci., 2017, 391, V. R. Satsangi, R. Shrivastav and S. Dass, Int. J. Hydrogen
72–123. Energy, 2012, 37, 18713–18730.
25 K. Maeda, J. Photochem. Photobiol., C, 2011, 12, 237–268. 53 Z. Li, W. Luo, M. Zhang, J. Feng and Z. Zou, Energy Environ.
26 K. Maeda and K. Domen, J. Phys. Chem. Lett., 2010, 1, 2655– Sci., 2013, 6, 347–370.
2661. 54 P. V. Kamat, J. Phys. Chem. C, 2007, 111, 2834–2860.
27 S. Chen, T. Takata and K. Domen, Nat. Rev. Mater., 2017, 2, 55 J. S. Jang, H. G. Kim and J. S. Lee, Catal. Today, 2012, 185,
17050. 270–277.
View Article Online
56 S. N. F. M. Nasir, H. Ullah, M. Ebadi, A. A. Tahir, J. S. Sagu 81 K. Sayama, K. Mukasa, R. Abe, Y. Abe and H. Arakawa, J.
and M. A. Mat Teridi, J. Phys. Chem. C, 2017, 121, 6218– Photochem. Photobiol., A, 2002, 148, 71–77.
6228. 82 K. Teramura, K. Maeda, T. Saito, T. Takata, N. Saito,
57 Q. Li, X. Ma, H. Liu, Z. Chen, H. Chen and S. Chu, ACS Appl. Y. Inoue and K. Domen, J. Phys. Chem. B, 2005, 109,
Mater. Interfaces, 2017, 9(22), 18836–18844. 21915–21921.
58 A. Fujishima and K. Honda, nature, 1972, 238, 37–38. 83 L. Du, A. Furube, K. Yamamoto, K. Hara, R. Katoh and
59 J. Masud, A. T. Swesi, W. P. Liyanage and M. Nath, ACS Appl. M. Tachiya, J. Phys. Chem. C, 2009, 113, 6454–6462.
Mater. Interfaces, 2016, 8, 17292–17302. 84 L. Yu, J. He, C. Huang, M. Li, Y. Zhang, X. Zhou and H. Zhu,
60 J. Masud, P. C. Ioannou, N. Levesanos, P. Kyritsis and RSC Adv., 2017, 7, 54485–54490.
M. Nath, ChemSusChem, 2016, 9, 3128–3132. 85 J. A. Schuller, E. S. Barnard, W. Cai, Y. C. Jun, J. S. White and
61 M. Shi, X. Pan, W. Qiu, D. Zheng, M. Xu and H. Chen, Int. J. M. L. Brongersma, Nat. Mater., 2010, 9, 193.
Hydrogen Energy, 2011, 36, 15153–15159. 86 P. K. Jain, X. Huang, I. H. El-Sayed and M. A. El-Sayed, Acc.
62 S.-W. Cao, Z. Yin, J. Barber, F. Y. Boey, S. C. J. Loo and Chem. Res., 2008, 41, 1578–1586.
C. Xue, ACS Appl. Mater. Interfaces, 2011, 4, 418–423. 87 S. C. Warren and E. Thimsen, Energy Environ. Sci., 2012, 5,
63 A. Nashim, S. Martha and K. Parida, ChemCatChem, 2013, 5, 5133–5146.
2352–2359. 88 D. B. Ingram and S. Linic, J. Am. Chem. Soc., 2011, 133,
64 J. H. Baek, B. J. Kim, G. S. Han, S. W. Hwang, D. R. Kim, 5202–5205.
I. S. Cho and H. S. Jung, ACS Appl. Mater. Interfaces, 2017, 89 Y.-P. Yuan, S.-W. Cao, L.-S. Yin, L. Xu and C. Xue, Int. J.
9(2), 1479–1487. Hydrogen Energy, 2013, 38, 7218–7223.
65 P. Luan, M. Xie, D. Liu, X. Fu and L. Jing, Sci. Rep., 2014, 4, 90 R. Kobayashi, S. Tanigawa, T. Takashima, B. Ohtani and
6180. H. Irie, J. Phys. Chem. C, 2014, 118, 22450–22456.
66 J. Johnson, N. Bakranov, M. Moniruddin, R. Iskakov, 91 L. Liao, Q. Zhang, Z. Su, Z. Zhao, Y. Wang, Y. Li, X. Lu,
S. Kudaibergenov and N. Nuraje, New J. Chem., 2017, 41, D. Wei, G. Feng and Q. Yu, Nat. Nanotechnol., 2014, 9, 69.
15528–15532. 92 Y. Hong, Z. Fang, B. Yin, B. Luo, Y. Zhao, W. Shi and C. Li,
67 D. D. Qin, C. H. He, Y. Li, A. C. Trammel, J. Gu, J. Chen, Int. J. Hydrogen Energy, 2017, 42, 6738–6745.
Y. Yan, D. L. Shan, Q. H. Wang and J. J. Quan, 93 Y.-X. Yu, W.-X. Ouyang, Z.-T. Liao, B.-B. Du and
ChemSusChem, 2017, 10, 2796–2804. W.-D. Zhang, ACS Appl. Mater. Interfaces, 2014, 6, 8467–
68 Y. Pihosh, I. Turkevych, K. Mawatari, J. Uemura, Y. Kazoe, 8474.
S. Kosar, K. Makita, T. Sugaya, T. Matsui and D. Fujita, 94 H. Zhao, W. Deng and Y. Li, Advanced Composites and
Sci. Rep., 2015, 5, 11141. Hybrid Materials, 2017, pp. 1–10.
69 P. M. Rao, L. Cai, C. Liu, I. S. Cho, C. H. Lee, J. M. Weisse, 95 J. Gu, J. A. Aguiar, S. Ferrere, K. X. Steirer, Y. Yan, C. Xiao,
P. Yang and X. Zheng, Nano Lett., 2014, 14, 1099–1105. J. L. Young, M. Al-Jassim, N. R. Neale and J. A. Turner,
70 X. Chang, T. Wang, P. Zhang, J. Zhang, A. Li and J. Gong, J. Nat. Energy, 2017, 2, 16192.
Am. Chem. Soc., 2015, 137, 8356–8359. 96 J. Gu, Y. Yan, J. L. Young, K. X. Steirer, N. R. Neale and
71 Z. Zou, J. Ye, K. Sayama and H. Arakawa, nature, 2001, 414, J. A. Turner, Nat. Mater., 2016, 15, 456.
625–627. 97 W.-T. Sun, Y. Yu, H.-Y. Pan, X.-F. Gao, Q. Chen and
72 M. Manikandan, T. Tanabe, P. Li, S. Ueda, G. V. Ramesh, L.-M. Peng, J. Am. Chem. Soc., 2008, 130, 1124–1125.
R. Kodiyath, J. Wang, T. Hara, A. Dakshanamoorthy and 98 J. Li, S. K. Cushing, P. Zheng, T. Senty, F. Meng,
S. Ishihara, ACS Appl. Mater. Interfaces, 2014, 6, 3790–3793. A. D. Bristow, A. Manivannan and N. Wu, J. Am. Chem.
73 B.-S. Huang and M.-Y. Wey, J. Nanopart. Res., 2014, 16, 2178. Soc., 2014, 136, 8438–8449.
74 K. Iwashina and A. Kudo, J. Am. Chem. Soc., 2011, 133, 99 F. Jiang, T. Harada, Y. Kuang, T. Minegishi, K. Domen and
13272–13275. S. Ikeda, J. Am. Chem. Soc., 2015, 137, 13691–13697.
75 Q. Wang, T. Hisatomi, Q. Jia, H. Tokudome, M. Zhong, 100 Y. Wang, W. Tian, L. Chen, F. Cao, J. Guo and L. Li, ACS
C. Wang, Z. Pan, T. Takata, M. Nakabayashi and Appl. Mater. Interfaces, 2017, 9, 40235–40243.
N. Shibata, Nat. Mater., 2016, 15, 611. 101 C.-H. Wang, D.-D. Qin, D.-L. Shan, J. Gu, Y. Yan, J. Chen,
76 Q. Wang, T. Hisatomi, Y. Suzuki, Z. Pan, J. Seo, Q.-H. Wang, C.-H. He, Y. Li and J.-J. Quan, Phys. Chem.
M. Katayama, T. Minegishi, H. Nishiyama, T. Takata and Chem. Phys., 2017, 19, 4507–4515.
K. Seki, J. Am. Chem. Soc., 2017, 139, 1675–1683. 102 J. Liu, Y. Liu, N. Liu, Y. Han, X. Zhang, H. Huang,
77 V.-H. Nguyen and J. C. Wu, Appl. Catal., A, 2018, 550, 122– Y. Lifshitz, S.-T. Lee, J. Zhong and Z. Kang, Science, 2015,
141. 347, 970–974.
78 M. Higashi, K. Domen and R. Abe, J. Am. Chem. Soc., 2012, 103 J. Hong, Y. Wang, Y. Wang, W. Zhang and R. Xu,
134, 6968–6971. ChemSusChem, 2013, 6, 2263–2268.
79 M. Higashi, R. Abe, T. Takata and K. Domen, Chem. Mater., 104 L. Ge, F. Zuo, J. Liu, Q. Ma, C. Wang, D. Sun, L. Bartels and
2009, 21, 1543–1549. P. Feng, J. Phys. Chem. C, 2012, 116, 13708–13714.
80 R. Kobayashi, T. Takashima, S. Tanigawa, S. Takeuchi, 105 Z. Dong, Y. Wu, N. Thirugnanam and G. Li, Appl. Surf. Sci.,
B. Ohtani and H. Irie, Phys. Chem. Chem. Phys., 2016, 18, 2018, 430, 293–300.
27754–27760.
View Article Online
106 Z. Zhang, K. Liu, Z. Feng, Y. Bao and B. Dong, Sci. Rep., 129 D. Li and Y. N. Xia, Adv. Mater., 2004, 16, 1151–1170.
2016, 6, 19221. 130 G. R. Yang, W. Yan, Q. Zhang, S. H. Shen and S. J. Ding,
107 X. Yu, A. Shavel, X. An, Z. Luo, M. Ibanez and A. Cabot, J. Nanoscale, 2013, 5, 12432–12439.
Am. Chem. Soc., 2014, 136, 9236–9239. 131 H. W. Bai, J. Juay, Z. Y. Liu, X. X. Song, S. S. Lee and
108 H. Kato, K. Asakura and A. Kudo, J. Am. Chem. Soc., 2003, D. D. Sun, Appl. Catal., B, 2012, 125, 367–374.
125, 3082–3089. 132 W. E. Teo and S. Ramakrishna, Nanotechnology, 2006, 17,
109 S. Chen, Y. Qi, T. Hisatomi, Q. Ding, T. Asai, Z. Li, R89–R106.
S. S. K. Ma, F. Zhang, K. Domen and C. Li, Angew. Chem., 133 I. Gonzalez-Valls and M. Lira-Cantu, Energy Environ. Sci.,
Int. Ed., 2015, 54, 8498–8501. 2009, 2, 19–34.
110 M. M. Momeni and Y. Ghayeb, J. Appl. Electrochem., 2015, 134 A. Tavakoli, M. Sohrabi and A. Kargari, Chem. Pap., 2007,
45, 557–566. 61, 151–170.

111 A. K. R. Police, S. Basavaraju, D. K. Valluri, S. Machiraju and 135 Y. L. Pang, S. Lim, H. C. Ong and W. T. Chong, Appl. Catal.,
J. S. Lee, Chem. Eng. J., 2014, 247, 152–160. A, 2014, 481, 127–142.
112 S. Zhu, F. Yao, C. Yin, Y. Li, W. Peng, J. Ma and D. Zhang, 136 N. Liu, X. Y. Chen, J. L. Zhang and J. W. Schwank, Catal.
Microporous Mesoporous Mater., 2014, 190, 10–16. Today, 2014, 225, 34–51.
113 J. Zhang, S. Z. Qiao, L. Qi and J. Yu, Phys. Chem. Chem. Phys., 137 M. Wu, W. J. Chen, Y. H. Shen, F. Z. Huang, C. H. Li and
2013, 15, 12088–12094. S. K. Li, ACS Appl. Mater. Interfaces, 2014, 6, 15052–15060.
114 Z. Yin, Z. Wang, Y. Du, X. Qi, Y. Huang, C. Xue and 138 J. B. Liu, H. Wang, S. Wang and H. Yan, Mater. Sci. Eng., B,
H. Zhang, Adv. Mater., 2012, 24, 5374–5378. 2003, 104, 36–39.
115 M. S. Akple, J. Low, S. Wageh, A. A. Al-Ghamdi, J. Yu and 139 Y. C. Pu, G. M. Wang, K. D. Chang, Y. C. Ling, Y. K. Lin,
J. Zhang, Appl. Surf. Sci., 2015, 358, 196–203. B. C. Fitzmorris, C. M. Liu, X. H. Lu, Y. X. Tong,
116 A. Kargar, K. Sun, Y. Jing, C. Choi, H. Jeong, G. Y. Jung, J. Z. Zhang, Y. J. Hsu and Y. Li, Nano Lett., 2013, 13,
S. Jin and D. L. Wang, ACS Nano, 2013, 7, 9407–9415. 3817–3823.
117 R. J. Candal, W. A. Zeltner and M. A. Anderson, Journal of 140 W. J. Zhou, Z. Y. Yin, Y. P. Du, X. Huang, Z. Y. Zeng,
Environmental Engineering, 1999, 125, 906–912. Z. X. Fan, H. Liu, J. Y. Wang and H. Zhang, Small, 2013,
118 M. Li, S. Ishihara, Q. M. Ji, Y. G. Ma, J. P. Hill and K. Ariga, 9, 140–147.
Chem. Lett., 2012, 41, 383–385. 141 L. M. Song, S. J. Zhang, B. Chen, J. J. Ge and X. C. Jia,
119 L. L. Hu, T. Yoko, H. Kozuka and S. Sakka, Thin Solid Films, Colloids Surf., A, 2010, 360, 1–5.
1992, 219, 18–23. 142 Y. Hou, F. Zuo, A. Dagg and P. Y. Feng, Nano Lett., 2012, 12,
120 Y. I. Song, G. Y. Kim, H. K. Choi, H. J. Jeong, K. K. Kim, 6464–6473.
C. M. Yang, S. C. Lim, K. H. An, K. T. Jung and Y. H. Lee, 143 X. W. Wang, G. Liu, G. Q. Lu and H. M. Cheng, Int. J.
Chem. Vap. Deposition, 2006, 12, 375–379. Hydrogen Energy, 2010, 35, 8199–8205.
121 Y. J. Lin, S. Zhou, X. H. Liu, S. Sheehan and D. W. Wang, J. 144 B. B. Lakshmi, C. J. Patrissi and C. R. Martin, Chem. Mater.,
Am. Chem. Soc., 2009, 131(8), 2772–2773. 1997, 9, 2544–2550.
122 G. Che, B. B. Lakshmi, C. R. Martin, E. R. Fisher and 145 F. Gu, S. F. Wang, M. K. Lu, G. J. Zhou, D. Xu and
R. S. Ruoff, Chem. Mater., 1998, 10, 260–267. D. R. Yuan, J. Phys. Chem. B, 2004, 108, 8119–8123.
123 L. Amirav and A. P. Alivisatos, J. Phys. Chem. Lett., 2010, 1, 146 K. Biradha and R. Santra, Chem. Soc. Rev., 2013, 42, 950–
1051–1054. 967.
124 Z. M. Huang, Y. Z. Zhang, M. Kotaki and S. Ramakrishna, 147 B. Freudenberg and A. Mocellin, J. Am. Ceram. Soc., 1987,
Compos. Sci. Technol., 2003, 63, 2223–2253. 70, 33–38.
125 J. Doshi and D. H. Reneker, J. Electrost., 1995, 35, 151–160. 148 E. Casbeer, V. K. Sharma and X. Z. Li, Sep. Purif. Technol.,
126 A. Greiner and J. H. Wendorff, Angew. Chem., Int. Ed., 2007, 2012, 87, 1–14.
46, 5670–5703. 149 DOE Technical Targets for Hydrogen Production from
127 M. Shang, W. Z. Wang, L. Zhang, S. M. Sun, L. Wang and Photoelectrochemical Water Splitting, https://
L. Zhou, J. Phys. Chem. C, 2009, 113, 14727–14731. www.energy.gov/eere/fuelcells/doe-technical-targets-hydrogen-
128 S. W. Choi, A. Katoch, J. Zhang and S. S. Kim, Sens. production-photoelectrochemical-water-splitting, (accessed
Actuators, B, 2013, 176, 585–591. 5/3/2018, 2018).

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Journal of

A heterojunction strategy to improve the visible

Cite this: J. Mater. Chem. A, 2018, 6,

Review Journal of Materials Chemistry A

Table 1 Photocatalytic performance of heterojunction particles

21698 | J. Mater. Chem. A, 2018, 6, 21696–21718

This journal is © The Royal Society of Chemistry 2018

This journal is © The Royal Society of Chemistry 2018

J. Mater. Chem. A, 2018, 6, 21696–21718 | 21699

Table 2 Photocatalytic performance of heterojunction ﬁlms

21700 | J. Mater. Chem. A, 2018, 6, 21696–21718

This journal is © The Royal Society of Chemistry 2018

This journal is © The Royal Society of Chemistry 2018

J. Mater. Chem. A, 2018, 6, 21696–21718 | 21701

Journal of Materials Chemistry A Review

perform the water redox reaction.41 For the hydrogen evolution

Retention of 80% of the 95

the initial photocurrent

Highest 2.3 mA cm2 at 41.67% decrease from

for a 10 minute run

rial for water splitting is 1.23 eV. However, in practice relatively

0.82 mA cm2 at 1.23 V —

vs. RHE from the type II

low activation barrier of the catalyst surface is preferable for the

water splitting reaction.44 Sometimes cocatalysts can be added

absorption, charge separation, and charge transportation

tronic conguration of the photocatalytic material.45 The phys-

The photocatalytic performance of a material is determined

by the solar to hydrogen (STH) energy conversion for overall

water splitting. The STH eﬃciency is dened as:

Incident solar light energy PSun AGeometric

33% IPCE at 330 nm

94% faradaic eﬃciency IPCE around 70%

where rH2 is the hydrogen production rate, DG is the Gibbs free

Thus, theoretical STH at a diﬀerent quantum eﬃciency can

be estimated using eqn (1) and (2).

to current conversion eﬃciency (IPCE) and photo-conversion

hydrothermal method, g-C3N4

where J is the photocurrent density at 0 V at a certain wave-

length (l), and Ilight represents irradiance intensity at l

where jp denotes the photocurrent density at the measured

Fe2PO5 protective layer

potential, V is the bias potential vs. RHE, and Io is the power

density of incident light.

number as a function of wavelength according to the data from

the standard AM 1.5G spectrum.39 The maximum theoretically

attainable STH eﬃciency is 48% at the integrated wavelength

Review Journal of Materials Chemistry A

1.2 Photoelectrochemical and particulate heterojunction

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review