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Development of efficient bismuth tungstate for photocatalytic
and photoelectrochemical reactions
Author:
Chung, Hoi Ying
Publication Date:
2019
DOI:
https://doi.org/10.26190/unsworks/3755
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DEVELOPMENT OF EFFICIENT
BISMUTH TUNGSTATE FOR
PHOTOCATALYTIC AND
PHOTOELECTROCHEMICAL
REACTIONS
By
Hoi Ying Chung
A thesis submitted to The University of New South
Wales in partial fulfilment of the requirements for the
degree of Doctor of Philosophy
School of Chemical Engineering

Faculty of Engineering
Sydney, Australia
March 2019
i
THESIS/DISSERTATION SHEET
PLEASE TYPE
THE UNIVERSITY OF NEW SOUTH WALES
THESIS/DISSERATAION SHEET
Surname or Family name: CHUNG
First name: HOI YING Other name/s:
Abbreviation for degree as given in the University calendar: PhD
School: School of Chemical Engineering Faculty: Engineering
Title: Development of Efficient Bismuth Tungstate for Photocatalytic and Photoelectrochemical

Reaction
Abstract
Sunlight-driven water splitting has emerged as a potential method in the production of clean energy carriers. The
bottleneck of water splitting reaction lies on water oxidation because of the involvement of four-electron transfer
mechanism. Bismuth tungstate (Bi2WO6) is a photoactive semiconductor capable of oxidising water into oxygen and with
a band gap of 2.7-2.9 eV (visible-light active). In this thesis, Bi2WO6 was designed to achieve improved photocatalytic and
photoelectrochemical (PEC) efficiency. Important factors and the underlying mechanisms involved were studied
systematically.
Firstly, the synthesis of hierarchical Bi2WO6 microspheres with controllable crystallinity and surface area was achieved
through a combination of hydrothermal/calcination processes. Though both crystallinity and surface area are affecting the
overall activities, it was found the degree of crystallinity dominates the reaction. As the bond length of tungsten (W) was
shorten accompanying the improved crystallinity, improved charge transportation was observed.
Following the investigation of crystallinity and surface area, by tuning the W precursor concentration in the synthesis,
Bi2WO6 was made into platelike-structure with well-defined crystal facets, in which the role of each crystal facet was
investigated. Bi2WO6 with a higher exposure extent of electron-dominated crystal facet reduces the charge transport
resistance and decreases the charge trapping. Moreover, by introducing more W in the Bi 2WO6, a self-doped phenomenon
that increases the charge carrier concentration and contains more W 5+ species were observed. These factors inhibit the
charge recombination and beneficial to the photo-oxidation process.
The performance of Bi2WO6 was further improved by the creation of heterojunction. Controlled transformation of tungsten
oxide (WO3) to Bi2WO6 via electrodeposition and hydrothermal method successfully introduced heterojunction
Bi2WO6/WO3. A higher interface between the Bi2WO6 and WO3 has lowered the amount of interfacial trapping of
photoelectrons. It directly optimises the PEC water splitting to an ideal situation, facilitated by smaller applied bias. Another
heterojunction was formed with the oxygen-deficient bismuth tungstate (Bi14WO24) and bismuth oxide, in which the
photocorrosion was suppressed owing to the promoted interfacial charge transfer between the two components. The
findings in this thesis could be applicable to other oxide-based photocatalysts.
Declaration relating to disposition of project thesis/dissertation
I hereby grant to the University of New South Wales or its agents the right to archive and to make available my thesis or
dissertation in whole or in part in the University libraries in all forms of media, now or here after known, subject to the
provisions of the Copyright Act 1968. I retain all property rights, such as patent rights. I also retain the right to use in
future works (such as articles or books) all or part of this thesis or dissertation.
I also authorise University Microfilms to use the 350 word abstract of my thesis in Dissertation Abstracts International
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ii
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‘I hereby grant the University of New South Wales or its agents the right to archive
and to make available my thesis or dissertation in whole or part in the University
libraries in all forms of media, now or here after known, subject to the provisions
of the Copyright Act 1968. I retain all proprietary rights, such as patent rights. I
also retain the right to use in future works (such as articles or books) all or part of
this thesis or dissertation.
I also authorise University Microfilms to use the 350 word abstract of my thesis in
Dissertation Abstract International (this is applicable to doctoral theses only).
I have either used no substantial portions of copyright material in my thesis or I
have obtained permission to use copyright material; where permission has not
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conversion to digital format.’
Signed ……………………………………………...........................
Date ……………………………………………...........................
v
Abstract
ABSTRACT
Sunlight-driven water splitting has emerged as a potential method in the production of
clean energy carriers. The bottleneck of water splitting reaction lies on water oxidation
because of the involvement of four-electron transfer mechanism. Bismuth tungstate
(Bi2WO6) is a photoactive semiconductor capable of oxidising water into oxygen and
with a band gap of 2.7-2.9 eV (visible-light active). In this thesis, Bi2WO6 was designed
to achieve improved photocatalytic and photoelectrochemical (PEC) efficiency.
Important factors and the underlying mechanisms involved were studied systematically.
Firstly, the synthesis of hierarchical Bi2WO6 microspheres with controllable crystallinity
and surface area was achieved through a combination of hydrothermal/calcination
processes. Though both crystallinity and surface area are affecting the overall activities,
it was found the degree of crystallinity dominates the reaction. As the bond length of
tungsten (W) was shorten accompanying the improved crystallinity, improved charge
transportation was observed.
Following the investigation of crystallinity and surface area, by tuning the W precursor
concentration in the synthesis, Bi2WO6 was made into platelike-structure with well-
defined crystal facets, in which the role of each crystal facet was investigated. Bi2WO6
with a higher exposure extent of electron-dominated crystal facet reduces the charge
transport resistance and decreases the charge trapping. Moreover, by introducing more W
in the Bi2WO6, a self-doped phenomenon that increases the charge carrier concentration
vi
Abstract
and contains more W5+ species were observed. These factors inhibit the charge
recombination and beneficial to the photo-oxidation process.
The performance of Bi2WO6 was further improved by the creation of heterojunction.
Controlled transformation of tungsten oxide (WO3) to Bi2WO6 via electrodeposition and
hydrothermal method successfully introduced heterojunction Bi2WO6/WO3. A higher
interface between the Bi2WO6 and WO3 has lowered the amount of interfacial trapping
of photoelectrons. It directly optimises the PEC water splitting to an ideal situation,
facilitated by smaller applied bias. Another heterojunction was formed with the oxygen-
deficient bismuth tungstate (Bi14WO24) and bismuth oxide, in which the photocorrosion
was suppressed owing to the promoted interfacial charge transfer between the two
components. The findings in this thesis could be applicable to other oxide-based
photocatalysts.
vii
Acknowledgement
ACKNOWLEDGEMENT
Foremost, I would like to express my sincere gratitude to my supervisor and co-
supervisors, Scientia Professor Rose Amal, Associate Professor Yun Hau Ng and
Associate Professor Jason Scott for their continuous support throughout my PhD research
journey. I am thankful for their patience, aspiring guidance, invaluable advice and
encouragement all the time, it would not be possible to conduct this research and
preparing this thesis without their precious guidance.
Besides my supervisors, I am grateful to all of those with whom I have had the pleasure
to work with during the research projects. Thank you for Dr Xiaoming Wen and Dr Judy
Hart collaboration in my research projects and insightful comments that greatly improved
the manuscript. Especially a sincere thanks to Dr Fatwa Firdaus Abdi and Prof Roel van
de Krol for providing an opportunity to join their team in the Institute of Solar Fuel,
Helmholtz (HZB) for a short exchange, which the visit has widened the perspectives of
my research in the solar field.
Next, I wish to thank all the insight and expertise that greatly assisted by Dr Yu Wang for
training me the XRD; Dr Anne Rich for the assistance on Raman spectroscopy; Mr Yin
Yao for the training and assistance in the SEM and cAFM; Ms Katie Levick for training
me in the TEM; Dr Bin Bill Gong for performing the XPS analysis; Ms Rabeya Akter
and Ms Dorothy Yu for conducting the ICP analysis for my samples in each project.
viii
Acknowledgement
Furthermore, I would also like to acknowledge with much appreciation for the crucial
role of the staff of Dr Mandalena Hermawan and Dr Victor Wong, who organise the lab
safety induction and acquiring all the essential equipment. Their help and support have
offered me the resources in running the experiments smoothly. I would also like to extend
my thanks to Ms Ik Ling Lau, Ms Ee Meen Iliffe, Mr John Starling, Mr Ravi
Shanmugarajah, Mr Phil Thompson and Mr Paul Brockbank for all the administrative and
technicians work in our chemical engineering faculty.
This research study would not be possible without the financial support from the
Australian Research Council under the Laureate Fellowship Scheme. A special thanks go
to my colleagues in Particle and Catalysis Research group, especially Dr Hui Ling Tan,
Dr Cui Ying Toe, Dr Xuelian Wu, Dr Ee Teng Kho, Dr Tze Hao Tan, Dr Roong Jien
Wong and Ms Deng Chen for stimulating discussions, sharing the happiness and for all
the fun we have had in the last four years.
Last but not least, I must express my very profound gratitude to my family, who have
supported me spiritually throughout the PhD, both by keeping me harmonious and
helping me putting pieces together. I will be grateful forever for all the loves given by my
family members.
ix
List of Publication
LIST OF PUBLICATION
Journal Publication
1. Chung, H.Y.; Chen, W.; Wen, X.; Hart, J.N.; Wu, H.; Lai, Y.; Amal, R.; Ng, Y.H.,
Oxygen-Deficient Bismuth Tungstate and Bismuth Oxide Composite Photoanode
with Improved Photostability. Science Bulletin, 2018, 63(15), 990-996
2. Chung, H.Y.; Wu, X.; Amal, R.; Ng, Y.H., Balancing the Crystallinity and Specific
Surface Area of Bismuth Tungstate for Photocatalytic Water Oxidation. Molecules
(submitted)
3. Chung, H.Y.; Toe, C.Y.; Abdi, F.F.; Wen, X.; Wong, R.J.; Amal, R.; Ng, Y.H.,
Manipulating the Fate of Charge Carriers with W Concentration: Enhancing PEC
Water Oxidation of Bi2WO6, Advanced Function Materials (in preparation)
4. Chung, H.Y.; Wong, R.J.; Amal, R.; Ng, Y., The Charge Transfer Phenomenon of
Homogeneous and Rigid Heterojunction of Bi2WO6/WO3 Thin Film, Journal of
Physical Chemistry C (in preparation)
x
List of Publication
Co-author Journal Publications
1. Wu, H.; Li, S.; Lu, X.; Toe, C.Y.; Chung, H.Y.; Tang, Y.; Lu, X.; Amal, R.; Li,
L.; Ng, Y.H., Pulsed Electrodeposition of Co3O4 Nanocrystals on One-
Dimensional ZnO Scaffolds for Enhanced Electrochemical Water Oxidation.
ChemPlusChem, 2018, 83(10), 886
2. Wu, X.; Ng, Y.H.; Wen, X.; Chung, H.Y.; Wong, R.J.; Du. Y.; Dou S.X.; Amal,
R.; Scott. J., Construction of a Bi2MoO6: Bi2Mo3O12 Heterojunction for Efficient
Photocatalytic Oxygen Evolution. Chemical Engineering Journal, 2018, 353,
636-644
xi
List of Publication
Conference Presentations
1. Energy Future Conference, 4-6 July, 2016, The University of New South Wales,
Sydney Australia (POSTER)
2. Chemeca, 23-26 July, 2017, Melbourne Convention and Exhibition Centre,
Melbourne, Australia (ORAL)
3. Asian Pacific Confederation of Chemical Engineering (APCChe), 23-27 August,
2017, Hong Kong Convention and Exhibition Centre, Wan Chai, Hong Kong
Republic of China (ORAL)
4. International Conference on nanoscience and Nanotechnology (ICONN), 29 January-
2 February, 2018, The University of Wollongong, Wollongong, Australia (ORAL
and POSTER) *Won the Best Oral Presentation*
5. International Symposium on advanced materials & sustainable technologies
(AM&ST), 22-25 July, 2018, Royal On The Park Hotel, Brisbane, Australia (Oral)
*Won the ECR Session Chair Award*
6. European Materials Research Society (EMRS), 17 - 20 September, 2018, Warsaw
University of Technology, Warsaw, Poland (POSTER)
xii
Table of Content
TABLE OF CONTENT
THESIS/DISSERTATION SHEET ............................ Error! Bookmark not defined.
ORIGINALITY STATEMENT .................................. Error! Bookmark not defined.
INCLUSION OF PUBLICATIONS STATEMENT .. Error! Bookmark not defined.
COPYRIGHT STATEMENT ..................................... Error! Bookmark not defined.
ABSTRACT ................................................................................................................. vi
ACKNOWLEDGEMENT .........................................................................................viii
LIST OF PUBLICATION............................................................................................. x
TABLE OF CONTENT .............................................................................................xiii
LIST OF ABBREVIATION ....................................................................................xviii
Chapter 1 Introduction .............................................................................. 1
1.1 Background ............................................................................................................. 1
1.2 Aim and Objectives ................................................................................................. 5
1.3 Thesis Outline ......................................................................................................... 7
1.4 References ............................................................................................................... 8
Chapter 2 Literature Review................................................................... 11
2.1 Introduction of Water Splitting ............................................................................. 11
2.2 Photocatalysis ........................................................................................................ 13
2.2.1 Photocatalytic Reactions ................................................................................ 14

xiii
Table of Content
2.2.2 Photoelectrochemical Reactions .................................................................... 16
2.2.3 Type of Photocatalyst ..................................................................................... 18
2.3 Fundamental Properties of Bi2WO6 ...................................................................... 20
2.3.1 Crystal Structure and Phases .......................................................................... 21
2.3.2 Electronic Band Structure and Optical Properties ......................................... 23
2.4 Synthesis of Bismuth Tungstate ............................................................................ 25
2.4.1 Powders .......................................................................................................... 26
2.4.2 Thin Film........................................................................................................ 30
2.5 Photocatalytic Performances and Limitation of Bi2WO6 ...................................... 34
2.6 Strategies in Improving Bi2WO6 in Photocatalysis Reaction ............................... 36
2.6.1 Increasing Light Absorption .......................................................................... 37
2.6.2 Improvement in Charge Separation ............................................................... 42
2.6.3 Improvement in Charge Transport ................................................................. 63
2.6.4 Improvement in Photocatalyst Stability ......................................................... 71
2.7 Knowledge Gap ..................................................................................................... 72
2.8 Summary ............................................................................................................... 73
2.9 References ............................................................................................................. 74
Chapter 3 Balancing the Crystallinity and Specific Surface Area of
Bi2WO6 for Photocatalytic Water Oxidation ......................................... 97
3.1 Introduction ........................................................................................................... 97

xiv
Table of Content
3.2 Experimental Procedures ...................................................................................... 99
3.2.1 Preparation of Hierarchical Bi2WO6 .............................................................. 99
3.2.2 Structure Characterisation .............................................................................. 99
3.2.3 Photocatalytic Oxygen Generation .............................................................. 100
3.2.4 Photoelectrochemical Activities................................................................... 101
3.3 Results and Discussion........................................................................................ 101
3.3.1 Physical Properties of Hierarchical Bi2WO6 microspheres ......................... 101
3.3.2 Morphology Study ....................................................................................... 104
3.3.3 Optical and Electronic Properties ................................................................ 107
3.3.4 Photocatalytic Water Oxidation using Bi2WO6 Microspheres .................... 109
3.4 Summary ............................................................................................................. 115
3.5 References ........................................................................................................... 116
Chapter 4 Manipulating the Fate of Charge Carriers with W
Concentration: Enhancing PEC Water Oxidation of Bi2WO6 ........... 121
4.1 Introduction ......................................................................................................... 121
4.2 Material and Method ........................................................................................... 123
4.2.1 Preparation of Bi2WO6 Film ........................................................................ 123
4.2.2 Photodeposition of Ag and MnOx ................................................................ 124
4.2.3 Characterisation............................................................................................ 124
4.2.4 Photoelectrochemical Measurement ............................................................ 126

xv
Table of Content
4.4 Summary ............................................................................................................. 145
4.5 References ........................................................................................................... 146
Chapter 5 The Charge Transfer Phenomenon of Homogeneous and
Rigid Heterojunction of Bi2WO6/WO3 Thin Film................................ 152
5.1 Introduction ......................................................................................................... 152
5.2 Experimental Method .......................................................................................... 154
5.2.1 Preparation of High and Low Interfacial Contact of Bi2WO6/WO3 film ..... 154
5.2.2 Characterisation............................................................................................ 155
5.2.3 Photoelectrochemical Measurement ............................................................ 156
5.3.1 Material Characterisation ............................................................................. 157
5.3.2 Photoelectrochemical Performance .............................................................. 161
5.3.3 Charge Transport .......................................................................................... 167
5.4 Summary ............................................................................................................. 168
5.5 References ........................................................................................................... 169
Chapter 6 Oxygen-deficient Bismuth Tungstate and Bismuth Oxide
Composite Photoanode with Improved Photostability ........................ 173
6.1 Introduction ......................................................................................................... 173
6.2 Experimental Method .......................................................................................... 175

xvi
Table of Content
6.2.1 Preparation of BWO/Bi2O3 Film.................................................................. 175
6.2.2 Characterisation of BWO/ Bi2O3 Film ......................................................... 176
6.2.3 Photoelectrochemical Test ........................................................................... 177
6.3.1 Material Characterisation ............................................................................. 178
6.3.1 Photoelectrochemical Performance .............................................................. 184
6.4 Summary ............................................................................................................. 190
6.5 References ........................................................................................................... 191
Chapter 7 Conclusion and Recommendations .................................... 196
7.1 Conclusion .......................................................................................................... 196
7.2 Recommendation................................................................................................. 199
7.2.1 Self-doping Bi3+: Fabrication, characterisation and optimisation for
photocatalytic water oxidation .............................................................................. 200
7.2.2 Performing Overall PEC water splitting and Engineering the Reactor........ 200
7.3 References ........................................................................................................... 202
xvii
List of Abbreviation
LIST OF ABBREVIATION
AgNO3 Silver Nitrate
B Boron
Bi Bismuth
Bi(NO3)3∙5H2O Bismuth Nitrate Pentahydrate
Bi2O3 Bismuth Oxide
Bi2WO6 Bismuth Tungstate
c-AFM Conducting Atomic Force Microscopy
CB Conduction Band
CO2 Carbon Dioxide
CTAB Cetyltrimethylammonium Bromide
Cu Copper
EDTA Ethylenediaminetetraacetic Acid
EG Ethylene Glycol
F Fluorine
Fe Iron
FTO Fluorine-doped tin oxide
FWHM Full Width Half Maximum
H2 Hydrogen
H2O Water
HER Hydrogen Evolution Reaction
HUMO High Occupied Molecular Orbital
I Current
ICP-MS Inductively Coupled Plasma Mass Spectroscoptry
IFCT Initiate Interfacial Charge Transfer
IPCE Incident Photon Conversion Efficiency
ITO Iodine-doped tin oxide
LUMO Low Occupied Molecular Orbital
Mo Molybdenum
xviii
List of Abbreviation
N Nitrogen
Nb Niobium
Na2SO4 Sodium Sulphate
Na2WO4∙2H2O Sodium Tungstate Dihydrate
NHE Normal Hydrogen Electrode
O2 Oxygen
OER Oxygen Evolution Reaction
PEC Photoelectrochemical
PL Photoluminescence
PVP Poly(vinyl pyrrolidone)
RHE Reversible Hydrogen Electrode
RhB Rhodamine B
SEM Scanning Electron Microscopy
T Temperature
Ta Tantalum
TiO2 Titanate Oxide
TEM Transmission Electron Microscopy
TRMC Time-resolved Microwave Conductivity
TRPL Time-resolved Photoluminescence
UV Ultraviolet
V Voltages
VB Valence Band
vs versus
W Tungsten
XRD X-ray Diffraction
XPS X-ray Photoelectron Spectroscopy
1D 1-dimensional
2D 2-dimensional
3D 3-dimensional
xix
Chapter 1. Introduction
CHAPTER 1
INTRODUCTION
1.1 Background
Ongoing industrial revolutions and human civilisation create tremendous and excessive
demands for energy to be consumed in order to enjoy a better life and a higher living
standard. The outcome becomes an overwhelming destruction of the environment and
turns out as a crisis. Sufficient supply of energy together with preservation of the
environment becomes increasingly important since the late 20th century. To date, our
current energy supply is mainly generated from combustion of fossil fuel such as coal,
natural gas, and oil. In the conventional fuel-to-electricity conversion process, a massive
amount of greenhouse gases (i.e. carbon dioxide, CO2) including some harmful
contaminants are released to the nature. A recent report stated that 37.1 ± 2 gigatons of
CO2 was emitted to the atmosphere in 2018, which is a 2.7% increase from 2017.1, 2 It is
only logical to expect this trend to continue due to population and economic growth.
These growth factors are key contributors to global energy consumption which is
currently rising at a pace that far exceeds the current rate of energy storage. Also, the
emission of CO2 resulted from the consumption of fossil fuel-based energy will worsen
the problem of global warming. Therefore, there is an urgent need to develop clean energy
1
based on renewable resources, before global warming reaches an irreversible tipping
point.
Imperative missions to develop a low-carbon technology that neither relies on fossil fuels
nor emit greenhouse gases have become the mainstream. The daunting global
environmental and energy concerns have drawn the most attention of the research
community to focus on the development of renewable energy, including solar energy.
Solar energy is an abundant and sustainable energy source, which unlike conventional
fossil fuel-based sources, there is no greenhouse gas release upon conversion to electricity.
It has been established that the average solar irradiance to the earth’s surface is
approximately 170 W/m2. When 170 W/m2 is integrated over 1 year, the resulting energy
of 5.4 GJ that is incident on 1 m2 are equivalent to the energy produced from one barrel
of oil or 200 kg of coal.3, 4 Hence, if solar energy can be harvested, converted and stored
efficiently in the form of electricity or chemical fuel, it can offer a promising solution to
tackle the energy and environmental problems encountered by mankind.
Photovoltaic or solar cells have seen rapid progress over the last three decades with
considerable solar energy conversion efficiency being achieved. Given the intermittence
nature of sunlight (i.e. unavailable at nights), the research community is also looking at
possibilities in storing solar energy in the form of chemical so that the versatility of solar
energy utilisation is greater. Splitting water into their elemental components (i.e.
molecular hydrogen (H2) and oxygen(O2)) assisted by sunlight becomes an attractive
method in converting solar energy into chemical energy (in the form of H 2). This solar-
2
driven water splitting is inspired by photosynthesis process in nature, where
semiconductor is used in place of a leaf.5 When a semiconductor with suitable energy
band structure is illuminated by sunlight, its intrinsic light absorption capability can
induce charge separation within the semiconductor. These photoexcited charges facilitate
redox reaction on the surface of semiconductor which oxides and reduces water into O2
and H2 at ambient temperature, respectively.6 The produced H2 is an energy carrier which
contains energy density of 141.8 MJ/kg. Additionally, H2 is also an eco-friendly energy,
in which water is the sole combustion product and no environmentally harmful substances
are produced. Fujishima and Honda first demonstrated the solar water splitting utilising
a photoactive titanium dioxide (TiO2) in 1972. It indicated that the semiconductor TiO2
is capable of harvesting the light energy and converts into chemical energy in the form of
H2.7 By following Fujishima-Honda's experiment, a rapid development in the topic of
photocatalysis is achieved. In general, photocatalytic reaction can be categorised into two
main branches: (i) powder suspension photocatalytic system and (ii) electrode-type
photoelectrochemical (PEC) system. The former utilises powder semiconductor, while
the latter involves the use of a thin film photoelectrode. Based on the current trends and
advancement in water splitting technology, Department of Energy in United States
estimated the future price of H2 to be approximately US$4.10-10.40 kg-1 and $1.60-3.20
kg-1 when the H2 gas is generated via photocatalytic and PEC systems, respectively.8 This
prediction is based on the assumption of solar-to-hydrogen conversion efficiency at just
above 10%. However, it is worth noting that current water splitting technologies have not
reached this desired conversion efficiency target. Therefore, it is important to find
solutions to minimise the system complexity (i.e. device cost) and to maximise the device
3
performance (i.e. attain a solar energy conversion rate of at least 10% with robustness of
the system for 10 years).9
After the pioneering work on the PEC water splitting on TiO2 electrodes reported by
Fujishima and Honda, a series of titania-based semiconductors was studied. Typically,
the performance of the photocatalytic and PEC water splitting system is highly dependent
on the semiconductor properties including the light absorption, charge transfer and
surface reactivities.10 Although the TiO2 is photoactive in the water splitting process, its
wide band gap of 3.2 eV has limited its light absorption to ultraviolet light (UV). It is
known that UV light occupies 5% of the entire solar spectrum whereas visible-light takes
up approximately 43%.11 Therefore, efforts have been devoted towards visible-light-
active semiconductors.12, 13 Non-metal oxide such as CdS14, 15, CuInS216, g-C3N417 and
Ta3N518 have been examined to be photoresponsive in visible-light. Nonetheless, many
of these semiconductors suffer stability issues and are incapable of carrying out reaction
over long periods of time. In this regard, research of Bi-based ternary metal oxides (such
as BiVO4, Bi2MoO6 and Bi2WO6) for water splitting process has attracted attention as
they are visible-light active and possess energetic valence band to oxidise water to form
molecular O2. Bismuth tungstate (Bi2WO6), a visible-light active semiconductor with a
reasonable band gap of 2.7-2.9 eV, has demonstrated its potential in photocatalytic/PEC
water oxidation and organic degradation under visible-light irradiation.
To date, Bi2WO6 particles with various morphological structures have been reported.
However, the multidisciplinary studies on the fundamental understanding of Bi2WO6 is
4
still lacking. The attained solar energy conversion efficiency using Bi2WO6 is still
unsatisfactory, mainly limited by the poor charge transportation properties: slow charge
kinetics, severe charge recombination, short charge diffusion length and short charge
lifetime. The underlying reasons for the above poor charge transportation are not well
understood. Hence, systematic investigation to gather the fundamental knowledge of
Bi2WO6 would be helpful to develop a more efficient photocatalyst by overcoming the
intrinsic limiting factors.
1.2 Aim and Objectives
The main aims of this project are to understand the fundamental properties of Bi2WO6
and to develop an efficient Bi2WO6 that capable of oxidising water to molecular O2 via
photocatalytic or PEC system. As known, Bi2WO6 is photoactive under visible-light as it
possesses suitable band gap energy. Given that the valence band of Bi2WO6 is ideally
located at an energy that capable of oxidising water, it is important to understand its
intrinsic properties (the strength and limitation) so that a highly efficient water splitting
photocatalyst can be constructed. The objectives are achieved by carefully formulating
four different experimental approaches (as elaborated below) to identify and recognise
the important factors governing the performance of Bi2WO6.
In general, particulate semiconductor with larger surface area should possess more active
sites for catalytic reactions while higher crystallinity would facilitate better charge
transport efficiency. In practice, the improvement in crystallinity is always accompanied
with a decrease in surface area. Crystallinity is usually improved using heat treatment,
5
which induces sintering of particle (resulting in a decrease in surface area). Thus, in order
to understand the dominant factor affecting the photocatalytic activities between surface
area and crystallinity, hierarchical Bi2WO6 particles with controllable crystallinity and
surface area modulated through thermal treatment are synthesised and studied. Detailed
evaluation of the features for each Bi2WO6 is examined to determine the prevailing factor
in achieving higher photo-oxidation activities.
Bi2WO6 can be employed in both photocatalytic (powder-type) and PEC (thin film or
photoelectrode-type) systems to oxidise water. PEC system offers the ease of catalyst
separation upon completion of reaction. Direct thin film fabrication is the most ideal
method to prepare Bi2WO6 photoelectrode with promising adhesion and stability
properties. Typically, morphologically featureless Bi2WO6 photoelectrodes were
prepared using direct thin film synthetic route. In this thesis, ratio of metallic precursors
is tuned and its impacts on the construction of plate-like Bi2WO6 with well-defined crystal
facets on thin film are investigated. By increasing the tungsten (W) concentration of the
precursor during the synthesis, preferential growth of specific crystal facet of Bi2WO6
can be controlled, which resulted in the formation of Bi2WO6 crystal with plate-like
structure. With this crystal facet control, the electron-accumulating facet is tuned and
maximised to facilitate charge transfer with suppressed charge trapping. The objectives
of this part of work are to assess the relationship between W concentration increase and
the facet-controlled phenomenon, with the corresponding charge properties (including
charge density, mobility and lifetime).
6
In addition to crystal facet engineering, construction of effective heterojunction between
Bi2WO6 and another semiconductor with suitable band energy alignment can be useful in
promoting charge transfer efficiency. An effective heterojunction suppresses internal
charge recombination within Bi2WO6, allowing the improved charge utilisation (i.e. water
oxidation). In this thesis, Bi2WO6 is interfaced with a thin layer of tungsten oxide (WO3)
on a charge collecting electrode. The effectiveness of heterojunction is determined by the
quality of the interface between Bi2WO6 and WO3. In this work, interfacial contact area
are manipulated and its impacts on the charge transportation are investigated.
Defect engineering through the oxygen vacancies modulation is studied in this thesis as
well. Though oxygen vacancies have been reported in various oxide semiconductors, its
usefulness as a tool to improve photoactivity of semiconductor cannot be generalised.
Both constructive and detrimental impacts of oxygen defects have been reported. In this
work, the primary role of defects and the benefits offered by the oxygen-deficient bismuth
tungstate (Bi14WO24) are identified.
1.3 Thesis Outline
This thesis underlines the key principles that regulate the performance of Bi2WO6. The
importance of inter-correlating the physical, optical and electronic properties of Bi2WO6
is elucidated throughout the entire thesis. The impacts of experimental variation on the
charge transportation properties (such as charge separation, diffusion, mobility and
lifetime) are carefully and systematically investigated. This chapter (Chapter 1) serves as
a general introduction of the works performed in the thesis. Chapter 2 is a literature review
7
chapter that comprehensively describes the basic principles of photocatalytic and PEC
water splitting. Fundamental properties of Bi2WO6 and the recent developments in
innovative fabrication methods are introduced and discussed. An overview of the current
practical applications of Bi2WO6 are also summarised. The following chapters (Chapter
3, 4, 5 and 6) focus on the design and modification of Bi2WO6 for the improved activity.
More specifically, Chapter 3 delineates insight into the impact of the Bi2WO6 properties
such as degree of the crystallinity and the surface area of the hierarchical Bi 2WO6
powders on the photocatalytic oxidation process. Subsequently, Chapter 4 illustrates the
preparation of the distinct platelike Bi2WO6 photoelectrodes, produced via the tuning of
W precursor concentration during fabrication. It also evaluates the advantage of Bi2WO6
with higher exposure extent of electron-dominant crystal facet in the suppression of
charge recombination upon photoexcitation. In Chapter 5, enhanced charge transfer
within Bi2WO6/WO3 heterojunctions with higher interfacial contact area is illustrated.
Subsequently, the study on bismuth- and tungsten-based heterojunction is extended to
Chapter 6 which assesses the benefits of forming a heterojunction between the oxygen-
deficient bismuth tungstate semiconductor and Bi2O3 for enhanced photostability. Finally,
a conclusion on key findings from each chapter and summary of future outlooks of
Bi2WO6 application in water splitting reaction are described in Chapter 7.
1.4 References
1. Figueres, C.; Le Quéré, C.; Mahindra, A.; Bäte, O.; Whiteman, G.; Peters, G.; Guan, D.,
Emissions are still rising: ramp up the cuts. Nature Publishing Group: 2018.
8
2. Jackson, R. B.; Le Quéré, C.; Andrew, R. M.; Canadell, J. G.; Korsbakken, J. I.; Liu, Z.;
Peters, G. P.; Zheng, B., Global energy growth is outpacing decarbonization.
Environmental Research Letters 2018, 13 (12), 120401.
3. Wu, J. C. S., Photocatalytic reduction of greenhouse gas CO2 to fuel. Catalysis surveys
from Asia 2009, 13 (1), 30-40.
4. World Energy Resouces: Solar; World Energy Council: London, 2013.
5. Abe, R., Recent progress on photocatalytic and photoelectrochemical water splitting under
visible light irradiation. Journal of Photochemistry and Photobiology C: Photochemistry
Reviews 2010, 11 (4), 179-209.
6. Maeda, K., Photocatalytic water splitting using semiconductor particles: History and recent
developments. Journal of Photochemistry and Photobiology C: Photochemistry Reviews
2011, 12 (4), 237-268.
7. Fujishima, A.; Honda, K., Electrochemical Photolysis of Water at a Semiconductor
Electrode. Nature 1972, 238, 37.
8. Wang, Q.; Hisatomi, T.; Jia, Q.; Tokudome, H.; Zhong, M.; Wang, C.; Pan, Z.; Takata,
T.; Nakabayashi, M.; Shibata, N.; Li, Y.; Sharp, I. D.; Kudo, A.; Yamada, T.; Domen,
K., Scalable water splitting on particulate photocatalyst sheets with a solar-to-hydrogen
energy conversion efficiency exceeding 1%. Nature Materials 2016, 15, 611.
9. Bornoz, P.; Abdi, F. F.; Tilley, S. D.; Dam, B.; van de Krol, R.; Graetzel, M.; Sivula,
K., A Bismuth Vanadate–Cuprous Oxide Tandem Cell for Overall Solar Water Splitting.
The Journal of Physical Chemistry C 2014, 118 (30), 16959-16966.
10. Hisatomi, T.; Kubota, J.; Domen, K., Recent advances in semiconductors for
photocatalytic and photoelectrochemical water splitting. Chemical Society Reviews 2014,
43 (22), 7520-7535.
9
11. Ni, M.; Leung, M. K. H.; Leung, D. Y. C.; Sumathy, K., A review and recent
developmfents in photocatalytic water-splitting using TiO2 for hydrogen production.
Renewable and Sustainable Energy Reviews 2007, 11 (3), 401-425.
12. Anpo, M.; Ichihashi, Y.; Takeuchi, M.; Yamashita, H., Design of unique titanium oxide
photocatalysts by an advanced metal ion-implantation method and photocatalytic reactions
under visible light irradiation. Research on chemical intermediates 1998, 24 (2), 143-149.
13. Kudo, A.; Ueda, K.; Kato, H.; Mikami, I., Photocatalytic O2 evolution under visible light
irradiation on BiVO4 in aqueous AgNO3 solution. Catalysis Letters 1998, 53 (3-4), 229-
230.
14. Pareek, A.; Hebalkar, N. Y.; Borse, P. H., Fabrication of a highly efficient and stable nano-
modified photoanode for solar H2 generation. RSC Advances 2013, 3 (43), 19905-19908.
15. Jiang, J.; Wang, M.; Li, R.; Ma, L.; Guo, L., Fabricating CdS/BiVO4 and BiVO4/CdS
heterostructured film photoelectrodes for photoelectrochemical applications. international
journal of hydrogen energy 2013, 38 (29), 13069-13076.
16. Zheng, L.; Xu, Y.; Song, Y.; Wu, C.; Zhang, M.; Xie, Y., Nearly monodisperse CuInS2
hierarchical microarchitectures for photocatalytic H2 evolution under visible light.
Inorganic chemistry 2009, 48 (9), 4003-4009.
17. Suryawanshi, A.; Dhanasekaran, P.; Mhamane, D.; Kelkar, S.; Patil, S.; Gupta, N.; Ogale,
S., Doubling of photocatalytic H2 evolution from g-C3N4 via its nanocomposite formation
with multiwall carbon nanotubes: Electronic and morphological effects. International
Journal of Hydrogen Energy 2012, 37 (12), 9584-9589.
18. Hara, M.; Hitoki, G.; Takata, T.; Kondo, J. N.; Kobayashi, H.; Domen, K., TaON and
Ta3N5 as new visible light driven photocatalysts. Catalysis Today 2003, 78 (1-4), 555-560.
10
Chapter 2. Literature Review
CHAPTER 2
LITERATURE REVIEW
2.1 Introduction of Water Splitting
Solar water splitting is one of the sustainable ways to split water (H2O) into hydrogen (H2)
and oxygen (O2). The produced H2 has been an attractive option for achieving green
energy since 1980. The H2 produced from water is considered a clean fuel that could be
stored and oxidised to release energy when required, reproducing water and therefore
creating a carbon-neutral energy cycle.1 The process that converts solar energy to
chemical energy is called ‘photocatalysis’. Photocatalytic water splitting is a
thermodynamically up-hill reaction with a large positive change in the Gibbs free energy
of 237.13 kJ mol-1 (Eqn. (2-1)). The half-reaction for producing H2 and O2 are described
in the Eqn. (2-2) and Eqn. (2-3).
2H2O → O2 + 2H2, ∆Gº = 237.13 kJ mol-1 Eqn. (2-1)
2H+ + 2e- → H2 Eqn. (2-2)
2H2O + 4h+ → 4H+ + O2 Eqn. (2-3)
Harnessing solar energy directly for water splitting was first demonstrated by Honda and
Fujishima using titanium dioxide (TiO2) semiconductor and platinum (Pt) in a
photoelectrochemical (PEC) water splitting system with an external bias.2 The

11
semiconductor, which is also known as a photocatalyst, is one of the crucial parameters
in photocatalysis since it influences the rate of the chemical reaction under light
irradiation. Numerous photoactive binary metal oxides (TiO2, ZnO, Fe2O3 , Cu2O)3-6,
non-metal oxides (ZnS, CdS, MoS2)7, 8 and the metal-free semiconductor (C3N4)9 had
been extensively studied for photocatalytic water splitting. The semiconductor absorbs
solar energy to achieve productive H2 conversion. However, the bulk photocatalyst attains
many limitations such as poor light absorption ability, inferior charge kinetics and
instability, hence lowering the production rate in the water splitting process. Therefore,
new strategies have been engaged to overcome the insufficiency of photocatalysts.
Recently, the Bi-based ternary oxide semiconductor has triggered lots of interest owing
to their unique band structure. Bismuth tungstate (Bi2WO6) possesses interesting physical
properties (such as ferroelectric piezoelectricity, pyroelectricity, catalytic behaviour and
a nonlinear dielectric susceptibility) and has been found not only favour degradation of
organic pollutants but also be able to evolve O2 from water in the presence of silver nitrate
(AgNO3). It greatly shows the potential of Bi2WO6 in solar energy conversion. However,
more advanced research is needed to improve the photocatalyst performance for industrial
scale application. In this review, fundamental properties and an overview of the recent
development in the design of Bi2WO6 powders and thin film are covered in the first part;
followed by the different strategies on improving the efficiency of Bi2WO6. The strategies,
including heterojunction construction, doping and co-catalyst loading, can particularly
enhance the light absorption ability, suppress the charge separation, increase the charge
transport and photostability of Bi2WO6. By reviewing other studies and researches, more
12
in-depth understanding has been obtained on the current progress of Bi2WO6, so as to
offer guidelines and perspectives to design a more efficient Bi2WO6 for photocatalysis
reaction.
2.2 Photocatalysis
(a) (b)
Figure 2-1. (a) Schematic diagram of the electronic band in a photocatalyst at one-step excitation
photocatalytic water splitting.10 (b) The mechanism of photoexcitation generating electron-hole pairs in
the semiconductor under light irradation.11
A semiconductor is a solid with its conductivity lying between a conductor and an
insulator. The structure of a semiconductor consists of two energy bands, namely
conduction band (CB) and valence band (VB). The former refers to the lowest unoccupied
molecular orbital (LOMO) at ground state while the latter is made up of the highest
occupied molecular orbital (HOMO) in energy level. The two energy bands are separated
by a band gap, which is an energy range in the solid where no electronic states exist due
to the quantisation of energy. When the semiconductor absorbs energy (either thermally
or photochemically) larger than its band gap energy, an electron is excited from the VB
13
to the CB, leaving a positively charged “holes” at the band edge of the VB. In
photocatalysis, the energy will be coming from light and the electrons generated in the
semiconductor move freely and act as charge carriers for chemical redox reactions. A
schematic diagram of the electronic band of a semiconductor is shown in Figure 2-1a.10
In the photocatalytic water splitting process, water is dissociated into H2 and O2 in the
presence of a photocatalyst under light irradiation. This process is classified into two main
types: the nanoparticles photocatalysis (including half-reaction or an overall water
splitting system) and the photoelectrocatalysis (including single-photoelectrode or dual-
photoelectrode system). The mechanism triggering both water splitting reaction is
described by four critical steps and is shown in Figure 2-1b: (i) semiconductor absorbs
light to generate electron-hole pairs; (ii) separates photoexcited carriers to the respective
CB and VB; (iii) transports electrons and holes to the surface of photocatalysts and (iv)
utilised the charges on the surface for redox reaction.12 Notably, most of the electron-hole
pairs generated in step (iii) are easily recombined, either at the bulk or at the surface sites.
The rate of charge recombination is strongly dependent on the structural and electronic
properties of the photocatalyst.11
2.2.1 Photocatalytic Reactions
One of the many examples of photocatalysis is photocatalytic water splitting. It is simply
a suspension of photocatalyst particles in a solution under light illumination without
additional external energy inputs in an inert atmosphere.13 Implementation of a single
photocatalyst in water splitting system is the ideal scenario for industrial application in
14
the future due to its simplicity (Figure 2-1a). Domen’s group has successfully
demonstrated that overall water splitting can be achieved by compressing a single
particulate photocatalyst into a sheet. However, critical challenges were found in the work
as the overall efficiency of such catalyst remains low.14 The reasons for the low efficiency
were the inferior electron-hole pair separation, severe charge recombination and
instability of the photocatalyst.15 Therefore, Z-scheme photocatalyst , which is two-
photon excitation system, is more commonly used to achieve the overall water splitting
(Figure 2-2). In the Z-scheme system, it requires both an n-type and a p-type
photocatalyst which enforce oxidisation (O2-evolution reaction, OER) and reduction (H2-
evolution reaction, HER) of the water into O2 and H2, respectively. An electron mediator
is often added into the system to facilitate the redox reaction.
Figure 2-2. Schematic diagram of photocatalytic water splitting based on Z-scheme system.16
Kudo et al. has illustrated a Z-scheme photocatalytic water splitting under visible-light
irradiation in 2002, which consisted of SrTiO3 doped with chromium and tantalum
element for H2 generation and WO3 for O2 generation, and an iodate/iodide redox couple
as an electron mediator. They have reported 19.8 and 9.7 mmol/h of H2 and O2 was
15
evolved, respectively.17 Although this seems to be promising approach to facilitate the
solar to chemical energy conversion, the backward reaction of the redox mediator, which
occurs simultaneously during the reaction, usually retards the gas evolution. Furthermore,
Liao et al. have claimed that Z-scheme reaction could be affected by the change in pH
and the light absorbance of the suspended photocatalyst, thereby prompting the
investigation on a visible-light active and efficient photocatalyst.18
2.2.2 Photoelectrochemical Reactions
Another photocatalytic water splitting is the photoelectrochemical (PEC) tandem system.
This process has found to have a better connection of the interface in the particle-substrate
compare to the particle-particle system, which promote the charge transport efficiency.
An ideal photoelectrochemical (PEC) tandem system should only comprises an n-type
photoanode and a p-type photocathode without the need for additional external energy
input to produce H2 and O2 directly from water (Figure 2-3c).
Figure 2-3. Schematic diagram of PEC water splitting using (a) n-type photoanode, (b) p-type
photocathode and (c) a tandem cell employing photoanode and photocathode. 19
16
However, combining heterogeneous photoactive catalysts to obtain a satisfactory electric
current through the external circuit in the system can be a challenging and complicated
process, owing to the inappropriate band gaps or non-matching band edges.20 Hence, a
setup of two-electrode or a three-electrode configuration is being researched, where at
least one electrode is photoactive. Once the minority charges are generated in the
semiconductor (holes and electron for the n-type and p-type semiconductor, respectively)
upon photoexcitation, the charges can be transported easily by an external bias, promoting
the redox reaction at the respective electrodes (explained in Figure 2-3a and b).21 One
major advantage of this approach is that the reduction and oxidation sites are separated,
therefore effectively hindering charge recombination and directly resulting in higher
efficiencies than simple suspension photocatalysis.12 In addition, studying the two-half
reactions separately for attaining a higher photocurrent density in each photoelectrode
simplifies the system to improve the overall water splitting efficiency. Nevertheless, PEC
systems often require the application of an external bias to achieve satisfactory
performance, as the separation of anode (oxidation site) and cathode (reduction site)
introduces an internal resistance to the system, which increases the energy input
requirement (energy cost).
Following the development of water splitting process, in order to achieve an excellent
catalyst system to drive photocatalytic and PEC water splitting, researchers have
recommended to improve both reduction and oxidation half-reactions individually (Eqn.
(2-2) and Eqn. (2-3)). Lately, the development of n-type semiconductor for OER (water
oxidation) has gained popularity, since it involves a four-electron transfer step and some
17
highly reactive intermediates, which is identified as the rate-limiting step in overall water
splitting reaction.22 Given the challenges of water photo-oxidation, the development of n-
type photocatalysts will be discussed in the following sections.
2.2.3 Type of Photocatalyst
Over the past decades, numerous n-type photocatalysts (including metal oxides and non-
metal oxides) have been explored for water oxidation. The selection of the photocatalyst
is crucial to trigger the water splitting process. In an ideal case, the photocatalyst or the
photoanode should meet the following criteria: (i) the VB levels are sufficiently positive
to achieve a thermodynamically favourable reaction; (ii) capable of absorbing light over
a broad range of the light spectrum; (iii) high mobility of the photo-induced charge
carriers for transportation and separation, to suppress charge recombination; (iv) high
chemical stability in aqueous media and low fabrication cost for industry requirement;
and (v) provide sufficient active state for quick surface reaction kinetics for O2
generation.23
TiO2 is one of the most widely studied photocatalytic materials due to its low cost and
large-scale preparation, yet the wide band gap of 3.2-3.5 eV limits the light absorption in
the UV range (3-5% from the solar spectrum).24 On the other hand, ZnO, WO3 and Fe2O3
have found to be active for O2 evolution. However, Zhu and Zäch stated ZnO is easily
being photocorroded by the photo-generated holes, while WO3 and Fe2O3 are unstable in
acidic condition. Poor electrical conductivity in these metal oxides has also negatively
impacted their photocatalytic performances.25 Meanwhile, non-metal oxides such as CdS,
18
CdSe and ZnS are also reported as potential photocatalyst due to their narrow band gaps,
allowing visible-light photoexcitation. Nevertheless, such non-metal oxides are photo-
catalytically unstable as the S2- and Se2- anions can be oxidised and the photocatalysts
will self-degrade during the reaction.26, 27
Apart from the drawbacks described above, previous studies show severe recombination
rate of the photogenerated electron-hole pairs, restricting majority of the binary metal-
oxides and non-metal oxides in facilitating the photo-oxidation process.28-31 Alternatively,
inspired by Kudo, a breakthrough in the binary oxide was reported, drawing more
attention towards bismuth-related ternary oxide (i.e. BiVO4, Bi2WO6, BiOCl, Bi12TiO20)
32-35
for the water photo-oxidation process. Most of the Bi-based ternary oxide are
intrinsic n-type visible-light-responsive photocatalysts and contain hybridised Bi 6s and
O 2p orbitals. It causes an upshift of the VB, which reduces the band gap to smaller than
3.0 eV.36, 37 Some of the Bi-based ternary oxide photocatalysts with corresponding flat-
band edge position is summarised in Figure 2-4. In addition, Bi-based ternary oxide VB
contains a 6s2 ‘lone pair’ that is advantageous over other metal oxides, resulting from an
s-p hybridised electronic structure. The orbital hybridisation induces the Bi lone pair to
lose its spherical symmetry and being projected out on one side of the cation, creates an
asymmetric metal coordination and a distorted crystal structure that could enhance the
mobility of photogenerated charges.38 In other words, Bi-based ternary oxides have
emerged as a promising material for further advancing the research in photocatalysis.
19
Figure 2-4. A summary of the flat-band edge positions and the band gaps of Bi-based semiconductor
photocatalysts.39
2.3 Fundamental Properties of Bi2WO6
Among the various Bi-based photocatalysts, conventional bismuth tungstate (Bi2WO6) is
a member of the Aurivillius structure, possessing a layered structure with a perovskite-
like slab of WO6. Bi2WO6 consists of an oxidised state of Bi3+ with 6s2 configuration and
W6+ with d0 structure. With this configuration, Bi2WO6 acquires interesting physical
properties such as ferroelectric piezoelectricity, pyroelectricity, catalytic behaviour and a
nonlinear dielectric susceptibility, all of these favour its role of as a photocatalyst.40 From
the band structure observed in Figure 2-4, the VB of Bi2WO6 is located much lower than
the redox potential of O2/H2O, proffering it has a strong oxidising capability. Other
stoichiometries of bismuth tungstate include Bi2W2O941, 42, Bi7W2O2743, and Bi2WO6-x44,
where the complex crystallography also imparts suitable band structure and electronic
properties that promotes photocatalysis. Among these bismuth tungstates, only Bi2WO6
20
can be excited under visible-light.43 Unlike WO3, Bi2WO6 does not suffer from
photocorrosion. It is chemically stable in neutral and also in slightly alkaline solution (>
pH 8).45 Due to the preferred unique layered structure and properties, Bi2WO6 shows
excellent potential in the utilisation of solar energy in the field of photocatalysis and
photoelectrocatalysis over the other Bi-based competing materials.
2.3.1 Crystal Structure and Phases
Figure 2-5. Illustration of the crystal structure of Bi2WO6.46
Bi2WO6 is the simplest member of Aurivillius compound, comprising a unique layer
structure with perovskite-like and fluorite-like slab. In general, the Aurivillius structural-
type is represented with the formula of Bi2An-1BnO3n+3, where A can be Ti, Nb, Ta, Mo,
W, Fe, and n is the number of perovskite layers present (i.e. n = 1 for Bi2WO6). The merit
of such layered structure is the generation of an internal electric field between the slabs
and electrons, which the charges are transported to the photocatalyst surface along the
21
layer network. It has been considered as an advantage to provide an efficient separation
of photoexcited charge carrier to improve the photocatalysis activity.33, 47 In Bi2WO6, the
perovskite-like WO4 layers of tilted corner-linked sharing with the WO6 octahedra
(including double [O]2- and single [WO2]2+ layers) are sandwiched between the fluorite-
like Bi2O22+ sheets, and the layers lie perpendicular to the long [010] axis as shown in
Figure 2-5.48, 49 The WO6 octahedral is constructed with a length of 1.7 Å W-O bonds.
On the other hand, the Bi2O22+ sheets are built up with Bi atoms and are bounded with six
O atoms, each Bi-O bond length is 2.17 – 2.56 Å.50 Besides, a stereochemically active Bi
6s2 lone pair is present in the Bi atoms, where the electron lone pair can overlap with the
crystal orbital (6s and 6p orbitals), leading to a strong bonding between the low-energy
Bi 6s and O 2p states. The strong electronic interaction between Bi 6s and O 2p electronic
states in Bi2WO6 arising from the hybridisation of s-p orbital should enhance the electron
transfer properties, thus, becoming a critical aspect in the design of photocatalysts.
In addition, the Bi2WO6 crystal exhibits the same structural phase transition in three
different space groups, which depends on the temperature range. Pure Bi2WO6 falls under
the orthorhombic space group P21ca at low temperature (T < 660°C);, the Aurivillius
phase with orthorhombic structure retains but B2cb and A2/m space group are established
once the temperature reaches from low to intermediate (660°C < T < 950°C) and high (T >
950°C), respectively.51, 52
McDowell et al. found that when the reconstructive phase
transition of Bi2WO6 occurs at high temperature, it losses the ferroelectricity and its
polarity, causing an unstable and poor photocatalytic performance of the Bi2WO6. When
temperature increases, the Bi2WO6 particle size increases and leads to significant
22
structural changes. It was observed that a loss of the octahedral tilt mode at intermediate
temperature (the differences are shown in Figure 2-6a and b), while an off-centre
octahedral distortion composed WO4 layers was being transformed from corner-sharing
to edge-sharing octahedral chains at high temperature (Figure 2-6c).53 Thus, most studies
have focused on the Bi2WO6 with orthorhombic space group P21ca in order to maintain
the ferroelectric and piezoelectric behaviour.
(a) (b) (c)
Figure 2-6. The view of the [WO4] layer at (a) the low temperature phase along [001], (b) the
intermediate phase along [001] and (c) crystal structure of the high temperature phase. 51
2.3.2 Electronic Band Structure and Optical Properties
The energy level and the band gap of the Bi2WO6 play the pivotal roles in determining
the photocatalytic performance. Based on the crystal structure, the electronic band
structure of Bi2WO6 was first determined by density functional theory (DFT) calculation
in several study groups.47, 48, 54 Figure 2-7 illustrates the typical electronic structure of
Bi2WO6, and the occupied bands are arranged into four bands. The HOMO shows the p
orbital of O atom and the s and p orbitals of the Bi atoms, accordingly, while the LUMO
23
is formed by a d orbital of the W atoms with a mixture of some degree of p orbital of O
atoms. Therefore, the HOMO and LUMO are composed of the hybrid orbitals of O 2p
and Bi 6s and the W 5d orbitals, respectively.48 Interestingly, the 6s electrons of Bi3+ can
be transited to the empty W5+orbital, since the 6s electrons usually exist at a lower energy
level than the charge transfer transition in WO66-.47 For this reason, the optical band gap
of the Bi2WO6 becomes narrower, in the range of 2.7 to 2.9 eV55-57, indicating such
photocatalyst absorbs not only the UV light but also extends the absorption range into the
visible-light region.
Figure 2-7. (a) Energy band diagram and (b) density of states of Bi2WO6 calculated by the DFT method.54
Aside from that, Kangrong et al. has revealed the hybridised Bi 6s and O 2p made the VB
largely dispersed, resulting in an improvement in the photoinduced holes mobility and
promotes the oxidation reaction.58 Therefore, the position of VB must be taken into
consideration for photocatalytic oxidation, as it dictates the oxidising potential of the
photocatalyst. The VB potential of Bi2WO6 is located at +2.94 eV, which is more positive
than the oxidation potential in O2 evolution (+1.23 eV vs RHE). Tang et al. has reported
24
that Bi2WO6 is a suitable photocatalyst for O2 evolution reaction in the presence of
AgNO3 as electron scavengers.59
Under this circumstance, the versatile nanochemistry of Bi2WO6 provides a high potential
in the area of photocatalysis in both organic degradation and water splitting processes. To
further explore the potential of Bi2WO6, the green synthetic routes of Bi2WO6
photocatalyst and photoanode preparation are established and comprehensively described
in the following sections.
2.4 Synthesis of Bismuth Tungstate
Many pioneering works on the fabrication of Bi2WO6 nanoparticles with various
methodologies have been reported with a satisfactory photocatalytic performance for fuel
production. Due to the materials availability and simple preparation method, the
manufacturing cost of Bi2WO6 is low. Eventually, special configurations of Bi2WO6
could be easily tuned into one-dimensional (1D), two-dimensional (2D) and three-
dimensional (3D) structures during the fabrication process, with each architecture
possessing unique intrinsic (such as high crystallinity, small grain size, large surface area)
and extrinsic (superior charge separation and transportation) properties. It is fully
recognised all these properties are closely interrelated especially for the photocatalytic
processes.60 The various synthesis methodologies of Bi2WO6 enables its functional
properties to be altered for each specific application. In this part of the review, the various
synthetic routes to prepare Bi2WO6 powders and thin film, with their corresponding
strengths and weaknesses in photocatalytic and PEC application, are discussed in detail.
25
2.4.1 Powders
2.4.1.1 Solid-State Method
Looking back at the development of Bi2WO6, solid-state reaction was the first reported
preparation method of pure Bi2WO6. The Bi2WO6 is usually formed by a mechanical
mixture of solid powders and heated up to at a high temperature (T > 800°C) for long
hours.61 With this method, a high crystalline Bi2WO6 was attained and approximately 2
μmol/h of O2 was generated during the photo-oxidation half reaction as reported by Kudo
and Hijii.43 However, the solid-state reaction preparation method is not ideal due to the
formation of large particle size and small surface area.62 The large particle size causes
high crystalline defects, trapping the electrons and holes in the bulk structure. Meanwhile,
the surface active site for the photocatalytic process is limited with a small surface area.63
Thus, the solid-state reaction is not immensely popular these days in synthesising
nanosized Bi2WO6 as it requires high temperature calcination.
2.4.1.2 Hydrothermal and Solvothermal method for Powders
Over the years, hydrothermal and solvothermal have become the predominantly
employed method for synthesising Bi2WO6, owing to the fast reaction kinetics, short
processing times, phase purity, high yield due to easy scalability, high crystallinity and
cost-effectiveness. Hydrothermal and solvothermal processes are defined as
heterogeneous reactions that are heated at the temperatures above the boiling point of the
minerals precursor solution within a closed system, where in the former method the major
mineralisers are water-based, and in the latter method are organic solvents.64 Numerous
morphologies including hierarchical65, plate66, red-blood cell67, hollow sphere68 and

26
nanocage69 shape, have highlighted the use of hydrothermal/solvothermal reaction for
Bi2WO6 preparation. Each morphology possesses certain advantages, for example the
hierarchical-like Bi2WO6 has a high surface area that increases the contact between the
active site and water for photo-oxidation reaction. Typically, the starting materials of
Bi2WO6 in hydrothermal/solvothermal is Bi(NO3)3∙5H2O and Na2WO4∙2H2O, and the
precursor solutions are kept at a temperature range of 100 – 200°C for a period of time.
The general formation mechanism of Bi2WO6 in hydrothermal/solvothermal often
consists of three main steps: (i) the reaction between hydrated tungsten oxide and Bi3+
ions to form Bi2WO6 nuclei, (ii) the development of 2D nanoplates (forming WO6
octahedral and Bi atoms sandwich layers structure) through anisotropic growth and
Ostwald ripening process, and (iii) the self-organisation of 3D Bi2WO6 structures from
the corresponding 2D nanoplates.70, 71
Basically, the morphology (including the size, shape and crystal structure) of Bi2WO6 can
be manipulated by adjusting the pH value, precursor concentration, growth time, and
addition of inorganic/organic surfactants during the hydrothermal/solvothermal process.
As illustrated in Figure 2-8, the shape evolution of Bi2WO6 structure can be altered easily
with different reaction conditions.72 Cui et al. found that the surface energy of the Bi2WO6
crystal can be tailored by the pH value of the precursor, thus, the crystal growth is mainly
controlled by the intrinsic crystal structure anisotropy.73 In an acidic medium (pH < 7),
a high intrinsic anisotropic surface energy led to assembly of Bi2WO6 nano-flakes to form
2D hierarchical structure. In contrast, the intrinsic anisotropic properties remain
unchanged when the solution pH value is higher than 7, resulting in the formation of
27
flake-like or sphere-like Bi2WO6 nanoparticles.72 Among all commonly reported
morphologies, the hierarchical Bi2WO6 has been reported as the desired structure for
photocatalytic reactions due to its moderately high surface area, which enhances the light
absorption and maximises the solid-liquid interaction between the photocatalyst and the
electrolyte.67
Figure 2-8. Shape evolution of Bi2WO6 structures prepared with different pH values and/or surfactants.
P123, triblockpoly(ethylene oxide)-block-poly(propylene oxide)-block(ethylene oxide) copolymer; CTAB,
cetyl trimethylammonium bromide; PVP, poly(vinyl pyrrolidone); IL, ionic liquid; EG, ethylene glycol.72
The organic/inorganic additives such as the addition of EDTA71, CTAB74, Na2SO475, and
ethylene glycol (EG)5 are commonly used in the hydrothermal reaction. The various type
of additives play a role in manipulating the morphology, uniformity and dispersion of the
final products by acting as an etching agent, an assembly agent, a reducing agent and a
reacting source.76 The addition of the surfactant has shown the ability of nucleation
28
growth retardation, suppressing the Ostwald ripening process and the aggregation process
of the nanoplates.77 Thus, Bi2WO6 with plate-like, nest-like and red-blood cell shape can
be formed instead of the hierarchical shape. Other examples have been published by
Zhang et al. and Lin et al. stating that in the presence of PVP and EDTA during synthesis,
specific plane of the Bi2WO6 was interacted selectively with the carbon-carbon bond in
the additives, which facilitated the anisotropic growth of (113) facets. Hence, the addition
of additives can promote the growth of a highly active crystal facet that facilitates the
separation of photogenerated electron-hole pairs, leading to improved photocatalytic
performance (further details in 2.6.2.1).71, 78
2.4.1.3 Others
The other synthetic routes for forming Bi2WO6 particles include sol-gel method79, sol-
gel-hydrothermal80 and co-precipitation method81. These chemical syntheses can produce
pure Bi2WO6 at low temperatures. A blue-shift has been observed in the UV-Vis spectrum
of Bi2WO6 synthesised via sol-gel method due to the quantum effect of small particle size
(< 10 nm), indicating a particle size effect on the light absorption range. Although sol-gel
preparation method forms irregular morphology, it allows the formation of smaller
particles with higher surface area, improving the solid-liquid interfacial contact between
the photocatalyst and the electrolyte.79 For the sol-gel-hydrothermal method, it combines
the advantages of both sol-gel and hydrothermal reaction, but a two-step synthesis method
will require a longer fabrication time.82
29
2.4.2 Thin Film
2.4.2.1 Single Step Method
In the particulate water splitting system, producing H2 and O2 simultaneously in a single
compartment without spatial separation is one of the major drawbacks. Product separation,
especially of two gases, is energy intensive and time-consuming. The fabrication of
Bi2WO6 photoanode has opened a route to overcome the gas separation problem. The
simplest method for the preparation of photoelectrodes is powder-based drop-casting.
Typically, a photocatalyst suspension in ethanol is dropped on a conductive substrate such
as fluorine-doped tin oxide (FTO) and iodine-doped tin oxide (ITO) glass, and is left until
it is dried.83 However, the PEC performance is easily affected by the particle size dropped
on the substrates. Smaller particle size has better attachment onto the substrate, which
improves the charge transport and charge collection efficiency. Meanwhile, larger particle
size has superior charge separation, owing to its higher crystallinity.84 Consequently,
optimisation of the particle size is necessary for maximise the PEC performance. It is
noteworthy, however, that drop-casted Bi2WO6 photoelectrodes suffer from poor
homogeneity and a high risk of particle detachment (structural instability of
photoelectrode) after long immersion in an electrolyte under irradiation.85 To prevent
particulate Bi2WO6 from being disengaged from the conductive substrate, single step
fabrication methods including spin-coating with thermal treatment86, electrospinning87
and hydrothermal88 routes for Bi2WO6 were attempted by researchers.
Dip coating or spin coating Bi2WO6 precursors onto a supporting substrate with
polystyrene sphere or carbon sphere monolayer as the template, has received attention
30
due to its unique porous structure. After the high temperature treatment, the pre-attached
polystyrene sphere and carbon sphere monolayer template were removed, establishing a
high crystalline and highly surface area porous Bi2WO6 structure. The porous structure
has demonstrated the shortening of the charge diffusion length (electrons and holes) in
the electrolyte and increases the light scattering, whereas directly enhancing the PEC
performance.86, 89 Besides, successful fabrication of flake-like Bi2WO6 on FTO substrate
via solvothermal treatment have been reported by Sun et al., and it exhibited excellent
PEC performance for the phenol degradation.88 Although the direct growth of Bi2WO6
photoanode via solvothermal reaction delivers a stable photoactivity, there are only a few
literatures reported on the fabrication Bi2WO6 photoanode with a single step. This is
because Bi2WO6 has a slow nucleation process and unbalanced reactivity of the W and
Bi precursors that hinder the Bi2WO6 growth on the substrate.90 Thus, there is a need to
explore single step fabrication of Bi2WO6 photoanode to a greater extent.
2.4.2.2 Multistep Method
In order to solve the unbalanced reactivity of the W and Bi on one-step fabrication, two-
step synthesis of Bi2WO6 is employed. Effort was devoted to the fabrication of hydrated
tungsten oxide seed layers to Bi2WO6 with an addition of Bi3+ ions is thermodynamically
favourable.90 Normally, the seed layer is formed by coating (including drop-casting91,
spray prolysis92, spin coating93), anodization94 or electrodeposition95, immediately
followed by hydrothermal reaction immediately. In a study reported by Ng et al., the
structural transformation of hydrated tungsten oxide occurred when the intercalated water
31
molecules were substituted by Bi2O22+ during hydrothermal treatment to form Bi2WO6
(Figure 2-9).94
Figure 2-9. The schematic structure of the transformation from hydrated tungsten oxide into Bi2WO6 94
On the other hand, the pulse electrodeposition technique has become an attractive method
in the fabrication of the hydrated tungsten oxide seed layers due to the ease in controlling
the seed layer morphology. Pulse electrodeposition is conducted in a three-electrode
system (with the substrate as working electrode, Pt as the counter electrode and Ag/AgCl
as the reference electrode), and the morphologies can be manipulated by varying the
plating solution with various solvents and temperatures. Apart from that, manipulating
the applied potential and current allows control of the nucleation and growth process as
well as monitoring the thickness of the hydrated tungsten oxide seed layer. These
parameters, which are made available in the pulse electrodeposition method, are
beneficial to the formation of semiconductor layers.45 Although there are no direct studies
on the electrodeposition of WO3 seed layer and its subsequent conversion to Bi2WO6,
there are numerous studies on electrodeposition of WO3 in controlling the film thickness
and porosity. For instance, Yun et al. reported that electrodepositing WO3 with a
dissolved tungsten powder in excess H2O2 as the plating solution under anodic potential
32
led to an enhanced energy storage capacity of the composite films.96, 97 Replacing the
water-based plating solution with EG solution increases the viscosity of the reaction
medium, resulting in a diffusion-limited growth and creating a high surface area thin
film.98 Hence, the electrolyte used in electrodeposition can tailor the properties of the
final WO3 electrode. A separate study by Choi et al. demonstrated by first
electrodepositing the dendrite shape Bi metal on the FTO substrate and later transformed
it into Bi2WO6 in the presence of tungsten precursors at high annealing temperature, the
reversed synthesis order created a W-rich phase on the surface of the Bi2WO6 electrode,
suggesting a decrease in surface recombination rate.56 As a result, the researchers have
demonstrated the potential of fabricating Bi2WO6 electrodes via a two-step synthesis,
with a hydrated tungsten seed layer as the starting material. The work also demonstrated
the possibility to improve the intrinsic and extrinsic factors of Bi2WO6 for photocatalytic
and PEC applications.
Overall, the various synthetic routes of Bi2WO6 demonstrate that the photocatalyst could
be fabricated with a simpler method. Although multiple steps are required for electrode
fabrication, the morphology and the intrinsic factors of the photocatalyst and photoanode
can be tailored, achieving a superior performance during the photocatalytic water splitting
reaction. From the application viewpoint, Bi2WO6 is not the optimum photocatalyst for
water splitting and is still facing a few challenges. Further modifications are necessary to
overcome the limitation of Bi2WO6, which are described in the next section.
33
2.5 Photocatalytic Performances and Limitation of Bi2WO6
Bi2WO6 photocatalyst has a strong oxidising potential and has been found that both
Bi2WO6 particulate and photoanode exhibit high photoactivity in dye and organic
compound degradation. Numerous reports mentioned that Bi2WO6 could
photocatalytically mineralise organic dyes54, phenols88, 99, aldehydes74, 100

, benzene79,
tetracycline75 and acetic acid.57 The photocatalytic performance of Bi2WO6 suggests it is
a potential candidate in environmental application, such as air purification and wastewater
treatment. Upon light irradiation, the photogenerated holes react with OH- to form •OH
(hydroxyl radicals) responsible for the oxidation of the adsorbed organic molecules. On
the other hand, the electrons react with atmospheric O2 to form superoxide radical (O2•-).
Bi2WO6 is capable of performing complete oxidation of organic pollutants, however the
photocatalytic activity is greatly influenced by the type of organics being degraded and
the type of electrolyte being used.54 Furthermore, although Ohtani and co-workers
discovered Bi2WO6 can achieve organics removal rate up to a thousand times faster than
commercial P25 TiO257, the photocatalytic activities can be affected by the morphology
of Bi2WO6. Shi and co-workers showed that the highest degradation rate of total organic
carbon (TOC) was achieved by the nest-like nanostructure Bi2WO6 with assembled
nanoplates compare to the nanorods and nanoplates due to its excellent charge mobility.75
Aside from the powders, a moderate electrochemical degradation of phenol (78% of
phenol removed in 3 hours) can be achieved in a three electrode system with the presence
of leaf-like Bi2WO6 photoanode. However, the phenol degradation rate in an
electrochemical process is considered to be very slow.88 Thus, advance understanding
and consideration in the correlation between the physicochemical properties (i.e.

34
morphology) and the Bi2WO6 kinetic properties is a pivotal aspect to achieve an efficient
and effective Bi2WO6 catalyst.
Apart from organic degradation, Bi2WO6 has also been shown to covert CO2 into valuable
solar fuels such as methane and methanol.101 The CO2 reduction capability of Bi2WO6
piques a lot of interests for further investigation due to the global challenges of energy
crises and global warming. In the area of photocatalytic water splitting, Kudo and Hijii
first revealed an evolution rate of 1.6 μmol/h and 24 μmol/h of H2 and O2, respectively,
by utilising Bi2WO6, with the addition AgNO3 as an electron acceptor.43 A few other
studies also clearly showed that PEC water splitting could be attained by applying an
external bias to produce clean H2 and O2. Ng et al. demonstrated the Bi2WO6 thin film
fabricated via transformation of WO3 produced approximately 0.1 μmol/h H2 and no O2
was detected at an applied bias of 1.0 V vs Ag/AgCl for 4 hours.94 Similarly, a porous
Bi2WO6 electrode produced ca. 1.1 μmol/h∙cm2 of H2 when 0.6 V potential vs Ag/AgCl
was applied, however the O2 collected was higher than the stoichiometric value of 2.0.
The unusual situation of imbalanced H2:O2 gas ratio was explained by the adsorption of
evolve O2 onto the photoanode and the high solubility of O2 in water.102 These preliminary
results clearly demonstrate the feasibility of Bi2WO6 photocatalyst as a candidate for
water splitting process. Noteworthy, it is difficult to fabricate a crystalline Bi2WO6
photoanode directly with superior adhesion to the supporting substrate. Moreover, it
remains a main challenge for PEC water splitting to reach ca. 100% faradaic efficiency
because Bi2WO6 is known to suffer from poor charge separation efficiency and low
charge carrier concentration. Despite the Bi2WO6 layer structure provides better
35
electronic properties, the superior charge mobility causes fast recombination within
picosecond. As mentioned earlier, the excited electrons and holes can be easily trapped
and recombined which suppresses the photocatalytic performance resulting in low
conversion efficiency. From a practical viewpoint, further research is essential to evaluate
the behaviour of photogenerated charges during the redox reaction to optimise the
photocatalytic performance of Bi2WO6 film.
Heretofore, there are only a few successful studies reporting on Bi2WO6 for water
splitting process. To fill the vacuity, the Result chapters of this thesis present the
development of a highly active Bi2WO6 for photo-oxidation process in water splitting
system. Before that, an overview of all the current research and findings on Bi2WO6 was
undertaken in order to have a better understand on the strategies in tailoring the bulk
Bi2WO6. So that the approaches could be made to overcome Bi2WO6 weaknesses and
optimise the design for O2 evolution.
2.6 Strategies in Improving Bi2WO6 in Photocatalysis Reaction
Bi2WO6 is generally employed in photocatalytic water oxidation process and organic
degradation or reforming (such as phenol and acetic acid), which removes the impurities
in the water or produces value-added organic products. Although a few literatures have
evidenced that pure Bi2WO6 could be applied in photocatalytic and PEC systems, the
performances were not promising enough for industrial scale purposes. To optimise the
conversion efficiency from solar to chemical energy, the integration of advanced
modelling into the design of photocatalytic materials is essential. In this section, some of
36
the critical parameters for the overall improvement in photocatalytic performance are
discussed, which include the strategies on increasing the light absorption, charge
separation, charge transportation improvement and the photostability Bi2WO6. These four
strategies could enhance the photocatalytic performance by altering the bulk properties,
surface properties, and interface properties of the semiconductor. Therefore, the efforts
and resources spent on the studies and researches on the photocatalysis can become solid,
quantifiable and established.
2.6.1 Increasing Light Absorption
The development of photocatalysts with visible-light photoresponse began from TiO2
photocatalytic water splitting. Since TiO2 possesses a wide band gap of 3.2 eV that limits
the light absorption in the UV range, restricting the range of solar spectrum being
absorbed for water splitting.24 As UV light only makes up 5% of the solar spectrum, there
is a huge incentive in increasing the light absorption range to efficiently utilise the sun’s
energy. Thus, to obtain a satisfied energy requirement for water splitting, numerous
approaches have been adopted in order to increase the light absorption ability for the
photocatalyst: (i) metal or non-metal ions doping for band gap narrowing and (ii) altering
the morphology.
2.6.1.1 Metal or Non-metal Doping
Considering the band structure of the photocatalyst, narrowing the band gap via metal ion
doping is one of the effective ways to achieve visible-light photoresponse, according to
the flat-band edge position energy diagram in Figure 2-4, the CB of each Bi-based
37
photocatalyst is located slightly lower or higher than the redox potential of H+/H2. In
contrast, all the VB positions are more positive than the redox potential of O2/H2O.
Basically, metal ions doping creates an intraband state (donor level or acceptor level that
is above the VB or below the CB edge, respectively), resulting in a redshift in the band
gap (increase in the absorption wavelength). Figure 2-10a and b illustrate the band
structure after metal ion doping, where a sub-band gap energy is formed, hence narrowing
the band gap of the semiconductor. On the contrary, the localised states of non-metallic
dopants can interact with the O 2p electrons at the VB edge, forming an impurity level.
The VB edge is then shifted upward, resulting in an extension in the optical absorption
edge of the semiconductor as portrayed in Figure 2-10c.103 Therefore, the modulation of
the band structure through the doping of metal ion or non-metallic ion technique is
preferred, achieving a visible-light active photocatalyst.11
(a) (b) (c)
Figure 2-10. (a) The donor level, (b) the acceptor level formed by metal ion doping, and (c) new valence
band formation by non-metal doping 11
The light absorption ability of Bi-based semiconductor can be enhanced by doping with
3d-transition elements or d10 and d10s2 configuration in the VB, as the hybridisation of s
38
or d-orbitals with O 2p orbital will up-shift the top of the VB edge.39 For instance, Parmar
et al. studied 12 different cationic elements doped into the site of BiVO4, including Mo6+,
W6+, Ta5+, Zr4+, Si4+, Ti4+, Fe3+ and Ag+, only Mo6+ and W6+ were able to substitute V5+.
Consequently, the VB edges of Mo- and W-doped BiVO4 were shifted to a more positive
potential by 30 mV and the visible-light-induced photocatalytic activities for OER in the
presence of AgNO3 were improved.104 A similar result has been reported for Mo-doped
Bi2WO6. The higher electronegativity of Mo 4d transition compared to the W 5d
counterparts, facilities the formation of covalent bonds with oxygen, resulting a narrower
CB with a smaller curvature. However, covalent bonds do not favour the movement of
photogenerated charge carriers, even though they promote photon absorption.105
Although metal ion dopants can minimise the band gap of Bi-based semiconductor, Meng
et al. have claimed the insertion of the localised d states metals into the band gap could
generate a recombination centre. More trapping sites for electrons and holes are formed
in the metal dopant compared to non-metal dopant, leading to a reduction in the
photocatalytic performance.39 Thus, some research has moved on to doping non-metal
ions. Non-metal dopants introduce an impurity state and subsequently narrow the band
gap of Bi-based photocatalyst. The p states of the non-metals could combine with O 2p
orbitals to create a VB maximum energy of the doped composites.103 Studies on non-
metal doping, such as N, B and F doped with Bi2WO6, found that it can be an effective
strategy to enhance the visible-light photocatalytic activity owing to the high ionisation
energies and the high electronegativity, which inhibit the recombination of the
photogenerated charge carriers. Besides, N-, F- and B- doped Bi2WO6 exhibits a stronger
39
absorption in the UV-visible range with a red shift in the band gap transition, resulting in
a strong specular reflection.106-109 Therefore, metal and non-metal doped Bi2WO6 are
considered to have improved efficiency in the photo-oxidation process since a narrower
band gap is obtained.
2.6.1.2 Morphology Control
Interestingly, altering the shape of the Bi2WO6 by different preparation methods have
been found to be one of the common strategies applied to increase the light absorption.
The optical properties of the generally known Bi 2WO6 morphology are summarised in
Table 2-1, revealing the Bi2WO6 band gap in the range of 2.65 eV to 3.0 eV. The
hierarchical and red-blood cell shape Bi2WO6 are categorised as 3D super-structure,
experiencing an induced band gap widening (blue-shift in the absorption edge) when
compared to the 1D and 2D structures. Xu and co-workers have explained that the blue-
shift in the absorption wavelength in the 3D structure is due to the small grain size of the
hierarchical and red-blood cell shape Bi2WO6, ensuing in a larger band energy of
semiconductor.110 Smaller grain size of the photocatalyst, will decrease the extent of
orbitals or energy level overlapping, reducing the number of transition states and causing
an increase in energy gap between the VB and CB. It is also noted with the thin film
structure, that smaller grain size of the semiconductor can avoid the random distribution
of grains on the film surface, achieving higher surface roughness and an increase in light
scattering at the interface.111
40
Table 2-1. Different morphologies of Bi2WO6 with the corresponding band gap
SEM images
Morphology Hierarchical Plate-like Red-blood cell

Band gap (eV) 2.85 2.75 3.06
65 101 67
Bi2WO6 Reference
Powders
SEM images
Morphology Rod-like Bipyramid Irregular

Band gap (eV) 2.70 2.65 2.72
75 78 79
Reference
SEM images
Bi2WO6
Thin Film
Morphology Nanoflake Porous Irregular
Band gap (eV) 2.82 2.75 2.63
88 86 112
Reference
Apart from the grain size, the particle size is also affecting the light absorption of the
semiconductor. At the nanoscale (10-100Å), the quantisation effect becomes significant.
The quantum size confinement effects create a large variation in momentum, leading to a
colour change of the material and a wider semiconductor band gap. Sun et al. have
identified the absorption edge of pure Bi2WO6 quantum dots located at 400 nm, which is
much lower than the 450 nm commonly reported in bulk Bi2WO6. Although the Bi2WO6
quantum dots have delineated an increase of the band gap, according to Gerischer theory
such phenomenon raised the thermodynamic potential of the electron-hole pairs, which
facilitate the charge transfer process between the semiconductor and the redox couple in
41
solution.113, 114 Thus, Bi2WO6 of various morphologies can have different grain sizes and
particle sizes that could affect the optical absorption and band gap energy of the
semiconductor. In addition, the hierarchical-like particles and porous nanoflakes Bi2WO6
photoanode have been emphasised by Zhu et al. and Gong et al. that both exhibit superior
performances with long-term stability under irradiation. The enhancement of the
performance in hierarchical structure is attributed to its large surface area, offering the
photocatalyst not only increased absorption site for light harvesting, but also increased
interfacial contact between the active site and water for photo-oxidation reaction.48, 95
Moreover, the porous structure of Bi2WO6 photoanode has improved light absorption
ability, where the curvature formed scatters the incident light within the film and reduces
the reflection loss.86, 89, 102
In summary, doping and altering the morphology of Bi2WO6 are effective approaches to
design the desired light absorption ability for increasing the number of photoexcited
electron and hole pairs. Furthermore, studies have revealed that higher density of oxygen
vacancies and increasing distortion of the semiconductor crystal structure could increase
its light absorption ability115, thus, further investigation into such factors will be beneficial
for Bi2WO6.
2.6.2 Improvement in Charge Separation
In the four major steps of photocatalysis described at the beginning of section 2.2, Xu et
al. have referred to the charge separation as the ‘energy pump’ process, which is an uphill
action to separate the electrons and holes after absorbing sufficient energy (> 1.23 eV)
42
from the sun.116 In this particular step, a high occurrence of the recombination of
photogenerated electron-hole pairs is observed within nanoseconds since there is
insufficient energy to withdraw and transfer the charge carriers from the photocatalyst.
Figure 2-11. Schematic diagram of the electrons and holes process at the semiconductor/liquid interface
under light illumination (thick vertical bar). The straight and wavy lines represent the radiative and
nonradiative processes, respectively. The electron energy (eV) is given relative to the vacuum level (0eV);
− +
𝑒𝑡𝑟 : electron trap, ℎ𝑡𝑟 : hole trap, 𝑒𝑟− : reactive electron surface site, and ℎ𝑟+ : reactive hole surface
sites.117
Figure 2-11 illustrates the two most probable pathways for the recombination of charge
carriers within the semiconductor: (i) the reactive electrons relax into the VB from the
CB directly and recombines with the holes, or (ii) the trapped electrons at a specific site
of the surface or in the bulk recombine with the holes at the VB. Likewise, the
photogenerated holes in the VB undergo a similar mechanism, in which the holes are
trapped either at the interband or on the surface and then recombine with the electrons.118
The rapid charge recombination in the bulk semiconductor has prohibited the electron
43
and holes to be transported for reduction or oxidation process, leading to a poor
photocatalytic and PEC performance. Thereby, strategies have been focused on
engineering the Bi2WO6 particles and thin film to promote the charge separation process.
2.6.2.1 Bulk Engineering
Without any extrinsic modification, advanced engineering of bulk semiconductor such as
the change in crystal phase and increasing crystallinity has affected a superior charge
carrier mobility, suppressing the charge recombination in the photocatalyst.
The crystal lattice structure largely influences the semiconductor properties. For example,
TiO2 has three main crystal phases, and it can be transformed into anatase (tetragonal),
rutile (tetragonal) and brookite (orthorhombic) at different temperatures. Among all, Carp
et al. found that the anatase TiO2 exhibits a higher photocatalytic activity due to the Fermi
level located at a higher energy level, with a lower capacity to absorb O 2 and a higher
degree of hydroxylation.119 A similar case has been reported in BiVO4 where monoclinic
scheelite phase is the most representative structure to evolve the highest amount of O2,
more superior than the tetragonal zircon BiVO4.120 Despite the various crystal phases
being beneficial towards charge separation, Bi2WO6 with different crystalline phases are
not achievable since only the orthorhombic structure is mainly formed at any temperature
as mentioned in the fundamental properties of Bi2WO6 (section 2.3.1). Alternatively, Lv
et al. suggested that bismuth tungstate with different stoichiometry such as Bi2WO6-x
contains a high concentration of surface oxygen vacancies that capture the photoexcited
electrons, achieving an efficient photogenerated charge carrier separations.44 The bismuth
44
tungstate with stoichiometry of Bi2W2O9 has also demonstrated a higher kinetic constant
due to the VB being made up of perovskite layers with higher hybridisation of Bi 6s and
O 2p orbitals. As a consequence, with a stronger hybridisation, more Bi lone pairs lose
their spherical symmetry and promote the electronic properties by improving the charge
mobility.38, 49
Besides, in the investigation of Zhang et al. and Huang et al., the highly crystalline
Bi2WO6 obtained via high temperature annealing had fewer electrons trapped below the
surface.121 The high temperature annealing minimises the defects in the photocatalyst and
promotes charge separation and transfers from the bulk centre to the surface active sites.
Although there is no direct evidence on the impact of different crystallinity degree of
Bi2WO6 thin film on PEC photoactivity, Dong et al. have explained the need of a highly
crystalline phase of Bi2WO6 as it improves the charge carrier transport.122 Thus, from the
crystallinity point of view, a higher crystallinity means the impurities in the photocatalyst
are no longer apparent which could enhance the carrier mobility. Yet, the calcination
temperature reaches the upper limit, resulting in the loss of surface active sites due
particles agglomeration and structural destruction. Interestingly, some researchers
reported that some semiconductors with low crystallinity or in amorphous condition
exhibited enhanced photocatalytic activity. The improved photocatalytic activity was due
to the existence of active centres for oxidation or reduction reaction through the
production of defects such as oxygen vacancies.123 Due to limited studies on the
correlation between the crystallinity and other factors (such as surface area), it is
45
necessary to investigate and optimise the governing factors in the photo-oxidation process
for Bi2WO6.
2.6.2.1 Crystal Facet Engineering
General speaking, a photocatalyst with more active sites being exposed to the light and
electrolyte will generate more charge carriers and active species for water oxidation.
However, it is also found that some of the active sites are only present on specific crystal
facets as different crystal facets have various degree of surface energy.124 In this regards,
researchers have gained interest in tailoring the high-energy crystal facets of the
photocatalyst owing to such facets permit the efficient separation of electron-hole pairs.125,
126
As demonstrated by Li et al., the metal-based reduction co-catalyst (such as HAuCl4,
H2PtCl6 and AgNO3) is selectively deposited on the {010} facets, while the metal-oxide-
based oxidation co-catalyst (such as MnOX and PbOx) are found mostly on the {110}
facets of the truncated bi-pyramid BiVO4 as shown in Figure 2-12. The proposed reason
for the metals or metal oxides selective deposition on certain crystal facets of the BiVO4
is due to the difference in intrinsic surface energy level of the CB and VB of each crystal
facet. The different energy field drives the electrons and holes spatially separated onto
different crystal facets, improving the charge mobility and separation efficiency.127
46
Figure 2-12. SEM images of dual components photo-deposited on the surface of BiVO4 (a)
Au/MnOx/BiVO4, (b) Pt/MnOx/BiVO4, (c) Ag/MnOx/BiVO4, (d) Ag/PbO2/BiVO4, (e) Au/PbO2/BiVO4 and
(f) Pt/PbO2/BiVO4. The contents of the deposited metals/metal oxides are all 5 wt%. The scale bar is 500
nm.127
Taking advantage of the different adsorption behaviours of various crystal facets, a facet-
dependent technique has been employed in Bi2WO6 fabrication to achieve superior charge
separation. Recently, Jolivet et al. discovered Bi2WO6 platelets grew preferentially along
the (010) surface orientation during hydrothermal reaction in an acidic medium, and a
detailed structure annotated with crystallographic planes is illustrated in Figure 2-13a.66
With a higher exposure of {010} crystal facet in Bi2WO6 to the electrolyte, it was found
an apparent improvement in the photocatalytic O2 evolution. The calculation of the
electronic density with respect to each Bi2WO6 crystal facet was performed by Wang’s
group, with the model being illustrated in Figure 2-13b. Based on the calculation result,
it was determined that the holes prefer to migrate around Bi atoms at the (060) crystal
facet surface due to the existence of more negative electronic density. The photogenerated
holes in Bi2WO6 concentrate around the {010} crystal facet family and acts as the active
47
reaction sites, giving an effective separation process of the electron-hole and superior
photocatalytic water oxidation activity.124 As indicated above, the migration pathway of
the electrons and holes correspond to the surface energy of the Bi2WO6 crystal facet,
thereby researchers started to tailor the extent of {010} and {100} crystal facet exposure
of Bi2WO6 for optimisation in photocatalytic water oxidation.128
(a) (b)
(c)(i) (c)(ii)
Figure 2-13. (a) Representation of Bi2WO6 platelet wtih different crystallographic planes.66 (b) The
Bi2WO6 density function theory (DFT) model of the electronic density differences of at (002), (060), and
(200) surfaces which are obtained by subtracting electronic densities of the surface losing an electron
from that of the corresponding neutral surface. The blue and yellow colours indicate negative and
positive electronic density, respeictively.124 (c)(i) Band energy diagrams of single-crystalline nanosheets
and nanosheet-assembled microspheres, and (c)(ii) transient photocurrent responses of the Bi2WO6 nano-
structure of nanosheet-assembled microspheres (red line), single-crystalline nanosheets (black line) and
nanoparticle-assembled microspheres (blue line). 129
48
Ma et al. systematically compared the photocurrent generated in the PEC system with
respect to the exposure of dominant {010} facet in Bi2WO6. The nanosheet-assembled
Bi2WO6 microsphere, which possesses a higher exposure of (010) facet, has a smaller
band gap (Figure 2-13c(i)) and exhibits a better photocurrent response than the single
crystalline nanosheet Bi2WO6 during organic degradation (Figure 2-13c(ii)). Apparently,
the microsphere Bi2WO6 is predicted to give higher performance due to a majority of
active dominant (010) facet was constructed. As the (010) facet is rich in charged oxygen
atoms, the electrophilic organic molecules are drawn to react with the holes distributed
on the (010) facet for degradation, while the electrons are being transported to the external
circuit.129 Contrary, Li et al. revealed from their DFT calculation, that dimer Bi-O
vacancy pairs are formed by retaining a large percentage of high surface energy (100)
facets in the bipyramidal Bi2WO6. The presence of (100) facet causes a large-scale atom
reconstruction, resulting in the distortion of Bi2WO6 crystal structure. The distortion
provides a larger space for polarizing the relevant atoms and orbitals, allowing an
improvement in the separation efficiency of the electron-hole pairs.78 In other words,
adjusting the growth of the Bi2WO6 crystal facet provide an opportunity for the electrons
and holes to reside and be exposed on the {010} or {100} facets, hence improving the
charge separation. To this end, charge trapping and charge recombination are decreased,
allowing the photocatalytic and PEC performance to be enhanced. However, there is no
specific experimental evidence to support the electron- and hole-dominant facet for
Bi2WO6 and quantify the amount of charges being exposed on the crystal facet, thus
further confirmation experiments are required for crystal facet engineering.
49
2.6.2.2 Heterojunction
In addition to the previously mentioned methods, heterojunction formation is one of the
common ways to modify Bi2WO6 to improve its photocatalytic and PEC performance.
The conventional heterojunction is defined as the interface between two different
semiconductors with unequal band structures, where band alignments between the two
semiconductors take place, promoting the separation of electrons and holes. Previously
studied heterojunction photocatalytic systems involving Bi2WO6 include WO3/Bi2WO694,
BiVO4/Bi2WO6130, BiOBr/Bi2WO6131, TiO2/Bi2WO6132, C3N4/Bi2WO6.133
Figure 2-14. Schematic diagram of the three different type of electron-hole pairs separation in the case of
conventional light responsive heterojunction photocatalyst: (a) type-I, (b) type-II, and (c) type-III
heterojunctions.134
Depending on the band position and the electron affinity of the semiconductors, the
heterostructures can be divided into three different types of conventional heterojunction
photocatalyst as depicted in Figure 2-14. In type-I heterojunction, the CB and VB level
of the semiconductor A are respectively higher and lower than the band position in
semiconductor B. When semiconductor A is in contact with semiconductor B, the
electrons and holes at the CB(A) and VB(A) migrate to the CB(B) and VB(B). Thus,
50
under light irradiation, the electrons and holes are accumulated in semiconductor B. For
the type-II heterojunction semiconductor, the CB and VB levels of semiconductor A are
slightly higher than those of semiconductor B. During photoexcitation, the electrons from
CB(B) will be transferred to CB(B), while the holes at the VB(B) will migrate to the
VB(B). Finally, the architecture of type-III heterojunction photocatalyst is similar to a
type-II heterojunction photocatalyst, except the CB and VB of both semiconductors do
not overlap, restricting the migration of the charge carriers. The theory of these three
different types of heterojunction can be implemented in Bi2WO6 in the form of powder or
photoanode.134 It has been reported that type-II heterojunction gives the best charge
separation efficiency, wide light absorption range and fast mass transfer when comparing
with the other types. Due to the chemical potential difference between semiconductor A
and B, a band bending will occur at the interface of heterojunction, which induces a built-
in field that drives the electrons and holes to move in opposite directions. Accordingly, a
spatial separation of the electrons and holes will accumulate at semiconductor A and B
of the heterojunction, respectively.118, 135 The type-II heterojunction can also be classified
into a p-n, n-n and p-p junction. Designing a p-n and n-n with Bi2WO6-based
heterojunction could overcome the ultrafast electron-hole recombination and promote the
charge transfer in the semiconductor. The impact of forming a type-II heterojunction on
the photocatalytic and PEC performance of Bi2WO6 are summarised in Table 2-2.
51
Table 2-2. A brief comparison of the improved performance of Bi2WO6-based type-II heterojunction
The improved performance

Heterojunction Type References
compares with the pure Bi2WO6
1.5 times faster for degradation of 136
Bi2O3/Bi2WO6 p-n
RhB in 3 hours
2 times faster for degradation of 36
BiOBr/Bi2WO6 p-n
Bi2WO6 RhB in 30 mins
Particles 2 times faster for degradation of 137
WO3/Bi2WO6 n-n
phenol in 2 hours
6.2 times faster for degradation of 138
Bi2S3/Bi2WO6 p-n
phenol in 2 hours
Photocurrent density is 2 times 139
Bi2WO6 TiO2/Bi2WO6 n-n
higher than the Bi2WO6 photoanode
Thin
Photocurrent density is 2.3 times 130
Film BiVO4/Bi2WO6 n-n
higher than the Bi2WO6 photoanode
For instance, when Bi2S3/Bi2WO6 forms a p-n heterojunction, the p-type Bi2S3 and n-type
Bi2WO6 contain a higher amount of positively and negatively charged species,
respectively. The p-n heterojunction creates a built-in potential in the space charge region
or so-called an internal electric field. Sun et al. have reported that the existence of an
internal electric field could trigger the migration of photoexcited electrons from the CB
of Bi2S3 to the CB of Bi2WO6 when the semiconductor is exposed to light irradiation. On
the other hand, the holes will move in the opposite direction (Figure 2-15a). As a result,
the presence of an internal electric field and the band bending have contributed to a
superior spatial charge carrier separation, where the electrons and holes are accumulated
in the n-type Bi2WO6 and p-type Bi2S3, respectively. Furthermore, the claim on p-n
heterojunction providing an excellent charge separation is supported by

52
photoluminescence (PL) spectroscopy, which evaluates the charge separation efficiency
of the photogenerated charge carries in the semiconductor. Figure 2-15b(i) compares the
PL spectra of the bulk Bi2WO6 and the Bi2S3/Bi2WO6 heterojunction. The lower PL
intensity recorded in Bi2S3/Bi2WO6 indicates a lower recombination probability of the
electrons and holes. With respect to the Bi2S3/Bi2WO6, the phenol degradation rate has
been accelerated due to decrease in charge recombination rate, as depicted in Figure
2-15b(ii). Nevertheless, reports of p-n heterojunction semiconductors are limited as most
heterojunction materials are known to be unstable. Additional strategies are required to
stabilise the p-type photocatalyst, such that the corrosion of the material could be
prevented, and to avoid degradation of the heterojunction structure.140 Meanwhile, the n-
type semiconductor combines with n-type Bi2WO6 is more commonly reported. As an
example of the n-n heterojunction, BiVO4/Bi2WO6 demonstrated not only a stable
photocatalytic performance with high recyclability, it also showed a narrow band gap
after the band alignment and improved the charge separation efficiency.141 When the two
semiconductors are in contact, the junction in between could effectively separate and
transfer the charge as described by the type-II heterojunction mechanism. Thereby, the
deficiencies of the bulk Bi2WO6 including the intrinsic short charge diffusion lengths and
low charge carrier mobility are overcome.116 In summary, the p-n and n-n junction has
been proven to be an effective strategy for charge separation, since the lifetime of the
charge carriers are increased, greatly minimising the surface traps of the carriers within
the semiconductor.
53
(a) (b)(i) (b)(ii)
Figure 2-15. (a) Schematic diagram of the electron-hole separation under the influence of the internal
electric field of a p-n heterojunction photocatalyst under light illumination. 134 (b)(i) PL spectrum and (ii)
the phenol degradation rate of Bi2WO6 and Bi2S3/Bi2WO6.138
For the heterojunction fabrication, researchers have implied other approaches to further
enhance. The electron-hole separation efficiency of the heterojunction could be further
enhanced by selecting an appropriate fabrication method. Firstly, the geometry of the
powder and thin film heterojunction play a vital role in the charge separation, as the
morphology of the resulting heterojunction directly affects the contact between the two
photocatalysts, which will affect the charge separation pathway and could influenced the
Schottky junction at the semiconductor-electrolyte interface. In an investigation by Wang
et al., a core-shell heterojunction was successfully synthesised with WO3 as the core and
Bi2WO6 as the shell. When the WO3/Bi2WO6 heterojunction is under illumination, band
alignment occurs between WO3 and Bi2WO6. Majority of the electrons accumulated at
the CB of WO3, while the holes were generated at the VB of Bi2WO6 as shown in Figure
2-16(i).
54
(i) (ii)
Figure 2-16. Photocatalytic degradation of RhB (i) WO3/Bi2WO6 core shell and (ii) Bi2O3/Bi2WO6 hollow
microsphere under visible-light irradiation (cut-off wavelength is larger than 442 nm and 554 nm,
respectively).136, 142
Although charges can be separated effectively in WO3/Bi2WO6, the WO3 is totally
encapsulated by the Bi2WO6 prohibiting the electrons to be in contact with the electrolyte
for redox reaction. Consequently, despite an increase in the charge carrier concentration
at the heterojunction that led to an enhancement in the photocatalytic reaction, the
separation of the electron-holes pairs would not improve significantly.142 In comparison
to Li et al. study on the heterojunction of a hollow Bi2WO6 microsphere with surrounded
Bi2O3 shell (Figure 2-16(ii)). The added advantage of this geometry facilitates electrolyte
diffusion into the hollow centre, allowing the electrons accumulated at the CB of Bi2WO6
to participate in the photocatalytic reaction. Correspondingly, the organics dye,
Rhodamine B (RhB), was completely decomposed by the Bi2O3/Bi2WO6 hollow
microsphere, while the encapsulated WO3/Bi2WO6 can only degrade 65% of the RhB in
3 hours. Therefore, the contact with the electrolyte for the photo-oxidation process is
profoundly affected by the geometry of the heterojunction constructed.
55
Secondly, an increase in the interfacial contact between the two semiconductors acted in
furtherance of charge separation. Xu et al. studied four different interfacial contacts of
TiO2-Bi2WO6 photoanode. To achieve a higher interfacial contact between the two
photocatalysts, coarse underlayer Bi2WO6 was first fabricated by controlling the dip
coating process. The graphical illustration of the photoanodes is displayed in Figure
2-17(i). The BWO-3/TiO2 thin film, which denoted as ‘c’ in the figure, has the highest
interfacial contact in comparison to the other thin films. It was found that BWO-3/TiO2
exhibited the highest photocatalytic activity, with the degradation rate of stearic acid
being 6.8 times faster than the unmodified TiO2/Bi2WO6 photoanode (see Figure 2-17
(ii)). The improvement is attributed a higher interfacial contact area between the two
photocatalysts, increasing the electron-hole pair separation efficiency that facilitates the
electrons and holes being exposed at the surface for photocatalytic reaction.139
(i) (ii)
Figure 2-17. (i) Graphical illustration of TiO2/Bi2WO6 heterojunction morphology (‘a’ represent the
common bilayer film. ‘b’, ‘c’, and ‘d’ correspond to the heterojunction of 1.5%, 3% and 5% Bi 2WO6
precursors used during fabrication with TiO2 heterojunction, respectively. (ii) Evaluation of the thickness
(in nm) of stearic acid degraded after 24 hrs by using TiO2/Bi2WO6 with different interfacial contact.139
56
Lastly, integration of the advantages of heterojunction in crystal facet engineering is
demonstrated to be beneficial for charge separation. Taking account of a photocatalyst,
each crystal facet possesses different surface energy that controls the direction of the
charge being separated and transported, thus, the combined faceted-Bi2WO6 and the
heterojunction could reduce the electrons and holes diffusion distances.143 Li et al. have
proposed a combination of thin layer of Bi2WO6 with the (040) and (110) BiVO4 facets
to form a heterojunction for PEC water splitting as illustrated in Figure 2-18. They have
inferred the electrons and holes in the BiVO4 are preferentially move to (040) and (110)
facet, respectively, due to the built-in electric field. With the n-n heterojunction
BiVO4/Bi2WO6 configuration, the exposed electrons at the (040)-BiVO4 migrate to
Bi2WO6, resulting in a suppression of the electrons and holes. The photocurrent density
recorded in the heterojunction has increased when compares to the bulk BiVO4 and
Bi2WO6.130 In conclusion, the geometry and the interfacial contact between both
photocatalysts of a heterojunction are one of the critical aspects to be considered for the
enhancement in photocatalytic and PEC performance. More investigation and
understanding on the relationship in the combination of two or more strategies with
heterojunction are useful, so that the limitation on the charge kinetics of bulk Bi2WO6
could be overcome.
57
Figure 2-18. (c) The working principle in the PEC process of the thin film that (040) and (110) BiVO4
combine with Bi2WO6.130
2.6.2.3 Doping, Self-doping and Substitution
Doping cation or anion into Bi2WO6 can expand the photo-response spectral range as well
as restrain the recombination of photogenerated electrons and holes. Typically, there are
two types of dopant (either electron donors or acceptors). When the dopant is introduced
into the lattice structure of Bi2WO6, the atomic arrangement, physical structure and
chemical composition are modified. The modification causes an increase in charge carrier
concentration, charge mobility, and the intrinsic charge separation efficiency of the
materials. Thus far, the doping of Cu144, Fe145, Ag146 and F147 into Bi2WO6 have already
been reported to improve the photocatalytic activity in dye degradation. In most cases,
transition metal dopants function as the electron receptors on the surface of a
photocatalyst, which inhibit the recombination of photogenerated charge carriers. For
example, Xia et al. have justified the Cu ions in the Cu-doped Bi2WO6 acting as an
electron pool, enabling the electrons to initiate interfacial charge transfer (IFCT), as
illustrated in Figure 2-19. The photogenerated electrons at the CB of Bi2WO6 were

58
directly reacted with Cu2+, reducing it to form Cu+. Due to its instability and the charge
compensation, Cu+ reduces oxygen molecules and re-oxidises to Cu2+. Therefore. By
trapping the photoelectron in Cu as Cu+ state, the electron lifetime is prolonged,
facilitating the reduction of O2 molecules to generate superoxide radicals during organic
degradation.144, 148 Likewise, Fe3+ dopant in Bi2WO6 is also reported as an excellent
mediator of the interfacial charge transfer. Wu et al. have stated that Fe3+ ions tend to
react with the photoexcited electrons and holes to form Fe2+ and Fe4+, respectively, when
the photocatalyst is subjected light irradiation. The Fe dopant could act as an electron or
hole trap that greatly reduces the charge recombination rate. However, excessive Fe3+
doping in Bi2WO6 could lead to cluster formation that covers the surface-active site of
Bi2WO6, resulting in deterioration of photocatalytic activity.145
Figure 2-19. Schematic diagrams illustrating the possible photocatalytic mechanism of Bi2WO6 and Cu-
doped Bi2WO6.144
59
In addition, doping rare earth metal such as Er3+ into hierarchical Bi2WO6 infuses
upconversion properties into the photocatalyst, allowing Bi2WO6:Er3+ to be activated by
visible-light beyond the absorption edge of pristine Bi2WO6.149 Zhu and his co-worker
have reported a blue-shift in the optical absorption edge of the Er3+-doped Bi2WO6
compared to undoped Bi2WO6, indicating the formation of new energy states below the
VB. With such small energy level, the electrons and holes are trapped at the CB and VB,
suppressing the recombination of the photoexcited charges.150 To exploit the full
advantages of Er3+ doping and achieves the maximum charge separation efficiency, recent
research effort has focused on developing the synergetic technique of metal ion doping
and formation of heterojunction with Bi2WO6. The combination of TiO2 and Bi2WO6 can
optimise charge carrier dynamics, meanwhile, the incorporation of Er3+ produces a
noticeable improvement in photocatalytic performance, as observed by Colón’s group.
Taking advantage of increased band gap in Er3+doped Bi2WO6, it enhanced the UV-
photo-assisted process as well as higher driving force to withdraw the electrons and holes.
The TiO2/Bi2WO6 system with Er3+ doping has significantly improved the charge
separation efficiency, doubling the photocatalytic reaction rate.151 Therefore, combining
the two strategies, namely heterojunction formation and metal ions doping, can achieve
notable improvement in charge separation properties suppressing the electrons and holes
recombination and resulting in photocatalytic activity enhancement.
On the other hand, Chen’s group presented F- dopant that serves as an electron trapping
site and promotes the interfacial electron separation rate, similar to the Cu, Fe and Er
dopant mentioned above.147 Interestingly, substitution of F- into W site of Bi2WO6 form
60
Bi2WO6-xF2x, which exhibited organic degradation rate two times faster than the
unmodified Bi2WO6. The enhanced photocatalytic activity is due to the presence of F 2p
orbitals that widen the CB and VB, which improves the charge mobility to be transported
to the active site, and also induces a stronger oxidation power.152 Besides, according to a
complementary study conducted by Yu et al. on the substitution of W site in Bi2WO6 with
Mo element (Bi2MoxW1-xO6), it was found the substitution reduced the curvature of CB
in Bi2MoxW1-xO6 photocatalyst, facilitating the effective photoelectron transfer in the
CB.153 Therefore, the development in metal or non-metal ions substitution in Bi2WO6
could considerably subdue the charge recombination to improve the photocatalytic
activity.
Recently, self-doping becomes an attractive method to enhance the activity photocatalyst.
Since self-doping avoids the mismatch in atomic diameters, it can prevent the negative
impact brought about by foreign dopants or impurities and simplify the fabrication
process, as it only requires varying the ratio of the metal precursors.154 For instance, self-
doping Ti3+ in TiO2 is able to extend the photo-response from the UV to visible-light, in
which the concomitant intrinsic oxygen vacancies are induced, forming a sub-level
electronic state below the CB that greatly enhances H2 production.103, 155 Inspired by the
Ti3+ self-doping technique, a study on self-doped Bi element into Bi2WO6 has found an
increase in charge carrier separation without altering its redox power. In a separate study,
Zhang et al. have reported when the Bi self-doped content in Bi2WO6, is increased by
substituting W6+ with Bi3+, higher oxidation states of Bi (Bi4+ or Bi5+) are present due to
charge compensation. Through Bi doping, a redistribution of Bi local chemical
61
environment occurs, suggesting the Bi-O bond is strengthened via the formation of non-
stoichiometric bismuth oxide or bismuth tungstate, which increases the carrier density
and encourages charge separation.154 Although literatures have reported metal W doping
in photocatalyst can induce a high oxygen vacancy concentration and reduction of W6+ to
W4+ that assists the charge carrier separation, there are no reports on self-doped W
element in Bi2WO6 so far.156 The behaviour of the charge kinetic properties in the self-
doped W of Bi2WO6 remains unknown.
In summary, doping or substituting a desired amount of metal or non-metal ions into
Bi2WO6 could promote the concentration and migration of charge carriers within the
crystal.
2.6.2.4 Loading suitable Co-catalyst
Semiconductors loaded with a small amount (< 1 wt%) of highly active co-catalyst (either
metal or metal oxide) have been popularly extensively studied. Addition of co-catalyst
affects the charge separation of the light absorber in two different ways. Noble metals,
such as Pt157, Au158 and Ag159, serving as an electron sink can significantly inhibit charge
recombination during photocatalytic reactions. A recent study by Gao et al. reported the
use of Pt-loaded Bi2WO6 for dye degradation, demonstrating a reaction rate twice as fast
in comparison to bare Bi2WO6. Owing to a Schottky barrier likely to be formed at the
interface between the Bi2WO6 and Pt, Pt with a more positive Fermi level facilitates the
channelling of the photogenerated electrons from the Bi2WO6 CB to the Pt particles
surface.160 Consequently, the Pt nanoparticles is attributed as an island with the capability
62
to withdraw and trap electrons, effectively reducing the electron-hole recombination rate
in Bi2WO6.161 On the other hand, metal oxides such as Co3O4162 and MnOx163 loaded on
Bi2WO6 have produced improved photocatalytic activity. MnOx is known to act as a hole
scavenger as Bi2WO6 has a more anodic VB. A hole scavenging co-catalyst, helps
preserve the active site for oxidation process by suppressing the charge recombination.
The results highlighted the importance of interfacial design and control for charge
transport optimisation in a photocatalytic system.
2.6.3 Improvement in Charge Transport
In order to achieve satisfactory O2 evolution rate or significant solar to chemical
conversion efficiency, it is necessary to maximise the photocatalyst photon capturing
ability and its charge carrier surface exposure. The photocatalytic efficiency greatly
depends on the competition between the surface charge carrier transfer rate and the
electron-hole recombination rate. The charge carrier transfer time is much longer
compared to the electron-hole recombination time. Therefore, more time and effort have
been invested on strategies to accelerate the charge transfer step, so that a larger fraction
of electrons and holes can be transported to the active sites for chemical reaction before
recombination occurs. For this purpose, composite carbon-based materials and the
construction of the photocatalyst have been developed to speed up the electrons and holes
transport in Bi2WO6. Two common strategies are reviewed below.
63
2.6.3.1 Carbon-based Composite
Carbon-based materials are described as an excellent platform for the photogenerated
electron-hole pairs to migrate from the bulk because of the delocalised conjugated π
structure. The research on Bi2WO6 composite with reduced graphene oxide (RGO)164,
fullerene (C60)165, carbon nanotubes (CNTs)166 and carbon nitride (C3N4)133 have verified
that the carbon materials assist in accelerating charge separation and transportation.
(a) (b)
(c)
Figure 2-20.(a) The TEM image of Bi2WO6-RGO 2% nanocomposite, (b)EIS Nyquist plots, and (c) Mott
Schottky plots of bare Bi2WO6 and Bi2WO6-RGO 2% nanocomposite 167
Reduced graphene oxide (RGO) has a unique 2D planar structure and numerous surface
groups, thus possessing good electron receiving and transferring ability when combine
with Bi2WO6.164 For example, Mo et al. discovered a thin layer of RGO nanosheet densely
wrapped around the Bi2WO6 particulate when prepared with a simple hydrothermal
method. The transition electron microscopy (TEM) image of RGO/Bi2WO6 (Figure
2-20a) clearly shows the RGO is in good contact with the Bi2WO6. When comparing the
64
removal rate of Bisphenol A, RGO-Bi2WO6 was 1.5 times faster than bare Bi2WO6.167
The enhancement in the degradation rate suggested a promotion in the charge transfer, as
the electrons excited from Bi2WO6 is injected into the RGO platform and transported to
the photocatalyst active sites via the delocalised electrons in the π- π graphitic carbon
network.168 The EIS Nyquist plot (illustrated in Figure 2-20b) are utilised to reveal the
charge transport efficiency, showing a remarkable reduction in the charge resistance of
Bi2WO6 when incorporated with RGO. Moreover, the Mott Schottky plot in Figure 2-20c
indicated a more negative flat-band potential in RGO-Bi2WO6, implying stronger
reducing ability.167
Figure 2-21. A schematic diagram of the Fermi level change and the charge transfer at the interface
under light irradiation from the graphene-Bi2WO6 nanocompoiste. Ø is the work function, Ec is the bottom
of the conduction band, Ev is the top of the valence band, Eg is the band gap, and EF1, EF2 and EF* are the
Fermi levels of graphene, Bi2WO6, and the graphene-Bi2WO6 nanocomposite, respectively.169
The benefits of RGO incorporation into Bi2WO6 was further revealed by Yao et al. via
DFT calculation. The results stated a built-in electric field was generated in RGO-Bi2WO6
65
under light irradiation. The electrons from the Bi2WO6 CB were injected into the RGO
(Figure 2-21). By exploiting the advantages of the 2D conjugated π structure, which
includes the superior electrical conductivity of graphene, it prolongs the lifetime of
electron-hole pairs and facilitate a faster transfer rate of the charge carriers to the
photocatalyst active sites. Notably, the photocatalytic reaction happens not only on the
surface of Bi2WO6 but also on the graphene, in which the graphene can offer more
reaction sites for oxidation reaction.169 However, one apparent drawback of RGO-
Bi2WO6 is the poor attachment between both materials. Only a small fraction of the
Bi2WO6 surface is in direct contact with RGO, hence presenting a significant challenge
to form an effective chemical interaction (hybridised structure) across the interface. Thus,
the superior electronic properties of RGO is not fully utilised, implying a relatively low
charge separation efficiency and quantum efficiency. On the other hand, excessive
loading of RGO to improve RGO-Bi2WO6 interfacial contact could potentially result in
the RGO blocking the incident light required for photoexcitation, hence decreasing the
photocatalytic performance.168
Similarly, other carbon-based materials including carbon nanotubes and graphene-like
C3N4 have been found to facilitate the photogenerated electron transfer. All reported
carbon Bi2WO6 composite possess a similar mechanism in terms of charge transfer, where
the unique π-π coupling bond hindered the charge recombination rate and suppress the
photocorrosion phenomenon.133, 170 Therefore, development in composite carbon-based
materials have great prospect for the practical application of photocatalytic water splitting.
66
2.6.3.2 Construction of the Photocatalyst on the Photoanode
Another important aspect of Bi2WO6 application in PEC water splitting is the photoanode
fabrication. The photocurrent density recorded in PEC measurement is often influenced
by the architecture of Bi2WO6 formed on the electrode substrate. Numerous literatures
argued the orientation with a 1-dimensional (1D) structure, a thinner layer, and a lower
surface contact is preferred in the facile transfer photogenerated holes to the electrolyte
to the external circuit before they recombine.
Aforementioned, few literatures reported on the direct fabrication of Bi2WO6 photoanode,
discouraged by the slow nucleation process and unbalanced reactivity of the W and Bi
precursors that inhibit the growth of Bi2WO6 on the substrate.90 However, several studies
have demonstrated a higher photocurrent density recorded for the direct growth of
Bi2WO6 photoanode compared to those drop-casted nanoparticles electrodes during PEC
measurement.84 Development on the direct photoanode fabrication as well as the
architecture of Bi2WO6 being formed on the substrate are vital. An innovative practice
was reported by Zhang et al., where a leaf-like Bi2WO6 fabricated via hydrothermal
reaction indicated an improvement in the charge transfer properties. A short hole diffusion
length and a direct pathway for electron transport were discovered due to the well-defined
2D structure of leaf-like Bi2WO6 (exposed electron-dominant and hole-dominant crystal
facets), and shown in Figure 2-22a.84 The reason for the superior charge transport in the
2D leaf-like Bi2WO6 is due to their typical oxide nanostructure with their corresponding
charge transfer and transport behaviour as depicted in Figure 2-22b. As 3D structure
particle drop-casted on the substrate obtains numerous grain boundaries and high surface
67
state density, which has not compromised the charge transport rate. Meanwhile, the well-
aligned 1D- and 2D-structured nanoarrays of Bi2WO6 have offered a reduction in the
electron diffusion length, which enables a rapid charge transport pathway and increases
the interfacial charge separation. The improved charge transport and separation in 1D and
2D structures have seen enhanced in the photocurrent density of about 10-50 times in
PEC system compared to the 3D structured Bi2WO6 or the nanoparticle drop-casted
photoanode.171
(a)
(b)
(c)
Figure 2-22. (a) The SEM image and a schematic model display the charge transport in leaflike Bi2WO6
films in a PEC cell.88 (b) Schematic diagram illustrates three typical photoelectrodes and their
corresponding charge transport behaviour.171 (c) The charge transport mechanism under illumination of
the conventional plate-like and mesoporous Bi2MoO6.172
68
In addition, when numerous plate-like Bi2WO6 were interlaced and grown on the
substrate, the complex structure hinders the smooth charge transfer from the
photoexcitation sites to the reaction sites. Since the charge carriers will have to overcome
multiple junction barriers in addition to the substantially longer charge transport distance.
Taking an example as demonstrated by Hao’s group, the manner of the electrons being
transported in the Bi2MoO6 is proposed and displayed in Figure 2-22c. A higher surface
contact and larger material size are distinguished, resulting in a higher charge
recombination rate.172 Therefore, the leaf-like Bi2WO6 is not the ideal morphology.
Further research in this area may led to the discovery of a suitable morphology or
composite semiconductor with other strategies for charge transport enhancement.
Figure 2-23. The SEM image and the mechanism of the charge transport in monolayer nanovoid compare
to conventional Bi2WO6 electrode.102
Meanwhile, Duret et al. and Russo et al. delineated the importance of optimising film
thickness to facilitate charge transport. When the planar thickness of the thin film is down
to ultrathin or monolayer level (within 5-100 nm thick), it offers an efficient visible-light
harvest and a short hole diffusion length to reach the electrolyte/electrolyte interface.173,
174
In this regard, studies on monolayer thin film have captivated the research community
69
as it provides the prerequisite for interactions with the reactants. Bahnemann et al.
fabricated a monolayer nanovoid Bi2WO6 photoanodes with a thickness of 123.2 nm,
where a high refractive index is attained and enhances the electric field in the Schottky
region, shortening the hole diffusion length. A demonstration of the advantage of such
design is shown in Figure 2-23. The variation of electrode film thickness (< 100 nm or >
1 μm) could result in the loss of large portion of light energy or shorter charge carrier
diffusion length, respectively.102 The present literature concludes that, finding the optimal
thickness of the Bi2WO6 is necessary for the superior charge transport.
Finally but importantly, the orientation of the illumination of the light source to the
photoanode during PEC measurement could affects the transportation pathway of the
electrons and holes within the materials. It was found the back-side illumination
generated much higher photocurrent. A poor electrical conductivity is the limiting factor
of the front-side illumination, since the electrons are transported slower than the holes
across the entire thickness of the film, causing a higher chance for charge recombination
before the electrons can reach the interface between the photocatalyst and the conductive
substrate.175 Thus, an appropriate morphology construction, a thin photocatalyst layer
(especially monolayer) and back-side illumination could aids the charge transport in
photocatalysis, because more active sites and ultra-fast charge separation would give an
improvement in the photocurrent density for water splitting system.
70
2.6.4 Improvement in Photocatalyst Stability
In many cases, owing to the slow charge transport in the photocatalyst, the holes are
accumulated in the VB and cause the photocatalyst to suffer from self-oxidation
(photocorrosion). Therefore, increasing the electron-hole pair lifetime could potentially
improve the photocatalyst stability, which would allow reusability and recoverability. The
stability of Bi-based semiconductor photocatalyst is mainly affected by the intrinsic
properties, solubility, as well as the pH of the electrolyte during the reaction.176, 177
Bi2WO6 has been proposed as a stable photocatalyst, yet it is unstable in acidic
environments. Zhu et al. have demonstrated the photocorrosion of Bi2WO6 in acidic
suspension (pH < 4.7), where Bi2WO6 is dissociated and transformed to the secondary
phase of H2WO4 and Bi2O3.54 Some solid particles was produced in the suspension and
are suspected to be the reaction products between the released Bi ions and the electrolyte
(i.e. Na2SO4). Nonetheless, the study did not focus on minimising the photocorrosion.
Eventually, Choi et al. demonstrated that by introducing a layer of O2 evolution co-
catalyst on the photocatalyst surface, the stability of Bi2WO6 can be dramatically
improved. As described in the section 2.6.2.4, co-catalyst can significantly suppress the
water oxidation kinetics as it acts as a protective layer.178 In addition, heterojunction is
another strategy recommended to chemically stabilise the Bi2WO6.133, 170

Although
Bi2WO6 is unstable in acidic condition, it is notable that Bi2WO6 is a promising class of
photocatalyst used to complement other unstable semiconductors such as Bi2O3.179 Due
to the excellent electronic properties of Bi2WO6, it is able to withdraw the holes from an
unstable semiconductor to inhibit photocorrosion. However, the fundamental knowledge
remains obscure, thus further research is strongly recommended.
71
2.7 Knowledge Gap
Morphology control is one of the strategies applied to improve the Bi2WO6 particulate
performance. In general, Bi2WO6 particles with large surface area are favourable in
promoting photocatalytic performances because of larger illuminated area (i.e. more
photoexcitation) and large contact interface between the electrolyte and active sites. On
the other hand, with improved photocatalyst crystallinity, it decreases the electrons
surface trap and thus promotes the charge separation and transportation. Typically,
improved crystallinity of photocatalyst (via thermal treatment) is accompanied with a
decrease of surface area. Water oxidation process relies on both surface area and
crystallinity degree of Bi2WO6, however, limited attentions were drawn on studying the
dominating factor between these two properties. To understand and find the balancing
point of these intrinsic factors is essential for the development of Bi2WO6 for
photocatalytic water oxidation.
In the configuration of electrode, modulation of crystallinity and surface area of Bi2WO6
would be limited as compared with the powder counterpart because of immobilisation of
Bi2WO6 on a pre-determined substrate. The common strategies to improve photoelectrode
include doping, crystal facet engineering and the construction of heterojunction with other
components. The correlation between each strategy is not clear as there are limited studies
on understanding the charge behaviour, especially when the changes are dynamic and
interrelated. To construct an ideal photoanode for photoelectrochemical water splitting,
inspecting the linkage between each strategy can provide an insight in the charge kinetics
properties of the Bi2WO6.
72
As mentioned, construction of heterojunction for Bi2WO6 can be useful in promoting the
performance of photoelectrode. In general, the creation of band energy gradient at the
junction will facilitate the charge transfer across two components and therefore affording
higher utilisation efficiency of charges. Although enhanced activities were repeatedly
observed in many reports, the importance of the quality of the heterojunction is not
evaluated in most cases. The role of the interfacial contact with respect to the carrier
transportation between Bi2WO6 and secondary component is relatively less investigated.
This thesis will aim to provide insight in this aspect.
In addition to the promotion of photoactivity by constructing a heterojunction,
photocorrosion of photoelectrodes can also be suppressed when an effective
heterojunction is formed. Defects engineering can be used as a tool to modify Bi2WO6 in
order to achieve the protection function of unstable photoelectrode. Considering the
oxygen-deficient bismuth tungstate possesses surface oxygen vacancies which affects the
charge migration, its impact on suppressing the photocorrosion of oxide semiconductor
would be worthwhile to investigate.
2.8 Summary
Arise from the environmental concerns caused by the use of traditional fossil fuel,
development of sustainable and renewable energy source to replace the carbon-based is
needed. Among all renewable energy sources, photocatalytic water splitting which
produces clean H2 and O2 without leaving carbon footprint is considered an ideal process.
In this literature review, the optical and chemical structure together with electronic
73
properties of Bi2WO6 are discussed comprehensively. Bi2WO6 shows potential in
photocatalytic water splitting reaction because of its visible-light response and suitable
band energy position for water oxidation. Various synthetic method which result in
Bi2WO6 nanoparticles with controllable morphological structure are summarised. As
indicated in most literature reports, the main application of Bi2WO6 is currently focused
on the removal of aqueous-based and airborne organic pollutants. Its deep valence band
energy offers a promising oxidising power for the oxidative removal of organic pollutants.
Attributed to the similar strength of Bi2WO6, this strong oxidising power enables to
oxidise water to produce O2 via water splitting reaction. However, the overall activity is
still not satisfactory because of a few factors. Therefore, this review also discusses the
performance of Bi2WO6 in different application, and the challenges associated. In brief,
the main challenges including the blockage of the active site, shielding of light absorption,
severe recombination rate of photogenerated carriers, poor charge transportation. Due to
these drawbacks, the solar conversion efficiency in photocatalytic and PEC performance
of Bi2WO6 remains low. Strategies adopted to improve the overall performance of
Bi2WO6 are discussed and summarised. Apparently, efforts and breakthrough are required
to achieve substantial progress using Bi2WO6 before commercialisation can be considered.
Systematic and in-depth studies need to be conducted to bridge the knowledge gap within
the Bi2WO6 area towards the feasible photocatalytic and PEC water splitting.
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Chapter 3. Balancing the Crystallinity and Specific Surface Area of Bi2WO6 for
Photocatalytic Water Oxidation
CHAPTER 3
BALANCING THE CRYSTALLINITY
AND SPECIFIC SURFACE AREA OF
Bi2WO6 FOR PHOTOCATALYTIC
WATER OXIDATION
3.1 Introduction
Splitting water into molecular O2 and H2 gas as carbon-free energy carrier has been
studied extensively to overcome the energy shortage crises. Water splitting induced by
light energy was discovered by Fuijishima in 1972 by utilising the simple binary oxide
TiO2 photoanode and Pt counter electrode. Although it was the first demonstration of
solar water splitting, due to the limitation of TiO2 with a wide band gap, it is only capable
of absorbing UV light (which is approximately 5% of the solar spectrum). It triggers
further research on developing an alternative photocatalyst that is active in visible-light
range.1 Among the efforts in developing visible-light active photocatalysts, specific
attentions have been paid towards the synthesis method and morphological design of the
photocatalyst to achieve high photocatalytic performances. Bismuth-based photoactive
97
materials have attracted immense interest such as BiVO42, Bi2WO63, Bi2MoO64,
Bi2Fe4O95 and BiOX (X = I, Cl, Br)6 as a narrow band gap photocatalysts. These materials
possess unique electronic structure of the hybridised O 2p and Bi 6s valence band, which
has a narrow band gap and is active for oxidising water under sunlight.7-10
Bi2WO6 belongs to Aurivillius family, which retains a layer structure with the perovskite-
liked slab of WO6. Studies have been established on morphological alteration, crystal
facet engineering, band structure modulation and doping strategies. Nevertheless, the
insights of the predominant factors that influence the photocatalytic water splitting still
require further clarification. Despite Bi2WO6 can be synthesised into different shapes, for
instance, nano-rod, nano-cage and nano-plate, the hierarchical spherical structure is more
favourable for fabrication. This is because hierarchical spherical particles can be
conveniently synthesised in a one-pot template-free hydrothermal reaction with the
occurrence of recrystallization of metastable precursors.11 This synthetic route can
produce particles with controlled shapes and uniform sizes; it can also be scaled up and
maintains high dispersion in the solution. Furthermore, Amano et al. suggested that the
hierarchical shape of Bi2WO6 was self-assembled with numerous rectangular platelets.
Each micron-size Bi2WO6 sphere has large specific surface area and high crystallinity.
The surface area and the crystallinity of Bi2WO6 appear to be critical parameters in
photocatalytic water photo-oxidation. However, there is no further investigation on the
importance of the crystallinity and specific surface area of the particles.12 This chapter
discusses the correlations between the photocatalytic O2 generations of hierarchical
spherical Bi2WO6 and their crystallinity and surface area. It provides useful information
98
on the critical role of crystallinity in powder-suspension type photocatalytic water
oxidation.
3.2 Experimental Procedures
3.2.1 Preparation of Hierarchical Bi2WO6
The hierarchical Bi2WO6 microspheres were fabricated using the hydrothermal method
reported previously.13 In a typical process, 1.38 g of Bi(NO3)3·5H2O was dispersed in a
40 mL of 0.4 M HNO3 at 40˚C. White precipitate was formed when 30 mL of 0.05 M
Na2WO4·2H2O solution was added dropwise to the above solution with stirring at room
temperature for 24 hrs. The slurry was transferred into a 100 mL Teflon-lined autoclave,
sealed in a stainless steel reactor and heated at 160˚C for 20 hours. Subsequently, the
autoclave was cooled down to ambient temperature, and the Bi2WO6 precipitate was
obtained. The products were centrifuged with deionised water followed by drying the
samples at 80˚C. The as-prepared Bi2WO6 powders were calcined at various temperatures
between 450˚C to 750˚C for 4 hours with a ramping of 5˚C/mins, respectively. The
samples were denoted as BiWO-X in which X stands for the calcination temperature used.
3.2.2 Structure Characterisation
Scanning electron microscopy (SEM) images were taken on a FEI Nova NanoSEM 450
FESEM microscope operated at 5 kV. X-ray diffraction (XRD) patterns were obtained by
PANalytical Xpert Multipurpose X-ray Diffraction System at ambient atmospheric
temperature which applied Cu Kα radiation (λ= 1.54 Å) with a potential and current of 45
99
kV and 40 mA, respectively. Diffuse reflectance spectra were obtained on a UV-3600
UV-VIS-NIR spectrometer and Kubelka-Munk plots were constructed. The Brunauer-
Emmett-Teller (BET) surface areas were measured from Micromeritics Tristar 3000
nitrogen adsorption apparatus. Steady-state photoluminescence (PL) emission spectra
were measured by Horiba Fluoromax-4 spectrofluorometer with 320 nm as the excitation
light source. The Raman spectra were acquired on the Renishaw inVia spectrometer
utilising a 514 nm wavelength of Argon ion laser with 1800 lines/mm grating. The X-ray
photoelectron spectroscopy (XPS) was performed on an ESCALAB250Xi with mono-
chromated Al Kα (energy 1486.68 eV) as the excitation source. The C ls was set to 284.8
eV as the reference for each specimen charge to correct the binding energy achieved in
the XPS spectral analysis.
3.2.3 Photocatalytic Oxygen Generation
Photocatalytic O2 evolution reaction was carried out in a top-irradiated quartz window
sealed cell with a 300 W Xe lamp. 100 mg of as-synthesised powder was dispersed in
0.05 M of 100 mL aqueous AgNO3 solution. Argon has been purged through the aqueous
solution for 30 minutes to remove air and dissolved O2. The O2 evolved was analysed
using a gas chromatography (Shimadzu GC, 8A) equipped with a thermal conductivity
detector and a packed column.
100
3.2.4 Photoelectrochemical Activities
The Bi2WO6 samples were first deposited on carbon paper (as electrode) by the drop-cast
method. The Bi2WO6 samples were suspended in ethanol solution and deposited on
carbon paper of 1.5 cm x 2 cm dimension. The photoelectrochemical (PEC) measurement
was conducted using three electrodes system (where the Bi2WO6 electrode, Pt foil and
Ag/AgCl (1 M) acted as working, counter and reference electrode, respectively) by a
potentiostat (Autolab PGSTAT12). A Xenon lamp was used as the light source while an
aqueous solution of 0.1 M sodium sulphate was used as the neutral electrolyte.
3.3 Results and Discussion
3.3.1 Physical Properties of Hierarchical Bi2WO6 microspheres
Figure 3-1. (a) XRD patterns, (b)(i) Raman Spectra and (b)(ii) Raman shift at 796 cm-1 and 826 cm-1
of the Bi2WO6 particles calcined at different temperatures
The crystal structure and the phase purity of the as-synthesised product were examined
by XRD as shown in Figure 3-1a. The characteristic peaks detected at 28.3˚, 32.7˚, 47.0˚,
101
and 55.8˚ are indexed to pure phase of orthorhombic Bi2WO6, (JCPDS 79-2381).14
Despite a higher calcination temperature applied to Bi2WO6, there are no significant
changes in the intensity ratios among the peaks. Noticeably, crystallinity of the Bi2WO6
has improved when calcination temperature increased. The degree of crystallinity
describes the position of the atoms or the molecules arrangement in the photocatalyst, and
the amorphous or semicrystalline framework is minimised when crystallinity enhanced.
Yu et al. stated the crystallinity can be estimated from the peak intensity of the XRD
pattern.15 Figure 3-1a illustrates evidently that the XRD peaks become narrower and
sharper that the peak intensities become stronger; a distinct split peak can even be
observed after heat treatment, supporting the observation of improved crystallinity. The
crystallite size of Bi2WO6 is calculated using Debye-Scherrer’s equation:
𝐾𝜆
𝐷= Eqn. (3-1)
𝛽𝑐𝑜𝑠𝜃
where D is the average of crystallite size, K is a constant taken as 0.9, 𝜆 is the wavelength
of the X-ray radiation used (Cu Kα = 0.154 nm), β is the band broadening full width half
maximum (FWHM) of the dominant peak and Ө is the diffraction angle. In this case, an
increase in the crystallite size was achieved when Bi2WO6 was calcined at high
temperatures, in which the calculation was based on the most intense peak at 28.3˚ with
the orientation of (113) (Table 3-1).
Furthermore, the Raman spectra of each Bi2WO6 samples were evaluated and shown in
Figure 3-1b(i). Raman spectroscopy is a reliable technique capable of probing the
molecular structure of materials, in which it reveals the bonding states and the interactive
102
forces in the coordination of a material. All the major vibration bands exhibited from the
as-prepared Bi2WO6 are 112 cm-1, 141 cm-1, 150 cm-1, 181 cm-1, 208 cm-1, 224 cm-1, 260
cm-1, 283 cm-1, 306 cm-1, 333 cm-1, 416 cm-1, 705 cm-1, 721 cm-1, 796 cm-1, and 824 cm-
1
. These fundamental bands match with the orthorhombic Bi2WO6 as in the reported
literature.16 Among all the bands, the characteristic Raman bands are located below 200
cm-1 as those bands are attributed to the lattice modes of the Bi ions. The bands in the
range of 200-1000 cm-1 are corresponding to the W-O stretching mode of WO6
octahedra.17 Figure 3-1b(i) shows a decrease in intensity for 285 cm-1 band (I285) while
the intensity of the peak at 306 cm-1 (I306) was increased upon elevated annealed
temperatures. This 306 cm-1 band is attributed to the translational modes of the
participating motions of Bi3+ and WO66-.18 The growth of this peak reflects the
rearrangement of the crystal structure, especially related to the W-O stretching bond
within the entire particle under high temperature.19 Besides, 721 cm-1 band is assigned as
the anti-symmetric bridging mode of WO6 octahedra with the bridging mode connected
to the O2 atoms within the layers. The intense bands at 796 cm-1 and 824 cm-1 are ascribed
as the anti-symmetric and symmetric stretching modes of the Ag terminal O-W-O groups,
respectively. As can be seen from Figure 3-1b(ii), slight negative and obvious positive
shifts are observed at the peak positions of 796 cm-1 and 824 cm-1, respectively. Also, an
increase in the ratio between these two peaks is observed. Nonetheless, the shifting has
stopped and reversed at the BiWO-750 samples. The relationship between Raman
stretching frequency and bond length was found to express in a simple exponential form:
υ = 25823 exp(-1.92R) Eqn. (3-2)
103
where υ is the Raman stretching frequency in wavenumbers and R is the W-O bond length
in angstroms.20 Therefore, the positive shifting of the stretching modes, 824 cm-1,
demonstrates the conformation of the shortened bond length when the crystallinity of
Bi2WO6 improved at elevated annealing temperatures. This has led to a firm interaction
of the metal-oxide but with a distorted structure.21
Table 3-1. Comparison of the Raman band intentisy between different wavenumber
Bi2WO6 Calcination Temperature (˚C) I285/I306 I796/I824

Uncalcined 0.84 1.22
450 0.87 1.70
550 0.98 2.45
650 1.04 2.76
750 1.01 3.07
3.3.2 Morphology Study
The morphological evolution of the Bi2WO6 samples annealed at elevated temperatures
was monitored under SEM as presented in Figure 3-2a to e. All SEM images reveal the
3-dimensional hierarchical microspheres, and each individual microsphere is composed
of an accumulation of nanometre size rectangular plates. As the calcination temperature
increases, the particle size of each Bi2WO6 microsphere remains comparable with the
diameter of 3-4 µm. It is generally perceived that the formation of Bi2WO6 microspheres
initiated from nucleation, followed by self-aggregation and Ostwald ripening process to
104
reach the final hierarchal structure. Further controls required for obtaining a
homogeneous sized and distributed hierarchical particle include the temperature of the
reaction process, pH, crystal growth time and the nature of the precursors. It has been
discovered that flower-liked particles could only be synthesised in an acidic reaction
medium (below pH 3) and requires sufficient growing time for aggregation of the
nanoplates to occur in forming Bi2WO6.13, 17 In this work, the SEM images demonstrate
that an increase in the thickness of the individual nanoplate of the hierarchical particles
is achieved with an increase in the calcination temperature. As a result, the exposed
surface area of the lateral surface has been raised. Although the continuing growth of
nanoplates was observed, the architecture of hierarchical shape was noticeably deformed
when temperature beyond 550˚C was used. Each nanoplate in the hierarchical Bi2WO6
microsphere has transformed from a rectangular shape to nano-ovoid. Deformation of
these nano-ovoids into largely fused particles was observed when 750°C applied, in
which a schematic diagram (Figure 3-2f) illustrates the growth of individual nanoplate
with a microsphere.
Figure 3-2. SEM images of Bi2WO6 samples calcined at different temperatures: (a) untreated, (b) 450˚C,
(c) 550˚C, (d) 650˚C, (e) 750˚. (f) Schematic diagram of the evolution of individual nanoplate within a
microsphere.
105
The surface area of Bi2WO6 was measured by BET and the results are summarised in
Table 3-2. Although no obvious difference in the particle size of each microsphere, the
uncalcined Bi2WO6 has a relatively large surface area and the surface area decreases
accordingly with higher calcination temperatures. The photocatalytic activity might be
influenced with a higher surface area of the semiconductor being exposed to reactant (i.e.
water in this study) which could provide more catalytic sites for water oxidation.16 A
drastic decrease in the specific surface area in respect of the elevated calcination
temperature of Bi2WO6 was attained, especially it reduced from 22.51 m2g-1 to 0.71 m2g-
1
when Bi2WO6 was heated up to 750˚C. The SEM images reveal that all individual plates
of BiWO-750 were agglomerated into a significantly fused ball shape thus leading to a
sharp shrinkage in their surface area. Interestingly, the surface area of BiWO-550 is
almost the same as that of BiWO-650 (approximately 4 m2g-1). It is mainly because of the
morphological evolution from the accumulated rectangular plate into a porous nano-
ovoids structure. Figure 3-3 illustrates the pore-size distribution of the Bi2WO6. Although
a similar pore diameter of 4 nm was observed for both BiWO-550 and BiWO-650 samples,
the latter has a higher pore volume. Thus, the hierarchical shape of BiWO-650 has
essentially transformed into interconnected small nano-ovoid with the existence of pores
which facilitated large accessible surface area for nitrogen in the BET measurement. As
a result, a similar surface area was achieved for both BiWO-550 and BiWO-650. This
morphological evolution can be considered as an appropriate platform for diffusion of
small molecules (including water) to enhance the photocatalytic performance.13
106
Table 3-2. Crystallite size and surface areas of each photocatalyst
Bi2WO6 Calcination Temperature (˚C) Crystallite Size (nm) Surface Area (m2g-1)
Uncalcined 12.9 22.52
450 25.0 8.11
550 47.7 4.01
650 57.6 4.22
750 69.6 0.71
Figure 3-3. Pore-size distribution of Bi2WO6 at different calcined temperatures
3.3.3 Optical and Electronic Properties
The optical band gaps were evaluated by UV-vis spectroscopy and the spectra are shown
in Figure 3-4. Most samples have similar absorbance an absorption edge of 430 nm. Tauc
plots of the UV-Vis spectra were constructed in the inset of Figure 3-4. The band gap
energies of the fabricated samples could be determined from the edge of the absorbance
107
recorded from the (αhv)2 versus the photon energy plot. In general, there is no significant
difference in the band gap for Bi2WO6 after calcining at various temperatures. They
remain in consistent with the reported literature value at ca. 2.9 eV.14 However, BiWO-
750 has a slight red shift towards a band gap of ca. 2.85 eV, in which it has the ability to
absorb further in visible-light range although the origin for this minor band gap narrowing
is not known at this stage.
Figure 3-4. UV-Vis absorption spectra of Bi2WO6 microsphere
108
3.3.4 Photocatalytic Water Oxidation using Bi2WO6 Microspheres
Figure 3-5. Photocatalytic O2 generation from aqueous AgNO3 solution using Bi2WO6. The result in each
experiment was an average over 3 runs with error bars corresponding to standard deviation.
Zheng et al. have suggested that photocatalyst with high surface area could enhance the
photocatalytic performance, as it creates more active sites for the photoactive
semiconductor to contact with the reactant in the suspension for water oxidation.22 On the
other hand, there are other researchers mentioned that improvement in the crystallinity of
the photocatalyst will lead an improved photocatalytic activity owing to the repair of
crystal defects which decelerate the time for charge carrier recombines. In this work,
hierarchical Bi2WO6 microspheres were employed to oxidise water in the presence of
AgNO3 electron scavengers under the light irradiation and the result are displayed in
Figure 3-5. The sequence of the photocatalytic activities obtained is untreated Bi2WO6 ≈
BiWO-450 < BiWO-750 < BiWO-550 < BiWO-650. It is clear that the Bi2WO6 calcined
109
at 650˚C released the highest amount of O2 during the reaction which produced
approximately 240 µmol after 6 hours illumination. Although BiWO-750 should generate
a relatively more O2 theoretically due to their highest crystallinity among the samples, the
photocatalytic oxidation was markedly deteriorated. 650˚C is the optimum calcination
temperature for the hierarchical Bi2WO6 microspheres to obtain the benefits of improved
crystallinity while not suffering from drastic drop in the surface area in facilitating water
oxidation.
Uncalcined
450˚C
Intensity (a.u.)
550˚C
650˚C
750˚C
330 350 370 390 410 430 450 470 490 510 530 550
Wavelength (nm)
Figure 3-6. (a) PL emission spectra of Bi2WO6 with excitation wavelength of 320 nm.
The improvement in the crystallinity of a photocatalyst possesses the ability to suppress
photo-excited charge carriers result in enhancement in photocatalytic performance, as
suggested by the PL analysis. The PL emission spectroscopy is a useful technique to
analyse the effectiveness of the separation of the photoinduced electrons and holes pairs
in a semiconductor. It is well established that higher the intensity recorded from the PL
emission spectrum reflects the semiconductor undergoing rapid recombination rate of the
free carriers.23, 24 Figure 3-6 shows a comparison of the PL spectra (excited at 320 nm)
110
for all the Bi2WO6 samples. The wavelength of the PL emission is comparable for all
samples reflecting the similar photoexcitation behaviour. However, the
photoluminescence intensity decreased accordingly when higher calcination temperatures
were applied. The emission peaks centred in between 370 nm and 390 nm are believed to
be attributed to the oxygen vacancies related to the defects emissions.25 The shoulder
peaks detected at 460 nm is ascribed as the trapped free electrons derived from the surface
defect in the conduction band. The PL results supported that higher crystallinity (also
with larger crystallite size) comes with the suppression of the recombination rate of the
charge carriers. This feature is favourable to enhance the photocatalytic activities as the
photoexcited charge carriers lifetime will be prolonged and it promotes the ability of
interfacial charge transfer to the adsorbed substrate.26 The results demonstrate that the
improvement in crystallinity of the hierarchical Bi2WO6 microspheres contribute more
significantly than that of surface area in the photocatalytic system. In spite of the surface
area has being halved and thus the active sites, the improved photocatalytic activities were
still observable owing to this suppression of charge recombination facilitated by the better
crystallinity.
111
(a) (b) (c) O1s

750°C Bi 4f7/2 Bi4f 750°C W 4f7/2 W4f 750°C
W 4f5/2
Bi 4f5/2
650°C 650°C 650°C

Intensity
Intensity
Intensity untreated
untreated untreated
168 166 164 162 160 158 156 41 39 37 35 33 535 533 531 529 527
Binding Energy (eV) Binding Energy (eV) Binding Energy (eV)
Figure 3-7. XPS spectra of (a) Bi 4f, (b) W 4f for Bi2WO6 and (c) O 1s spectra for Bi2WO6
Surface composition and the chemical state of the element in Bi2WO6 were measured by
XPS. According to the XPS spectra of the uncalcined, BiWO-650 and BiWO-750, all
samples are composed of Bi, O, and W only. In the Bi 6f spectrum of Bi2WO6 (Figure
3-7a), the sample possesses two signals at binding energies of 159.3 eV (Bi 4f7/2) and
164.6 eV (Bi 4f5/2), which are attributed to the Bi in the Bi3+ oxidation state. The peaks
located at 35.6 eV (W 4f7/2) and 37.7 eV (W 4f5/2) are assigned to the W6+ oxidation
state.18 Interestingly, uncalcined Bi2WO6 contains new doublet peaks located at 161.2 eV
and 166.6 eV in the core spectrum of Bi 4f, as well as the doublet peaks at 36.6 eV and
38.7 eV in the core spectrum of W 4f. These are ascribed as the doped ions Bi 4+ and/or
Bi5+ in replacing W6+.27 Such high oxidation state is reflecting a breakage in the W-O-W
bond leads to the substitution of Bi4+/Bi5+ for W6+ during the synthesis process. The
replacement is subjected to the reduction of the number of Bi valence electrons on the
112
surface and will create oxygen vacancies on the surface in this manner. Oxygen vacancies
introduce new subgap states which could improve charge transport and extend the light
absorption ability. Nonetheless, the doped ions do not aid the oxidation of water into O2
since the ions do not contain a strong metal oxygen bond. The O 1s peaks displayed in
Figure 3-7c can be deconvoluted into three different peaks, where the binding energies
are found to be at 530.7 eV, 531.7 eV and 533.23 eV, which are corresponding to the
chemical bonding of W-O, Bi-O and surface adsorbed hydroxyl oxygen, respectively.
The O 1s level has shifted to a higher binding energy by ~0.6 eV in the uncalcined
Bi2WO6, which suggests that a weakened interface between the metal and the oxide.18 It
has proved from the Raman spectra that the length of the W-O bond has shortened which
reflects stronger bond interaction. Tan et al. have also reported that shorter W-O bond
length leads to the overlapping of Bi 6p and O 2p orbital, where these overlapping
enhanced the migration of photo-excited holes of the surface of Bi2WO6 to improve the
photocatalytic reaction.28, 29 Thus, the benefit of possessing stronger W-O bonding is the
suppression of the recombination rate of the photoinduced charge carriers from the
interior to the surface of Bi2WO6. Furthermore, the doped ion from the uncalcined sample
has disappeared, while the thermal treatment has strengthened the interaction of unit cell
and resulted in the reduction of the interlayer spacing, altering the crystal lattice of
Bi2WO6.
Additionally, the PEC performances of the hierarchical Bi2WO6 microspheres also
suggested a less decisive role of surface area in the photocatalytic system (Figure 3-8).
At low anodic bias (+0.1 V) in which the photocurrent generated is more determined by
113
the intrinsic charge transportation behaviour of the Bi2WO6, BiWO-650 recorded the
highest photocurrent density, compared to those with higher surface area (i.e. uncalcined
BiWO, BiWO-450 and BiWO-550). In contrast, at a much higher anodic bias (+0.75 V)
in which this external bias is sufficient to overcome the internal charge transportation
within the Bi2WO6 grains, all samples generated similar photoresponse at ca. 1 µA/cm2.
Note that BiWO-750 has the lowest PEC performance due to weak adhesion on the
electrode. Combined the two investigation of photocurrent density recorded at +0.1 V and
+0.75 V, it suggests that the surface area parameter is less determining factor for
photocatalytic performances as the activities were more relied on the quality of the charge
transportation (which is a property defined by crystallinity). Thus, it is reasonable to
observe poorer photocatalytic activities in the uncalcined Bi2WO6 and BiWO-450
although both have the relatively higher surface area with more active site. It is expected
that the improvement in the crystallinity and the presence of the nanopores morphology
in BiWO-650 facilitated a shortened charge diffusion length, thus increases the
photocatalytic efficiency. Given the results from Raman spectra which revealed a shorter
W-O bond length (indicated by the positive band shifting) in BiWO-650, it also suggested
the distortion of lone pair around Bi cation which can facilitate the active Bi lone pairs
for photo-oxidation reaction.30, 31 It is also confirmed in this work that obtaining high
surface area is not as significant as that of high crystallinity in ensuring a better
photocatalytic water oxidation.
114
(a) 4.5 (b) 13

750˚C
750˚C
12
4
11
Photocurrent Density (µA/cm2)
Photocurrent Density (µA/cm 2)

Light on 650˚C
3.5 Light on Light off Light off
650˚C 10
9
3
8 550˚C
2.5 550˚C 7
2 6
450˚C
5
1.5 450˚C 4
1 3
Bare
2
0.5 Bare
1
0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Time (seconds) Time (seconds)
Figure 3-8. Photocurrent density of hierarchical Bi2WO6 calcined at various temperatures with bias of
(a) 0.1 V and (b) 0.75 V vs Ag/AgCl
3.4 Summary
In this first study, a hierarchical microsphere of Bi2WO6 was self-assembled with
numerous rectangular platelets was achieved via hydrothermal reaction. The crystallinity
improvement along with a decreased in surface area of Bi2WO6 was attained by
implementing thermal treatment towards the photocatalyst. The experimental results in
the photocatalytic water oxidation activities and photoelectrochemical measurements has
highlighted the crystallinity of the Bi2WO6 is the major priority factor in the preparation
of an efficient photocatalyst when comparing with surface area. The optimal balance
between crystallinity and surface area was found the calcination temperature at 650°C for
Bi2WO6. At this Bi2WO6 annealed at 650°C generated the highest amount of O2, up to
240 μmol of O2 was evolved. Although the large surface area can provide more active
sites for reactions, photocatalytic performances are more reliant upon the quality of the
115
charge transportation behaviour of a photocatalyst, in which charge transportation is
highly dependent on the crystallinity.
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Chapter 4. Manupulating the Fate of Charge Carriers with W Concentration:
Enhancing PEC Water Oxidation of Bi2WO6
CHAPTER 4
MANIPULATING THE FATE OF
CHARGE CARRIERS WITH W
CONCENTRATION: ENHANCING
PEC WATER OXIDATION OF
Bi2WO6
4.1 Introduction
In the previous chapter, the hierarchical spherical Bi2WO6 was examined and illustrated
that crystallinity was the predominant factor in order to enhance in photocatalytic water
oxidation. Aside from powdery system, the photoelectrochemically separating water to
produce H2 as an alternative energy resource to substitute the non-environmentally
friendly fossil fuels also attracted attention. Recent research focused on developing an
efficient semiconductor that harvests sunlight to generate sufficient charge carrier for the
water splitting reaction. Kim et al. have reported the benchmark TiO2 drives a superior
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photoactivity performance by engineering the crystal facet.1 However, TiO2 has a wide
band gap of 3.2 eV that requires ultraviolet light for photoactivation.
Conventional strategies such as coupling with another active photocatalyst to form
heterojunction, loading co-catalyst, and doping with metal have played a conspicuous part
in the improvement of photoelectrochemical (PEC) performance. TiO2-Cu2O/CuO2, and
N-modified TiO23 overcome the limitation of TiO2 by expanding the light absorption into
the visible range. These modifications also provide charge trapping sites for the
photogenerated carriers, which improves the charge separation and electron transport
efficiency. However, the modified photocatalysts require two-step fabrications to prepare
the photoanode.
Bismuth tungstate (Bi2WO6), on the other hand, is a promising Aurivillius family of layer
perovskite-like Bi-based metal oxide. The Bi 6s and O 2p orbital interaction at the top of
the valence band has a relatively smaller band gap, allowing photoactivation under
visible-light. In an earlier study, Ohtani and co-worker have revealed the performance
could be enhanced by increasing the relative amount of W during the fabrication of the
flake-ball Bi2WO6 particle.4 Generally, the catalytic efficiency of a photocatalyst is
dictated by its crystal structure, crystal size, surface area and morphology. However, the
work of Ohtani et. al., the influence of excessive W content in the precursor solution on
the physiochemical properties of Bi2WO6 was not clarified.
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In this work, low-cost plate-like Bi2WO6 photoanodes are simply synthesised by a one-
pot hydrothermal reaction with different concentrations of W. The charge transport
properties of the plate-like Bi2WO6 is elucidated by deeply investigating the carrier
density, charge mobility, charge separation and the charge transfer resistance of the thin
film, as these are interrelated during the water oxidation process. Aside from that, the
excessive W has identified to induce ‘self-doping’, leading to higher charge carrier
density and lower charge transfer resistance, which greatly enhance the PEC performance.
4.2 Material and Method
4.2.1 Preparation of Bi2WO6 Film
All the chemicals received were of analytical grade and were used without further
purification in the present work.
The Bi2WO6 films were fabricated via a simple hydrothermal reaction. First, the
transparent conducting fluorine-doped tin oxide glass (FTO, 1.5 cm × 5 cm in size) was
washed with acetone, ethanol and water consecutively under sonication and dried in air
before use. Subsequently, the cleaned FTO was placed inside a 100 mL Teflon-lined
autoclave, leaning vertically against the Teflon wall. Before the hydrothermal reaction, 2
mmol of Bi(NO3)3·5H2O was dissolved into 14 mL of ethylene glycol under sonication
until a colourless solution was obtained. After that, 2 mmol of EDTA was added, followed
by dropwise addition of Na2WO4·2H2O at various concentration to the above solution to
achieve a total of 70 mL. The concentration of Na2WO4·2H2O used was 1, 2, and 3 mmol,
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where the mole ratio of W to Bi were 0.5, 1.0, and 1.5, respectively. 2.5 M NaOH was
used to adjust the solution until it reached pH 9. After 1 h of stirring, the solution was
transferred into the above 100 mL Teflon-lined autoclave (with the FTO glass) and kept
at 180˚C for 20 h. The as-synthesised sample was rinsed with water and annealed in air
at 450˚C to enhance the crystallinity of the products.
4.2.2 Photodeposition of Ag and MnOx
For the photodeposition, Ag and MnOx were photodeposited on the photocatalyst by
immersing the Bi2WO6 thin film in a solution containing 0.25 mM of AgNO3 and 0.88
mM of MnCl2·4H2O for 30 minutes under irradiation (300 W Xe lamps), respectively.
Constant stirring and argon purging in the electrolyte was performed throughout the
photodeposition.
4.2.3 Characterisation
The morphology of each thin film was analysed under scanning electron microscopy
(SEM, FEI Nova NanoSEM 450 FE-SEM). Transmission electron microscopy images
(TEM) images were obtained by Philips CM200 instrument and the corresponding
energy-dispersive X-ray spectroscopy (EDS) of the elemental mapping were determined
by scanning transmission electron microscope (ac-STEM, JOEL JEM-ARM200F) at an
electron accelerating voltage of 200 kV. Structural properties were examined by
PANalytical Empyrean Thin-Film X-ray diffraction (XRD) using Cu Kα radiation (λ =
1.5406 Å) with a voltage of 45 kV and current of 40 mA at room temperature. The UV-
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visible diffuse reflectance spectra were measured by Perkin Elmer Lambda 950
spectrophotometer equipped with integrating sphere. X-ray photoelectron spectroscopy
(XPS) was performed using the ESCALAB250Xi instrument with mono-chromated Al
Kα (1486.68 eV) X-ray source. Raman spectroscopy was carried out with Reinshaw inVia
Spectrometer and utilising an argon ion laser (λ = 532 nm, 1800 lines/mm grating). The
conductive atomic force microscope (cAFM) image was taken using the JEOL 5400 MkII
Environmental SPM. The surface conductance and the current-voltage (I-V) behaviour of
the thin films were acquired with a Platinum-coated silicon probe (SCM-PIC-V2 from
Bruker AFM probes) in contact mode. A bias voltage of V = ± 20 V was applied to the
sample under ambient temperature, and the corresponding current was measured with a
current pre-amplifier, both in the presence and absence of UV light. The light source taken
was equipped with a 20 mWcm-2 fibre-coupled LED lamp at an angle of 20˚. The time-
resolved photoluminescence (TRPL) was measured by the time-correlated-single-photon-
counting technique on Microtime 200 system (Picoquant) with the excitation of a 373 nm
pulse laser. For the time-resolved microwave conductance (TRMC) measurement was
performed under a 355 nm microwave source (Q-switched Nd:YAG laser). The samples
were prepared by drop-casting the sample powders (removed from the thin film by
ultrasonication) onto a 25 mm x 12 mm quartz window. The photoexcited carrier in the
form of conductance (G) was determined by equation Eqn. (4-1). The microwave power
from the cavity (P/P) was detected throughout the measurement with the resonant
frequency of 8.15 GHz. Next, the correlation between the total of the carrier mobility (Σµ)
and the photoconductance was determined with equation Eqn. (4-2).
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∆𝑃 Eqn. (4-1)
(𝑡) = −𝐾∆𝐺(𝑡)
𝑃
∆𝐺 Eqn. (4-2)
𝜙∑𝜇 =
𝐼𝑜 𝛽𝑒𝐹𝐴
4.2.4 Photoelectrochemical Measurement
The photoelectrochemical (PEC) measurement including the electrochemical impedance
spectroscopy (EIS) was conducted with Autolab model PGSTAT 12 potentiostat in a
three electrode system (the photoanode thin film, Pt foil, and Ag/AgCl were used as the
working electrode, counter electrode and reference electrode, respectively) in an
electrolyte of 0.1 M Na2SO4. An area of 0.72 cm2 was illuminated with an equipped light
source of 300 W Xe lamps. The Nyquist plot was carried out in the frequency range from
0.1 to 10000 Hz at the potential of 0.5 V vs Ag/AgCl under illumination using the same
condition for the PEC measurement.
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Figure 4-1. SEM images of (a) Bi-W1 (b) Bi-W2 (c) Bi-W3 fabricated with 1 mmol, 2 mmol and 3 mmol of
Na2WO4·2H2O, respectively. (d) HRTEM (inset are the FFT (left) and TEM images (right)) of the Bi-W1.
(e) A schematic illustration of the crystal structure of Bi2WO6.
Plate-like Bi2WO6 thin films were grown directly on FTO substrates through
hydrothermal method using various concentrations of W. At a low W concentration (1
mmol), Bi2WO6 of distinct sheet-like structure with single plate length of ca. 4.8 µm and
thickness of ca. 24 nm was observed from the scanning electrons microscopy (SEM)
image (Figure 4-1a). Interestingly, when higher W concentrations of 2 mmol or 3 mmol
were employed, the length of the Bi2WO6 plate was reduced to ca. 2.9 µm and 1.6 µm
(Figure 4-1b and c), respectively. Meanwhile, the thicknesses of the plates have increased
to ca. 55 nm and 104 nm. Hereafter, the resultant samples fabricated with 1 mmol, 2
mmol, and 3 mmol of W precursors (Na2WO4·2H2O) are denoted as Bi-W1, Bi-W2 and
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Bi-W3, respectively. Despite the distinct amount of W precursor, all three samples were
shown to be densely grown on the FTO substrate with well-defined interlacing Bi2WO6
plates, as observed in Figure 4-2.
5 µm 5 µm 5 µm
Figure 4-2. Photograph of the as-prepared thin films of (a) Bi-W1, (b) Bi-W2 and (c) Bi-W3 with
corresponding SEM images
To identify the exposed facet of the samples, a fragment of Bi-W1 was scratched from
the resultant thin film for dark-field TEM analysis. Close examination of the high-
resolution TEM (HRTEM) image revealed the existence of distinctive lattice spacing in
the sample. As demonstrated in Figure 4-1d, the lattice fringes with d spacing of 2.74 Å,
2.76 Å, and 1.95 Å correspond to the (060), (002) and (260) planes of orthorhombic
Bi2WO6, respectively. In addition to the successful formation of plate-like Bi2WO6
observed under TEM (inset of Figure 4-1d), a labelled angle of 90.2˚ was measured from
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its corresponding fast Fourier transform (FFT) image. The angle is equivalent to the
theoretical angle between the (060) and (002) facet5, consistent with both facets being
perpendicular to each other. Based on the above characterisations, the dominant top and
bottom surfaces are corroborated to be {100} facet while the lateral sides of the Bi2WO6
plate belong to the family of {010} and {001} facets. The schematic illustration of the
crystal facet family for a single Bi2WO6 plate is shown in Figure 4-1e.
(a) (b) (c)

(040) (262)
plane plane
Bi-W3
Bi-W2 Bi-W3
Bi-W1 Bi-W2
Bi-W1
Figure 4-3. (a) XRD diffraction pattern, (b) the prominent {010} peaks and (c) the prominent {101} peaks
of Bi-W1, Bi-W2 and Bi-W3 locate at 2Ө = 19.4˚ and 58.4˚.
Table 4-1 The ratio of {010}/{101} plane from the XRD diffraction pattern
Sample {010}/{101} ratio
Bi-W1 0.69
Bi-W2 0.91
Bi-W3 0.93
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Figure 4-3a demonstrates the XRD patterns of Bi-W1, Bi-W2 and Bi-W3 samples. The
development of distinct diffraction peaks that are readily indexed to an orthorhombic
phase of Bi2WO6 (JCPDS No. 39-0256) has signified the growth of pure and highly
crystalline samples. Although all three samples exhibited the same diffraction peak
positions, the ratio of (040)/(262) peaks that were observed at 2Ө = 19.4˚ and 58.4˚
(Figure 4-3b and c) confirmed the increase in thickness of the crystal. Mclaren et al. have
clarified that the relative intensity of two XRD peaks could represent the change in
particle shape.6 Therefore, the larger ratio of (040)/(262) exhibited by Bi-W3 was
attributed to the growth of {010} facet (Table 4-1). In accordance to the SEM images
(Figure 4-1c), the XRD results delineated the preferential growth of the Bi2WO6 crystal
in the z-direction (Figure 4-1e) when W rich medium was used as the feed solution.
Furthermore, the optical absorption of the Bi2WO6 thin films in Figure 4-4 shows that
the measured absorption band edge (λ) of Bi-W1, Bi-W2 and Bi-W3 are 425 nm, 429 nm
and 431 nm, respectively. These resulted in the optical band gap energies of ca. 2.9 eV,
which are similar to the previously reported band gap value of Bi2WO6. 7, 8
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Figure 4-4. UV-visible spectrum of Bi-W1, Bi-W2 and Bi-W3.
Though the above characterisations, increasing amount of W precursor were shown to
alter the particle size and the thickness of {010} facet of the Bi2WO6 plate. The change
in crystal morphology is attributed to the change in growth direction, in which the possible
formation mechanism of the Bi2WO6 plate is proposed in Figure 4-5. First, EDTA acting
as a chelating agent plays a crucial role in coordinating itself with the Bi3+ ions to form
[Bi(EDTA)-] complex. This prevented the spontaneous precipitation of Bi3+ with WO42-,
which retarded the Bi2WO6 grain growth.9 Under high temperature and pressure, the
hydroxyl molecules from ethylene glycol were reacted with NaWO4·2H2O to produce
WO42- anion.10 Meanwhile, the [Bi(EDTA)-] complex bond was weakened, resulting in
the gradual release of Bi3+ ions. The increasing concentration of Bi3+ free ions in the
solution promotes the reaction with WO42-, forming Bi2WO6 nuclei on the FTO substrate.
After prolonged growth of Bi2WO6 nuclei, plate-like Bi2WO6 was obtained via the
Ostwald ripening process.11 It is noted that during this process, the alkaline medium of
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the feed solution aids to hinder the aggregation of the plates to form a hierarchical ball.4
Zhang et al. has stated the ability of EDTA to control the growth of the particle along
different crystal axes. Since different exposed facets possess distinct surface energies,
EDTA2- molecules were known to preferentially adsorb on the active {010} facet.5 Thus,
more [Bi2O2]2- layers were built in x- and y-directions at low W mole ratio, forming a
thin and large Bi2WO6 sheet. On the other hand, excess WO42- competes with the released
EDTA at the {100} facet, and the [Bi2O2]2+ layers were more likely to construct a
sandwiched structure with WO6 octahedral layers. As a result, an extensive exposed area
of {010} facet was generated12, 13, which is consistent to the above findings.
WO42- Bi3+ EDTA Bi(EDTA)- Bi2WO6
Figure 4-5. Schematic diagram of the plate-liked Bi2WO6 formation
In order to explore the impact of W concentration on the PEC performance, chopped
linear sweep voltammetry measurements of Bi-W1, Bi-W2 and Bi-W3 were conducted
(LSV, Figure 4-6a). The results indicated that the PEC performances followed the trend
of BI-W1 < Bi-W2 < Bi-W3. The photocurrent density of Bi-W3 reached a maximum
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value of 1 mA/cm2 at 1.0 V vs Ag/AgCl. Besides, anodic and stable photocurrent densities
are observed from the corresponding amperometric I-t curves at an applied voltage of 0.5
V vs Ag/AgCl (Figure 4-6b), reflecting the n-type behaviour of the highly stable Bi2WO6
samples. More importantly, the amperometric results also demonstrated the same
photoactivity trend as the LSV measurements, which implied that the thin film fabricated
with higher W concentration (Bi-W3) exhibited an enhanced PEC performance. A similar
observation has also been reported by Amano et al., where the excess W precursor used
during the synthesis of Bi2WO6 was recognised to promote the photoactivity.4 Since the
variation of W concentration has led to the difference in Bi2WO6 morphologies which in
turns affects the charge transport properties, understanding the samples from the
perspective of electrical conductivity, charge mobility, charge transfer, charge separation,
and internal impedance is imperative to determine the factors that governing the
photoactivity. Contribution of the light absorption ability to the enhanced performance is
deemed negligible, given the similar absorption and band gap energy (Figure 4-4).
(a) (b) 0.60

1.4
Bi-W3
1.2 Bi-W3 Bi-W2
Photocurrent Density (mA/cm2)
Photocurrent Density (mA/cm 2)
0.50
Bi-W2
Light on Bi-W1
Light off
1.0
Bi-W1 0.40
0.8
0.6 0.30
0.4
0.20
0.2
0.0 0.10
-0.2 0.00
-0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 400 500 600 700 800 900 1000
Potential (V vs Ag/AgCl) Time (seconds)
Figure 4-6. (a) Linear sweep voltammetry curves and (b) amperometric I-t curve with constant voltage of
0.5 V vs Ag/AgCl of Bi-W1, Bi-W2 and Bi-W3 in 0.1 M Na2SO4 under light illumination.
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The optical-electro properties of the Bi2WO6 thin films were investigated by using
conductive atomic force microscopy (cAFM) technique. This technique has been
extensively employed to measure the thickness of graphene sheet and the conductivity
between the graphene and a semiconductor.14-16 Herein, the I-V curves obtained from the
cAFM (under dark and light condition) have enabled the evaluation of the electrical
conductivity of the Bi2WO6 samples. The electrical conductivity of the photoactive
semiconductor is correlated to its charge transfer efficiency, charge mobility and the
carrier density.17, 18 A basic sketch of the cAFM setup is illustrated in Figure 4-7a, where
a UV-light source was inserted at an angle of 20˚ for illumination and the Pt tip was in
contact with the sample surface at ±20 V applied bias. Figure 4-7b demonstrates the
principle of the charge movements in the Bi2WO6 samples during the cAFM measurement.
Under zero-bias, the photoexcited thin films behave as an insulator with the electrons and
holes allocated randomly on the bulk surfaces. Upon a negative applied bias, the
photogenerated electrons flow towards the positively charged Pt tip to complete the
circuit. The conductive surfaces of the Bi2WO6 thin films at this stage allowed the
formation of electron tunnel for electrons transfer. In contrast, when a positive voltage
was applied to the system, the reversed electrical polarity will alter the electron flow
direction and a negative photocurrent was measured. After the repetition of cAFM scans
on multiple locations of the samples, the representative I-V curves for Bi-W1, Bi-W2 and
Bi-W3 are shown in Figure 4-7c. Although Bi2WO6 should act as an insulator under dark
condition, the small amount of dark current detected from all the samples illustrates less
amount of electrons were forced to flow throughout the circuit under high voltage, an
indication of the extent of electrical barrier. When the thin film was illuminated,
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photoexcited charges will flow through the external circuit to generate photocurrent,
which represents the formation of electron tunnel. If the samples possess high carrier
density and charge mobility, an increased photocurrent will be recorded in the cAFM I-V
plot, demonstrating high conductivity. By observing the cAFM photoresponse (Figure
4-7c), a maximum photocurrent of ±8 nA was attained by Bi-W3, while lower
photocurrents were recorded for Bi-W1 (±0.02 nA) and Bi-W2 (±2 nA). The higher
photocurrent exhibited by Bi-W3 infers its high charge population and low electrical
resistance, facilitating the charge transfer throughout the thin film.
(a) (b)
At Zero Bias At -20 V Bias At +20 V Bias
LED Lamp
A Pt Pt + Pt -
Electron
Hole
FTO FTO - FTO +

(c) 0.02 2 12
Bi-W1 Bi-W2 10 Bi-W3
0.01
1.5
8
0
1 6
Current (nA)
Current (nA)
Current (nA)
-0.01 4
-0.02 0.5 2
-0.03 0
0 -2
-0.04 Dark
Dark Dark -4
-0.5
-0.05 Light -6 Light
Light
-0.06 -1 -8
-20 -10 0 10 20 -20 -10 0 10 20 -20 -10 0 10 20
Voltage (V) Voltage (V) Voltage (V)
Figure 4-7. (a) Schematic diagram of photo-conductive AFM setup, (b) schematic illustration of the flow
of electrons and holes under no (left), positive (middle) and negative (right) bias on the FTO substrate
under illumination, (c) Current-voltage (I-V) of dark and illuminated state of Bi-W1, Bi-W2 and Bi-W3
with standard of ± 20V bias.
135
According to the discussion from the cAFM measurement, the enhanced conductivity of
Bi-W3 could reflect its higher carrier mobility. However, results from the time-resolved
microwave conductance (TRMC) have signified a decrease trend in charge mobility was
observed among the Bi2WO6 thin films. TRMC has been used to study the carrier
dynamics including the carrier mobility, decay lifetime and the trapping state of the
photoexcited carriers.19 The power law calculated from the conductivity decay curves of
the Bi2WO6 samples that were drop-casted on quartz substrates at a photon flux of ~109
photon·pulse-1·cm-2 are illustrated in Figure 4-8a. According to the previously derived
equation Eqn. (4-2), the peak of the measured signal represents the carrier mobility, and
the decay curves can be fitted exponentially to determine the carrier lifetime. It is
observed from Figure 4-8a that the carrier mobility of Bi-W1, Bi-W2 and Bi-W3 are 0.07
cm2V-1s-1, 0.04 cm2V-1s-1, and 0.02 cm2V-1s-1, respectively. Furthermore, by measuring
the microwave photoconductance at different laser pulsed intensities, the conductance
with decreasing photon flux (Figure 4-8b) attributed to the less pronounced higher-order
recombination at the lower light intensity. In addition, the linearity of the plots indicates
that no trap states were present within the samples. Given that the calculated charge
mobility of the Bi-W1 is higher than Bi-W3, however Bi2WO6 samples are notably lower
than other binary oxide photocatalysts (such as Bi2O3 and WO3).20 The insignificant
differences of these values (in the same order of magnitude) delineated that carrier
mobility of the samples is independent to the W precursor concentration and morphology
of the particle. The comparable microwave conductivity reflected that the increase of W
concentration in Bi2WO6 does not improve the carrier mobility, and thus, the attained
PEC performance does not rely on the carrier mobility.

136
(a) (b)
Time (s) Intensity (photon.pulse-1.cm-2)
Figure 4-8. (a) The power laws calculated from the TRMC signals recorded for Bi-W1, Bi-W2 and Bi-W3
using excitation of 355 nm at a photon flux of ~109 photon·pulse-1·cm-2 (b) Logarithmic of the TRMC
signals recorded for Bi-W1, Bi-W2 and Bi-W3 using excitation of 355 nm at a photon flux of ~109
photon·pulse-1·cm-2
Table 4-2. The average decay time on time-resolved photoluminescence (TRPL).

Bi-W1 Bi-W2 Bi-W3
A1 0.051 0.072 0.093
τ1 2.39 2.16 2.02
A2 0.011 0.013 0.017
τ2 12.88 11.73 10.29
Average Time (ns) 8.14 6.99 6.02
The influence of interfacial charge separation and the charge transfer resistance of the
samples are studied to further understand the enhancement in PEC performance. The
former was examined by the time-resolved photoluminescence (TRPL) while the latter
137
was investigated via EIS spectroscopy (such as Nyquist plots). The PL decay curve was
fitted with a biexponential model, to yield two distinct decay components: (1) the fast
decay component ( 𝜏1 ) decribed as the intrinsic channel of the electron-hole pair
recombination, and (2) the long decay component (𝜏2 ) corresponding to the indirect
recombination of electrons being trapped in the defects at the valence band.21, 22 As
summarised in Table 4-2, the comparable 𝜏1 (approximately 2 ns) for all samples, imply
their similar charge separation efficiency and recombination rate. In contrast, the
difference in 𝜏2 for Bi-W1, Bi-W2 and Bi-W3 (i.e. 12.88 ns, 11.73 ns and 10.29 ns,
respectively) indicates the distinct tendencies of the carriers captured by the donors before
they recombine indirectly, suggesting effective transportation.
500 Bi-W1
Bi-W2
400 Bi-W3
300
-Z"(Ω)
100
200 80
-Z"(Ω)
60
40
100 20
0
0 100 200
Z'(Ω)
0
0 500 1000 1500 2000 2500 3000
Z'(Ω)
Figure 4-9. (a) EIS Nyquist plot of Bi-W1, Bi-W2 and Bi-W3 electrodes under 0.5 V vs Ag/AgCl in 0.1 M
Na2SO4 under illumination
138
For the investigation of interfacial charge transfer resistance, Nyquist plots of Bi 2WO6
samples were obtained from EIS impedance spectroscopy (Figure 4-9). The first arc of
the Nyquist plot at the high frequency region is commonly used to describe the charge
transfer resistance between the oxide layer and the electrolyte, while the second arc (1 -
100 Hz) corresponds to the resistance within the Bi2WO6 samples.23 In the low frequency
region (10 mHz - 1 Hz), the arc represents the charge resistance of the interface between
Bi2WO6 and the substrate. The larger arc diameters for Bi-W1 and Bi-W2 at the low
frequencies (Figure 4-9) indicates their higher charge transfer resistance within the
sample-substrate interfaces.24 In this regard, the lower charge transfer resistance of Bi-
W3 facilitated the transfer of photogenerated carriers, thereby promoted the photocurrent
generation. Meanwhile, inset of Figure 4-9 reveals similar arc diameter for all the
samples at higher frequency regions, which was ascribed to the similar charge transfer
resistance between Bi2WO6 and the electrolyte.
MnOx
Ag 500 nm 500 nm
Figure 4-10. SEM images of Bi-W2 photodeposited with (a) Ag metal and (b) MnO x.
139
The higher PEC performance of Bi-W3 was attributed to the better charge transfer
efficiency observed from the Nyquist plots. This can be related to the higher exposure
extent of {010} and a shorter charge transfer pathway, originated from a higher W
concentration. To further investigate the influence of crystal facet on charge transfer
efficiency, selective photo-deposition of Ag and MnOx on Bi-W2 were performed to
determine the electron- and hole-dominating crystal facet.25 SEM images in Figure 4-10a
and Figure 4-10b reveal that large Ag particles are photo-reduced on the {010} facets,
while fluffy MnOx flakes are photo-oxidised across the {100} surfaces. This was further
verified by TEM-EDS elemental mapping, where large particle of Ag was observed on
the lateral side of the sample (Figure 4-11a), and Mn is detected on the surface of the Bi-
W2 plates (Figure 4-11b). Consequently, it can be deduced that the photo-excited
electrons and holes are preferentially accumulated on the {010} and {100} facet,
respectively. Since photoinduced electrons are accumulated on the {010} facets, Bi-W3
with larger {010} facet was suggested to have a larger driving force for electrons to be
exposed to the bulks surface. Therefore, a higher electron density on the surface of Bi-
W3 promoted the electron transfer through the external circuit, generating a higher
photocurrent density. On the contrary, Bi-W1 is said to have lower exposure extent of
{010} facet, which resulted in longer charge transfer distance, larger charge transfer
resistance, resulting in poorer PEC performance. The schematic diagram (Figure 4-12a)
illustrates the postulated electrons and holes movement in Bi-W1 and Bi-W3. The size
reduction and higher exposed area of electron-dominating {010} facet of Bi-W3 facilitate
effective electron transport from inner to the bulk surface.26
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(a) (b)
Figure 4-11. (a)(i) TEM dark-field images of Bi-W2 with photodeposited of Ag metal. (ii-iv) Elemental
mapping of (ii) Ag, (iii) Bi and (iv) W. (b)(i) TEM dark-field images of Bi-W2 with photodeposited of
MnOx (ii-iv) Elemental mapping of (ii) Mn, (iii) Bi and (iv) W.
Apart from the high exposure {010} facets, the reduction of the bond length in the self-
doped Bi-W3 also enhanced the PEC performance. The local bonding structure was
examined from the Raman spectroscopy (Figure 4-12b). Line broadening and decrease
in the spectrum intensities of the peaks are observed with the increase of {010} facet
thickness in the Bi2WO6 plate. This is due to the particle size decrease as seen from the
SEM images, which agrees with earlier findings reported in literatures.27-30 Furthermore,
the Raman peaks appearing at 266 cm-1, 283 cm-1, 306 cm-1, 332 cm-1, 417 cm-1, 707 cm-
1
, 722 cm-1, 794 cm-1, and 813 cm-1 are ascribed to the bending and stretching mode of
the W-O and O-W-O bond.31, 32 Upon closer inspection (Figure 4-12b, inset), the Raman
peak at 813 cm-1 (Bi-W1) is shifted to 826 cm-1 (Bi-W2) and 831 cm-1 (Bi-W3),
respectively. The peak shifting indicates the surface bond of W-O and Bi-O become
141
shorter, resulting in a stronger interaction of the metal-oxide interface, which promotes
the active Bi lone pairs for photo-oxidation process.33
(a) (b)
Electron Hole
Recombination Separation
Long
Short
Thick
Thin {010} facet
{010} facet
Bi-W1 Bi-W3
Figure 4-12. (a) The schematic diagram of the photogenerated charge carrier transportation mechanism
of the Bi-W1 and Bi-W3 under illumination. (b) Raman spectra of Bi-W1, Bi-W2 and Bi-W3.
Given the interdependency of donor density and conductivity, donor density is another
important parameter that should not be neglected. Mott Schottky measurement was
conducted to determine the flat-band potential and donor density of Bi2WO6 samples.
Figure 4-13a illustrates a similar onset potential of -0.27 V vs NHE at pH = 0 for all
Bi2WO6 samples. According to the Mott Schottky equation (Eqn. (4-3)), the gradient of
the slope can be used to determine the donor density of the samples, where steeper slope
commonly denotes lower donor density.34 The donor density of the fabricated thin films
were calculated by using Eqn. (4-3), where ND is the donor density, e0 is the electron
charge constant, ɛ is the dielectric constant of Bi2WO6, ɛ0 is the permittivity of vacuum
or the electric constant and SMS is the slope obtained from the Mott-Schottky plot. The
142
Mott-Schottky profile was used in the range from -0.4 to -0.8 V versus Ag/AgCl to
calculate the slope, and the dielectric constant of Bi2WO6 used in this calculation is 50.35
Hence, the calculated donor density of Bi-W1, Bi-W2 and Bi-W3 is 2.16 x 1018 m-3, 2.71
x 1018 m-3 and 5.97 x 1018 m-3, respectively.
ND = (2/e0ɛɛ0)(SMS)-1 Eqn. (4-3)
The Bi-W3 with higher carrier density is again associated with the above findings that
indicates the better electron transfer and higher surface electron density of Bi-W3.
Evidently, the higher carrier density and charge transfer efficiency have contributed to
the enhanced PEC performance. These results therefore suggest that Bi2WO6 with higher
donor density and lower charge transfer resistance can be achieved by increasing the
concentration of W precursor during the fabrication process.
(a) (b) (c)

Bi-W1
Bi-W2
Bi-W3
(1/Cp2) ((1/F)2)
-1 -0.8 -0.6 -0.4 -0.2 0

Potential (V vs Ag/AgCl)
Figure 4-13. (a) Mott Schottky plot under illumination and XPS spectrum of (b) W 4f, (c) Bi 4f of Bi-W1,
Bi-W2 and Bi-W3 electrodes
143
Table 4-3. SEM-EDX of the relative atomic percentage of Bi, W and O element in each thin film.
Bi-W1 Bi-W2 Bi-W3
Bi 21.1 23.4 23.4
W 16.3 19.6 19.9
O 62.6 57 56.7
Stoichiometry of Bi:W:O 1 : 0.77 : 2.96 1 : 0.83 : 2.43 1 : 0.85 :2.42
The W enrichment in Bi-W3 can be correlated to its ‘self-doped’ phenomenon36, as
inferred from the SEM-EDX analysis in Table 4-3. The atomic percentage ratio of W to
Bi is 0.85 in Bi-W3, which is 8% higher than Bi-W1. However, the carrier density
enhancement could also be explained by the oxidation state of the Bi, W and O attained
from X-ray photoelectron spectroscopy (XPS). The W 4f spectra in Figure 4-13b shows
the major doublet peaks are fitted at 35.3 eV and 37.4 eV, associated to W5+ 4f7/2 and 4f5/2,
respectively. The W5+ peaks of Bi-W3 show obvious shift to a lower binding energy (0.4
eV) when compared to Bi-W1. The lower binding energy of W5+ in Bi-W3 indicates the
formation of electron-rich W. Basically, lower binding energy was commonly used to
describe the higher carrier density of an element.37 Hence, the higher amount of free
electrons in Bi-W3 increases its conductivity and charge transfer efficiency for better PEC
performance. This notion is further supported by Zhao et al., they have mentioned from
their DFT calculation that doping W atoms allows more electrons to be donated to the
host lattice for reaction.38, 39 In addition, a broadening of the W5+ peak with a shoulder at
higher binding energy is deconvoluted in the Bi-W2 and Bi-W3 XPS spectrum. The
second doublet peaks positions at 35.8 eV and 37.9 eV are corresponded to W6+species
144
in term of W 4f7/2 and 4f5/2, respectively. As suggested by Kumar et al., electrons trapped
at the conduction band leads to a fast reduction of W6+ to W5+.40 By studying the ratio
intensity of W6+/W5+ and Bi4+/Bi3+ from the W and Bi XPS spectra, Bi-W3 contains more
W6+ and Bi4+ species (Table 4-4). It infers a lower recombination of the charge carriers
with the existence of W6+ which the charges could transfer to W5+. Thus, the self-doped
Bi-W3 with a high amount of W possessing abundant charge carrier density is more likely
to improve the PEC performance as it favours electron migration, which in turns is being
consumed in the water oxidation process.
Table 4-4. The intensity ratio between the W6+/W5+ and Bi4+/Bi3+ in the XPS spectra.
Bi-W1 Bi-W2 Bi-W3
W6+/W5+ 0 0.21 0.38
Bi4+/Bi3+ 0 0.22 0.29
4.4 Summary
With a higher W precursor concentration introduced in the fabrication process, a well-
defined plate-like Bi2WO6 has been achieved and shows that the photoanode is highly
efficient for PEC water splitting. Investigation has been carried out in observing the
differences of PEC performance with more W in Bi2WO6 in terms of electrical
conductivity, charge mobility, charge recombination rate, interfacial resistance and the
charge carrier concentration. Based on the morphology engineered Bi-W3, it is most
likely that the smaller particle size and higher exposure of {010} crystal facet lead to an
145
improved PEC performance. Consequently, Bi-W3 indicates an enhancement in the
charge transportation (as the charge migration pathway is reduced) and higher surface
electron density to participate in the water oxidation reaction. In addition, a higher ratio
of W in the synthesis reaction allows a formation of a W ‘self-doping’ in Bi2WO6, where
the self-doped photocatalyst permits to promote a higher charge carriers concentration
and shorter W-O bond length, giving a superior charge transport. Based on this work, an
insight on the changes in physicochemical properties with respect to the increase in W
concentration during fabrication is significant to help in photoanode designs for water
oxidation in the future.
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Improved Charge ‐ Carrier Dynamics in Well ‐ Designed Hetero ‐ nanostructural
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impedance spectroscopic study of the electronic and ionic transport properties of LiCoO2
cathode. Chinese Science Bulletin 52 (9), 1187-1195.
24. Wang, S.; Chen, H.; Gao, G.; Butburee, T.; Lyu, M.; Thaweesak, S.; Yun, J.-H.; Du,
A.; Liu, G.; Wang, L., Synergistic crystal facet engineering and structural control of WO3
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separation of photogenerated electrons and holes among {010} and {110} crystal facets of
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photocatalytic activity enhancement of ordered mesoporous Bi2MoO6 crystals prepared via
a novel vacuum-assisted nanocasting method. RSC Advances 2016, 6 (42), 35709-35718.
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TiO2 nanosheets dominated with {001} facets: thickness-controlled synthesis, growth
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28. Mann, A. K. P.; Steinmiller, E. M. P.; Skrabalak, S. E., Elucidating the structure-dependent
photocatalytic properties of Bi2WO6: a synthesis guided investigation. Dalton Transactions
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properties of nanosized bismuth layered ferroelectric material-Bi2WO6. Journal of Raman
Spectroscopy 2010, 41 (9), 1059-1066.
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synthesis and visible-light-responsive photocatalytic activity of Bi2WO6 fluffy microsphere
with hierarchical architecture. Journal of Colloid and Interface Science 2012, 370 (1), 132-
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(17), 3223-3230.
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C.; Li, Y., Computational and Photoelectrochemical Study of Hydrogenated Bismuth
Vanadate. The Journal of Physical Chemistry C 2013, 117 (21), 10957-10964.
35. Newkirk, H. W.; Quadflieg, P.; Liebertz, J.; Kockel, A., Growth, crystallography and
dielectric properties of Bi2WO6. Ferroelectrics 1972, 4 (1), 51-55.
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TiO2 nanoparticles with a high-performance photocatalysis. Journal of Catalysis 2013, 297,
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bimetallic synergy with light: the effect of UV light pre-treatment on catalytic oxygen
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into nanostructured BiVO4 films for efficient photoelectrochemical water oxidation.
Physical Chemistry Chemical Physics 2012, 14 (19), 7065-7075.
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151
Chapter 5. The Charge Transfer Phenomenon of Homogeneous and Rigid
Heterojunction of Bi2WO6/WO3 Thin Film
CHAPTER 5
THE CHARGE TRANSFER
PHENOMENON OF
HOMOGENEOUS AND RIGID
HETEROJUNCTION OF
Bi2WO6/WO3 THIN FILM
5.1 Introduction
Optimisation of various types of semiconductor has been researched extensively, such as
improving the crystallinity, specific surface area, charge kinetics and the stability factors
to enhance the PEC performance.1-3 However, there seems a high possibility the
heterogeneous films for PEC are being photocorroded and attaining a high recombination
rate of the photogenerated carriers under irradiation. Owing to fast recombination, the
photoexcited electrons and holes must be consumed immediately upon generation in
order to enable the water splitting reaction carry out continuously. Previously in Chapter
4, the modification on the photoactive bare Bi2WO6 associate with crystal facet
152
engineering and self-doped technique has improved the charge separation, increased the
charge carrier concentration and lower the charge transfer resistance in PEC application.
Aside from modifying bare Bi2WO6, heterojunction formation with a higher interfacial
contact area that can potentially suppress the charge recombination and facilitate the
charge transport.4, 5
The formation of heterojunction films such as Cu2O/TiO26, ZnO/TiO27 and WO3/BiVO48
have suggested exhibiting high PEC performance due to their favourable band positions,
resulting in an improvement in the charge carrier separation and transportation.
Furthermore, studies on introducing a passivation layer between the two photocatalyst are
able to reduce the surface charge recombination or push the water oxidation kinetics. Low
mobility and short lifetime are the drawbacks of the photoexcited holes, where the
presence of the passivation layer allows the holes to be transferred and trapped in the
layer before it recombines.9 However, it requires an additional step in the synthesis
method to form the passivation layer. Hence, this chapter studies the charge carrier
dynamics at the heterojunction interface of the thin film with different interfacial contact
area during the PEC reaction. This could provide a new insight into the mechanism of the
charges transport in the photocatalyst to aid the future fabrication of photoanodes.
Herein, comparison of the charge transport in the two Bi2WO6/WO3 heterojunction thin
films with low and high interfacial surface area are investigated respectively. Zhang et al.
mentioned the interface between the two photocatalysts at the heterojunction plays an
important role in the water splitting process as it could affect the charge diffusion in the
153
catalyst.10 The reasons for this improvement, however, are not yet fully understood. A
previous study in our group, the transformation of Bi2WO6 from WO3 via hydrothermal
reaction was presented.11 Thus, the lower and higher interfacial contact of Bi2WO6/WO3
are fabricated in two steps, starting with the electrodeposition of WO3 subsequently by
hydrothermal reaction with addition of Bi to transform into Bi2WO6. The
electrodeposition method is known to fabricate various morphology and thickness by
simply tuning the concentration and the pulsing time, which aids the deposited coverage
of the substrate with a superior adhesion.12 In addition, the feasibility of transforming a
layer of WO3 to Bi2WO6 creates interesting partial interfacial charge transfer.13 Thus, the
charge properties are examined within the Bi2WO6/WO3 thin film under illumination.
5.2 Experimental Method
5.2.1 Preparation of High and Low Interfacial Contact of Bi2WO6/WO3 film
The bilayer heterojunction Bi2WO6/WO3 films were synthesised sequentially via
electrodeposition and hydrothermal method. For the high interfacial contact
Bi2WO6/WO3, the WO3 layer was first fabricated with an electrodeposition method,
which was modified from Yun et al. work.14 A conducting fluorine-doped tin oxide (FTO)
was washed with acetone, ethanol and water consecutively, and dried in air before use.
The electroplating solution was prepared by dissolving 25 mM of Na2WO4·2H2O and 30
mM of H2O2 in distilled water. The pH of the solution was tuned to 1.4 by using 2 M of
HNO3. After that, a standard three-electrode cell configuration was utilised for
electrodeposition, the FTO as the working electrode, Pt foil as the counter electrode, and
154
the Ag/AgCl (1M of KCl) as the reference electrode. The washed FTO substrate (1.5 cm
x 2 cm) was immersed in the plating solution, and an alternating continuous waveform of
a cathodic pulse (-0.8 V, 5 s) and relaxation voltage pulse (0 V, 5 s) were applied
periodically with an alternate for 720 cycles. After that, the deposited film was placed in
the Teflon cell with 0.5 mmol of Bi(NO3)3·5H2O for 24 hours at 160˚C. On the other hand,
the low interfacial contact Bi2WO6/WO3 film was prepared by electrodeposition with an
alternate of 360 cycles and was dried in the air for 24 hours at ambient atmosphere. After
that, the thin film was electrodeposited with another 360 cycles, and then placed in the
Teflon cell for hydrothermal reaction. Besides, the pure Bi2WO6 and WO3 were
synthesised by electrodepositing 720 cycles and followed by hydrothermal reaction with
5 mmol of Bi(NO3)3·5H2O while WO3 were calcined directly. Lastly, in order to increase
the crystallinity of each samples, all the thin films were calcined at 450˚C for 2 hours with
the ramping rate of 5˚C/mins.
5.2.2 Characterisation
The PEC experiment including Mott Schottky plot, were carried out with Autolab model
PGSTAT12 potentiostat in a three-electrode configuration with a Bi2WO6/WO3/FTO as
the working electrode and platinum sheet as the counter electrode and Ag/AgCl (1M of
KCl) as the reference electrode. An area of 0.72 cm2 was illuminated with a 300 W Xe
lamps. 0.1 M Na2SO4 aqueous solution was used as the electrolyte. Bode plot
measurement were performed with a frequency range from 0.1 to 10000 Hz at the
155
potential of 0.5 V, while a frequency of 500 Hz was applied for Mott Schottky
measurements.
5.2.3 Photoelectrochemical Measurement
The PEC experiment including Mott Schottky plot, were carried out with Autolab model
PGSTAT12 potentiostat in a three-electrode configuration with a Bi2WO6/WO3 as the
working electrode and platinum sheet as the counter electrode and Ag/AgCl (1M of KCl)
as the reference electrode. An area of 0.72 cm2 was illuminated with a 300 W Xe lamps.
0.1 M Na2SO4 aqueous solution was used as the electrolyte. Bode plot measurement were
performed with a frequency range from 0.1 to 10000 Hz at the potential of 0.5 V, while a
frequency of 500 Hz was applied for Mott Schottky measurements.
156
5.3.1 Material Characterisation
5.3.1.1 Physical Properties
500 nm 500 nm
5µm Sn Bi W
5µm Sn Bi W
Figure 5-1. Top-view and side-view SEM images and EDS elemental mapping of the photoanode (a and
c) H-BWO/WO and (b and d) R-BWO/WO thin film.
Figure 5-1a and b show the top-view scanning electron microscopy (SEM) images of the
high and low interfacial contact film, denoted as H-BWO/WO and R-BWO/WO,
respectively. In both films, flake-like morphology is observed but with different
arrangement. The H-BWO/WO has stacks of flakes randomly distributed on top of the
thin film. Meanwhile, the R-BWO/WO is grown with several irregular large plates and
they interlaced with the smaller flakes. Mali et al. found that a high surface area at the top
layer can enhance charge carrier separation and transportation for the holes to the
157
electrolyte interface.15 Nonetheless, both Bi2WO6/WO3 thin films displayed the flakes are
in good contact with each other, suggesting no significant difference in charge transfer
during PEC reaction comparison that influenced by the surface area. The cross-section
SEM revealed a similar thickness for both films with c.a. 3μm. Furthermore, the cross-
section SEM-EDS elemental mapping in Figure 5-1c clearly portrays the Bi and W
elements are homogeneously distributed across the film, indicating the formation of a
high interfacial contact between Bi2WO6 and WO3 in the H-BWO/WO. In contrast, cross-
section SEM image in Figure 5-1d shows two distinct rigid layers are observed from the
cross-section SEM image, and a dense Bi element is recorded which indicates more
Bi2WO6 are formed on the top layer in the R-BWO/WO. Thus, the interface between the
Bi2WO6 and WO3 in the R-BWO/WO film is lower.
5.3.1.2 Structural and Optical Properties
(a) (b) (c)

Bi2WO6 Bi2WO6 Bi2WO6
WO3 WO3 WO3

Intensity (a.u.)
R-BWO/WO
Intensity (a.u.)
Intensity (a.u.)
3˚
3˚
1˚
1˚
H-BWO/WO H-BWO/WO
R-BWO/WO
5 15 25 35 45 55 65 75 13 23 33 43 13 23 33 43
2Ө (˚) 2Ө (˚) 2Ө (˚)
Figure 5-2. (a) XRD patterns and GAXRD patterns of (b) H-BWO/WO and (c) R-BWO/WO thin film at 1˚
and 3˚ glancing angle.
158
The X-ray diffraction pattern (XRD) from Figure 5-2a confirms that orthorhombic
Bi2WO6 (JCPDS 01-079-2381) and hexagonal WO3 (JCPDS 04-007-2322) are achieved
in both H-BWO/WO and R-BWO/WO. Additionally, this implies the WO3 layers formed
after electrodeposition has successfully transformed into Bi2WO6, i.e. Bi has entered the
WO3 layer during the hydrothermal reaction. The sharp and intense XRD peaks indicate
that crystalline thin film is formed. The interfacial contact between Bi2WO6 and WO3
were further analysed by using GAXRD. GAXRD enables analysis of the materials on
the thin film at different depths. A smaller glancing angle (i.e. 1˚) can detect the top layer
of the film, while a larger glancing angle (i.e. 3˚) can detect the deeper layers of the film.
It is worth noting that the WO3 peak intensity has no significant changes between layers
in the H-BWO/WO (Figure 5-2b). This result supports the finding observed from the
SEM-EDS elemental mapping, proving WO3 is distributed homogeneously in Bi2WO6.
On the other hand, an apparent increase of WO3 peaks intensity is attained in the R-
BWO/WO sample at glancing angle of 3˚ (Figure 5-2c). Two distinct rigid layers were
composed in the R-BWO/WO film, representing the top layer is Bi2WO6 and WO3 is
position underneath. The overview structure of Bi2WO6 and WO3 arrangement within the
films are illustrated in Figure 5-3.
159
H-BWO/WO R-BWO/WO
Bi2WO6 particles WO3 particles
Figure 5-3. Schematic diagram of the distribution of Bi2WO6 and WO3 in the H-BWO/WO and R-
BWO/WO film
The optical properties of the H-BWO/WO and R-BWO/WO were measured by UV-
visible spectroscopy. The result in Figure 5-4 shows H-BWO/WO and R-BWO/WO have
the same absorption wavelength of 420 nm and 460 nm. The absorption data was
converted to Tauc plot (inset of Figure 5-4) with the assumption of Bi2WO6 has an
indirect band gap; both samples had the bandgap of 2.7 eV and 3.0 eV corresponding to
the bandgaps of WO3 and Bi2WO6, respectively, irrespective of the interfacial contact
area.16-18
Absorbance (a.u.)
250 300 350 400 450 500 550

Time (seconds)
Figure 5-4. UV-visible spectra of H-BWO/WO and R-BWO/WO thin film
160
5.3.2 Photoelectrochemical Performance

(a) (b) 4
110 H-BWO/WO

90 R-BWO/WO 3
Pure Bi₂WO₆
70
2
50
30 1
10
0
-10
-30 -1
-50 -2
-0.2 0 0.2 0.4 0.6 0.8 1 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Potential (V vs Ag/AgCl) Potential (V vs Ag/AgCl)
(c) 60 (c)
(d)
H-BWO/WO (Light)
50
H-BWO/WO (Dark)
40 R-BWO/WO (Light)
Photocurrent (pA)
R-BWO/WO (dark)
((1/F)2)
30 B1
20
(1/Cp2)
A1
10 B2
0
A2 H-BWO/WO
-10 R-BWO/WO
-20
0 5 10 15 20 -0.2 0 0.2 0.4 0.6 0.8 1
Voltage (V) Potential (V vs Ag/AgCl)
Figure 5-5. (a) LSV curves of H-BWO/WO and R-BWO/WO, (b) LSV curve of pure Bi2WO6, (c) cAFM
current-voltage (I-V) of dark and illuminated state H-BWO/WO and R-BWO/WO, and (d) Mott Schottky
plot of H-BWO/WO and R-BWO/WO.
Comparison of the PEC performance between H-BWO/WO and R-BWO/WO, chopped
linear sweep voltammetry (LSV) was accomplished and displayed in Figure 5-5a. A
similar photocurrent was recorded at high voltage bias (> 0.6 V). However, when a low
bias is applied (< 0.6 V), a higher photocurrent was measured in the H-BWO/WO than
the R-BWO/WO. In fact, the LSV of pure orthorhombic Bi2WO6 was carried out as
reference (Figure 5-5b), and low photocurrents with approximately 4 μA/cm2 at +1 V vs

161
Ag/AgCl was recorded. This proves that heterojunctions structure can improve the PEC
performance. Since the LSV only shows the performance of the thin film in the liquid-
state, further investigation of the performance was conducted in solid-state condition by
employing conductive atomic force microscopy (cAFM). Referring to the work in
Chapter 4, it has demonstrated that the point I-V scan obtained from cAFM enables the
evaluation of electronic properties specifically on the charge transport behaviours by
observing the currents recorded. Figure 5-5c illustrates the representative cAFM I-V
curves of H-BWO/WO and R-BWO/WO with the absence and presence of UV light
source, showing a higher photocurrent was measured at +10 V in H-BWO/WO (referring
to the plot, where A1 > A2). In contrast, a photocurrent of ca. 22 pA was observed at +20
V (referring to the plot, where B1 = B2) in both samples. The result agrees with the
conclusion drawn from the LSV results. Therefore, the approach of fabricating a higher
interface between WO3 and Bi2WO6 yielded an enhancement in the electrons
transportation through the circuit. Notably, the flat-band potential of the Bi2WO6/WO3
films is found to be unaffected by the interfacial contact are as seen from the Mott
Schottky measurement (Figure 5-5d). Taking the Mott Schottky measured at 500 Hz,
both samples showed positive linear slope, implying the expected n-type semiconductor.
The x-intercepts of the Mott Schottky plots suggested the onset potential of both films are
located at +0.41 V vs NHE at pH = 0. Additionally, donor density within the thin film can
be calculated by using the slope from the linear region of the Mott Schottky plots.19 It has
demonstrated the gradient obtained by the R-BWO/WO film is slightly smaller, but not
significantly different when compared to the H-BWO/WO film. Therefore, no change in
162
the onset potential and no enhancement in the concentration of the charge carriers were
observed, indicating the PEC performance is not influenced by these factors.
(a) 10 (b) 9000

0.1 V
0.1 V H-BWO/WO
R-BWO/WO
8000
8 Light on 7000
Light off
6000
6
|Z| (Ω)
5000
4000
4
3000
2 2000
1000
0 0
0 100 200 300 400 500 600 700 0.01 1 100 10000
(c) Time (seconds) (d) Frequency (Hz)

25000
0.5 V
25 0.5 V
20000
Light on
20 Light off
15000
|Z| (Ω)
15
10000
10
5 5000
0 0
0 100 200 300 400 500 600 700 0.01 1 100 10000
(e) Time (seconds)
(f) Frequency (Hz)
40000
40
0.75 V 35000 0.75 V
35
Light on 30000
30 Light off
25000
25
-Z"(Ω)
20 20000
15 15000
10 10000
5 5000
0 0
0 100 200 300 400 500 600 700 0.01 1 100 10000
Time (seconds) Z'(Ω)
Figure 5-6. Amperometric I-t curve and Bode blot under light illumination of Homogenous and R-
BWO/WO thin film under constant bias of (a and b) 0.1 V, (c and d) 0.5 V and (e and f) 0.75 V vs
Ag/AgCl.
163
As mentioned above, H-BWO/WO and R-BWO/WO do not show the same reactivity
below 0.6 V. The electrons are expected to move more efficiently in the H-BWO/WO
due to a higher interfacial contact area between the WO3 and Bi2WO6 that could lower
the recombination rate of charges. To further verify the role of low and high interfacial
contact area in the H-BWO/WO and R-BWO/WO film, the amperometric I-t curve and
the Bode plot measurements at various applied voltages were carried out (i.e. 0.1 V, 0.5
V and 0.75 V vs Ag/AgCl) as shown in Figure 5-6. Zhang et al. have reported a
heterojunction structure with a high surface roughness interfacial contact in between the
photocatalysts can enhance the PEC performance. This is due to the combination of two
photocatalyst as well as high interface area provides suitable valence band which separate
charge effectively. Meanwhile, the heterojunction shifted the absorption edge to a longer
wavelength that increases the visible-light absorption. Thus, the interfacial contact area
builds in the heterojunction thin film affects the photoanodic performance.10 From the
amperometric plots, H-BWO/WO produced higher photocurrent with a difference of 4
µA/cm2 and 3 µA/cm2 observed at 0.1 V and 0.5 V vs Ag/AgCl, respectively. The results
specify the homogeneously distributed Bi2WO6 and WO3 in the film has greatly improved
the charge transportation. This is supported by the bode plot in Figure 5-6b and d that
the higher contact between the layers is able to suppress the recombination of the charges
and decreased the charge transfer resistance. Bode plot is a technique measuring the
electron lifetime in the nanostructure and different frequency regions represent the speed
of charge transfer at the interface of the electrode. 20 Interestingly, the amperometric plot
in Figure 5-6e shows no significant change in the photocurrent generated. The Bode plot
in Figure 5-6f is an evidence emphasising the photoexcited charge recombination is

164
minimised in the R-BWO/WO once a higher bias is applied since the same charge transfer
efficiency is observed. At a high potential, the strong external power forces the electrons
to withdraw from the photocatalyst and transport to the external circuit. Theoretically,
when a high bias is applied in the system, more photoexcited electrons are being taken
from the photocatalyst valence band as it reduces the carrier recombination. To confirm
the benefits of forming a heterojunction film with homogeneous distribution, the
photocurrent response of single layer monoclinic WO3 and orthorhombic Bi2WO6 were
examined under chopped chronoamperometric conditions at 0.5 V vs Ag/AgCl (Figure
5-7). For the single layer WO3, although a monoclinic is formed instead of hexagonal
structure by using the same methodology, a gradual decrease of photocurrent is observed,
representing its instability. Similarly, a poor PEC performance of 2 μA/cm2 was observed
in pure Bi2WO6 sample. This emphasised a huge advantage in forming a heterojunction
Bi2WO6/WO3 for photo-oxidation process.
H-BWO/WO
R-BWO/WO
WO3
Bi2WO6
Figure 5-7. Amperometric I-t curve of H-BWO/WO, R-BWO/WO, WO3 and Bi2WO6 thin film under
constant bias of 0.5 V vs Ag/AgCl.
165
Furthermore, anodic spikes were observed in the R-BWO/WO under light irradiation. The
spikes generated were caused by the surface traps from the photogenerated holes at the
beginning of illumination.21 Large amount of the charges are excited once the thin film is
illuminated, however sharp spikes occur because the recombination rate of the electrons
and holes is faster than being withdrawn to the outer circuit. The spikes can be vanished
with increasing applied bias as reported by Bendova et al. which is due to a strong electric
field drift drawing the electrons away from the valence band of the materials.22
Comparing the amperometric plot obtained at 0.1 V vs Ag/AgCl (Figure 5-6a), distinct
spikes are recorded for the R-BWO/WO which most probably indicates high
concentration of charges were generated but with poor charge transfer rate. Notably, no
sharp attenuation was observed in the H-BWO/WO, and the photocurrent increases faster
than that of the R-BWO/WO. This is attributed to the photoelectrons being trapped at the
defect states can be readily moved away from the traps to transfer from WO3 to Bi2WO6,
thus extending the decay time of the photoexcited charges.
166
5.3.3 Charge Transport
(a) (b) (c) (d)

e- e-
e- e- CB e- e- e- e- e- e-
e- reduction
reduction reduction reduction
2.9eV
2.7eV
oxidation oxidation oxidation oxidation
h+ VB h+ h+ h+ h+ h+ h+ h+
h+ h+ h+
H-BWO/WO R-BWO/WO Bi2WO6 WO3

(Homogeneously distributed (Two distinct rigid layer)
layer)
Figure 5-8. The schematic diagram on the charge transportation in the thin film
The merit of increasing the interfacial contact area between the bilayer can enhance the
PEC performance at low bias. This approach optimises the charge transport within the
thin film and reduces the energy consumption for the water splitting process. Based on
the above results, a possible of the charge transfer mechanism in the pure WO3, Bi2WO6,
H-BWO/WO, and R-BWO/WO are proposed in Figure 5-8. In comparison to the single
layer of WO3 and Bi2WO6, the H-BWO/WO and R-BWO/WO films have demonstrated
enhance photocurrent density and higher stability in the PEC measurements. The reason
for such improvement is due to the formation of type-II heterojunction structure, which
facilitates an effective charge transfer that significantly reduces the electron-hole
recombination. Meanwhile, a higher photocurrent density was recorded by H-BWO/WO
at a low applied bias when compared to R-BWO/WO. H-BWO/WO film possesses a
higher interfacial contact between WO3 and Bi2WO6 that provides direct electron
tunnelling through the interface. On the other hand, R-BWO/WO has a weak adhesion
167
between the two distinct layers due to the film being electrodeposited separately. The low
and poor interfacial contact area has caused less electron tunnelling and a higher
resistivity for charge transfer, respectively, exhibiting a lower performance. This is
demonstrated in the Bode plot (Figure 5-6b), in which the higher resistivity restricted the
charge diffusion in the space-charge region of the semiconductor.23 Nevertheless, a
comparable photocurrent density was observed from H-BWO/WO and R-BWO/WO thin
films during the PEC measurement with a higher applied bias. This can be explained by
the strong driving force under a high bias (i.e. > 0.6 V vs Ag/AgCl) that withdrew the
trapped charge carriers from the interface of R-BWO/WO film, overcoming the
interfacial resistance, corresponding to the findings of Deng et al.24 Therefore, by
manipulating the interfacial contact in a heterojunction, the charge transport can be
significantly improved.
5.4 Summary
In summary, a heterojunction of WO3 and Bi2WO6 photoanode with a low and high
interfacial contact area were successfully synthesised by simple electrodeposition and
hydrothermal method. The SEM-EDS has shown clearly two distinct layers are formed
in the R-BWO/WO, while the WO3 and Bi2WO6 is distributed evenly in the H-BWO/WO
with higher interfacial contact area between the two photocatalysts. The concept of having
a higher interfacial contact area between Bi2WO6 and WO3 shows an improvement in the
PEC performance, which could be due to the presence of a direct electron tunnelling that
reduces charge carrier recombination. The photoexcited electrons can be migrated more
168
easily, allowing a lower applied voltage to be used. The homogeneous distribution in the
heterojunction highly promote the interfacial electron transfer within the thin film, which
is a significant finding compare to the bare Bi2WO6 and WO3.
5.5 References
1. Sallard, S.; Brezesinski, T.; Smarsly, B. M., Electrochromic stability of WO3 thin films
with nanometer-scale periodicity and varying degrees of crystallinity. The Journal of
2. Zhou, L.; Wang, W.; Liu, S.; Zhang, L.; Xu, H.; Zhu, W., A sonochemical route to
visible-light-driven high-activity BiVO4 photocatalyst. Journal of Molecular Catalysis A:
Chemical 2006, 252 (1-2), 120-124.
3. Tran, P. D.; Batabyal, S. K.; Pramana, S. S.; Barber, J.; Wong, L. H.; Loo, S. C. J., A
cuprous oxide–reduced graphene oxide (Cu2O–rGO) composite photocatalyst for hydrogen
generation: employing rGO as an electron acceptor to enhance the photocatalytic activity
and stability of Cu2O. Nanoscale 2012, 4 (13), 3875-3878.
4. Low, J.; Yu, J.; Jaroniec, M.; Wageh, S.; Al-Ghamdi, A. A., Heterojunction
Photocatalysts. Advanced Materials 2017, 29 (20), 1601694.
5. Wang, H.; Zhang, L.; Chen, Z.; Hu, J.; Li, S.; Wang, Z.; Liu, J.; Wang, X.,
Semiconductor heterojunction photocatalysts: design, construction, and photocatalytic
performances. Chemical Society Reviews 2014, 43 (15), 5234-5244.
6. Siripala, W.; Ivanovskaya, A.; Jaramillo, T. F.; Baeck, S.-H.; McFarland, E. W., A
Cu2O/TiO2 heterojunction thin film cathode for photoelectrocatalysis. Solar Energy
Materials and Solar Cells 2003, 77 (3), 229-237.
169
7. Xiao, F.-X., Construction of highly ordered ZnO–TiO2 nanotube arrays (ZnO/TNTs)
heterostructure for photocatalytic application. ACS applied materials & interfaces 2012, 4
(12), 7055-7063.
8. Su, J.; Guo, L.; Bao, N.; Grimes, C. A., Nanostructured WO3/BiVO4 Heterojunction Films
for Efficient Photoelectrochemical Water Splitting. Nano Letters 2011, 11 (5), 1928-1933.
9. Liu, R.; Zheng, Z.; Spurgeon, J.; Yang, X., Enhanced photoelectrochemical water-splitting
performance of semiconductors by surface passivation layers. Energy & Environmental
Science 2014, 7 (8), 2504-2517.
10. Xu, Q. C.; Wellia, D. V.; Ng, Y. H.; Amal, R.; Tan, T. T. Y., Synthesis of Porous and
Visible-Light Absorbing Bi2WO6/TiO2 Heterojunction Films with Improved
Photoelectrochemical and Photocatalytic Performances. The Journal of Physical Chemistry
C 2011, 115 (15), 7419-7428.
13. He, G.-H.; He, G.-L.; Li, A.-J.; Li, X.; Wang, X.-J.; Fang, Y.-P.; Xu, Y.-H., Synthesis
and visible light photocatalytic behavior of WO3(core)/Bi2WO6 (shell). Journal of
Molecular Catalysis A: Chemical 2014, 385, 106-111.
14. Yun, G.; Balamurugan, M.; Kim, H.-S.; Ahn, K.-S.; Kang, S. H., Role of WO3 Layers
Electrodeposited on SnO2 Inverse Opal Skeletons in Photoelectrochemical Water Splitting.
170
15. Mali, M. G.; Yoon, H.; Kim, M. W.; Swihart, M. T.; Al-Deyab, S. S.; Yoon, S. S.,
Electrosprayed heterojunction WO3/BiVO films with nanotextured pillar structure for
enhanced photoelectrochemical water splitting. Applied Physics Letters 2015, 106 (15).
16. Zhou, Y.; Peng, Y.; Yin, Y.; Zhou, F.; Liu, C.; Ling, J.; Lei, L.; Zhou, W.; Tang, D.,
Modulating memristive performance of hexagonal WO3 nanowire by water-oxidized
hydrogen ion implantation. Scientific Reports 2016, 6, 32712.
17. Huang, K.; Zhang, Q.; Yang, F.; He, D., Ultraviolet photoconductance of a single
hexagonal WO3 nanowire. Nano Research 2010, 3 (4), 281-287.
18. Li, Y.; Liu, J.; Huang, X.; Li, G., Hydrothermal Synthesis of Bi2WO6 Uniform
Hierarchical Microspheres. Crystal Growth & Design 2007, 7 (7), 1350-1355.
20. Xiao, B.-C.; Lin, L.-Y.; Hong, J.-Y.; Lin, H.-S.; Song, Y.-T., Synthesis of a monoclinic
BiVO4 nanorod array as the photocatalyst for efficient photoelectrochemical water
oxidation. RSC Advances 2017, 7 (13), 7547-7554.
21. Shi, Q.; Murcia-López, S.; Tang, P.; Flox, C.; Morante, J. R.; Bian, Z.; Wang, H.;
Andreu, T., Role of Tungsten Doping on the Surface States in BiVO4 Photoanodes for
Water Oxidation: Tuning the Electron Trapping Process. ACS Catalysis 2018, 3331-3342.
22. Bendova, M.; Gispert-Guirado, F.; Hassel, A. W.; Llobet, E.; Mozalev, A., Solar water
splitting on porous-alumina-assisted TiO2-doped WOx nanorod photoanodes: Paradoxes
and challenges. Nano Energy 2017, 33, 72-87.
23. Wu, C. Y., Interfacial layer‐thermionic‐diffusion theory for the Schottky barrier diode.
Journal of Applied Physics 1982, 53 (8), 5947-5950.
171
24. Xiao, J.; Zhang, Y.; Chen, H.; Xu, N.; Deng, S., Enhanced Performance of a Monolayer
MoS2/WSe2 Heterojunction as a Photoelectrochemical Cathode. Nano-Micro Letters 2018,
10 (4), 60.
172
Chapter 6. Oxygen-Deficient Bismuth Tungstate and Bismuth Oxide Composite
Photoanode with Improved Photostability
CHAPTER 6
OXYGEN-DEFICIENT BISMUTH
TUNGSTATE AND BISMUTH OXIDE
COMPOSITE PHOTOANODE WITH
IMPROVED PHOTOSTABILITY
6.1 Introduction
Despite a considerable amount of literature reporting photocorrosion of the photocatalyst
such as Bi2O31, CuO2 and Fe2O33 in photocatalytic and PEC applications, a few efforts
has been allocated on applying strategies to improve its photostability. The instability of
the photocatalyst could cause a significant decrease of performance over a long course of
photocatalysis reaction. It has been found that the instability issue is mainly caused by
photocorrosion which originated from the self-oxidation of the photogenerated holes in
the materials.4, 5 The photoinduced charge carriers must be consumed rapidly or combined
with another active material, so as to prevent direct contact with the holes to inhibit self-
oxidation. From the prior findings in Chapter 5, the formation of the Bi2WO6 transformed
from WO3 has increased the interfacial contact, promoting the charge transfer and
173
prolonging the PEC performance. By exploiting the findings from the previous chapter,
a formation of heterojunction with bismuth tungstate has the potential to inhibit the
instability. Therefore, attempts to extend the functionality of the bismuth tungstate with
binary oxide remains as an interesting study.
Bismuth oxide (Bi2O3) is a semiconductor with a direct transition band gap of ca. 2.8 eV,
which suggests its photoexcitation can be prompted by visible-light with wavelength
shorter than 445nm. Together with its high refractive index, dielectric permittivity, and
high ion and photo-conductivity, Bi2O3 appears to be suitable for a range of photo-related
applications. Furthermore, Bi2O3 can be conveniently synthesised using various methods
including electrodeposition, hydrothermal synthesis, and solid-state reactions.6-8
Photocatalytic activities of Bi2O3 in organic degradation, dye decolourisation, and water
oxidation have been reported.9, 10 However, it was observed by Hajra and co-workers that
a Bi2O3 photoanode suffered from a significant loss of photocurrent.1 Rapid decay of
photocurrent was observed in the first 100 seconds and almost all photoresponse
disappeared after 15 mins of UV-visible (UV-Vis) light illumination. Similarly, Shaikh
et al. also reported the benefits of introducing ZnO as a surface passivation layer on top
of a Bi2O3 photoanode to improve its photoactivity in a dye-sensitised solar cell.11
Combined with the investigation, which will be discussed in the following sections, the
issue of Bi2O3 photostability is apparent and it needs to be addressed.
In this work, oxygen-deficient bismuth tungstate (Bi14WO24) was homogeneously
introduced into Bi2O3 to facilitate efficient charge transfer upon photoexcitation and to
174
provide a protective layer that can minimise the accumulation of excited charges that lead
to the photocorrosion of Bi2O3. Unlike the commonly used surface passivation techniques
that usually yield two-distinct layers (e.g. ZnO on a Bi2O3 film11, TiO2/CuO on a Cu2O
film12, Nb2O5 on a TiO2 film13), the unique characteristic of the composite Bi14WO24 and
Bi2O3 (hereafter referred to as BWO/Bi2O3 film) photoanode reported herein is the
absence of a distinct interface between the two components. The nature of the
homogenous mixture of Bi14WO24 and Bi2O3 is analogous to a solid solution. With this
intimate contact, the excited charge shuttling between the two components is favourable.
A photocurrent can be produced by the composite film for at least three hours under
continuous illumination without decay. In contrast, for the unmodified Bi2O3 photoanode,
80% of the photoresponse was lost in 1.5 hours. Thus, the strategy demonstrated in this
work of introducing a homogeneously distributed passivation component is useful and
might be applicable to other unstable photoactive thin film materials.
6.2 Experimental Method
6.2.1 Preparation of BWO/Bi2O3 Film
All reagents were purchased from Sigma-Aldrich and used as received without further
purification. Transparent conducting fluorine-doped tin oxide (FTO) substrates (1.5 cm ×
5 cm in size) were cleaned sequentially in acetone, ethanol and water, under sonication
and dried in air before use. Pure Bi metal was deposited on the cleaned FTO using the
pulse electrodeposition method developed by another group.14 A standard three-electrode
cell configuration was used for electrodeposition, with FTO as the working electrode, Pt
175
foil as the counter electrode and Ag/AgCl (1 M KCl) as the reference electrode. An
ethylene glycol solution containing 20 mM of Bi(NO3)3·5H2O was used as the plating
electrolyte. Typically, a FTO substrate of dimensions 1.5 cm × 2 cm was immersed in the
electrolyte, and a continuous waveform of a cathodic pulse (-1.2 V, 0.5 s) and relaxation
voltage pulse (0 V, 2 s) were then being applied alternately for 7200 cycles to result in
the deposition of Bi particles on the substrate. This waveform was generated by an
AUTOLAB potentiostat combined with Nova software. The employment of the 2 seconds
relaxation time was to allow Bi3+ ions to be replenished at the surface, which can increase
the nucleation density of Bi on the working electrode to achieve a better deposit coverage.
After this pulse electrodeposition process, the Bi-deposited thin films were carefully
rinsed with ethanol and dried by blowing air. 200 μL ethylene glycol was subsequently
dropped on one of the Bi-deposited thin films, following by calcination in air at 600 °C
for 4 hours to provide a superior attachment on the FTO. The Bi2O3 film was obtained
after calcination. To form a composite of BWO/Bi2O3, 200 μL of Na2WO4·2H2O (0.75
M) was dropped on the Bi metal layer prior to calcination in air at 600 °C for 4 hours.
6.2.2 Characterisation of BWO/ Bi2O3 Film
The phase purity and crystallinity of the product were analysed by PANalytical Empyrean
Thin-Film X-ray diffraction (XRD) using Cu Kα radiation (λ = 1.5406 Å) with a voltage
of 45 V and current of 40 mA at room temperature. Rietveld refinement is conducted by
fitting and analysing the XRD pattern diffractogram using the High Score program
developed by PANalytical. Scanning electron microscopy (SEM) images were obtained
176
with a FEI Nova NanoSEM 450 FESEM microscope operated at 5 kV to examine the
morphology of the thin film. The elemental mapping and distribution were determined by
X-ray energy dispersion spectrum (EDS). Transmission electron microscopy (TEM and
HRTEM) images were obtained by Philips CM200 instrument in bright field mode. The
UV-visible absorption spectra were recorded using Shimadzu UV-3600
spectrophotometer, with BaSO4 powder used as the reference. The absorbance was
calculated from the measured reflectance using Kubelka-Munk function to identify the
band gaps of the films. The elemental composition was quantified by PerkinElmer
quadrapole Nexion inductively coupled plasma mass spectroscopy (ICP-MS). X-ray
photoelectron spectroscopy (XPS) was carried out using ESCALAB250Xi (Thermo
Scientific) with a mono-chromated Al Kα source. All the peak position was calibrated
using the binding energy of C 1s at 284.8 eV. The time-resolved fluorescence (PL decay)
was conducted by the time-correlated-single-photon-counting (TCSPC) on Microtime-
200 system (Picoquant) with excitation of a 405 nm pulsed laser. Using the bi-exponential
decay function𝑦 = 𝐴1 𝑒𝑥𝑝(−𝑡/𝜏1 ) + 𝐴2 𝑒𝑥𝑝(−𝑡/𝜏2 ), each PL decay trace can be nicely
fitted to determine the decay times. The average lifetimes are obtained using 𝜏𝐴𝑉 =
𝐴21 𝜏1 +𝐴22 𝜏2 15
.
𝐴1 𝜏1 +𝐴2 𝜏2
6.2.3 Photoelectrochemical Test
All photoelectrochemical measurements including electrochemical impedance
spectroscopy (EIS) were conducted in an electrolyte of 0.1 M Na2SO4 (pH 6.8-7.2) with
a three-electrode system (Pt foil and Ag/AgCl were used as the counter electrode and
177
reference electrode, respectively) using a potentiostat (Autolab model PGSTAT 12) with
frequency response analyser (Autolab FRA2 modules). The light source was a 300 W Xe
lamp. Back illumination was performed with an exposed thin film area of 0.72 cm2. The
flat-band potential of the thin films was estimated by Mott-Schottky analysis, where the
measurement was performed at frequency of 500 Hz.
6.3.1 Material Characterisation
Figure 6-1. (a) Photographs of the thin films consisting of metallic Bi, Bi 2O3, and BWO/Bi2O3 (left to
right); (b) SEM images and (c) XRD patterns of the Bi 2O3 and BWO/Bi2O3 films.
Upon pulse electrodeposition, a compact black layer of metallic Bi was evenly coated on
the FTO substrate (Figure 6-1a). Pulse electrodeposition has the obvious merit of
depositing a dense layer. Achieving a dense layer of Bi is important because it serves as
the seeding precursor for the subsequent conversion to Bi2O3 and BWO/Bi2O3 thin films.
SEM images (Figure 6-2) of the Bi-deposited FTO substrates prepared using pulse and
non-pulse systems clearly differentiate the quality of the Bi-deposited films. As shown in
178
Figure 6-2, the coverage of metallic Bi on FTO was comprehensive for the pulse
electrodeposited film, while the continuous non-pulse electrodeposition produced a
patchy distribution of metallic Bi with a significant portion of the FTO surface found to
be exposed and uncovered. The difference in coverage is due to the relaxation pulse (0V,
2s) that allows the replenishment of Bi3+ ions at the FTO surface for subsequent
deposition.14 All the Bi2O3 and BWO/Bi2O3 films examined in this work were, therefore,
prepared using the pulse electrodeposited Bi.
Figure 6-2. SEM images of (a and b) pulsed and (c and d) non-pulsed electrodeposited Bi-metal thin film
After the thermal treatment of the Bi-deposited films with or without W precursor
addition, the films had a yellowish appearance (Figure 6-1a) suggesting successful
formation of Bi2O3 and BWO/Bi2O3 (these two materials usually have a yellow colour
due to their narrow optical band gaps of around 2.8 eV). Compact but featureless films
179
were observed from the SEM images of the resultant Bi2O3 and BWO/Bi2O3 films
(Figure 6-1b). Figure 6-1c shows the XRD patterns of the prepared thin films. Although
both films are highly crystalline, the bare Bi2O3 film obtained from direct annealing was
confirmed to be the monoclinic phase and indexed with the JCPD 03-2034 pattern. The
additional W precursor treatment yielded a mixture of monoclinic Bi14WO24 (JCPD 80-
5931) and Bi2O3 after being calcined. The relative amounts of Bi14WO24 and Bi2O3 in the
BWO/Bi2O3 film were determined using Rietveld refinement. The film was estimated to
be composed 29.1% Bi2O3 with the rest Bi14WO24 (Figure 6-3 and Table 6-1).
(a) (b)
Figure 6-3. (a) The original and (b) the Rietveld refinement fitted XRD spectrum
Table 6-1. Agreement Indices of Rietveld refinement of the XRD diffraction pattern
Agreement Indices
Bi2O3 monoclinic crystallography data 15072-ICSD
Bi14WO24 monoclinic crystallography data 183463-ICSD
R expected 7.77
R profile 16.1
Goodness of Fit 9.28
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Bi14WO24 is considered as an oxygen-deficient or bismuth-rich bismuth tungstate.16 Note
that the Bi2O3 would not be fully transformed into Bi14WO24 with the addition of much
higher concentration of tungsten precursors. The XPS result illustrates the Bi14WO24 was
made composite with Bi2O3 (Figure 6-4). In the Bi 4f spectrum, the Bi 4f peaks of Bi2O3
thin films are located at 158.5 eV and 163.8 eV, which are attributed to Bi3+.17 However,
the doublet Bi 4f peak is shifted to a lower binding energy for ca. 0.2 eV, proposing a
change in the interfacial structure due to the introduction of W.18 In the W 4f spectrum,
strong signals are detected in the composite of BWO/Bi2O3 thin film only. The binding
energy of the doublet peak is located at 34.5 eV and 36.6 eV, and they are assigned to the
W 4f7/2 and W 4f5/2 of the W6+ species, respectively.19, 20
Figure 6-4. XPS spectra with (a) Bi 4f and (b) W 4f spectrums of Bi 2O3 and BWO/Bi2O3 thin film (no W
signal in Bi2O3 are detected).
As the formation of the BWO/Bi2O3 composite is driven by the surface-to-bulk diffusion
of WO42- ions into the film during the simultaneous formation of Bi2O3 at elevated
181
temperature, the homogeneity of the tungstate distribution throughout the bulk
BWO/Bi2O3 needs to be examined. The previous studies on hydrothermally transforming
WO3 into Bi2WO6 and MoO3 into Bi2MoO6 had found a gradient in bismuth concentration
through the film thickness.21, 22

Therefore, it is also interesting to characterise this
BWO/Bi2O3 film to obtain insight into these two different synthesis methods. Figure 6-5
shows the cross-sectional SEM-EDS images of the BWO/Bi2O3 film with its relevant
elemental mapping. The distribution of tungsten is homogeneous through the film, which
indicates the uniform dispersion of Bi14WO24 within the composite film. There is no
obvious region within the film showing separation of Bi14WO24 from Bi2O3. Comparing
with the cross section SEM-EDS images of bulk Bi2O3, no W element was detected along
the film. This “solid-solution”-like composite of Bi14WO24 and Bi2O3 is expected to be
favourable for photoexcited charge transfer owing to the intimate contact between the
components.
Figure 6-5. Cross-sectional SEM image of the BWO/Bi2O3 film (top) and pure Bi2O3 (bottom) with its
elemental (Bi, W and O) distribution through the film.

182
Further evidence of this well-mixed BWO/Bi2O3 composite is obtained using HRTEM
analysis. Figure 6-6 shows TEM images of the bare Bi2O3 and BWO/Bi2O3. Their
respective high resolution images demonstrate the polycrystalline nature of the materials.
Lattice fringes with spacing of 2.75Å and 3.22Å were measured for the BWO/Bi2O3
composite, corresponding to the (103), (3̅ 01), (231) and (150) planes of monoclinic
Bi14WO24. The lattice spacing of 2.70Å, 3.25Å and 3.31Å observed for both the Bi2O3
and BWO/Bi2O3 films are consistent with the (121), (120), (1̅21), (111) and (1̅12) planes
of monoclinic Bi2O3. Hence, the combination of XRD, XPS, SEM-EDX, and HRTEM
results confirm the successful formation of Bi14WO24 throughout the Bi2O3 films. More
interestingly, the Bi14WO24 was homogeneously distributed throughout the film, which is
expected to be advantageous for the transport of photocharges upon excitation.
Figure 6-6. TEM images of (a) Bi2O3 and (c) BWO/Bi2O3 films and their corresponding high resolution
images showing the lattice spacing (b and d).
183
Figure 6-7. UV-Vis absorption spectra of Bi2O3 and BWO/Bi2O3
The optical band gaps of the Bi2O3 and BWO/Bi2O3 films were determined using UV-
Vis absorption spectroscopy. The UV-Vis absorption spectra in Figure 6-7 shows the
absorption edges of Bi2O3 and BWO/Bi2O3 at a similar wavelength, λ ≈ ca. 430 nm. The
optical band gap (Eg) derived from the Tauc plot (inset of Figure 6-7) is 2.9 eV, consistent
with previous reports of Bi2O3.23
6.3.1 Photoelectrochemical Performance
Although both the bare Bi2O3 and BWO/Bi2O3 films have the similar light absorption,
other electronic characterisation suggests that Bi2O3 has superior properties for electron
transportation. Figure 6-8a and b shows the Mott-Schottky and EIS conductance plots of
both films. In the Mott-Schottky analysis, capacitance of the space charge layer (C) of the
film was measured as a function of applied potential. The conductivity type and charge
184
carrier density (or donor density) of the films can be determined from the results.24, 25 The
latter can be calculated by the following Equation (1)):
1 −1
2 𝑑 ( 2)
𝑁𝑑 = ( )[ 𝐶 ] Eqn. (6-1)
𝑒0 𝜀𝜀0 𝑑𝑉
where e0 is the electron charge, ɛ is the dielectric constant, ɛ0 is the permittivity of vacuum,
Nd is the donor density, V is the applied bias at the electrode, and C is the capacitance of
the space charge layer. According to Eqn. (6-1), the donor densities in the different films
can be qualitatively compared since it is inversely proportional to the gradient of the Mott-
Schottky plot.
Both the bare Bi2O3 and BWO/Bi2O3 films demonstrate a positive slope in the Mott-
Schottky plots, indicating that they are n-type semiconductor.24 The bare Bi2O3 film gives
a lower gradient than the BWO/Bi2O3 film, suggesting that it has a higher charge density.
Higher donor density could enhance the PEC performance as the charge transfer between
the oxide layer and FTO substrate is improved. The flat-band potential (Fb) of Bi2O3 is at
+0.37 V versus normal hydrogen electrode (NHE) at pH 0, which is comparable with the
literature value.25 Given that to Fb of BWO/Bi2O3 has shifted to +0.11 V vs NHE at pH 0,
it suggests that the band structure of this composite has been altered. Figure 6-8b shows
the EIS conductance as a function of frequency for the Bi2O3 and BWO/Bi2O3 films, the
curve is correlated to the electrical behaviour at the interface of the photoelectrode within
the system. In the high frequency response (>100 Hz) the conductivity is dominated by
185
the interface between the film and the Na2SO4 electrolyte. The conductance of both films
at the high frequency region is identical for both films. The other frequency regions, the
conductance of the bulk oxide films (medium frequency range, 1 Hz – 100 Hz) as well as
the conductance at the interface of the oxide and FTO substrate (low frequency range, 10
mHz – 1 Hz) can be evaluated. The medium frequency region is ascribed to the electrical
ability of the interior of the bulk oxide film, while the low frequency region shows the
conductance at the interface of the oxide and FTO substrate. The conductance of the bulk
Bi2O3 is only marginally higher than that of BWO/Bi2O3, indicating the lower charge
diffusion of the composite material. However, the bare Bi2O3 has significantly better
electron mobility at the interface with the FTO substrate.
Figure 6-8. (a) Mott-Schottky and (b) EIS conductance plots of the Bi2O3 and BWO/Bi2O3 films.
The photocurrent densities measured under constant voltage (amperometry, Figure 6-9a)
confirm that both the Bi2O3 and BWO/Bi2O3 films are photoresponsive, and the anodic
photocurrent verifies their n-type semiconducting behaviour.26 The bare Bi2O3 film
demonstrated higher anodic photocurrent than the BWO/Bi2O3 film. This was also
186
supported by the linear sweep voltammogram measurement where higher photocurrent
was displayed by the bare Bi2O3 film across the entire potential bias compared to the
composite film (Figure 6-9b). This is consistent with the better electrochemical
properties (donor density and conductivity) indicated by Mott-Schottky and EIS
conductance analyses.
(a) 40 (b) (c) 1.2

Bi₂O₃
Light On 20 µA/cm2
Photocurrent Density (µA/cm 2 )
Photocurrent Density (μA/cm2)
Photocurrent Density Ratio (I/I₀)

Light Off 1 Bi14WO24/Bi2O3
30
0.8
Dark
Bi2O3 Light
20 0.6
0.4
10
BiWO/Bi2O3
0.2
Bi2O3
0
0
0 100 200 300 400 500 -0.2 0 0.2 0.4 0.6 0.8 1 0 0.5 1 1.5 2 2.5 3
Time (s) Voltage (V) Time (hours)
Figure 6-9. (a) Amperometric photocurrent density at 0.75 V vs Ag/AgCl and (b) Linear Sweep
Voltammogram of Bi2O3 and BWO/Bi2O3 thin film and (c) photocurrent density ratio (I/Io where Io is the
initial current) of the Bi2O3 and BWO/Bi2O3 films.
Although the photocurrent generation was higher for the bare Bi2O3 film (as expected),
the photocurrent decayed noticeably and rapidly within 10 mins of on-off illumination
cycling, while the photoresponse of BWO/Bi2O3 remained unchanged. This observation
of photo-instability for Bi2O3 is consistent with the previous work by Hajra et al.1 To
further investigate the stability of both films under illumination, the photocurrent decay
of the Bi2O3 and BWO/Bi2O3 films was measured over an extended 3-hour period of
continuous illumination (Figure 6-9c). The photocurrent decay in Figure 6-9c is
presented as the ratio of the measured photocurrent (I) to the initial photocurrent (Io). The
187
photocurrent density half-life for the Bi2O3 film was ca. 50 mins (i.e. half of the
photoactivity was lost in less than one hour), indicating that the bare Bi2O3 film is not
ideal for a photoelectrochemical system due to its photostability issue. After 2 hours of
illumination, the Bi2O3 film lost almost all of its photoresponse. In contrast, the
BWO/Bi2O3 film was able to maintain its photocurrent density over the whole
illumination duration without noticeable decay. Thus, the advantage of introducing
Bi14WO24 to form a composite with Bi2O3 can be observed in the photostability
improvement, albeit its relatively low absolute photocurrent value can be further
enhanced by other modifications.27
Figure 6-10. XRD patterns measured before and after PEC measurement for (a) Bi 2O3 and (b)
BWO/Bi2O3 films. (c) Energy band structure for the BWO/Bi2O3 films.
The photocurrent decay of the Bi2O3 film was accompanied by the formation of a new
crystal phase after the 3-hour illumination period, as observed in XRD diffractogram
(Figure 6-10a). An additional high-intensity peak was observed at 27.9˚ for the Bi2O3
188
film after illumination, which can be indexed to either Bi14SO24 or Na2O. The formation
of these new compounds is reasonable as Na2SO4 was used as the electrolyte in the
photoelectrochemical measurement. In contrast, the XRD patterns of the BWO/Bi2O3
film before and after the illumination are essentially the same (Figure 6-10b).
Furthermore, the significant loss of photocurrent in the Bi2O3 film can also be associated
with anodic photocorrosion (i.e. self photo-oxidation of Bi2O3) ICP-MS characterisation
shows there was 175 µg/L of Bi ions leach into the electrolyte used for PEC measurement
of the Bi2O3 after 3-hour illumination. This type of photocorrosion occurs when the
interfacial transfer of photoexcited holes is slow and subsequently leads to the
accumulation of holes that induces self-oxidation. The introduction of Bi14WO24 to Bi2O3
facilitates the transfer of photoexcited charges. With the promotion of excited charge
transfer, accumulation of holes within a single component is prevented and
photocorrosion is suppressed. Figure 6-10c shows the postulated band energy structure
of bismuth oxide and tungstate based on previous reports.28-31 The Mott-Schottky plot has
illustrated the Fermi level has been shifted upward for BWO/Bi2O3 composited. Owing
to the band alignment, the excited electrons from the Bi14WO24 are transferred to bismuth
oxide while the migration of holes happens in the opposite direction. This promoted
charge transfer can be indicated by the prolonged charge lifetime evaluated by the time-
resolved PL. Based on the PL results of the thin films (Figure 6-11), decay time for the
charges in the BWO/Bi2O3 composite (τaverage = 1.85 ns) is slower than that of the Bi2O3
(τaverage = 0.94 ns). Supported by the close proximity of the components as evidenced by
189
the PL decay, SEM-EDS and HRTEM, this improved charge transfer is expected to
contribute to the long-term stability of BWO/Bi2O3.
Figure 6-11.. Time-resolved fluorescence of Bi2O3 and BWO/Bi2O3 thin film
6.4 Summary
In short, although Bi2O3 is a potential photoactive semiconductor with several ideal
electronic properties, its instability is a significant issue that causes a deterioration of the
PEC performance within a short period of time. In this work, a strategy to stabilise Bi2O3
was demonstrated to introduce a homogeneously distributed Bi14WO24 component. This
composite film can be prepared by a method combining pulse electrodeposition and
thermal treatment. Compared with bare Bi2O3, the composite film has much more stable
photoactivity under long-term illumination. The photostability improvement is attributed
to the improved charge transfer between the two semiconductors which in turns
suppresses the photocorrosion. These findings suggested the applicability to other
photocatalysts with stability challenges.
190
6.5 References
1. Hajra, P.; Shyamal, S.; Mandal, H.; Fageria, P.; Pande, S.; Bhattacharya, C.,
Photocatalytic activity of Bi2O3 Nanocrystalline Semiconductor developed via Chemical-
bath Synthesis. Electrochimica Acta 2014, 123, 494-500.
2. Toe, C. Y.; Zheng, Z.; Wu, H.; Scott, J.; Amal, R.; Ng, Y. H., Photocorrosion of Cuprous
Oxide in Hydrogen Production: Rationalising Self ‐ Oxidation or Self ‐ Reduction.
Angewandte Chemie 2018, 130 (41), 13801-13805.
3. Mishra, M.; Chun, D.-M., α-Fe2O3 as a photocatalytic material: A review. Applied
4. Wang, M.; Cai, L.; Wang, Y.; Zhou, F.; Xu, K.; Tao, X.; Chai, Y., Graphene-draped
semiconductors for enhanced photocorrosion resistance and photocatalytic properties.
Journal of the American Chemical Society 2017, 139 (11), 4144-4151.
5. Zhen, W.; Ning, X.; Yang, B.; Wu, Y.; Li, Z.; Lu, G., The enhancement of CdS
photocatalytic activity for water splitting via anti-photocorrosion by coating Ni2P shell and
removing nascent formed oxygen with artificial gill. Applied Catalysis B: Environmental
2018, 221, 243-257.
6. Bohannan, E. W.; Jaynes, C. C.; Shumsky, M. G.; Barton, J. K.; Switzer, J. A., Low-
temperature electrodeposition of the high-temperature cubic polymorph of bismuth(III)
oxide. Solid State Ionics 2000, 131 (1), 97-107.
7. Li, X.; Sun, Y.; Xiong, T.; Jiang, G.; Zhang, Y.; Wu, Z.; Dong, F., Activation of
amorphous bismuth oxide via plasmonic Bi metal for efficient visible-light photocatalysis.
Journal of Catalysis 2017, 352, 102-112.
191
8. Liang, Z.; Cao, Y.; Li, Y.; Xie, J.; Guo, N.; Jia, D., Solid-state chemical synthesis of rod-
like fluorine-doped β-Bi2O3 and their enhanced photocatalytic property under visible light.
Applied Surface Science 2016, 390, 78-85.
9. Adhikari, S. P.; Dean, H.; Hood, Z. D.; Peng, R.; More, K. L.; Ivanov, I.; Wu, Z.;
Lachgar, A., Visible-light-driven Bi2O3/WO3 composites with enhanced photocatalytic
activity. RSC Advances 2015, 5 (111), 91094-91102.
10. Wang, C.; Shao, C.; Wang, L.; Zhang, L.; Li, X.; Liu, Y., Electrospinning preparation,
characterization and photocatalytic properties of Bi2O3 nanofibers. Journal of colloid and
interface science 2009, 333 (1), 242-248.
11. Shaikh, S. M. F.; Rahman, G.; Mane, R. S.; Joo, O.-S., Bismuth oxide nanoplates-based
efficient DSSCs: Influence of ZnO surface passivation layer. Electrochimica Acta 2013,
111, 593-600.
12. Wang, P.; Wen, X.; Amal, R.; Ng, Y. H., Introducing a protective interlayer of TiO 2 in
Cu2O-CuO heterojunction thin film as a highly stable visible light photocathode. RSC
Advances 2015, 5 (7), 5231-5236.
13. Chen, S. G.; Chappel, S.; Diamant, Y.; Zaban, A., Preparation of Nb 2O5 Coated TiO2
Nanoporous Electrodes and Their Application in Dye-Sensitized Solar Cells. Chemistry of
Materials 2001, 13 (12), 4629-4634.
15. Wen, X.; Feng, Y.; Huang, S.; Huang, F.; Cheng, Y.-B.; Green, M.; Ho-Baillie, A.,
Defect trapping states and charge carrier recombination in organic–inorganic halide
perovskites. Journal of Materials Chemistry C 2016, 4 (4), 793-800.
192
16. Watanabe, A. J. S. s. i., Polymorphism in Bi14WO24: A monoclinic low-temperature stable
form with β≈90° and its displacive transformation to an orthorhombic intermediate
form at about 40° C. 2005, 176 (13-14), 1281-1289.
17. Wu, J.; Duan, F.; Zheng, Y.; Xie, Y., Synthesis of Bi 2WO6 nanoplate-built hierarchical
nest-like structures with visible-light-induced photocatalytic activity. The Journal of
18. Gui, M.-S.; Zhang, W.-D.; Su, Q.-X.; Chen, C.-H., Preparation and visible light
photocatalytic activity of Bi2O3/Bi2WO6 heterojunction photocatalysts. Journal of Solid
State Chemistry 2011, 184 (8), 1977-1982.
19. Li, X.; Huang, R.; Hu, Y.; Chen, Y.; Liu, W.; Yuan, R.; Li, Z., A templated method to
Bi2WO6 hollow microspheres and their conversion to double-shell Bi2O3/Bi2WO6 hollow
microspheres with improved photocatalytic performance. Inorganic chemistry 2012, 51
(11), 6245-6250.
20. Leghari, S. A. K.; Sajjad, S.; Chen, F.; Zhang, J., WO3/TiO2 composite with morphology
change via hydrothermal template-free route as an efficient visible light photocatalyst.
Chemical Engineering Journal 2011, 166 (3), 906-915.
22. Lou, S. N.; Scott, J.; Iwase, A.; Amal, R.; Ng, Y. H., Photoelectrochemical water
oxidation using a Bi2MoO6/MoO3 heterojunction photoanode synthesised by hydrothermal
treatment of an anodised MoO3 thin film. Journal of Materials Chemistry A 2016, 4 (18),
6964-6971.
193
23. Moniz, S. J. A.; Blackman, C. S.; Carmalt, C. J.; Hyett, G., MOCVD of crystalline Bi2O3
thin films using a single-source bismuth alkoxide precursor and their use in
photodegradation of water. Journal of Materials Chemistry 2010, 20 (36), 7881-7886.
25. Chai, S. Y.; Kim, Y. J.; Jung, M. H.; Chakraborty, A. K.; Jung, D.; Lee, W. I.,
Heterojunctioned BiOCl/Bi2O3, a new visible light photocatalyst. Journal of Catalysis 2009,
262 (1), 144-149.
26. Qin, D.-D.; Wang, T.; Song, Y.-M.; Tao, C.-L., Reduced monoclinic BiVO4 for improved
photoelectrochemical oxidation of water under visible light. Dalton Transactions 2014, 43
(21), 7691-7694.
27. Jiang, J.; Wang, M.; Chen, Q.; Shen, S.; Li, M.; Guo, L., Synthesis and characterization
of nanoporous Bi3NbO7 films: application to photoelectrochemical water splitting. RSC
Advances 2014, 4 (21), 10542-10548.
28. Tang, Y.; Traveerungroj, P.; Tan, H. L.; Wang, P.; Amal, R.; Ng, Y. H., Scaffolding an
ultrathin CdS layer on a ZnO nanorod array using pulsed electrodeposition for improved
photocharge transport under visible light illumination. Journal of Materials Chemistry A
2015, 3 (38), 19582-19587.
29. Zhong, S.; Zhang, F.; Lu, W.; Wang, T.; Qu, L., One-step synthesis of Bi2WO6/Bi2O3
loaded reduced graphene oxide multicomponent composite with enhanced visible-light
photocatalytic activity. RSC Advances 2015, 5 (84), 68646-68654.
30. Sheng, J.; Li, X.; Xu, Y., Generation of H2O2 and OH Radicals on Bi2WO6 for Phenol
Degradation under Visible Light. ACS Catalysis 2014, 4 (3), 732-737.
194
31. Peng, Y.; Yan, M.; Chen, Q.-G.; Fan, C.-M.; Zhou, H.-Y.; Xu, A.-W., Novel one-
dimensional Bi2O3-Bi2WO6 p-n hierarchical heterojunction with enhanced photocatalytic
activity. Journal of Materials Chemistry A 2014, 2 (22), 8517-8524.
195
Chapter 7. Conclusion and Recommendation
CHAPTER 7
CONCLUSION AND
RECOMMENDATIONS
7.1 Conclusion
To date, photocatalytic Z-scheme and photoelectrochemical (PEC) water splitting have
been successfully performed using Bi-based semiconductors for water oxidation.
However, further enhancement requires to achieve higher conversion effiency in water
oxidation process for industrialisation in the future. Hereby, research was conducted on
bismuth tungstate (Bi2WO6), to enhance photocatalytic and PEC water oxidation
reactions, by studying the key influencing factors to achieve increased light absorption,
improved charge separation and transport, and diminish photocorrosion within the oxide
material. This thesis explored various synthesis methods along with the corresponding
effects on physiochemical properties and charge kinetics within Bi2WO6 photocatalyst.
The effect of crystallinity and surface area properties of the oxide catalyst on
photocatalytic water oxidation was first investigated. Hierarchical Bi2WO6 microspheres
calcined at various temperatures (i.e. 0°C, 450°C, 550°C, 650°C and 750°C) were
employed. Apart from increased degree of crystallinity, higher annealing temperatures
also resulted in decreased Bi2WO6 total surface area. The optimal calcination temperature
196
was found to be 650°C. This sample exhibited the highest performance in photocatalytic
oxygen (O2) evolution, generating up to 240 µmol of O2. Thus, the improvement of the
photo-oxidation process using Bi2WO6 calcined at higher temperature demonstrated the
higher crystallinity is the more prevailing factor that influenced the photoactivity when
compared to surface area. Under a high calcination temperature, alteration in Bi2WO6
atomic crystal structure was discovered with shortened W-O length confirmed via Raman
spectroscopy. The shortened bond induced overlap between Bi 6p and O 2p orbitals in
Bi2WO6. This caused distortion of the lone pairs around the Bi cation and facilitated the
migration of photogenerated charge carriers to the bulk surface, which is proved to be
advantageous for water to O2 oxidation.
Apart from the investigation on Bi2WO6 powders, Bi2WO6 photoanode synthesis methods
were explored to probe its photoactivity in PEC measurement. By simply tuning the
tungsten to bismuth precursor ratio (W:Bi) during the hydrothermal synthesis step, a
series of plate-like Bi2WO6 with different morphologies were fabricated. With a higher
W:Bi ratio, the resulting plate-like Bi2WO6 displayed to have higher exposure extents of
the electron-dominated {010} crystal facet and more W self-doping. The larger exposed
{010} electron-dominated facet can explicitly address the higher photogenerated charge
density, indicating more electrons and holes can be exposed to the active site. On top of
that, although the W self-doping lowered the charge mobility, the higher charge carrier
concentration and lower charge transfer resistance allowed the generation of higher
photocurrent. Thus, higher W concentration during Bi2WO6 synthesis is demonstrated to
play a significant role in improving overall PEC performance.
197
The development of photoanode was further extended into fabricating thin film consists
of dual photocatalysts (i.e. Bi2WO6 and WO3). It is well known that heterojunction
formation promotes PEC water splitting performances. Unlike previous studies that focus
on the effects of facet engineering and self-doping, this research place emphasis on
understanding charge transfer efficiency in Bi2WO6/WO3 heterojunction with different
interfacial contact areas. For this purpose, a two-step process (electrodeposition followed
by hydrothermal treatment) was utilised to produce two thin film samples with difference
architectures: one thin film has a homogeneous distribution of Bi2WO6 and WO3 whereas
another had two distinct layers of the oxide species. A comparison revealed that the
photoanode that with homogenous distribution of WO3 and Bi2WO6 has higher interfacial
contact and exhibited greater photoresponse without additional bias during PEC
measurements. On the other hand, the photoanode with two rigid layers of WO3 and
Bi2WO6 demonstrated a much inferior performance. This was ascribed to the interfacial
barrier within the two distinct layers, where minimal electron transfer from Bi 2WO6 to
WO3 occurred, resulting in high recombination rate in the bulk materials.
In the ensuing study, photostability of photoanode comprising oxygen-deficient bismuth
tungstate (Bi14WO24) and Bi2O3 heterojunction was assessed. Leaching of Bi ions from
the Bi2O3 resulted in its instability and hence photocorrosion. With the presence of
protective and photoactive Bi14WO24 layer, photocorrosion of Bi2O3 was prevented. The
photogenerated holes were effectively withdrawn from the Bi2O3 when in contact with
Bi14WO24, thereby, restricting its self-oxidation reaction. Improved Bi2O3 stability upon
198
heterojunction formation with Bi14WO24 was demonstrated via the stable photoresponse
in long hours of PEC measurements.
In conclusion, these findings provided useful details on the strategies to design Bi 2WO6
particulate and photoelectrode for photocatalytic and PEC water oxidation reactions: high
crystallinity, sufficient W presence during synthesis to enable W self-doping, and
heterojunction structure. These characteristics were shown to contribute towards
photocatalytic performance through a common pathway: improved charge kinetics. These
findings play a key role in informing future strategies applicable to engineering of Bi-
based photocatalysts in enable the realisation of photocatalytic or PEC water oxidation at
an industrials scale.
7.2 Recommendation
In order to fabricate a Bi2WO6 powder or photoanode for effective photocatalytic and
PEC water oxidation, understanding its key influencing physicochemical properties is
herein shown to be important. The findings uncovered in this thesis further evoked
interesting avenues not only in material engineering, but also reactor system design and
the integration of both to bring upon the design of an innovative solution for a large scaled
photocatalysed water splitting. Proposed approaches are as detailed below.
199
7.2.1 Self-doping Bi3+: Fabrication, characterisation and optimisation for

photocatalytic water oxidation
From the studies, it is known that charge separation, high carrier density, and low charge
transfer resistance are the fundamental factors to enhance photoreactivity. This was
previously achieved by enriching Bi2WO6 with electron-dominated facet and enabling W
self-doping during synthesis. It is known that Bi self-doping in Bi2WO6 resulted in an
internal electric field within the Bi-O bond. This subsequently facilitate charge transport.1
Thus, further inquiry on the impact of Bi precursor concentration against PEC
performance is recommended. This investigation will expand our understanding
physicochemical modification in Bi2WO6, such as morphology and the charge kinetics
properties upon precursor ratio variation. A systematic inspection of charge carrier
density and mobility of Bi self-doped Bi2WO6 photoanode via EIS and TRMC
measurement is also necessary. The results can be further compared with the W self-
doped Bi2WO6 to provide a more comprehensive understanding on Bi2WO6 photoanode.
In addition, density functional theory (DFT) computational studies can be employed to
calculate the surface energy of each crystal facet. The computed results can inform
decisions on how the material can be tailored to maximise exposure extent of the most
active facet for greater separation and thus better PEC performance.
7.2.2 Performing Overall PEC water splitting and Engineering the Reactor
Chapters 4 to 6 revealed the generation of high photocurrent density under small applied
bias for plate-like Bi2WO6 and heterojunction (Bi2WO6/WO3 or Bi2WO6/Bi2O3)
photoanodes. However, the performance measured by utilising Bi2WO6 is only based on
200
the oxidation half-reaction, the conversion efficiency from the overall PEC water splitting
process is not clarified. Therefore, implementing an overall water splitting reaction with
the incorporation of Bi2WO6 and H2 evolving catalyst (such as InGaN2 and CuGaSe23) in
a two- or three-electrode system (including the n-type and p-type catalyst as the working
electrode, and Ag/AgCl as the reference electrode) is recommended. This allows
determination of the effectiveness of the Bi2WO6 photoanode, so as to further modify the
semiconductor for achieving a higher H2 and O2 production yield. Apart from researching
efficient semiconductors for overall water splitting process, a specific effort should also
be devoted in optimising the design of the water splitting reactor. It is known that a back
reaction could occur when the produced H2 and O2 recombined.4 Thus, modification of
the water splitting reactor is recommended to further enhance the overall efficiency
because some designs could potentially impede the production of H2 and O2 in PEC
system. One of the important parameters involved in reactor design is the distance,
between the working electrodes, in which larger distance causes higher charge transfer
resistance. The distance between the working electrodes to the light source could also
influence the photon flux received on the surface of the semiconductors. Furthermore,
other components, such as the type of membrane used to separate the cathode and anode
compartments and material used to construct the illumination window will eventually
affect the overall performance.5, 6 Therefore, integration of well-designed reactor system
is just as important as designing an effective Bi2WO6 photoanode to strategize an
enhancement in overall PEC conversion efficiency.
201
7.3 References
1. Ding, X.; Zhao, K.; Zhang, L., Enhanced photocatalytic removal of sodium
pentachlorophenate with self-doped Bi2WO6 under visible light by generating more
superoxide ions. Environmental science & technology 2014, 48 (10), 5823-5831.
2. Kibria, M. G.; Chowdhury, F. A.; Zhao, S.; AlOtaibi, B.; Trudeau, M. L.; Guo, H.; Mi,
Z., Visible light-driven efficient overall water splitting using p-type metal-nitride nanowire
arrays. Nature communications 2015, 6, 6797.
3. Moriya, M.; Minegishi, T.; Kumagai, H.; Katayama, M.; Kubota, J.; Domen, K., Stable
hydrogen evolution from CdS-modified CuGaSe2 photoelectrode under visible-light
irradiation. Journal of the American Chemical Society 2013, 135 (10), 3733-3735.
4. Xiao, L.; Wu, S.-Y.; Li, Y.-R., Advances in solar hydrogen production via two-step water-
splitting thermochemical cycles based on metal redox reactions. Renewable Energy 2012,
41, 1-12.
Reviews 2010, 11 (4), 179-209.
6. Minggu, L. J.; Wan Daud, W. R.; Kassim, M. B., An overview of photocells and
photoreactors for photoelectrochemical water splitting. International Journal of Hydrogen
Energy 2010, 35 (11), 5233-5244.
202

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Surname or Family name: CHUNG

First name: HOI YING Other name/s:

Abbreviation for degree as given in the University calendar: PhD

School: School of Chemical Engineering Faculty: Engineering

Title: Development of Efficient Bismuth Tungstate for Photocatalytic and Photoelectrochemical

Declaration relating to disposition of project thesis/dissertation

………………………………………… ……………………………………..…………….. ……….……………………...

FOR OFFICE USE ONLY Date of completion of requirements for Award:

UNSW is supportive of candidates publishing their research results during their

Publications can be used in their thesis in lieu of a Chapter if:

Please indicate whether this thesis contains published material or not.

☐ has been documented in the relevant Chapters with

Postgraduate Coordinator’s Declaration (to be filled in where publications are used

because of the involvement of four-electron transfer mechanism. Bismuth tungstate

(Bi2WO6) is a photoactive semiconductor capable of oxidising water into oxygen and

to achieve improved photocatalytic and photoelectrochemical (PEC) efficiency.

Firstly, the synthesis of hierarchical Bi2WO6 microspheres with controllable crystallinity

and surface area was achieved through a combination of hydrothermal/calcination

transportation was observed.

recombination and beneficial to the photo-oxidation process.

The performance of Bi2WO6 was further improved by the creation of heterojunction.

Controlled transformation of tungsten oxide (WO3) to Bi2WO6 via electrodeposition and

hydrothermal method successfully introduced heterojunction Bi2WO6/WO3. A higher

of photoelectrons. It directly optimises the PEC water splitting to an ideal situation,

components. The findings in this thesis could be applicable to other oxide-based

preparing this thesis without their precious guidance.

my research in the solar field.

my thanks to Ms Ik Ling Lau, Ms Ee Meen Iliffe, Mr John Starling, Mr Ravi

technicians work in our chemical engineering faculty.

the fun we have had in the last four years.

supported me spiritually throughout the PhD, both by keeping me harmonious and

Oxygen-Deficient Bismuth Tungstate and Bismuth Oxide Composite Photoanode

with Improved Photostability. Science Bulletin, 2018, 63(15), 990-996

Surface Area of Bismuth Tungstate for Photocatalytic Water Oxidation. Molecules

Manipulating the Fate of Charge Carriers with W Concentration: Enhancing PEC

Water Oxidation of Bi2WO6, Advanced Function Materials (in preparation)

Homogeneous and Rigid Heterojunction of Bi2WO6/WO3 Thin Film, Journal of

Physical Chemistry C (in preparation)

Co-author Journal Publications

L.; Ng, Y.H., Pulsed Electrodeposition of Co3O4 Nanocrystals on One-

Dimensional ZnO Scaffolds for Enhanced Electrochemical Water Oxidation.

ChemPlusChem, 2018, 83(10), 886

R.; Scott. J., Construction of a Bi2MoO6: Bi2Mo3O12 Heterojunction for Efficient

Photocatalytic Oxygen Evolution. Chemical Engineering Journal, 2018, 353,

Sydney Australia (POSTER)

2. Chemeca, 23-26 July, 2017, Melbourne Convention and Exhibition Centre,

Melbourne, Australia (ORAL)

3. Asian Pacific Confederation of Chemical Engineering (APCChe), 23-27 August,

Republic of China (ORAL)

4. International Conference on nanoscience and Nanotechnology (ICONN), 29 January-

2 February, 2018, The University of Wollongong, Wollongong, Australia (ORAL

and POSTER) *Won the Best Oral Presentation*

5. International Symposium on advanced materials & sustainable technologies

*Won the ECR Session Chair Award*

6. European Materials Research Society (EMRS), 17 - 20 September, 2018, Warsaw

University of Technology, Warsaw, Poland (POSTER)

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and POSTER) Won the Best Oral Presentation

Won the ECR Session Chair Award