Fabrication of High Quality One Material Anode

Fabrication of High Quality
One Material Anode and Cathode

for Water Electrolysis in Alkaline Solution
By
Jingshu JIA
A Thesis Submitted to
The Hong Kong University of Science and Technology
in Partial Fulfilment of the Requirements for
the Degree of Master of Philosophy
in the Environmental Engineering Program
School of Engineering
December 2008, Hong Kong
Copyright © by Jingshu JIA 2008
HKUST Library i
Reproduction is prohibited without the author’s prior written consent
Acknowledgements
I would like to express my deepest appreciation to my supervisor Prof.
Guohua Chen, for introducing this exciting research topic to me. During my
whole master studies, he gave me excellent guidance, invaluable
suggestions, enthusiastic encouragement. I always feel inspired by his
dedication to excellence, and careful attention to details. My overseas
experience to Tokyo Institute of Technology would not be possible without his
support. I feel lucky to have Prof. Guohua Chen as my supervisor.
I wish to thank Prof. Xijun Hu and Prof. Chii Shang for their serving on the
committee and providing constructive comments.
I would like to thank my group mates, Dr. Wei Wang, Dr. Caideng Yuan, Dr.
Liang Guo, Dr. Minyong Xiong, Mr. Huanjun Zhang, Mr. Xusong Qin, Mr. Bin
Yang, Mr. Jing He, Miss Shanshan Wang, Miss Mo Lin and Miss Molenda for
their friendship assistance, discussion and encouragement during my study. It
is fortune for me to have many friends in HKUST, Dr. Ke Yao, Dr. Junde Lv,
Mr. Qilei Zhang, Mr. Feng Zhou, Dr. Huan Wang, Miss Wenjing Zhang, Miss
Min Zuo, Ms. Rujie Wang, Miss Yan Geng, Miss Wuman Luo and Mr. Zhiyan
Li. Miss Yan Geng, Miss Wenjing Zhang，Miss Shanshan Wang and Mr. Jing
He have lent their kind help during my thesis writing and revision. Without
their help, I cannot imagine how I can complete this work in less than a month.
I would like to express my thanks to the technicians in the Department of

Chemical and Bimolecular Engineering, Civil and Environmental Engineering,
and MCPF, especially Mr. Ho, Mr. Huang, and Ms. Cheung, for their helpful
assistance in my research.
I would like to thank my friends outside HKUST, including Mr. Guanghui

Wang, Miss Jiahua Huang, Miss Xuesong Du. They always provide moral
support to me at the needed time.
Finally, I would like to thank my parents for their unconditional love,

understanding and support. Without their encouragement and care, this work
could not have been finished in such a short time.
iv
Table of Contents
Title i
Authorization ii
Signature iii
Acknowledgements iv
Table of Contents v
List of Figures viii
List of Tables xi
Abstract xii
Chapter 1 INTRODUCTION 1
1.1 Background 1
1.2 Research Objectives 4
Chapter 2 LITERATURE REVIEW 5
2.1 Introduction of Electrochemistry 5
2.2 Electrode Fabrication Methods 6
2.2.1 Thermal Decomposition Method 7
2.2.2 Sol-gel Method 7
2.2.3 Electrostatic Spray Deposition (ESD) 8
2.2.4 High-energy Ball Milling (HEBM) 9
2.2.5 Chemical Vapor Deposition (CVD) 9
2.3 Application of Electrochemistry 10
2.4 Electrochemical Technology in Environmental
Application 10
2.5 Electroflotation 12
2.5.1 Overview 12
2.5.2 Electrodes for O2 Evolution 14
2.5.2.1 Graphite, PbO2 and Pt 14
2.5.2.2 DSAs 14
2.5.3 Electrodes for H2 Evolution 17
v
2.5.3.1 Metals and Alloys 17
2.5.3.2 DSAs 18
2.6 Summary 20
Chapter 3 EXPERIMENTAL SET UP 22
3.1 Chemicals and Materials 22
3.2 Preparation of Ti/metal Oxide Electrodes 23
3.2.1 Pretreatment of Ti Substrate 23
3.2.2 Precursor Solution Preparation 23
3.2.3 Electrode Preparation 23
3.3 Accelerated Service Life Tests 24
3.4 Physiochemical Characterization 25
3.4.1 Scan Electron Microscopy (SEM) 25
3.4.2 X-ray Diffraction (XRD) 26
3.4.3 X-ray Photoelectron Spectroscopy (XPS) 26
3.4.4 Inductively Coupled Plasma Mass
Spectrometry (ICP-MS) 26
3.4.5 Coating Resistivity 26
3.5 Electrochemical Characterization 26
Chapter 4 SEARCHING FOR PROPER ELECTRODE
MATERIALS 29
4.1 Introduction 29
4.2 Experimental Results 31
4.2.1 Ir-based Electrodes 31
4.2.2 Other Metals-based Electrodes 34
4.2.3 Ru-based Electrodes 37
4.2.4 Co-based Electrodes 43
4.3 Summary 52
Chapter 5 STUDIES OF Ti/CuxCo3-xO4 ELECTRODES FOR
BOTH OXYGEN AND HYDROGEN EVOLUTION IN
ALKALINE SOLUTION 53
5.1 Introduction 53
5.2 Molar Ratio Optimization 54
vi
5.2.1 Accelerated Service Life Test 54
5.2.2 EDX 56
5.3 Electrolyte Temperature Effect on Accelerated
Service Life 56
5.4 Physicochemical Characterization 57
5.4.1 SEM 57
5.4.2 XRD 59
5.4.3 XPS 61
5.4.4 ICP 63
5.4.5 Coating Resistivity 63
5.5 Electrochemical Behavior 64
5.5.1 Cyclic Voltammetry 64
5.5.2 Polarization Curves for Hydrogen Evolution 65
5.6 Electrode Surface Changing and Mechanism of
Oxygen and Hydrogen Evolution in Alkaline Solution 69
5.6.1 Fixed Current Direction Electrolysis Process 69
5.6.2 Alternating Current Direction Electrolysis
Process 72
5.7 Summary 88
Chapter 6 CONCLUSIONS 89
6.1 Conclusions of Present Study 89
6.2 Recommendations for Future Work 90
Reference 92
vii
List of Figures
Figure 2.1 Schematic diagram of the experimental apparatus

used for electrostatic spray deposition 8
Figure 3.1 The process of Ti substrate pretreatment 23
Figure 3.2 Experimental setup for accelerate service life test 25
Figure 3.3 Schematic diagram of a three-electrode cell 27
Figure 4.1 SEM picture of Ti/IrO2-Sb2O5-SnO2 electrode 32
Figure 4.2 SEM picture of Ti/PdO-Sb2O5-SnO2 electrode 33
Figure 4.3 SEM picture of Ti/IrO2-Sb2O5-SnO2 with PdO-Sb2O5-
SnO2 electrode 33
Figure 4.4 SEM picture of Ti/RhOx-Sb2O5-SnO2 electrode 34
Figure 4.5 SEM picture of Ti/PtOx-Sb2O5-SnO2 electrode 35
Figure 4.6 SEM picture of Ti/Au electrode 36
Figure 4.7 SEM picture of Ti/Au-Sb2O5-SnO2 electrode 37
Figure 4.8 SEM picture of Ti/ RuO2-Sb2O5-SnO2 electrode 38
Figure 4.9 SEM picture of Ti/RhOx-RuO2-Sb2O5-SnO2 electrode 38
Figure 4.10 SEM picture of Ti/PdO-RuOx-Sb2O5-SnO2 electrode 40
Figure 4.11 SEM picture of Ti/ RuO2-TiO2 electrode 41
Figure 4.12 SEM picture of Ti/RuO2-TiO2-CeO2 electrode 41
Figure 4.13 SEM picture of Ti/RuO2-ZrO2 electrode 43
Figure 4.14 SEM picture of Ti/Ru0.9Co2.1O4 electrode 44
Figure 4.15 SEM picture of Ti/Rh0.1Co2.9O4 electrode 45
Figure 4.16 SEM picture of Ti/Ir0.9Co2.1O4 electrode 47
Figure 4.17 SEM picture of Ti/Ni1.5Co1.5O4 electrode 48
Figure 4.18 SEM picture of Ti/Cu0.3Ni1.35Co1.35O4 electrode 49
Figure 4.19 SEM picture of Ti/Cu1.5Co1.5O4 electrode 50
Figure 4.20 Cathode accelerated service life in acid electrolyte
with fixed current direction electrolysis process 51
Figure 4.21 Cathode accelerated service life in alkaline electrolyte
with alternating current direction electrolysis process 51
viii
Figure 5.1 Temperature effect on accelerated service life 57
Figure 5.2 SEM images of oxide coating surfaces. (a) Co3O4;
(b) Cu0.1Co2.9O4; (c) Cu0.3Co2.7O4; (d) Cu0.6Co2.7O4;
(e) Cu0.9Co2.1O4; (f) Cu1.2Co1.8O4; (g) Cu1.5Co1.5O4 59
Figure 5.3 XRD patterns for Ti/CuxCo3-xO4 electrodes (x=0, 0.3,
1.5), pure titanium substrate and Ti/CuO electrode 60
Figure 5.4 XPS spectra of Ti/Cu0.3Co2.7O4 electrode 62
Figure 5.5 Cyclic votammograms for Ti/Cu0.3Co2.7O4 in 1M
NaOH obtained at a sweep rate of 50 mV/s. The
electrodes had an area of 2.55 cm2 65
Figure 5.6 Potential versus current density curves for hydrogen
evolution from 1 M NaOH on a Ti/Cu0.3Co2.7O4
electrode. (1) First run; (2) second run. Arrows
indicate the direction of potential variation 67
Figure 5.7 Application of Equation 5.2 in the text to the current-
potential data (2nd run, reverse direction) of Figure
5.6 to derive ohmic drop and Tafel slopes. Insert:
enlargement of initial part of the main plot to give
evidence to the intercept 68
Figure 5.8 Experimental data corrected for IR drop 68
Figure 5.9 XRD patterns of Ti/Cu0.3Co2.7O4 virgin electrode 70
Figure 5.10 XRD patterns of fixed current direction electrodes.
(a) anode, (b) cathode 71
Figure 5.11 XRD patterns of the first pair (one day using) of
electrodes. (a) anode (E 1), (b) cathode (E 2) 74
Figure 5.12 SEM pictures of the first pair (one day using) of
Figure 5.13 SEM pictures of the second pair (two days using) of
Figure 5.14 XRD patterns of the second pair (two days using) of
Figure 5.15 XRD patterns of Ti substrate 78
ix
Figure 5.16 XRD patterns of the third pair (ten days using) of
Figure 5.17 SEM pictures of the third pair (ten days using) of
Figure 5.18 SEM pictures of the fourth pair (twenty days using) of
Figure 5.19 XRD patterns of the fourth pair (twenty days using) of
Figure 5.20 XRD patterns of the fifth pair (thirty days using) of
Figure 5.21 SEM pictures of the fifth pair (thirty days using) of
Figure 5.22 SEM pictures of the sixth pair (forty days using) of
Figure 5.23 XRD patterns of the sixth pair (forty days using) of
Figure 5.24 XRD patterns of the used out electrodes. (a) anode (E
1), (b) cathode (E 2) 86
Figure 5.25 SEM pictures of the used out electrodes. (a) anode (E
1), (b) cathode (E 2) 87
x
List of Tables
Table 2.1 Economic parameters in treating oily effluents 12
Table 4.1 Accelerated service life of Ti/RuO2-ZrO2 electrode 42
Table 4.2 Accelerated service life of Ti/Ru0.9Co2.1O4 electrode 44
Table 4.3 Accelerated service life of Ti/Rh0.1Co2.9O4 electrode 45
Table 4.4 Accelerated service life of Ti/Ir0.9Co2.1O4 electrode 46
Table 4.5 Accelerated service life of Ti/Ni1.5Co1.5O4 electrode 48
Table 4.6 Accelerated service life of Ti/Cu0.3Ni1.35Co1.35O4
electrode 49
Table 4.7 Accelerated service life of Ti/Cu1.5Co1.5O4 electrode 50
Table 5.1 Accelerate service life of Ti/CuxCo3-xO4 electrodes in
1 M NaOH solution under 10,000 Am-2 at 35 °C 55
Table 5.2 Atomic ratios for Ti/CuxCo3-xO4 electrodes nominal
and experimental obtained by EDX techniques 56
Table 5.3 Surface compositions of Cu0.3Co2.7O4 films measured
by XPS 63
Table 5.4 Effect of Cu content on coating resistivity 64
xi
Fabrication of High Quality
One Material Anode and Cathode
for Water Electrolysis in Alkaline Solution
By
Jingshu JIA
Environmental Engineering Program
School of Engineering
The Hong Kong University of Science and Technology
Abstract
Electroflotation is receiving more and more attention for wastewater treatment.
This electrochemical process employs the oxygen and hydrogen gas bubbles
evolved from the surfaces of anode and cathode during water electrolysis. The
lack of ideal electrodes that can service as both anode and cathode has been a
problem since the very beginning of the study of this process. This dissertation
reports a kind of unique electrode that can partly solve this problem.
xii
After careful examination of 16 different materials including metal oxides of Ir,
Ru, Rh, Pt, Sb, Sn, Ti, Cu, Pd, Ni and Co, the CuxCo3-xO4 combination was
found to be the candidate for the one material electrode. The Ti/CuxCo3-xO4
electrode (x = 0~1.5) developed in the present work was much more stable
compared with the other electrodes. All the electrodes were prepared by
thermal decomposition at 550 °C from metal chloride salts precursors which
were dissolved in a mixture of 37 % HCl and isopropanol solution. The stability
of Ti/Cu0.3Co2.7O4 electrode was found to be the best, lasting for 1080 h under
daily alternative anodic and cathodic polarization in 1 M NaOH electrolyte.
The Ti/CuxCo3-xO4 electrodes were characterized by different techniques such

as scanning electron microscopy connected with energy-dispersive X-ray (SEM-
EDX), X-ray diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS),
cyclic voltammetry and quasi-steady state polarization curves. The effect of
crystallographic properties and surface morphology have been analyzed
systemically before and after this one material electrodes used in water
electrolysis process. Under hydrogen evolution condition, cobalt oxide could be
reduced to amorphous metal Co and Co(OH)2. The formation of the amorphous
Co is the key process for this kind of electrode to be served as both anode and
cathode under alternative current. It is also the main reason leading to the
failure of the electrode eventually.
xiii
CHAPTER 1 INTRODUCTION
1.1 Background
Since the early 16th and 17th centuries, electrochemistry went through several
evolutions involving complex theories such as conductivity, electrical charge and
mathematical methods, till late 19th century when the term electrochemistry was
used to describe electrical phenomena. Nowadays, electrochemistry has
become an area of current research, including research in batteries and fuel
cells, corrosion prevision of metals, and techniques in electrolysis cells
improvement (Wikipedia). Scientists and engineers working in diverse areas
need to locate and use electrochemical technology (Bard, 2006).
For decades electrochemical technologies have contributed successfully to

environmental protection (Janssen and Koene, 2002) mainly dealing with water
and wastewater, wastes and soils treatment. A particular focus is given to
electrocoagulation (EC), electrodeposition (ED), electroflotation (EF),
electrokinetic (EK), electrooxidation (EO), electrochemical disinfection (ECD)
and photoelectrooxidation (PEO) processes. These technologies are effective in
improving the treatment quality of industrial wastes, wastewater and drinking
water on integration into a treatment plant or replacement of conventional
processes that are found to be less effective to eliminate specific organic and
inorganic pollutants (Patrick et al., 2007). All these technologies are conducted in
electrolysis cells, which have three basic components: an electrolyte and two
electrodes. The performance of electrode could restrict efficiencies of all these
electrochemical processes (Macdonald and Schmuki, 2007).
Electroflotation, one of the environmental protection wastewater treatment

technologies, is an attractive method at present (Chen et al., 2002), because of
its high efficiency, compact facility, and easy operation (Bockris and Khan, 1993;
Sequeira, 1994) and could be considered as the most effective process in
1
removing colloidal particles, oil & grease, as well as organic pollutants (Chen,
2004).
In an electrofloatation (EF) process, pollutants adhered onto tiny bubbles of

hydrogen and oxygen generated from electrolysis of water. The electrochemical
reactions at the cathode and anode are hydrogen and oxygen evolution,
respectively. Considering the increasing importance of EF as a tool for
environmental application (Casqueir et al., 2006), many electrodes have been
fabricated for electroflotation, with Dimensional Stable Anodes (DSAs) being the
most widely used. For example, Ti/IrO2-Sb2O5-SnO2 (Chen et al., 2001) should
be considered as one of the best DSAs which could last for 1600 h in 3 M H2SO4
solution under a current density of 1 Acm-2 at 35 °C. Besides Ti/IrO2-Sb2O5-SnO2
electrode, Chen and Chen (2005) also developed Ti/RuO2-Sb2O5-SnO2
electrode which had a good performance with accelerated service life of 307 h in
3 M H2SO4 solution under a current density of 0.5 Acm−2 at 25 °C for anode which
is believed to be stable enough for applications in which low current densities
(<0.02 A cm-2) are required.
In real electroflotation application, DSAs and metal such as stainless steel are
employed as anode and cathode, respectively. After a certain time of working, a
lot of substances or produced polymers would attach onto the surfaces of both
electrodes which may severely decrease the current efficiency of the
electroflotation. If chloride and heavy metal ions contained wastewater is treated
by electroflotation process, the metal cathode can suffer from poisoning effect by
chloride corrosion and metal deposits which also influence the electroflotation
efficiency (Nidola and Schira, 1990).
To solve these problems, it is proposed to find a DSA-based electrode that can

be utilized as anode and also cathode. The main benefits of using one material
for both anode and cathode are listed below:
2
• Self-cleaning. After certain operating time of electroflotation, the anode
and cathode may have some foreign materials deposited. Such a
deposition would hinder the performance of the electrodes. If one material
electrodes are installed in the electrolysis cell, the deposited materials
may be removed by changing the polarity of the electrodes. This
operation would lead to the self-cleaning of the electrode surfaces
automatically.
• Tolerating chlorides and metal ions. The service life of platinum or

nickel cathode is influenced greatly by the concentration of chloride and
metal ions in solution, which could easily deactivate the cathode surface.
As a consequence of the surface chemistry of oxides, compared to the
respective metals, metal oxides may be less sensitive to the poisoning by
chloride and metal deposits (Nidola and Schira, 1990).
• Reducing the cost from mal-operation. Anode material is usually more

expensive than the cathode materials in an electroflotation system.
However, as discussed before, a quick loss of stability may be resulted
when there is a human error in the installation and operation of the
system, if the material can only function as an anode. One material
electrode would eliminate such a problem since the electrode is
insensitive to the polar connection.
• Saving electricity cost. The most conventional cathode materials used

today are mild steel, stainless steel and nickel exhibiting overvoltages
ranging from 300 to 400 mV. These overvoltages are much higher than
the anode overvoltage with a level normally lower than 50 mV (Cornell
and Simonsson, 1993). The one material electrodes made of metal oxides
similar to those Dimension Stable Anodes (DSAs) could decrease the
cathode overvoltage dramatically to 70 mV (Houda et al., 2003). This
would proportionally reduce the electrical energy consumption.
3
1.2 Research Objectives
With the background of research as introduced above, the research objectives of

this study are therefore
• to fabricate highly dimensional stable electrodes to be applied as both
anode and cathode with long service life, good activity and low cost,
• to investigate physicochemical and electrochemical characteristics of
the target electrodes,
• to evaluate the performance of the novel electrode for oxygen and
hydrogen evolutions, and,
• to explore the mechanism of the electrode failure.
4
CHAPTER 2 LITERATURE REVIEW
2.1 Introduction of Electrochemistry
Electrochemistry is the branch of chemistry concerned with the interrelation of

electrical and chemical effects. A large part of this field deals with the study of
chemical changes caused by the passage of an electric current and the
production of electrical energy by chemical reactions (Bard, 2006).
Modern electrochemistry presents itself as a strongly diversified field, which one

would call “applied electrochemistry”, ranging from electrochemical processes
for synthesis of inorganic or organic compounds, energy conversion, sensor
development, electro-analytical devices, electrolytic anti-corrosion to solid-state
ionic, electrode fabrication methods and any kind of system where charge
transfer is involved at an electrified interface between electronic and ionic
conductors. Research is more and more specialized on very particular problems,
to find proper electrode material for different electrochemical processes for
example (Macdonald and Schmuki, 2007).
Applied electrochemistry can provide valuable cost efficient and environmentally

friendly contributions to industry process development with a minimum of waste
or toxic material production. Examples are the implementations of
electrochemical effluent treatment, such as the removal of suspended solids
from solutions, destruction of organic pollutants, or abatement of toxic gases
(Macdonald and Schmuki, 2007).
The main advantages of electrochemical processes are as follows (Macdonald

and Schmuki, 2007):
• Versatility: Direct or indirect oxidation and reduction, phase separation,

concentration or dilution, biocide functionality, applicability to a variety of
5
media and pollutants in gases, liquids, and solids, and treatment of small
to large volumes from microliters up to millions of liters.
• Energy efficiency: Lower temperature requirements than their
nonelectrochemical counterparts, for example, anodic destruction of
organic pollutants instead of thermal incineration; power losses caused by
inhomogeneous current distribution, voltage drop, and side reactions
being minimized by optimization of electrode structure and cell design.
• Amenability to automation: The system inherent variables of
electrochemical processes, for example, electrode potential and cell
current, are particularly suitable for facilitating process automation and
control.
• Cost effectiveness: Cell constructions and peripheral equipment are
generally simple and, if properly designed, also inexpensive.
Since electrochemical reactions take place at the interface of an electronic

conductor, the electrode, and an ion conductor, the electrolyte, electrochemical
processes are heterogeneous in nature. This implies that, despite the
advantages mentioned above, the performance of electrochemical processes
suffers from the performance of electrode and the size of the limited electrode
area. Another crucial point is also concern with the stability of cell components
which always in contact with aggressive media; in particular, the durability and
long-term stability of the electrode material and catalyst (Parsons, 1961).
2.2 Electrode Fabrication Methods
Electrodes can be fabricated in many ways. For pure metal electrodes, they are
relatively easy to fabricate. For example, current industrial carbon electrodes are
typically manufactured by blending petroleum coke particles (the filler) with
molten coal tar pitch (the binder) and extruding the resultant mix to form the
“green electrode”. This is then baked under controlled conditions. In case of
usage as anodes in steel electric furnaces (or as other carbon and graphite
products), the electrodes could undergo further processing like pitch
6
impregnation or graphitization (Adumbrava et al., 1999). In the following text,
some typical electrode fabrication methods in these days’ research and
application will be reviewed.
2.2.1 Thermal Decomposition Method
The thermal decomposition method is commonly used nowadays, due to its easy
condition and low equipment cost (Beer, 1972, 1973, 1980, 1982; Novak et al.,
1982). The detailed schematic diagram of thermal decomposition method for
metal oxide electrode producing will be shown in next chapter and all electrodes
fabricated in this project are applied thermal decomposition method. When apply
this method, normally the corresponding metal chloride salts and metal nitrate
salts are used as the respective metal sources, which are dissolved into mixture
of isopropanol and hydrochloric acid to form precursor solution (Fachinotti et al.,
2006). The main principle of thermal decomposition method is oxidation
reactions which happened on electrode surface in high temperature furnace. By
changing brush cycles, calcination temperature and precursor compositions,
electrochemical and physicochemical properties of electrodes could be easily
controlled (Chen, 2002).
2.2.2 Sol-gel Method
The sol-gel process is a wet-chemical technique (Chemical Solution Deposition)

for the fabrication of materials starting either from a chemical solution (sol short
for solution) or colloidal particles (sol for nanoscale particle) to produce an
integrated network surface morphology (Wikipedia). Sol-gel synthesis is widely
used for making transition-metal oxide solids with fine-scaled microstructures
(Anderson and Bard 1995; Antonelli and Ying 1995; Lakshmi et al., 1997).
Sol-gel preparation, which involves the formation of a sol followed by formation
of a gel, typically uses either colloidal dispersions or inorganic precursors as the
starting material. With an alkoxide (M(OR)n) as a precursor solution, sol-gel
chemistry can be described in terms of two classes of reactions (Ward and Ko,
1995):
7
Hydrolysis: MOR + H2O → MOH + ROH (2.3)
Condensation: MOH + ROM → MOM + ROH (2.4)
or MOH + HOM → MOM + H2O (2.5)
Sol-gel research grew to be so important that in the 1990s more than 35,000
papers were published worldwide on the process (Wikipedia).
2.2.3 Electrostatic Spray Deposition (ESD)
The ESD technique has shown many advantages over several conventional
deposition techniques, such as a simple set-up, inexpensive and nontoxic
precursors, high deposition efficiency and, in particular, easy control of the
surface morphology of the deposited layers by changing various parameters,
such as precursor concentration, deposition temperature, deposition time and
liquid flow rate. This technique is widely used in fabrication cathode for energy
conversion using solid oxide fuel cells (SOFCs) because of its capability of
providing un-agglomerated mono-disperse particles in the nanometer diameter
range (Taniguchi et al., 2002).
Figure 2.1 Schematic diagram of the experimental apparatus used for

electrostatic spray deposition. 1.Micro feeder, 2.Srainless steel nozzle,
3.Test section, 4.Substrate, 5.Heating element, 6.D.C. high voltage supply,
7.CCDcamera and monitor, 8.Light source
8
2.2.4 High-energy Ball Milling (HEBM)
HEMB is known as an effective means of preparing nonequilibrium and

metastable phases, amorphous alloys etc. In summary, high-energy mechanical
alloying by ball-milling consists of a powder mixture by repeated mechanical
deformations. During milling, numerous structural defects are created which
increase the interatomic diffusion, thereby allowing a solid-state reaction to
proceed. Also strain is introduced in the lattice during milling, which results in
crystal breaking into smaller pieces down to the nanometer range. Metal oxides
is milled together, added water and polytetraflorthylene to form slurry, then slurry
is painted on substrate and dried under a nitrogen flow. HEMB method could
resist precipitation kinetics of two (or more) dissimilar metallic ions (Gaudet et al.,
2005). But the adhesion effect between substrate and metal oxide film is poor.
2.2.5 Chemical Vapor Deposition (CVD)
CVD has been a powerful technique in synthesizing film-structured materials with

a variety of morphologies and properties such as metal oxide semiconductors,
diamond-related materials, carbon nanotubes, etc. In a typical CVD process, the
substrate is exposed to one or more volatile precursors, which react and/or
decompose on the surface of the substrate to produce the desired deposit.
Frequently, volatile byproducts are also produced, which are removed from the
reaction region by gas flow though the reaction chamber (Zhang et al., in press).
Particularly in the fabrication of film-structured diamond electrodes, some new
techniques have been incorporated on the basis of the traditional CVD and such
new methods as hot-filament vapor deposition (HFCVD). Boron-doped
diamond-film-coated titanium (Ti/BDD) has fabricated by HFCVD, the
accelerated working lifetime was significantly increased to 804 h for the 2-T
electrode, compared with 244 h for the diamond-film electrode fabricated under
the one-temperature (1-T)-stage method (Guo and Chen, 2007).
9
2.3 Application of Electrochemistry
Electrochemistry principle involves redox reactions (shorthand for

reduction-oxidation reactions) which describe all chemical reactions where an
electron is transferred to or from a molecule or ion changing its oxidation state.
This reaction can occur through the application of an external voltage or though
the release of chemical energy. Redox reactions are the foundation of
electrochemical cells (Milos, 1990; 1996).
Electrochemical reactions have many applications, but those electrochemical

reactions which take place in cells have unique applications because cell
reactions can involve electricity flowing through metallic conductors. For this
reason, electrochemical cells can serve as sources of electrical power such as in
a fuel cell. The same processes are also responsible for the deleterious
corrosion of metals. Electrochemical reactions which consume electrical power
can have useful effects, as in the processes of industrial electrolysis (Plambeck,
1998).
Electrolytic industrial processes for metals include the production of metals

themselves from their compounds, which is called the electrowinning of metals;
the electrolytic purification of metals; and the deposition or electroplating of
metals on conducting surfaces. In all these types of electrolytic process, the
reactions are reduction of ions of the metal in solution in some carefully selected
electrolyte. While most of the electrolytic processes that involve metals are
reductions, most of the electrolytic processes that involve nonmetals are
oxidations. Among them, electrolysis of water process uses both the anodic
oxidation and cathodic reduction processes (Plambeck, 1998).
2.4 Electrochemical Technology in Environmental Application
Electrochemical technology has contributed successfully to environmental

protection for over a century (Chen, 2004; Janssen and Koene, 2002).
10
Electrocoagulation (EC) can be used for clarifying water or to eliminate organic,
inorganic and microbial pollutants from wastewater. The technology delivers in
situ coagulant by anodic dissolution of sacrificial electrodes (aluminium or iron)
and is finding wider applications with the possible improvements in the reduction
of energy consumption and metallic sludge production. Electrodeposition (ED) is
a well-established process for toxic metal removal whose effectiveness can be
greatly improved by selecting suitable electrode material (type and geometry of
the electrode). Electroflotation (EF) technology is effective in removing
suspended solids, colloidal particles and oil & grease suspension. Electrokinetic
(EK) technology is a promising method to remove toxic metals from the matter
with low hydraulic permeability or to enhance dewaterability of wastes including
soils and sludge. The development of new, more stable and active catalytic
electrodes has led to a renewed interest in Electrooxidation (EO) for degrading
toxic or biorefractory pollutants (Chen, 2004; Patrick et al., 2007).
Electrodisinfection (ECD) is a process in an electrolytic system equipped with
electrodes on which electric current is applied and it can be considered as
effective method because of its primary advantage of in situ production of
disinfectants in the treatment system (Fang et al., 2006).
The performance of an electroflotation system is affected by the pollutant

removal efficiency and the power and/or chemical consumptions. The pollutant
removal efficiency is largely dependent on the size of the bubbles formed. For
the power consumption, it relates to the cell design, electrode materials as well
as the operating conditions such as current density, water conductivity, etc.
(Chen, 2004). Table 2.1 summaries the comparison of different flotation
processes for treating oily wastewater (Il’in and Sedashova, 1999).
11
Table 2.1 Economic parameters in treating oily effluents
Treatment type EF DAF IF Settling

Bubble size (μm) 1-30 50–100 0.5–2
Specific electricity consumption 30–50 50–60 100–150 50–100

3
(W/m )
Air consumption (m3/ m3) water 0.02–0.06 1
Chemical conditioning IC OC +F OC IC + F
Treatment time (min) 10–20 30–40 30–40 100–120
Sludge volume as percent of 0.05–0.1 0.3–0.4 3–5 7–10

treated water
Oil removal efficiency (%) 99–99.5 85–95 60–80 50–70
Suspended solids removal 99–99. 5 90–95 85–90 90–95

efficiency (%)
Low cost and easy operation characters are the advantages of electroflotation
process, since the objective of this project is searching one material as both
anode and cathode, more details of electroflotation analysis will be given in next
section.
2.5 Electroflotation
2.5.1 Overview
In wastewater treatment, flotation is an indispensable process for the separation

of oil and low-density suspended solids from wastewater (Lafrance and Grasso,
1995; Chen and Horan, 1998; Huang and Liu, 1999; Vaughan et al., 2000;
Manjunath et al., 2000). Electroflotation was first proposed by Elmore (1905) for
flotation of valuable minerals from ores. This process is essentially an
electrochemical version of flotation. It differs from dissolved air flotation which is
12
the traditional source for flotation mainly in the mechanism of bubble generation
(Chen, 2002).
Electroflotation has been receiving more and more attention because of its
important features of high separating efficiency, compact facility, and easy
operation. It can be used to treat palm oil mill effluent that about 40% of the COD
of the dissolved substances could be anodically destroyed together with 86% of
suspended particles, and then floated off (Ho and Chan, 1986) When apply to
oil-water emulsion which the oil separation reached 65% at optimum conditions;
75% in the presence of NaCl (3.5% by wt. of solution); and 92% with the
presence of NaCl and at optimum concentration of flocculant agent (Hosny,
1996). For mining wastewater for the condition that wastewater of an opencast
mine containing about 50 mg/L copper ions is purified (Alexandrova et al., 1994).
Groundwater that the electroflotation device was used successfully to remove Ni,
Zn, Pb, Cu/CN in a polluted groundwater obtained from directly under a
contaminated site, meeting the pretreatment standards of the pollutants for the
local POWT sewer (Poon, 1997). In restaurant wastewater treatment, the
removal efficiencies of oil and grease, COD, and SS are high, being 99, 88, and
98%, respectively (Chen et al., 2000). And crude oil wastewater remediation
could reach to 40% COD removal after 12 h (Santo et al., 2006).
In electroflotation, the useful small O2 and H2 bubbles are generated on an anode

and a cathode, respectively, as below:
OH- – 2e- → ½ O2 + ½ H2O on an anode (2.1)

H2O + 2e- → ½ H2 + OH- on a cathode (2.2)
High stability, high electrical efficiency electrodes for electroflotation play a

crucial role in the whole process. High stability means long working life time with
stable working performance and little contamination to the environment coming
from the dissolution of the metal oxides. High electrical efficiency is closely
related to the electrocatalysis performance. However, the performance of
13
electrolytic cell is not dictated only by the quality of its anodic and cathodic
electrocatalysts but also by the resistance of the electrolyte between the two
electrodes, which must be minimized, and by the rates of mass transport of
reactants and products to and from the two electrodes (Macdonald and Schmuki,
2007). Detailed information about electrodes applied in electrochemistry industry
will be reviewed subsequently.
2.5.2 Electrodes for O2 Evolution
The selection of anode material, on the other hand, is difficult because severe
electrochemical corrosion always occur when common metals and alloys are
used as anodes. Actually, stable anode materials are quite limited in
electrochemistry (Chen, 2002).
2.5.2.1 Graphite, PbO2 and Pt
The most common non-consumable anode materials are normally Graphite,

PbO2 and Pt. Graphite and PbO2 anodes are cheap and easily available, and thus
have been widely investigated for O2 evolution in electroflotation (Ho and Chan,
1986; Hosny, 1996; Burns et al., 1997). However, the durability of graphite is
poor; the service life of graphite is only 6-24 month due in part to the oxidation of
C to CO2 and to physical wear arising from gas evolution (Novak et al., 1982).
The stability of PbO2 is also poor. Ho et al. (1986) investigated the corrosion of
PbO2 anodes and found that the concentrations of Pb2+ ions present in solutions
ranged from 0.06 to 0.68 mgL-1 after 24 hours of electrolysis. Therefore, graphite
and PbO2 are not good O2 candidates for electroflotation. A few researchers
reported the use of Pt or Pt-plated meshes as anodes for electroflotation (Ketkar
et al., 1991; Poon, 1997). They are much more stable than graphite and PbO2.
However, their known high costs make large-scale industrial applications
impracticable (Chen, 2002).
2.5.2.2 DSAs
The DSAs are the most important anodes nowadays in electrochemical

engineering, invented by Beer in the late 1960s which stands for Dimensional
14
Stable Anodes. Due to the high stability under high current density loading and
high electrical efficiency for chlorine gas production, mixed oxide of ruthenium
and titanium on titanium substrate has become the most popular electrode in
industrial application (Beer, 1980). Usually, DSAs use conductive precious metal
oxides (RuO2, IrO2, etc.) as electrocatalysts and non-conductive metal oxides
(TiO2, Ta2O5, ZrO2, Nb2O5, etc.) as dispersing or stabilizing agents, which are
coated on valve metal substrates (Ti, Ta, Zr, W, Nb, Bi).
a) Ruthenium oxide based electrode (RuOx)
RuO2 is the most widely used electrocatalyst in DSAs. This oxide exhibited
excellent activity for both Cl2 and O2 evolution. The Tafel slope for O2 evolution is
only 0.031-0.066 Vdec-1 (Yeo et al., 1981; Melsheimer and Ziegler, 1988).
Unfortunately, RuO2 is not stable in acidic environments, and the O2 evolution
overpotential increases strictly with time (Burke et al., 1977; Loucka, 1977). The
electrochemical stability can be significantly improved by incorporating other
components into RuO2. Burke and McCarthy (1984) reported that the addition
of 20 molar percent of ZrO2 to the RuO2 layer increased the service life of the
electrode for O2 evolution. Iwakura and Sakamoto (1985) studied the effect of
addition of SnO2 to RuO2 on the service life, and found that the optimal molar
ratio of Ru:Sn was 30:70. The electrodes with a molar ratio of Ru:Sn = 30:70 had
a service life about 12 h, four times higher than the pure RuO2 coated electrode,
under the accelerated life test conditions (5,000 Am-2, 0.5 M H2SO4, 30 oC).
Despite significant improvement in electrochemical stability by introducing
various components, the durability of RuO2-based DSAs is still insufficient for
industrial application. Chen et al. (2005) discovered ternary metal oxide
Ti/RuO2–Sb2O5–SnO2 had a service life of 307 h in 3 M H2SO4 solution under a
current density of 0.5 Acm-2 at 25 °C, which was a great improvement for
ruthenium oxide based electrode’s service life.
15
b) Iridium oxide based electrode (IrO2)
In the last two decades, IrO2-based DSAs have received more and more
attention. When adding the same amount of IrO2 and RuO2, the former presents
a service life about 20 times longer than the latter (Alves et al., 1998).
Nevertheless, IrO2 is much more expensive than RuO2 and its activity is slightly
lower. To save cost and to improve the coating property, other components are
usually added. For optimizing the higher activity and lower cost, Stucki and
Muller (1980) researched on combined IrO2 with RuO2. Subsequently, Hutchings
et al. (1984) developed a ternary IrO2-RuO2-SnO2 catalyst containing 25 mol %
IrO2 and 25 mol % RuO2, leading to a further electrode cost reduction and
durability improvement. In 1991, Balko and Nguyen investigated IrO2-SnO2 over
a composition range of 5 to 100 mol % IrO2. It was found that 80 mol % IrO2 can
be replaced by SnO2 without noticeable deterioration of the coating property.
Ti/IrO2-Ta2O5 electrodes prepared by thermal decomposition of the respective
metal chlorides were successfully employed as oxygen evolving electrodes for
electroflotation of waste water contaminated with dispersed peptides and oils.
Service lives and rates of dissolution of the Ti/IrO2-Ta2O5 electrodes were
measured by means of accelerated life tests, electrolysis in the condition of 0.5
M H2SO4 at 25°C and current density was 2 Acm–2. The steady-state rate of
dissolution of the IrO2 active layer was reached after 600-700 h (R. Mráz and
J. Krýsa, 1994). Chen et al. (2001) fabricated a excellent anode named
Ti/IrOx-Sb2O5-SnO2 electrode had a service life of 1600 h in 3 M H2SO4 solution
under a current density of 1 Acm-2 at 35 °C, which could last more than 20 years
for real electroflotation process and save money by introducing only 10 mol % of
IrOx nominally in the coating.
c) Cobalt oxide based electrode (Co3O4)
Electrode based on Co3O4 have been studied for a long time, a spinel oxide,
shows excellent physicochemical properties that make its application possible as
a noble metal in the preparation of DSAs (Liu et al., 1999; Grupioni and Lassali,
16
2001). Generally, when the research is focus on using Co3O4 as an oxygen
anode, efforts are directed at improving both electrode stability and
electrocatalytic activity. The presence of small amounts of Rh in the Ti/Co3O4
spinel coating increases the oxide electrocatalytic activity towards the oxygen
evolution reaction, acting on the geometric factors and decreasing the ohmic
drop which is an advantage with respect to the performance of the Ti/Co3O4
electrode (Nunes et al., 2005). The IrO2+Co3O4 binary oxide mixed electrodes
were prepared as a candidate for capacitor devices. The oxide layer shows an
amorphous nature made up of a mixture of crystalline and hydrous amorphous
oxides with an inhomogeneous surface composition and segregation of the
component of larger atomic mass. These characteristics lead to a significant
increase in the surface area of the oxide coating (Grupioni and Lassali, 2001).
Accelerated service life tests of the Ti/CuxCo3-xO4 electrodes were performed by
anodic polarization in 1 M NaOH solution showing the best performance after 25
deposition steps and service life efficiency reached to 184 Ahmg-1 (Rosa-Toro et
al., 2006).
2.5.3 Electrodes for H2 Evolution
2.5.3.1 Metals and Alloys
There are many metals and alloys that can be used as cathodes. Stainless steel,
for example, is a good cathode material for electroflotation (Hosny, 1996; Poon,
1997; Chen et al., 2000). But the over potential on the steel cathode today is
about 500 mV compared to about 40 mV on the anode side (Colman, 1981). If
the former could be lowered, to say 100 mV, it would lead to a cut in production
costs of electricity by 10-15%. The benefits of an activated, non-corroding
cathode is obvious (Cornell and Simonsson, 1993)
Another material usually used for cathode in water electrolysis is Ni. It resists to
the strongly alkaline environment, however, it is not very stable and its activity
decreases progressively with time (Tavares and Trasatti, 2000).
17
2.5.3.2 DSAs
As the name shown for DSAs, dimensionally stable anodes which normally used
for anode application. Nowadays, more and more chemists pay their attention on
H2 evolution with DSAs electrodes. However, the most important thing made
metal oxides receiving more and more interested for cathode material
application. As a consequence of the different surface chemistry, oxides may be
less sensitive to poisoning by metal deposits compared with other pure metals or
alloys (Kotz and Stucki, 1987).
a) Ruthenium oxide based electrodes (RuOx)
RuO2 was received no attention to be used as a cathode material for a long time.
The first exception is that Kotz and Stucki (1987) demonstrated that metallic
oxides like RuO2 were insensitive towards poisoning by metal deposition during
hydrogen evolution in acid media. In addition, the catalytic activity of RuO2 for H2
evolution fell between those of platinum and nickel. The exchange current density
of 6×10-5 Acm-2 in combination with a Tafel slope of 40 mV per decade resulted in
an overpotential for hydrogen evolution reaction which was about 50 mV higher
than that of platinum at a current density of 0.1 Acm-2. After that a lot of research
conducted on RuO2 hydrogen evolution electrode. Ni/ (Ni + RuO2) electrodes are
prepared by simultaneous electrodeposition method from a suspension
electrolyte (Watts bath) of RuO2 particles under vigorous stirring condition and
they are found to have excellent characteristics as an active cathode for
hydrogen evolution in hot concentrated alkaline solution (Iwakura et al., 2001).
Ruthenium dioxide as electrocatalyst on an activated cathode can also be used
for chlorate production which is investigated with respect to its activity towards
hydrogen evolution, hypochlorite reduction, and chlorate reduction, respectively.
Ruthenium dioxide is an active electrocatalyst for hydrogen evolution in chlorate
electrolyte with about 300 mV (depending on coating thickness) lower
overvoltages than corroded iron at the technical current density 3 Kam-2 (Cornell
and Sinomsson, 1993). Cathodic activation of the RuO2 (1 1 0) surface is
interpreted as the formation of metallic ruthenium sites which can be re-oxidized
18
to ruthenium dioxide. This process is reversible in the early stages of activation
when no significant surface corrugation is produced. Irreversible surface
roughening can be produced with activation at very negative potentials. On the
other hand, the activation of the RuO2 (1 0 0) surface leads, under even very mild
conditions, to an irreversible increase in surface pseudocapacitance and the
appearance of new voltammetric features. This behavior is attributed to
irreversible morphological changes following hydrogen intercalation into the
subsurface region (Lister et al., 2003).
b) Iridium oxide based electrode (IrOx)
A renewed interest has occurred in the field with the publication a few years ago
of a number of papers reporting that conducting ceramic oxide materials could be
suitable electrocatalysts for hydrogen evolution in both acidic and basic media. In
this respect, IrO2 have been shown to be promising candidates (Chen and Guay,
1996). Hydrous iridium oxide films are highly resistant to reduction under cathodic,
hydrogen gas evolution, conditions in aqueous acid or base. Such behavior is not
in agreement with simple thermodynamic (Pourbaix) data based on the
assumption that the system behaves in a reversible manner (Burke et al., 2006).
A lot of researchers pay their attention on mixture RuxIr1–x Oxide for cathodic
polarization and hydrogen evolution. The CV spectra of mixed Ru-Ir oxide
electrodes possessed both pure RuO2 and IrO2 electrode characteristics,
whereas their electrochemical behavior was close to that exhibited by a pure
IrO2 electrode. Wen and Hu’s study (1992) showed that the maximum
electrocatalytic activity (rated in terms of q*) was demonstrated by the
Ru0.3Ir0.7O2 electrode.
c) Rhodium oxide based electrode (RhOx)
Ti/RhOx electrode shows higher catalytic performance for hydrogen evolution

during cathodic polarization more active than RuO2 as well as IrO2 (Morimitsu et
al., 2000; Campari et al., 2002; Hussanova et al., 2003). The main outcome of
19
hydrogen evolution on RhOx in acid solution is that the oxide is unstable toward
cathodic reduction for calcination temperatures lower than 550°C. While the
apparent electrocatalytic activity increases with decreasing calcination
temperature, the opposite is the case for the true electrocatalytic activity. This
suggests that, below 550°C, the cathodic reduction of the oxide gives rise to a
finely subdivided metal surface whose activity is essentially related to an
increase of surface area (Campari et al., 2002).
d) Cobalt oxide based electrode (Co3O4)
Amorphous metallic alloys (AMAs) have interesting mechanical, magnetic and

electrical properties. Co3O4 is considered as one of AMAs sources applied in
electrochemical systems, the AMAs have been the object of several studies
because of their enhanced corrosion resistance and the possibility that they may
present a good catalytic activity toward complex electrochemical reactions like
the hydrogen evolution reaction (HER) (Raj and Vasu, 1992). The hydrogen
evolution reaction was conducted on nickel-cobalt-molybdenum electrodes in a
30 wt% KOH solution at temperatures from 298 to 353 K. It showed good
adhesion to the substrate, high surface roughness and they enhanced the HER
in water electrolysis compared with nickel, cobalt, nickel-molybdenum and
cobalt-molybdenum deposited electrodes (Fan et al., 1994). Electrodes made
from Co-Pd mixtures were found to be more porous and were more efficient
catalysts compared to the individual metal powders and alloys in HER that
conducted in 6 M KOH electrolyte (Elumalai et al., 2002). Doping Co3O4 with
RuO2 increases the electrocatalytic activity for hydrogen evolution in alkaline
solutions by about two orders of magnitude as the doping content is only 10
mol% RuO2. In this composition range the surface of the mixed oxides is
dramatically enriched with Ru (Krstajic and Trasatti, 1997).
2.6 Summary
Based on the above literature review, it is clear that DSAs remains a promising
20
anode for electroflotation application. Especially, Ti/IrOx-Sb2O5-SnO2 electrode
has a service life of 1600 h in 3 M H2SO4 solution under a current density of 1
Acm-2 at 35 °C, which could last more than 20 years for real electroflotation
process. DSAs have also been tested as cathode for hydrogen evolution in
recent years, however, most of authors pay their attention to electrochemical
properties, and for example, Tafel slope, reaction order and cyclic
voltammograms etc. parameters with their service lives seldom reported.
It is possible for one DSA material to be suitable to serve as an anode and also a
cathode. For the cathode DSA materials, the test of service life is requested to fill
the need for industrial design and operation plan. It is well known that an
electrode is eventually worn out or failed after certain time operation. In order to
prolong the service life of an electrode, it is essential to understand the
mechanism of its failure so that one can prevent the failure based on theory.
These research demands therefore become the objectives of the present study
and some interesting results are obtained as seen subsequently.
21
CHAPTER 3 EXPERIMENTAL SET UP
3.1 Chemicals and Materials
The major chemicals and materials used are listed as follows:

A. CeCl3 (99.99+%, Aldrish, USA)
B. CoCl2 (97%, Aldrish, United Kingdom)
C. CuCl2⋅ 6H2O (99%, AnalaR, England)
D. H2SO4 (98%, Acros, NJ, USA)
E. Hydrochloric acid (37%, Riedel-deHaen, Seelze, German)
F. IrCl4⋅ x H2O (53.89% Ir, STREM Chemicals, USA)
G. Iso-propanol (99.7 %, Lab-scan, Bangkok, Thailand)
H. KCl (99%, AnalaR, England)
I. NaOH (99%, AnalaR, England)
J. Na2SO4 (99+%, Aldrich, WI, USA)
K. NiCl2⋅6H2O (99.9%, Aldrish, USA)
L. PdCl2 (99.9+%, Sigma-Aldrish, USA)
M. PtCl4 (98%, Aldrish, USA)
N. RhCl3 (98%, Aldrich, USA)
O. RuCl3⋅ x H2O ( ReagentPlus, Sigma-Aldrish, USA)
P. SbCl3 (99+%, Acros, NJ, USA)
Q. SnCl4⋅5H2O (98+%, Acros, NJ, USA)
R. Platinum wire (EG&G, USA)
S. TiCl4 (solution, Sicherheits-Flasche, Hohenbrunn, Germany)
T. Titanium rods, 5 mm in diameter (98%, EnFeiTaiYe, Shenzhen,
China)
U. ZrCl4 (99.5+% metals basis, Aldrish, USA)
22
3.2 Preparation of Ti/metal Oxide Electrodes
3.2.1 Pretreatment of Ti Substrate
Titanium substrate was treated by sandblasting, tap water washing, ultrasonic

cleaning, acid etching and ultrasonic cleaning again. The specific process is
addressed in Figure 3.1.
Sandblasting
Tap water washing
10 mins ultrasonic cleaning in DDI water
2 mins of etching in boiling 37% hydrochloric acid
10 mins ultrasonic cleaning in DDI water
Figure 3.1 The process of Ti substrate pretreatment
3.2.2 Precursor Solution Preparation
The metal chlorides were dissolved in isopropanol and hydrochloric acid with in a
volume ratio of 7:1.The metal salts were added in the required molar ratio into
the solvents keeping a total concentration of 0.5 molL-1. This precursor solution
underwent an ultrasonic to make sure all salts are dissolved; and for the hard
dissolving cases, the precursors were under ultrasonic from very beginning until
the last brushing cycle. Normally precursor solutions are fresh prepared just
before electrode fabrication procedure.
3.2.3 Electrode Preparation
Titanium was used as substrate in the shape of cylinder of 5 mm in diameter and

30 mm in length, half of the substrate (15 mm length) was machined into screw
23
shape for the electrical connection. Thus the effective surface area was 2.55 cm2.
All electrodes were prepared by a thermal decomposition method. After
pretreatment, the titanium substrates were first brushed at a room temperature
with the precursor solution, dried at 80 oC for 5 minutes to allow the solvents to
vaporize, and then calcinated at 550 oC for another 5 minutes. This procedure
was repeated until a total oxide coating loading reached to at least 20 gm-2,
usually the whole procedure need 18 to 20 rounds. Finally, the electrodes were
annealed for an hour at the calcination temperatures for the sake of stabilizing
the active layer.
3.3 Accelerated Service Life Tests
Generally, when focus on fabricating electrodes for electrolysis, efforts are

directed at improvement electrode stability. In order to evaluate the stability of
targeted metal oxide electrodes, the accelerated life test was applied. The tests
were conducted in a standard thee-electrode cell. Both anode and cathode
made in the same material were mounted on Teflon holders as shown in Figure
3.2, and Ag/AgCl, KCl (sat.) served as a reference electrode. The
electrochemical reactor was in form of 80 cm in diameter and 110 cm in length.
The electrolyte were fresh prepared 3 M H2SO4 or 1 M NaOH and the volume
was kept as 400 ml by adding DDI water every day, the working temperature
was settled at 35 oC using a water bath (Model 3028H, Fisher Scientific, USA). A
DC power supply (HY 3005-2, SHENZHEN MASTECH, China) was used to
provide a constant current density of 10,000 Am-2. Both cell potential and
potential of anode were periodically monitored. Due to generation of a large
amount of bubbles, use of a Luggin capillary was impossible. However, the
reference electrode was placed as close as possible to the working electrode.
Because the ohmic drop from the solution was not compensated, the true
potential could be a bit smaller than the measured value. The service life test
was end at the time point when the potential between anode and reference
electrode suddenly rise up.
24
Figure 3.2 Experimental setup for accelerate service life test. 1 & 2. one
material electrodes performed as anode and cathode, 3. Reference
electrode (Ag/AgCl, KCl), 4. Electrolyte (3 M H2SO4 or 1 M NaOH), 5. Water
bath (normally settled at 35 °C), 6. Signal connection between DC power
and computer
3.4 Physicochemical Characterization
3.4.1 Scan Electron Microscopy (SEM)
Surface morphology of metal oxide electrode samples are checked by SEM

(JEOL 6300 or JEOL 6300F). The samples are mounted on a circular copper
holder by conductive carbon adhesion. Both SEM machines connected with an
Energy-dispersive X-ray (EDX), which can analyze sample surface elements
25
composition. The acceleration voltage is settled at 15 KV or 20 KV.
3.4.2 X-ray Diffraction (XRD)
Coating microstructure and morphology are analyzed by X-Ray Diffraction. XRD

analysis is conducted by a Philps PW 1830 powder X-ray diffraction system with
a primary target of Cu Kα (wavelength of 1.54 A). The X-ray power is 1.6 KW
and diffractograms are recorded with a 2 Theta range of 20 → 80° with a step of
0.05° and scan speed of 0.025°/min.
3.4.3 X-ray Photoelectron Spectroscopy (XPS)
Surface composition was measured by X-ray Photoelectron Spectroscopy (XPS,

PHI 5600, Physical Electronics, USA) equipped with an Al monochomatic X-ray
source.
3.4.4 Inductively Coupled Plasma Mass Spectrometry (ICP-MS)
Electrode surface coating metal concentration is measured by ICP-MS (Optima

2000, VARIAN, USA). It is based on coupling together an inductively coupled
plasma as a method of producing ions (ionization) with a mass spectrometer as
a method of separating and detecting the ions.
3.4.5 Coating Resistivity
Electrode surface coating resistivity is measured using resistivity/Hall

measurement system (HL5500PC, Bio-Rad).
3.5 Electrochemical Characterization
Electrochemical characterization was performed with a potentiostat/galvanostat

(PGSTAT 100, Autolab, The Netherlands) and a standard thee-electrode cell
(RDE0018, EG&G) as shown in Figure 3.3. Pt wire was used as a
counter-electrode, and saturated Ag/AgCl, KCl (0.197 V vs. NHE) with a Luggin
capillary as a reference-electrode. Electrode potentials are quoted with respect
26
Figure 3.3 Schematic diagram of a three-electrode cell
27
to normal hydrogen electrode (NHE). The resistances between a working
electrode and the Luggin capillary were measured using the frequency response
analyzer of the potentiostat/galvanostat. The ohmic drops of the solutions were
compensated. Solutions were purged with nitrogen gas before electrochemical
experiments for about 30 min. Open-circuit potential was examined in 1 M NaOH
solution (Krstajic and Trasatti, 1997; Fachinotti et al., 2006). In chlor-alkali and
bleaching industries, high concentration alkaline solution is needed like 1 M
NaOH, thus cyclic voltammetry was carried out in 1 M NaOH solution with 50
mVs-1 as a settled scan rate. Quasisteady state polarization curves were
recorded by first holding the electrode at -150 mV vs Ag/AgCl for 10 min (this is
close to the open-circuit potential), then at -1.0 V for 5 min and stepping the
potential by 10 mV and reading the current after 90 second up to a potential that
current density was reach to 100 mA. The direction of potential variation was
then reversed and the run continued until the current became anodic.
28
CHAPTER 4 SEARCHING FOR PROPER
ELECTRODE MATERIALS
4.1 Introduction
Looking back at the past decades of electrochemistry development, one can

witness the expansion of electrocatalysis in both the range of electrode reactions
and the range of electrode materials pushed by science or drawn by the industry
demands. Electrode materials is definitely more striking then electrode reactions
from both the experimental and the theoretical point of view; normally electrode
reactions are essentially confined to H2 and O2 evolution (water electrolysis), O2
reduction, H2 ionization and organic oxidation (fuel cell and air batteries).
Electrocatalysis has benefited from the improvement in the preparation and the
control of electrode materials quality, as well as from a better understanding the
structure of electrode surfaces (Trasatti, 2000). This is certainly the case of oxide
electrodes, world-wide known as DSAs (Dimensionally Stable Anodes). These
electrodes have met in electrochemistry with a great success and could be
considered as one of the greatest technological breakthrough of the past 50
years of electrochemistry with the advantages of excellent electrocatalytic
properties and long service life (Trasatti, 2000).
DSAs are mostly applied in chlor-alkali industry mainly for Cl2 evolution, organic
material oxidation process (electrooxidation) and water electrolysis process
(electroflotation) etc. Among them, electroflotation received more and more
attention due to its high separating efficiency, simple operation, and few
accessories required (Chen et al., 2002; Chen, 2003). Chen et al. (2001) had
already fabricated a promising anode, Ti/IrO2-Sb2O5-SnO2, which could last 1600
h in 3 M H2SO4 solution under a current density of 1 A cm-2 at 35 °C. Even
though Ti/IrO2-Sb2O5-SnO2 has achieved such a success; the lack of ideal
electrode material for both O2 and H2 evolution troubled engineers a lot. The
29
aspiration for searching a better material as both anode and cathode electrode is
continuing.
If one material DSA-based anode and cathode can be developed for

electrofloation industry, which means both anode and cathode are made of the
same DSA material, the electrodes can perform self-cleaning with current
direction alternating. The reasons for seldom researching of metal oxides as a
cathode material are obvious. Firstly, oxides in general are non-conducting or
semiconducting which makes them less attractive as cathode electrode material.
Secondly, noble metal oxides are expected to be reduced to the metal phase by
hydrogen in which will lower their long-term stability (Kotz and Stucki, 1987). If
we can decrease the reduction rate of metal oxide in cathode, balance anode
and cathode service life, the profound goal ⎯ one material electrodes as both
anode and cathode for water electrolysis could achieve. By the way, as a
consequence of the different surface chemistry of oxide, compared to the
respective metals, oxides may be less sensitive to poisoning by metal deposits.
For metals like platinum or nickel, poisoning by metal deposits is well known
(Kotz and Stucki, 1987).
In this chapter, electrodes prepared in different prescriptions are checked by

SEM for surface morphology and service tested life under accelerated condition.
Normally, the same material electrodes conducting in electrolysis process in acid
solution, the anode service life is much longer than cathode. Thus the first step
for this project was optimizing a good material for cathode.
30
4.2 Experimental Results
4.2.1 Ir-based Electrodes
a) Ti/IrO2-Sb2O5-SnO2
In our group’s former work, titanium anodes coated with ternary iridium, antimony,
and tin oxide mixture were investigated for oxygen evolution. In the active oxide
coating, SnO2 serves as a dispersing agent, Sb2O5 as a dopant, and IrO2 as a
catalyst. Experimental results showed that the Ti/IrOx-Sb2O5-SnO2 electrode
containing only 10 mol % of IrOx nominally in the coating had a service life of
1600 h in 3 M H2SO4 solution under a current density of 1 Acm-2 at 35 °C (Chen
et al., 2001). IrO2-Sb2O5-SnO2 was chosen as the starting material for this
project. The substrates were brushed with the precursor solution with a molar
ratio of Ir:Sb:Sn = 10:10:80 for 20 times. Similar result was obtained for
accelerated service life in 3 M H2SO4 solution under a current density of 1 Acm-2
at 35 °C; Ti/IrO2-Sb2O5-SnO2 anode lasted for 1430 h. But when it is applied as a
cathode, the total service life was severely decreased to 5 h 20 min. If changing
the electrolyte to 1 M NaOH, the situations were significantly different;
Ti/IrOx-Sb2O5-SnO2 anode accelerated service life was 355 h and
Ti/IrOx-Sb2O5-SnO2 cathode service life was 99 h. SEM picture (Figure 4.1)
shows the smooth and compact coating of newly made Ti/IrO2-Sb2O5-SnO2
electrode with only a few cracks. The generation of cracks may be associated
with the rod shape substrates.
31
Figure 4.1 SEM picture of Ti/IrO2-Sb2O5-SnO2 electrode
b) Ti/IrO2-Sb2O5-SnO2 with PdO-Sb2O5-SnO2
Palladium exists mainly as PdO, which is semiconducting in nature (Shivastava

and Moats, 2008). Addition of palladium to ruthenium–titanium-based coatings
shows improved corrosion resistance (Kawashima et al., 1984). Thus Pd is
chosen as electrode catalyst replacing Ir. A precursor solution with a molar ratio
of Pd:Sb:Sn = 1:1:8 was brushed on titanium rod substrates. The cathode
accelerated service life (9 h) was even longer than anode accelerated service
life (3 h 15 min).
Since IrO2-Sb2O5-SnO2 anode could last more than 1,000 h in acid solution. It is
anticipated that if Ir/Sb/Sn and Pd/Sb/Sn precursors were alternately brushed on
substrates with each precursor brushed 10 times, the Ir and Pd mixture could
have synergetic effect. However, this kind of cathode could only last for 3 h 50
min, considered as the shortest of all. SEM pictures reveal that alternative
procedure induces cracks on electrode surface illustrating by Figure 4.3 and
Ti/PdO-Sb2O5-SnO2 was flat with nearly no cracks on electrode surface, Figure
4.2.
32
Figure 4.2 SEM picture of Ti/PdO-Sb2O5-SnO2 electrode
Figure 4.3 SEM picture of Ti/IrO2-Sb2O5-SnO2 with

PdO-Sb2O5-SnO2 electrode
33
4.2.2 Other Metals-based Electrodes
a) Ti/RhOx-Sb2O5-SnO2
RhOx electrode is one kind of gas evolution electrodes, which shows similar
electrocatalytic activity for oxygen gas evolution with IrO2, but lower stability than
IrO2 during anodic polarization (Hussanova et al., 2004). However, it shows
higher catalytic performance for hydrogen evolution during cathodic polarization
(Morimitsu et al., 2000; Campari et al., 2002). RhCl3, SbCl5 and SnCl3 were used
as precursor solution metal sources with a molar ratio of Rh:Sb:Sn = 10:2.5:87.5.
The cathode accelerated service life was 45 h 24 min and the anode accelerated
service life was far more than two times under acid electrolyte of a current
density of 1 Acm-2. The surface morphology (Figure 4.4) is different from that of
Ti/IrO2-Sb2O5-SnO2 electrode of Figure 4.1, with bigger and wider cracks.
Figure 4.4 SEM picture of Ti/RhOx-Sb2O5-SnO2 electrode
34
b) Ti/PtOx-Sb2O5-SnO2
Pt is a kind of inert metal that shows good electrocatalytic property. A reasonable

explanation for the improved electrode kinetics by adding Pt into electrode
composition is based on the electron tunneling between Pt particles on the
surface of the oxide film and the underlying metal electrode. It was proposed in
earlier work that the resonance tunneling is responsible for the enhanced
electron-transfer rate on the Pt-doped passive oxide electrodes (Schmickler and
Stimming, 1981). The result found in the present work was not good with anode
accelerated service life which lasted for 12 h and cathode accelerated service
life could only reach 5 h 56 min in acid electrolyte. It can be observed from the
SEM picture, Figure 4.5, the coating shows large cracks severely with
introducing 3 molar % Pt.
Figure 4.5 SEM picture of Ti/PtOx-Sb2O5-SnO2 electrode
c) Ti/Au and Ti/Au-Sb2O5-SnO2
Among the various metals, Gold is regarded as an anti-corrosion metal due to its
low chemical reactivity. It can be hardly oxidized in most conditions. In view of
this good feature, gold could be a qualified electrode material. Some
prescriptions with Au were tested. The Ti substrate was coated with pure AuCl3
35
and AuCl3 combined with SbCl5 and SnCl3, because incorporation of Sb2O5 and
SnO2 metal oxides improves the coating structure of DSA electrodes (Chen and
Chen, 2005). Pure gold coated titanium cathode performed relatively long: the
deactivation took place after 49 hours under cathodic H2 evolution. But in anode
application the deactivation effect was observed after 4 minutes only. This is due
to the oxidization reaction “Au+ + e- → Au” with a standard potential of E = +1.83
Volt in acidic aqueous solution ([H+] = 1 molL-1), and the operating voltage
between anode and reference electrode was 3.46 Volt (read from the DC power
screen) to keep current density settled as 1 Acm-2, that is one of the possible
reason that metal gold was oxidized quickly. The coating surface of Ti/Au
exhibits a very rough and non-compact structure, Figure 4.6. Ti/Au-Sb2O5-SnO2
electrodes performed badly either as anode or cathode. After 6 min, 90% of the
cathode coating was dissolved. Ti/Au-Sb2O5-SnO2 is, as expected, more
compact but covered with cracks, Figure 4.7.
Figure 4.6 SEM picture of Ti/Au electrode
36
Figure 4.7 SEM picture of Ti/Au-Sb2O5-SnO2 electrode
4.2.3 Ru-based Electrodes
a) Ti/RuO2-Sb2O5-SnO2
RuO2–Sb2O5–SnO2 is a promising electrocatalyst for O2 evolution. It has a

compact microstructure with its metal oxides existing in a solid solution. The
accelerated life test showing that the Ti/RuO2-Sb2O5-SnO2 electrode containing
12.2 molar percent of RuO2 nominally in the coating had a service life of 307 h in
a 3 M H2SO4 solution under a current density of 0.5 Acm−2 at 25 °C, over 15
times longer than other typical RuO2-based electrodes. Ti/RuO2–Sb2O5–SnO2
electrodes are believed to be stable enough for applications in which low current
densities (<0.02 Acm−2) (Chen and Chen, 2005). A precursor solution of RuCl3,
SbCl5 and SnCl3 with molar ratio of Ru:Sb:Sn = 3:1:7 was brushed on substrates
in this study. The result was much better than the former results, anode
accelerated service life was far more than 51 h 25 min and cathode accelerated
service life was 26 h 25 min. Figure 4.8 presents a typical SEM image of a
Ti/RuO2-Sb2O5-SnO2 electrode. The film had fewer cracks which may indicate
that incorporation of Ru could improve coating surface morphology.
37
Figure 4.8 SEM picture of Ti/ RuO2-Sb2O5-SnO2 electrode
Figure 4.9 SEM picture of Ti/RhOx-RuO2-Sb2O5-SnO2 electrode
38
b) Ti/RhOx-RuO2-Sb2O5-SnO2
A combination of RhOx and RuO2 was chosen to serve as electrode catalyst;

SnO2 and Sb2O5 serve as a dispersing agent and a dopant, respectively. The
molar ratio of Rh:Ru:Sb:Sn was 5:5:10:80. However, the mixture did not prolong
the service life but made it even shorter than RuO2 performed as catalyst alone.
Ti/RhOx-RuO2-Sb2O5-SnO2 cathode accelerated service life was 10 h 5 min
under acid condition testing. SEM image, Figure 4.9, shows a comparable flat
surface with no cracks and pores.
c) Ti/PdO-RuOx-Sb2O5-SnO2
RuO2-Sb2O5-SnO2 combination was discovered to be good as cathode when

tested in 3 M H2SO4 solution which was used before for the accelerated life test
of PdO containing electrodes. The solution showed light yellow color from the
dissolved Pd2+. When conducting the service life test of Ti/RuO2-Sb2O5-SnO2 in
this Pd containing 3 M H2SO4 solution, the color of electrolyte disappeared
gradually and both cathode and anode worked considerably longer than in fresh
3 M H2SO4 solution. Consequently Pd2+ was adsorbed on the oxide coating
surface, which had a positive effect on the accelerated service life.
Ti/PdO-RuOx-Sb2O5-SnO2 was tested with a molar ratio in precursor solution of
Pd:Ru:Sb:Sn = 5:30:10:70 and 10:30:10:70 fabricated by thermal decomposition
method. The former cathode accelerated service life could reach 40 h and the
latter cathode accelerated service life could last even longer — 48 h. In contrary,
Ti/RuO2-Sb2O5-SnO2 cathode represent a cathode accelerated service life time
of 18 h only. All the facts illustrated that with incorporation of Pd, cathode
accelerated service life was obviously improved in acid solution. The possible
explanation is that Pd2+ is easier reduced than Ru4+, thus introducing Pd content
into RuO2-Sb2O5-SnO2 could protect cathode from reduction deactivation. Figure
4.10 shows the SEM image of a Ti/PdO-RuOx-Sb2O5-SnO2 electrode, which
presents a typical crack-mud structure.
39
Figure 4.10 SEM picture of Ti/PdO-RuOx-Sb2O5-SnO2 electrode
d) Ti/RuO2-TiO2 and Ti/RuO2-TiO2-CeO2
Roginskaya et al. (1982) studied the structure of RuxTi1-xO2 (x=0.1-0.9) and

found that a solid solution with a rutile structure exists in those coatings. The
properties of (RuO2 + TiO2) based industrial electrodes (DSA) are usually
modified by the addition of a third component (or even more) to optimize activity,
selectivity, and stability (Trasatti and Lodi, 1981). The apparent activity increased
with CeO2 content, whereas the true electrocatalytic properties, estimated by
normalizing the current to unit surface charge, decreased in the presence of
CeO2 with a minimum of 10% CeO2. The presence of CeO2 also makes the
oxide layers more prone to mechanical erosion by the evolving gas bubbles
(Faria et al., 1997). Mixed oxide layers on a Ti support were prepared by thermal
decomposition of RuCl3, TiCl4 (liquid) and CeCl3 under an O2 atmosphere. The
molar ratio of Ru:Ti and Ru:Ti:Ce were 3:7 and 3:7:1, respectively. Under acid
condition, Ti/RuO2-TiO2 anode accelerated service life was 31 h 25 min and
cathode accelerated service life was 142 h 35 min. However, the anode and
cathode accelerated service life of Ti/RuO2-TiO2-CeO2 were 13 h 35 min and 105
h. Compared with the previous results, cathode accelerated service life was
improved a lot.
40
Figure 4.11 SEM picture of Ti/ RuO2-TiO2 electrode
Figure 4.12 SEM picture of Ti/RuO2-TiO2-CeO2 electrode
41
In 1 M NaOH solution, situations were changed a lot that anode accelerated
service life was 76 h 30 min and cathode accelerated service life was 176 h 30
min with the prescription of RuO2-TiO2. And for Ti/RuO2-TiO2-CeO2, anode and
cathode accelerated service life were 8 h 30 min and 76 h 30 min, respectively. It
can be simply concluded that replacement of TiO2 with CeO2 bring benefit in
increasing in the electrocatalytic activity for oxygen evolution while the layer
becomes more prone to mechanical corrosion (lower accelerated service life).
Comparing the surface morphologies (Figure 4.11 and 4.12) indicate few
differences between these two prescriptions.
e) Ti/RuO2-ZrO2
One of the major components of DSAs is RuO2, which imparts its electrocatalytic
activity, and TiO2, which brings in its chemical inertness. In the search for new
components with varied surface properties, ZrO2 has been proposed as a
candidate to replace TiO2 in strongly aggressive environment (Burke and
McCarthy, 1984; Comninellis and Vercesi, 1991; Subramanian and Guruvish,
1986). ZrO2 is an inert oxide with interest in the fields of catalysis (Tanabe, 1985)
and surface chemistry (Ardizzone and Bassi, 1990; Randon et al., 1991). Ti/
RuO2-ZrO2 had been studied with a molar ratio of Ru:Zr = 3:7. This time service
life test was under switching condition. Electrodes 1 and 2 were immersed into 3
M H2SO4, thus electrode 1 performed as anode and electrode 2 performed as
cathode in the first 5 h, then current direction was changed in the following 5 h,
namely electrode 1 performed as the cathode but electrode 2 performed as the
anode.
Table 4.1 Accelerated service life of Ti/RuO2-ZrO2 electrode
Electrode Working Total As Anode As Cathode
Name Condition Service Life Service Life Service Life
1 3M H2SO4 10h* 5h* 5h*
2 3M H2SO4 10h* 5h* 5h*
3 1M NaOH 144h* 70h15min* 74h45min*
4 1M NaOH 144h* 74h45min* 70h15min*
(* means the service life test was under switching condition)
42
Figure 4.13 SEM picture of Ti/RuO2-ZrO2 electrode
In alkaline solution, the same switching current condition was conducted;

electrode accelerated service life was much longer than in acid solution, so 24 h
was chosen as alternating current direction rate. SEM picture shows special
cloudy like porous structure, Figure 4.13.
4.2.4 Co-based Electrodes
a) Ti/Ru0.9Co2.1O4
Ru in the rutile structure can be demonstrated on Ru–Co–O ternary system

which was studied previously (Jirkovsky et al., 2006; Silva et al., 2007). The
problems in synthesis of a single phase Ru–Co–O oxide with rutile structure can
be overcome by the implementation of sol-gel synthesis which can produce
phase pure materials, whose chemistry differs from that of RuO2 or Co3O4. Such
single phase materials do exist, however, only in a limited composition interval
(Jirkovsky et al., 2006). The activity of these electrode materials differs from that
of the un-doped RuO2. The activity towards oxygen evolution in acid chloride
free media, in contrast to pure RuO2, is affected in opposite way by the variation
in particle size (Makarova et al., 2007). The origin of such a behavior was
43
tentatively attributed to a specific effect of cobalt; a conclusive explanation of this
effect remains, however, unknown (Jirkovsky et al., 2006). A precursor of RuCl3
and CoCl3 was brushed on titanium substrate with a molar ratio of Ru:Co = 3:7.
Table 4.2 Accelerated service life of Ti/Ru0.9Co2.1O4 electrode

1 3M H2SO4 17h25min 17h25min /
2 3M H2SO4 27h55min / 27h55min
3 1M NaOH 366h* 235h30min* 130h30min*
4 1M NaOH 366h* 130h30min* 235h30min*
SEM picture is shown below indicating a crack structure with a lot of layers
overlapped, Figure 4.14.
Figure 4.14 SEM picture of Ti/Ru0.9Co2.1O4 electrode
44
b) Ti/Rh0.1Co2.9O4
A single-phase oxide coating with the nominal composition of Rh0.1Co2.9O4, was

stable in alkaline solutions under oxygen evolution (Pereira et al., 2001). One
reason for the choice of rhodium as a substitute of cobalt is the high stability of
Rh3+ and its large preference to occupy the octahedral sites in the spinel
structure (Nunes et al., 2005).
Table 4.3 Accelerated service life of Ti/Rh0.1Co2.9O4 electrode

1 3M H2SO4 1h 1h /
2 3M H2SO4 1h / 1h
3 1M NaOH 366h* 235h30min* 130h30min*
4 1M NaOH 366h* 130h30min* 235h30min*
Figure 4.15 SEM picture of Ti/Rh0.1Co2.9O4 electrode
45
The cationic distribution commonly accepted in the literature for the Co3O4 spinel
is represented as Co2+[Co23+]O4, where the Co2+ and Co3+ species occupy the
tetrahedral and octahedral sites, respectively, in the spinel structure (Miyatami et
al., 1966). Once Rh3+ is replacing Co3+ it should stay in the octahedral sites in
the spinel structure and the cationic distribution should be Co2+[Co1.953+
Rh0.053+]O4 (Nunes et al., 2005). The accelerated service life in alkaline solution
was much longer than in acid solution, demonstrated in Table 4.3. It is clear to
see that the surface morphology is affected by the presence of Rh. The
Rh-containing coatings show a cracked dried-mud-like morphology, Figure 4.15.
c) Ti/Ir0.9Co2.1O4
The IrO2-Co3O4 binary oxide mixture shows characteristics that suggest high
potential as an electrode material for electrochemical capacitors. The oxide layer
shows an amorphous nature made up of a mixture of crystalline and hydrous
amorphous oxides with an inhomogeneous surface composition and segregation
of the component of larger atomic mass. These characteristics lead to a
significant increase in the surface area of the oxide coating (Grupioni and Lassali,
2001). The molar ratio of Ir:Co was 3:7. Compared with Ti/IrO2-Sb2O5-SnO2
electrode, accelerated service lives in alkaline solution were greatly improved,
however, in acid solution were decreased. The surface morphology of
Ti/Ir0.9Co2.1O4 was similar to that of Ti/ IrO2-Sb2O5-SnO2 electrode (Figure 4.1)
but with more cracks on surface, Figure 4.16.
Table 4.4 Accelerated service life of Ti/Ir0.9Co2.1O4 electrode

1 3M H2SO4 6h 6h /
2 3M H2SO4 6h / 6h
3 1M NaOH 334h* 188h* 146h*
4 1M NaOH 334h* 146h* 188h*
46
Figure 4.16 SEM picture of Ti/Ir0.9Co2.1O4 electrode
d) Ti/Ni1.5Co1.5O4
Ni and Co oxides exhibit interesting electrocatalytic activities, which make them

attractive for O2 evolution (Schumacher et al., 1990; King and Tseung, 1974).
For instance, in cobaltite spinels (MCo2O4), the mixed valences of the cations
are helpful in the reversible adsorption of oxygen by providing donor–acceptor
sites for chemisorptions. Co3O4 and NiCo2O4 has long been known to be an
active and stable bi-functional catalyst for oxygen evolution and reduction in
alkaline media, as well as a catalyst in alcohol and amine electro oxidation
(Singh et al., 1990; Rashkova et al., 2002). Hence the investigation of the
electrocatalytic synergism of Ni+Co mixed oxides has attracted considerable
attention in view of their potential applications in electrocatalysis (Gang et al.,
2004). To study Ni-Co combination electrode accelerated service life, a
precursor solution with a molar ratio of Ni:Co=1:1 was brushed on substrates.
Compared with accelerated service life tested in alkaline condition, it could only
last for 10 min in acid solution. Thus, introducing Co content as one of electrode
materials, the electrode is severely unstable. And from SEM pictures, there are a
lot of crystals presenting on Ti/Ni1.5Co1.5O4 electrode surface.
47
Table 4.5 Accelerated service life of Ti/Ni1.5Co1.5O4 electrode
1 3M H2SO4 10min 10min /
2 3M H2SO4 10min / 10min
3 1M NaOH 374h* 227h* 147h*
4 1M NaOH 374h* 147h* 227h*
Figure 4.17 SEM picture of Ti/Ni1.5Co1.5O4 electrode
e) Ti/Cu0.3Ni1.35Co1.35O4
Since both NixCo3-xO4 and CuxCo3-xO4 showed excellent result in alkaline

solution, Co+Ni+Cu ternary oxides would be investigated as well. The active
sites of Co+Ni+Cu ternary oxides for oxygen evolution could mainly result from
the contribution of Co3+ and Ni2+ without Cu2+ on the surface of electrodes. The
intercalation of Cu2+ in Co3O4/NiCo2O4 matrixes did cause an inhomogeneous
distribution of the cations which increases q* and i, depending on the amount of
Cu spices (Wen and Kang, 1997). A precursor solution of Cu:Ni:Co=2:9:9 was
prepared for electrode making. Even though the electrochemical properties
probably improved by adding Cu, compared with Ti/Cu1.5Co1.5O4 electrode, the
accelerated service life did not prolong significantly.
48
Table 4.6 Accelerated service life of Ti/Cu0.3Ni1.35Co1.35O4 electrode
3 1M NaOH 443h30min* 224h15min* 219h15min*
4 1M NaOH 443h30min* 219h15min* 224h15min*
Figure 4.18 SEM picture of Ti/Cu0.3Ni1.35Co1.35O4 electrode
f) Ti/Cu1.5Co1.5O4
Substitution of another foreign divalent metal ion into cobalt ions would result in
spinel structures with better catalytic activity and stability. Among them,
copper-substituted cobaltite spinels combine advantageously high stability and
activity with low cost and availability (Tavares et al., 1999; Singh et al., 2000). A
nominal molar ratio of Cu:Co=1:1 was chosen for electrode preparation. Cu-Co
combination electrode shows mesoscopic structure which is a lot different from
all above electrode surfaces and the accelerated service life in alkaline solution
was the longest of all, also.
49
Table 4.7 Accelerated service life of Ti/Cu1.5Co1.5O4 electrode
3 1M NaOH 460h* 217h10min* 242h50min*
4 1M NaOH 460h* 242h50min* 217h10min*
Figure 4.19 SEM picture of Ti/ Cu1.5Co1.5O4 electrode
50
RuTiCe
RuTi
AuSbSn
Au
Electrode composition
PdRuSbSn
RuSbSn
NiRuSbSn
RhRuSbSn
PtSbSn
IrSbSn+RuSbSn
IrSbSn+PdSbSn
IrSbSn
0 20 40 60 80 100 120 140

Service life (h)
Figure 4.20 Cathode accelerated service life in acid electrolyte with fixed
current direction electrolysis process
CuNiCo
CuCo
Electrode composition
NiCo
IrCo
RhCo
RuCo
RuZr
0 100 200 300 400 500

Service life (h)
Figure 4.21 Cathode accelerated service life in alkaline electrolyte with

alternating current direction electrolysis process
51
Figures 4.20 (in acid solution) and 4.21 (in alkaline solution) show the cathode
accelerated service life time of all tested materials in different electrolytes,
respectively. Figure 4.20 illustrates that most of the cathode materials did not
perform for longer than 15 hours under acid condition. The deactivation process
of all cathodes exhibits a change of the color of the solution or a black powder on
the bottom of the beaker within a short time after life test started. The
detachment of the oxide coating from the substrate could be observed.
It is important to see that the cathodes service lives in alkaline solution are much
longer than in acid solution. Cu-Co combination shows the best accelerated
service life and is therefore chosen as the candidate for more in-depth
investigation in the next stage of this project.
4.3 Summary
From all cathodes accelerated service life time data which were tested in acid
solution, it is obvious to know that acid surrounding is not an appropriate choice
for one material anode and cathode application. Reduction reactions happened
quickly for most cathode electrodes. The Co-based anodes were influenced by
deactivation effect which could induce the sharp increase of potential between
anode and reference electrodes. Thus, the whole cell potential would rise up
accordingly.
Ti/RuO2-TiO2 and Ti/RuO2-TiO2-CeO2 performed well in acid electrolyte as

cathode, but their accelerated service life as anodes are short. Hence this
material cannot be considered as a candidate for one material electrode
fabrication. In contrast, Ti/CuxCo3-xO4 showed a remarkably high stability when it
is employed as a cathode. Such a material has been proven in reported literature
to be an ideal anode. Therefore, it can be considered as a candidate for one
material electrode testing. A systemic study on this material is reported in next
chapter.
52
CHAPTER 5 STUDIES OF Ti/CuxCo3-xO4
ELECTRODES FOR BOTH OXYGEN AND
HYDROGEN EVOLUTION IN ALKALINE
SOLUTION
5.1 Introduction
Extensive use of the electrocatalytic processes in practice drives the

development of cheap and easily available electrode materials having high
activity and reasonable selectivity (Trasatti, 1980). Along with the general pattern
of development of heterogeneous chemical catalysis (Koreskov, 1977), in which
ever increasing importance is acquired by complex compounds as catalysts,
investigation of the electrode properties of non-metals and semiconducting
compounds have become the main trend in the selection of new types of
electrocatalysts. The widest class of non-metal substances investigated in
electrocatalysis is the oxide system which have used for a long time in
heterogeneous catalysis (Trasatti, 1980). Amongst the oxide catalysts,
electrodes based on Co3O4 which is a complex oxide with spinel structure have
been studied for a long time due to its various properties and practical
applications (Burke and McCarthy, 1988; Kinoshita, 1992; Trasatti, 1994; Trasatti
and Lodi, 1980; Hamdani et al., 1988). The interest in this kind of material is
mainly due to their low cost, wide disposability, stability in alkaline solution and
good electrocatalytic properties (Silva et al., 2000). However, Co3O4 spinel
oxides behave the inconvenience of being anodically unstable in acid solution,
low specific surface and relatively high electric resistance, making its application
is mainly restricted to alkaline solutions.
The solution of the above problems requires the substitution of new materials
53
into Co3O4 spinel oxides (Trasatti, 1980). Substituting another metal ion,
especially divalent metal ion, could enhance both catalytic activity and stability of
the spinel thin film, which is widely known as the “synergetic effect”. For this
reason, the morphology, crystallinity, composition, and electrochemical
properties of binary spinel oxides of the type MxCo3-xO4 (with M = Ni, Cu, Mn,
etc.) (Singh et al., 2000; Rios et al., 2000; Marco et al., 2001) and of ternary
spinel oxides involving Ni-Cu-Co (Tavares et al., 1998; Tavares et al., 1999) or
Cu-Zn-Co (Lee et al., 1996) have been the subject of comprehensive research in
an attempt to establish clearly defined composition-structure-properties
correlations. Among them, copper-substituted cobaltite spinels combine
advantageously high stability and activity with low cost and availability (Tavares
et al., 1999, Singh et al., 2000, Gautier et al., 1997).
In this chapter, Cu-Co combination will be chosen as the candidate material for
study. The Cu/Co molar ratio optimization will be found out first to get the best
performing candidate electrode. The effects of the precursor composition
variation on the stability and activity of the electrodes will also be investigated.
The electrochemical behavior and the kinetics of H2 evolution on the optimal
composition electrode will be examined. Finally, the physicochemical properties
of the coatings will be measured for all anodes and cathodes conducting water
electrolysis in alkaline solution. The electrodes would be examined daily until
used out condition to study the mechanism of electrodes failure.
5.2 Molar Ratio Optimization
5.2.1 Accelerated Service Life Test
Table 5.1 shows the accelerated service life results under current density of
10,000 Am-2 at 35 °C in 1 M NaOH solution. The effect of Cu content on the
electrochemical stability of Ti/CuxCo3-xO4 electrode is clearly illustrated. When
the Cu content is zero, the coating is a single oxide Co3O4. The Ti/Co3O4
electrode has a service life of 406 hours only. However, when 3 molar percent of
Cu was added in the precursor, the service life of the Ti/Cu0.1Co2.9O4 electrode
54
increased by 81% to 735 hours. This reveals that Cu plays a very important role
in enhancing electrode stability. The maximum service life achieved was that
having 10 percent of Cu in the Cu-Co combination. Further increase of the Cu
content resulted in a slight decrease in the service life instead.
Table 5.1 Accelerate service life of Ti/CuxCo3-xO4 electrodes in 1 M NaOH

solution under 10,000 Am-2 at 35 °C
Electrode Total service As anode As cathode
composition life Service life Service life
Co3O4 (1) 406h 215h15min 190h45min
Co3O4 (2) 382h 190h45min 191h15min
Cu0.1Co2.9O4 (1) 735h 383h50min 351h10min
Cu0.1Co2.9O4 (2) 699h 351h10min 347h50min
Cu0.3Co2.7O4 (1) 1080h 561h35min 518h25min
Cu0.3Co2.7O4 (2) 1008h 518h25min 489h35min
Cu0.6Co2.4O4 (1) 891h30min 473h55min 417h35min
Ti/Cu0.3Co2.7O4 service life of 1080 hr equals to 252.66 Ahmg-1 in the form of

service life efficiency (Ahmg-1 means the ratio of the total charge passing to the
oxide loading), that is much longer than the results reported by Rosa-Toro et al.
(2006). In Rosa-Toro’s report Ti/Co3O4 had shown the best service life efficiency
of 184 Ahmg-1.
55
5.2.2 EDX
The O/M values (O stands for the oxygen and M stands for the total amount of
metal) determined by EDX also listed in Table 5.2. It is clear that the amount of
oxygen is lower than the theoretical one (4/3=1.333) for all spinel coatings
including pure Co3O4, except Cu0.3Co2.7O4. It was reported previously (Li et al.,
1990) that oxygen excess could lead to structural improvement involved in the
electrical conduction. This may be one of the reasons that Ti/Cu0.3Co2.7O4
electrode lasts longer than the other Ti/CuxCo3-xO4 electrodes. The higher O/M
value for this particular electrode suggests that the morphology of this
combination is different from others. In order to find out why this electrode gives
the longest service life, more characterizations are necessary as seen
subsequently.
Table 5.2 Atomic ratios for Ti/CuxCo3-xO4 electrodes nominal and

experimental obtained by EDX techniques
Electrode Nominal Precursor Cu/Co O/M
Composition Cu/Co Cu/Co EDX EDX
Co3O4 / / / 1.213
Cu0.1Co2.9O4 0.035 0.037 0.013 0.965
Cu0.3Co2.7O4 0.111 0.113 0.065 1.471
Cu0.6Co2.4O4 0.250 0.252 0.103 1.176
Cu0.9Co2.1O4 0.429 0.431 0.221 0.942
Cu1.2Co1.8O4 0.667 0.661 0.519 0.985
Cu1.5Co1.5O4 1 1.001 0.938 0.861
5.3 Electrolyte Temperature Effect on Accelerated Service Life
Since Ti/Cu0.3Co2.7O4 prescription shows the best performance in 1 M NaOH

electrolyte at 35 °C, its stability should be checked under various temperatures.
Figure 5.1 shows the accelerated service life variation with changing of
56
electrolyte temperature. When the temperature is increased from 35 °C to 70 °C,
the accelerated service life is accordingly decreased to 456 h. It is worth to
re-emphasize that the service life was measured with a daily switching of the
polarity under accelerated life test condition mentioned in Chapter 3. It should be
noted that an accelerated service life of 456 h can be estimated to be 15 years
when the current density is 300 Acm-2. This tolerance of high temperature by this
electrode makes it possible to be applied in electrochemistry industries where
high temperature operation is usually encountered.
1100
1000
Accelerated service life time (h)
900
800
700
600
500
400
40 50 60 70
o
Electrolyte temperature ( C )
Figure 5.1 Temperature effect on accelerated service life
5.4 Physicochemical Characterization
5.4.1 SEM
Figures 5.2(a)-(g) show the typical SEM images of Ti/CuxCo3-xO4 coatings with
different precursor compositions. Upon increasing the amount of incorporated
Cu, the surface became progressively more porous and rougher; some even
showed mesoscopic structure, such as Figure 5.2(e)-(g). At low Cu doping levels
57
(Figures 5.2(a)-(d)), the surfaces maintained the smooth and compact texture.
Even though the difference between Figure 5.2(a) and (b) was not obvious, the
service lives changed a lot. The CuxCo3-xO4 coating prepared using a Cu content
of 10 mol% in the precursor (Figure 5.2 (c)) is the most compact, with few pores
and cracks detected; suggesting that proper incorporation of Cu component can
improve the coating structure effectively.
It is necessary to notice that the physical structure of the Ti/Cu0.3Co2.7O4

electrode is distinctively different from others. Its compact structure certainly
favor stability (Chen et al., 2002), consistent with that shown in Table 5.1.
(a) (b)
(c) (d)
58
(e) (f)
Figure 5.2 SEM images of

oxide coating surfaces.
(a) Co3O4;
(b) Cu0.1Co2.9O4;
(c) Cu0.3Co2.7O4;
(d) Cu0.6Co2.4O4;
(e) Cu0.9Co2.1O4;
(f) Cu1.2Co1.8O4;
(g) Cu1.5Co1.5O4.
(g)
5.4.2 XRD
The X-ray diffraction patterns of Ti/CuxCo3-xO4 electrodes with different levels of

Cu doping (x=0, 0.3, 1.5) are shown in Figure 5.3. For comparison purposes, the
figure also includes the Ti substrate and a Ti/CuO electrode that were fabricated
by the same experimental procedure as that for copper-cobalt electrodes.
59
Ti/CuO
Ti/Cu1.5Co1.5O4
Ti/Cu0.3Co2.7O4
Ti/Co3O4
Ti substrate
20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100
2 Theta
Figure 5.3 XRD patterns for Ti/CuxCo3-xO4 electrodes (x=0, 0.3, 1.5), pure
titanium substrate and Ti/CuO electrode
The XRD of sample Ti/Co3O4, Ti/Co0.3Cu2.7O4 and Ti/Co1.5Cu1.5O4 show 2θ =

31.271, 36.852, 38.541, 44.808, 59.357, 65.236 and 77.338° (International
Centre for Diffraction Data) which are indexed to a cubic spinel lattice. The two
peaks at 2θ = 35.543 and 38.708° (International Centre for Diffraction Data) from
CuO are not obvious for Ti/Co0.3Cu2.7O4 case. Comparing the five spectra, one
can conclude that the titanium substrate has been well covered by the coating.
The differences between Ti substrate and Ti/Co3O4 are that the main Ti peak at
2θ = 40.170° (International Centre for Diffraction Data) is visibly decreased and
the width of 2θ = 70.661, 76.218 and 77.368° (International Centre for Diffraction
Data) are narrowed. In addition, the crystal morphology of Ti/Co0.3Cu2.7O4
60
resembles that of Ti/Co3O4 indicating that Cu is replacing Co to have spinel
structures, whereas Ti/Co1.5Cu1.5O4 electrode shows the formation of CuO in
addition to Co3O4 spinel structure. The XRD patterns for Ti/Co1.5Cu1.5O4 show
clearly the peaks of Co3O4 and CuO are mixture, not in a solid solution.
Rosa-Toro et al. (2006) showed that peaks of CuO cannot detected with x up to
1.5, attributing to the formation of too small size or amorphous CuO.
5.4.3 XPS
Quantitative analyses of Ti/CuxCo3-xO4 electrodes coating compositions were

analyzed by XPS. Figure 5.4 shows the XPS spectra of the coating prepared
from a precursor with Cu:Co = 1:9 in terms of the emitted electron intensity
against binding energy.
Table 5.3 shows the atomic concentrations of the Cu0.3Co2.7O4 coatings

measured by XPS based on the peaks of Co 2p, Cu 2p3, O 1s and C 1s. The
molar ratios of O/M = 47.81/ (23.47+4.7) = 1.70 which is agreeable with the EDX
result. Since there is no Cl observed, 550 °C is therefore high enough to oxidize
the precursor solution to metal oxides. The maximum sampling depth of XPS is
only 5-8 nm, thus no Ti was detected which implies that the substrate is fully
covered by metal oxide thin film, consistent with the XRD results. The C is from
instrument chamber and N is perhaps sourced from a contaminant, such as
nitrogen gas adsorbed on the coating surface. The two shake-up peaks shown in
Figure 5.4 beside Cu 2p3/2 and Cu2p1/2 peaks demonstrate that the copper is
indeed existed as Cu2+ state. It is surprising to note that Cu/Co is 0.186 much
bigger than 1:9 or 0.111, indicating more Cu exist on the surface layer.
61
80000
Co 2p3
70000
Cu 2p3
O KLL
Co LMM
60000
Na 1s
50000
O 1s
C KLL
Counts
40000
Co LMM
Cu LMM
30000
N 1s
20000
C 1s
Na KLL
10000
0
0 200 400 600 800 1000 1200 1400
Binding energy (eV)
14500
22000
Co 2p3/2 Cu 2p3/2
20000 14000
18000
13500
16000 Co 2p1/2 shake-up shake-up
Cu 2p1/2
Counts
Counts
14000 13000
12000
12500
10000
12000
8000
6000 11500
4000
930 940 950 960 970
760 770 780 790 800 810 820
Binding energy (eV) Binding energy (eV)
Figure 5.4 XPS spectra of Ti/Cu0.3Co2.7O4 electrode
62
Table 5.3 Surface compositions of Cu0.3Co2.7O4 films measured by XPS
Element C N O Co Cu
Atomic
concentration 22.43 0.15 47.81 23.47 4.7
in film, %
5.4.4 ICP
To further check the exact Cu/Co molar ration in the electrode coating, a fresh
Ti/Cu0.3Co2.7O4 electrode was immersed into a mixture of 20 ml 68%-70% HNO3
and 20 ml 37% HCl under ultrasonic waves at 80 °C for about 10 h. The 40 ml
high concentration acid solution was then diluted into 200 ml after filtration
treatment. ICP result shows that 2.369 mg/L of Ti, 31.22 mg/L of Co and 3.354
mg/L of Cu from the 200 ml solution. The high concentration of Ti indicates the
complete dissolution of the coating. A real Cu/Co molar ratio is 0.113 which is
close to the precursor solution of 3/27=0.111. According to Co3O4 and CuO
mixture, the total electrode coating which dissolved in Nitric acid and HCl
solution is 8.50 mg (Co3O4) plus 0.84 mg (CuO) = 9.34 mg a bit less than the
oxide loading of 9.7 mg. This may be because of oxygen excess in electrode
coating which is consistent with the EDX result.
The results of EDX, XPS and ICP shown above suggest that Cu is accumulated
on top surface of the coating film.
5.4.5 Coating Resistivity
Co3O4 is a semiconductor with high resistivity at room temperature. However, its

conductivity can be improved significantly by doping as mentioned previously.
Table 5.4 exhibits the effect of the Cu content on the resistivity of the
63
Ti/CuxCo3-xO4 electrodes. When Cu = 0, the coating resistivity was as high as
17.4 ohm*cm. Once 3.3 % of Cu was added, the coating resistivity decreased to
0.267 ohm*cm, nearly 60 times lower. Obviously, Cu plays a very important role
in improving the conductivity of Ti/CuxCo3-xO4. Further increase in Cu shows little
additional effect.
Table 5.4 Effect of Cu content on coating resistivity
Electrode composition Electrode coating resistivity

(ohm*cm)
Co3O4 17.4
Cu0.1Co2.9O4 0.267
Cu0.3Co2.7O4 0.246
Cu1.5Co1.5O4 0.294
5.5 Electrochemical Behavior
5.5.1 Cyclic Voltammetry
Figure 5.5 shows the cyclic votammograms of Ti/Cu0.3Co2.7O4 conducted in 1 M

NaOH at a sweep rate of 50 mVs-1. It is found that the CVs of the later scans
display some changes with respect to the first scan. At the first scan, reduction
peaks are different from others with the inset of C1 much earlier and without the
appearance. After the fifteen cycles, the voltammogram curves keep almost
identical. Since the electrode under goes negative and positive polarization, the
CV curves showing in Figure 5.5 are different from those reported where only
positive polarization were studied (Wen and Kang, 1997; Nunes et al., 2005;
Grupioni amd Lassali, 2001; Rosa-Toro et al., 2006). Since no reference is now
available the peaks notified may be assigned to the following reactions. Because
there is no counter-part for C2 peak, it means that this reaction 5.2 is irreversible.
64
0.003
The first cycle
The fifth cycle
0.002 The tenth cycle A1
The fifteenth cycle
0.001
-2
j/ A cm
0.000
-0.001
C1
-0.002
C2
-0.003
-0.004
-1.5 -1.0 -0.5 0.0 0.5 1.0
E/V (vs. Ag/Ag/Cl)
Figure 5.5 Cyclic votammograms for Ti/Cu0.3Co2.7O4 in 1M NaOH obtained

at a sweep rate of 50 mVs-1. The electrodes have an area of 2.55cm2
A1/C1 can be considered as a reversible couple, peaks associate with Co3+/Co4+
CoOOH+OH- ↔ CoO2+H2O+e- (5.1)
C2 irreversible peaks relate with the reduction process
Co3O4+2H2O+2H++2e- → 3Co(OH)2 (5.2)
Thus, one of the results of using it as a cathode is the consumption of Co3O4.

Hence, it explains partly why alternating current direction process gives a longer
life.
5.5.2 Polarization Curves for Hydrogen Evolution
The first run of the polarization curves shows a marked hysteresis, irrespective
of electrode composition. In the second run the hysteresis disappears, as
65
evident in Figure 5.6. Hysteresis has been observed in pure Co3O4 (Veggetti et
al., 1992) that the surface turns out to be “prepared” to hydrogen evolution by
some sort of reduction and/or site rearrangement. Since hydrogen is evolved on
Ti/Cu0.3Co2.7O4 electrode surface, significant kinetic data are only those taken in
the backward direction of potential variation. Furthermore, to attain more stable
surface conditions, the whole kinetic analysis has been carried out on the data
recorded in the backward direction during the second run.
All polarization curves show deviations from a Tafel line at higher current
densities. They are related to uncompensated ohmic drops, but they can also
affect Tafel slope. Uncompensated ohmic drops include electrode, as well as
electrolyte, resistance. The resistance tends to increase with increasing current
density due to the presence of gas bubbles in the electrolyte. As a rule, the
eventual presence of gas bubbles on the electrode surface reduces the effective
surface area. Both effects attribute to increased deviations from the actual Tafel
line with increasing overpotential.
With the aim of distinguishing between ohmic effects and change in Tafel slope,
the experimental data were treated by assuming that the electrode potential, at
each current, is given by the equation:
E = a + b log10(I)+ RI (5.3)
Where a and b are Tafel constant and slope, respectively, and R is the
uncompensated resistance. In Equation 5.3 R is assumed to be a constant
independent of current. Differentiating with respect to current:
dE/dI = b/I + R (5.4)
Thus, plotting dE/dI (where dE is the potential variation between two consecutive
experimental points and dI is the related current variation) against 1/I should
result in a straight line whose slope is b and whose intercept is R. The value of
66
1/I was taken in the middle of the dI interval. The resulting R was then used to
correct the experimental polarization curve.
Figures 5.7 and 5.8 combination shows a typical analysis of the kinetic data. In
Figure 5.7, it is evident that two Tafel lines are hidden in the nonlinear sections of
the polarization curves at high current densities. Figure 5.8 shows the
experimental data when corrected using the value of R extrapolated from Figure
5.7. In the case of single Tafel slope, a value of R increases with current density.
Therefore, the observed shape of the plot can only be attributed to a change in
Tafel slope to a higher value with increasing current density. R value is
calculated as 2.4 Ω and may be quantitatively in error up to 20% (Krstajic and
Trasatti, 1997). Figure 5.8 shows that subtraction of IR values from the
experimental potential, E, results in a reasonably linear plot for j > 0.25 mAcm-2
showing a Tafel slope is 101 mVdec-1.
-1.0
1
-1.1
E vs Ag/AgCl / V
-1.2 2
-1.3
-1.4
-0.5 0.0 0.5 1.0 1.5
-2
j / mA cm
Figure 5.6 Potential versus current density curves for hydrogen evolution
from 1 M NaOH on a Ti/Cu0.3Co2.7O4 electrode. (1) First run; (2) second run.
Arrows indicate the direction of potential variation
67
50
40
2
(dE/dI) / ohm cm
12
30
10
2
(dE/dI) / ohm cm
8
20
6
4
10
0.02 0.04 0.06 0.08 0.10
-1 2 -1
j / cm mA
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
-1 2 -1
j / cm mA
Figure 5.7 Application of Equation 5.2 in the text to the current-potential

data (2nd run, reverse direction) of Figure 5.6 to derive ohmic drop and
Tafel slopes. Insert: enlargement of initial part of the main plot to give
evidence to the intercept
-1.00
-1.05
-1.10
E vs Ag/AgCl / V
Corrected for IR drop

-1.15
-1.20
-1.25 Experimental data

-1.30
-1.35
-1.40
-1.45
-0.5 0.0 0.5 1.0 1.5 2.0
-2
j / mA cm
Figure 5.8 Experimental data corrected for IR drop
68
5.6 Electrode Surface Changing and Mechanism of Oxygen and
Hydrogen Evolution in Alkaline Solution
The detailed mechanism of electrode failure will be disclosed in this section by

examining the electrode material changing from fresh virgin condition to used out
condition in 1 M NaOH electrolyte. Discussion will be divided into two parts; one
part is on fixed current direction electrolysis process and the second part is one
material electrodes for anode and cathode by alternating current direction in
electrolysis process. Working conditions were as follows: surrounding
temperature was kept constantly at 35 °C, current density was 10,000 Am-2,
alternating anodic and cathodic polarization was conducted every 24 h. All the
electrodes were examined by techniques such as XRD and SEM, etc.
5.6.1 Fixed Current Direction Electrolysis Process
Fixed polarization electrolysis procedure was conducted for finding the trend of
electrode material changing. The accelerated service life was only 696 h.
Figure 5.9 shows an enlarged version of XRD result of Ti/Cu0.3Co2.7O4 electrode

freshly prepared without any treatment. As having seen in Figure 5.3 no Cu
peaks can be found, although XPS, EDS and ICP results, all show the existence
of Cu. This explains that Cu does not exist separately as CuO, it is highly
possible to stay in the crystal lattice of the spinel. Pure Co3O4 and Ti could be
seen clearly and no Cu related crystal could be found. SEM picture of virgin
Ti/Cu0.3Co2.7O4 electrode is shown in Figure 5.2 (c), and the surface morphology
was very flat and with rare cracks on it.
69
250
Co3O4
200
150 Co3O4
Counts
Co3O4
100
Co3O4
Co3O4
Ti Co3O4 Co3O4
50
Ti Ti
Ti
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
Figure 5.9 XRD patterns of Ti/Cu0.3Co2.7O4 virgin electrode
From the anode XRD result, it is clear to see, compared with virgin
Ti/Cu0.3Co2.7O4 electrode, in addition to Co3O4 crystal peaks the Ti and TiO2
peaks are also found. This implies that oxygen evolution does not change
electrode surface composition significantly and anode deactivation is due to the
consumption of the coating material, and detachment of oxides leaving the
substrate surface exposed. For the cathode, only amorphous Co can be
detected, which demonstrated that cathodic polarization is the key step in the
formation of Co. The results have are consistent to those reported before for the
alternating current cases.
70
Ti
250
200
Co3O4
Counts
150
Ti
Co3O4
100 Ti TiO2
Ti
Ti
50 Co3O4 Co3O4 Co3O4
TiO2 Co3O4
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(a)
50
Co
40
30
Counts
20
10
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(b)
Figure 5.10 XRD patterns of fixed current direction electrodes.
(a) anode, (b) cathode
71
5.6.2 Alternating Current Direction Electrolysis Process
Seven pairs of Ti/Cu0.3Co2.7O4 electrodes were placed in electrolysis cells at the

same time. The first pair of electrodes worked for only one day without changing
current direction. The second pair worked for two days with one time current
direction change. The third, fourth, fifth and sixth pairs worked for ten days,
twenty days, thirty days and forty days, respectively. The last pair of electrodes
was tested until both anode and cathode used out in alkaline solution. In addition,
electrode 1 and electrode 2 from every pair are represented as E 1 and E 2.
After one day using in 1 M NaOH electrolyte, from XRD results, the anode (E 1)
is nearly unchanged compared with the original one, except that Ti peaks
become stronger. But the cathode (E 2) changed significantly with some metal
Co peaks showing up. This is maybe because reduction reaction happened on
cathode electrode (E 2) surface, Con+ + ne → Co (n=2, 3) and under cathodic
polarization effect, electrode material begins to change from crystal to
amorphous phase indicate by the large number of noisy peaks showing up. The
above phenomena are consistent with the fixed current direction electrolysis
process discussed above.
SEM pictures, Figure 5.12, show some tiny cracks randomly distributed on the
surface of both anode (E 1) and cathode (E 2). This should be because of the
generation of oxygen and hydrogen gases with these gas bubbles intensively
bumped electrodes surface.
After first 24 h electrolysis, anode and cathode were reversed by changing

current direction which means at the beginning E 1 was employed as anode and
E 2 was employed as cathode, after one day operation, E 1 was became as
cathode and E 2 performed as anode for the following 24 h electrolysis. After two
days electrolysis, the anode (E 2) from the second pair shows similar result to
the cathode (E 2) from the first pair of electrodes in terms of the XRD peaks. The
metal Co still can be found in metal oxides surface and seems not oxidized
under anodic polarization, consistent with the CV curves seen in Figure 5.5.
72
Such a phenomenon may be explained by the trapping of elemental Co inside
the “cage” structure of spinel crystals and oxygen evolution effect would not
change electrode surface crystal phase significantly. Hence metal Co is not
dissolving into the solution and does not be re-oxidized to Co2O3 as well. For the
cathode (E 1) part, Co(OH)2 peaks are detected on the electrode surface. It
should be a reduction process:
Co3O4 + 2H2O + 2e- → 3Co(OH)2 (5.5)
The same behavior was observed from cyclic voltammograms (Figure 5.5). Thus,
there are two main reduction products, Co and Co(OH)2, found from two day
operation electrode (E 1) surface as detected by XRD.
73
250
Co3O4
200 Co3O4
150
Counts
Co3O4
100
Co3O4 Co3O4
Co3O4
Ti
Ti Co3O4
50 Ti
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(a)
50
Co3O4 Ti
Co
40
Ti
Ti
Counts
30
Co
Co3O4 Co
20 Co3O4
10
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(b)
Figure 5.11 XRD patterns of the first pair (one day using) of electrodes.
(a) anode (E 1), (b) cathode (E 2)
74
(a) (b)
Figure 5.12 SEM pictures of the first pair (one day using) of electrodes.
(a) (b)
Figure 5.13 SEM pictures of the second pair (two days using) of electrodes.
75
60
50
40
Co3O4
Co
Counts
Ti
30
Co
Ti Ti
Co3O4 Co
20
Co3O4
10
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(a)
Co(OH)2
80
60
Co Ti
Counts
Ti Co(OH)2 Ti
40 Co(OH)2
Co
Co
20
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(b)
Figure 5.14 XRD patterns of the second pair (two days using) of electrodes.
76
Figure 5.13 shows the SEM pictures of the second pair of electrodes after two
days application. Compared with Figure 5.12, the cracks are more obvious which
is related with gas evolution effect on electrodes surface directly. EDX data show
48.84% Co and 5.66% Cu with little Ti and Na (probably came from sodium
hydroxyl solution) detected, illustrating the electrode surfaces were fully covered
by Cu0.3Co2.7O4 metal oxide thin film. The molar ratio of Cu/Co is 0.116, slightly
bigger than the theoretical value of 0.111.
Besides, peaks of Co3O4 are no longer discovered from the cathode (E 1)

surface (Figure 5.14 (b)). It could be concluded that two kinds of reactions
happened to the original Co3O4-Cu spinel material at the same time; one is
reduction reactions and the other one is the crystal Co3O4 changing into
amorphous Co3O4 and Co.
After ten days using under alternative anodic and cathodic polarization process;
Co3O4 crystals could no longer be observed by XRD from both anode (E 2) and
cathode (E 1) surfaces. Although EDX results (34.61% Co and 5.75% Cu) show
that there is plenty of Co and Cu remaining. This result reveals that Co and Cu
contents exist in metal oxide film in an amorphous phase. For the anode (E 2),
some TiN was found as well whose source could be from Ti substrate, which can
be verified by XRD peaks of a Ti substrate after pretreatment work.
Comparing Figures 5.15 and 5.16, it is obvious to see that the intensity of TiN
peaks is turning stronger; the generation of extra TiN may be from electrode
preparing procedure in 550 °C furnace and exist firmly between substrate
surface and metal oxide thin film.
77
200
Ti
180
160
140
120
Counts
100
80
Ti
60
Ti Ti Ti
TiN
40 Ti Ti
TiN
20
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
Figure 5.15 XRD patterns of Ti substrate
From SEM pictures (Figure 5.17) of ten-days-using anode (E 2) and cathode (E

1), it is clear to see big cracks appearing at the surfaces, the gaps became
bigger under day by day gas evolution effect and the lower layer of metal oxide
could be seen clearly. After twenty days electrolysis of water in alkaline condition,
the upper layer detached from substrate as shown by Figure 5.18. The
roughness of the surface increased along with the formation of cavities.
The XRD patterns of the fourth pair of anode (E 2) illustrate apparently the same
outcome with the anode (E 2) of the third pair (10 days using). The only
difference is that small amount of TiO2 could be found from electrode surfaces
after twenty days operation. For the cathode (E 1), there are three differences: (a)
TiO2 appeared on twenty days cathode (E 1); (b) TiN appeared on twenty days
cathode (E 1); (c) No Co(OH)2 can be found from twenty days cathode (E 1)
surface.
78
140 Ti
120
100
Counts
80
60
TiN
Ti TiN TiN Co
40
Ti
Co TiN Ti Ti
20
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(a)
45
40 Ti
Co
Ti
35
Co Co(OH)2
Co(OH)2 Ti Co
30
25 Co(OH)2
Counts
20
15
10
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(b)
Figure 5.16 XRD patterns of the third pair (ten day using) of electrodes.
79
(a) (b)
Figure 5.17 SEM pictures of the third pair (ten days using) of electrodes.
(a) (b)
Figure 5.18 SEM pictures of the fourth pair (twenty days using) of
electrodes. (a) anode (E 2), (b) cathode (E 1)
80
Ti
120
100
80
Counts
60 Ti
Ti
TiN
TiN Ti
Ti
40 TiN TiO2
TiO2 Co TiO2 Co Ti
Co TiN
20
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(a)
80
70 Ti
60
50 TiN
TiN Ti
Counts
TiN
40
Co TiN Ti
Ti
30 Ti Co
TiO2 Co
20
10
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(b)
Figure 5.19 XRD patterns of the fourth pair (twenty day using) of electrodes.
81
After thirty days electrolysis, a lot of noise could be found from the XRD spectra
of the cathode (E 1) surface and it is hard to determine whether TiN or TiO2 exist,
Figure 5.20. There is a possibility that the noise is due to amorphous Co and Cu.
The anode (E 2), Figure 5.20 (a), gives similar XRD spectra to those from
cathode after twenty days operation cathode (E 1), Figure 5.19 (b).
SEM pictures of Figures 5.21 and 5.22 show that the morphology of the
electrodes after thirty days operation became rougher and with deeper cavities
generated at more locations.
After forty days electrolysis, it seems that there is no distinctive difference

between the anode (E 2) and cathode (E 1) in term of the XRD peaks. However,
more and more black powders could be seen at the bottom of the electrolysis cell
which was derived from metal oxide thin films of both electrodes. It could be
preliminarily concluded that the deactivation mechanism of one material
Ti/Cu0.3Co2.7O4 electrodes performed as both anode and cathode for electrolysis
application is a combination of metal oxide film detachment from electrode
surface and generation of TiO2 inner layer. The similar XRD results from Figure
5.23 (a) (b) do not mean the anode (E 2) and the cathode (E 1) had become the
same material, but because a lot amorphous or small sized Cu and Co oxides
cannot be distinguished by XRD technique.
82
80 Ti
70 TiN
60
Ti
50 TiO2
Ti
TiN Ti TiN
Counts
40 Ti
Co Co Ti
TiO2
30
TiO2 TiN
20 Co
10
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(a)
45
40 Ti
35 Ti
30 Co
Co
25 Co Ti
Counts
20
15
10
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(b)
Figure 5.20 XRD patterns of the fifth pair (thirty days using) of electrodes.
83
(a) (b)
Figure 5.21 SEM pictures of the fifth pair (thirty days using) of electrodes.
(a) (b)
Figure 5.22 SEM pictures of the sixth pair (forty days using) of electrodes.
84
140
Ti
120
100
TiN
80
Counts
TiN
60
TiO2 TiN Ti
TiN
40 Ti TiO2
TiO2 Co Ti
Co
20 Co
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(a)
Ti
100
80 TiN
Counts
60
Ti Ti
TiN
TiO2 TiN
40
TiO2 Ti TiO2 TiO2
Ti Co Co Ti
20
Co
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(b)
Figure 5.23 XRD patterns of the sixth pair (forty days using) of electrodes.
85
250
Ti
200
150
Counts
TiN TiN
100
Ti
Ti
50
Ti TiN TiN Ti
TiO2 Ti
TiN
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(a)
120
TiN
100
80
Ti
Counts
60
TiN TiN
TiN
40 Cu
Ti Cu Ti Cu
20
0
20 25 30 35 40 45 50 55 60 65 70 75 80
2 Theta
(b)
Figure 5.24 XRD patterns of the used out electrodes.

86
(a) (b)
Figure 5.25 SEM pictures of the used out electrodes.

After forty-two days using, one of the seventh pair electrode (E 2) deactivated
and cannot be applied as an anode any more with the anode voltage increased
sharply exceeding 15 volt. Hence, the current direction was reversed until the
other electrode (E 1) cannot perform as an anode, either. The total electrolysis
procedure lasted forty five days from the very beginning until both electrodes
deactivated. At the end, no Co could be detected from Figure 5.24 (a) (b) but
metal Cu showed up finally which may be related to Cu deposition on the
cathode surface. EDX result for the used out cathode (E 2) shows 11.79% Cu
and 8.15% Co.
Figure 5.25 shows the surface of the electrodes after 1000 hours acceleration
test. These figures are dramatically different from those seen for the virgin
electrodes. They are also very much different from those shown in Figure 5.22
where anode and cathode were similar. The rough surface of the anode in Figure
5.25 may be the TiO2 formed while the deposits on the cathode could be Cu and
Co. In any case, the thin film of Cu0.3Co2.7O4 should have been used up.
87
5.7 Summary
Incorporation of Cu into Co3O4 can significantly improve the stability of

Ti/CuxCo3-xO4. The optimum Cu content is 10 molar percentages in Cu-Co
combination. XPS analysis demonstrated that titanium substrate was fully
covered by Cu0.3Co2.7O4 thin film with no Ti detected. SEM analysis reveals that
Cu0.3Co2.7O4 films are very compact, with few pores or cracks. With application in
electrolysis, surface morphology of the electrodes shows a trend of no cracks →
tiny cracks → big cracks → top surface film detachment from substrate →
development of cavity on surface → many holes randomly distributed. EDX
analysis together with SEM images demonstrate all the electrodes covered with
cobalt and copper oxide thin film even after 1080 h using under alternative
anodic and cathodic polarization process. XRD patterns show that freshly
prepared Ti/Cu0.3Co2.7O4 mainly exhibit pure Co3O4 peaks without obvious Cu or
CuO peaks. Eight pairs parallel experiments combined with no switching current
electrolysis in alkaline solution reveal how crystal structure changing after 1 d, 2
d, 10 d, 20 d, 30 d, 40 d and until electrodes used out in 45 d.
It seems oxidation reaction did not change electrode surface crystal significantly
no matter the anode materials are in crystalline phase or in amorphous phase.
But when reduction reaction happened, there were two kinds of reduction
products found, Co and Co(OH)2. Combined XRD and EDX results show that
crystal Co3O4 turned into amorphous Co or small sized Co3O4. From the
experimental results, it is hypothesized that metal Co and small sized Co3O4
exist in a cage of the spinel lattice. With the process time increasing, more and
more black powders could be discovered in the electrolysis cell. A preliminary
electrode deactivation mechanism can be derived as the metal oxide film
gradual detachment from the substrate, consumption of Co3O4 structure and
generation of TiO2 inner layer. It is worth to note that alternating current direction
process can prolong anode service life, with this phenomenon clearly explained
by the redox reaction of Co4+/Co3+, Co3+/Co2+ and the trapping of reduced Co or
Cu inside the crystal structure.
88
CHAPTER 6 CONCLUSIONS
6.1 Conclusions of Present Work
In this dissertation, major efforts were devoted to the fabrication and

characterization of high-performance electrodes for both hydrogen and oxygen
evolutions. The academic contributions are summarized subsequently.
• 16 types of metal oxides were tested for water electrolysis in acid or

alkaline solution, with Ti/Cu1.5Co1.5O4 found to give the longest service
life.
• Ti/CuxCo3-xO4 was found to be able to act as one material anode and

cathode in an electrolysis cell with x varying from 0 to 1.5. The optimal
value of x = 0.3 was determined, with the ultimate service life reached
1080 h under accelerated life test in 1M NaOH.
• The surface morphology of the as-prepared Ti/CuxCo3-xO4 electrodes

become gradually smooth and compact until x reached to 0.3 then turn to
be porous and mesoscopic structure with further increasing in Cu content.
When the Ti/Cu0.3Co2.7O4 is applied in water electrolysis, surface
morphology shows a trend of no cracks → tiny cracks → big cracks → top
surface film detachment from substrate → porous structure → many holes
randomly distributed.
• XRD diffraction analysis shows that Ti/Cu0.3Co2.7O4 electrodes display a

similar diffraction pattern compared with pure Co3O4 which indicates that
Cu is replacing Co in the spinel structure of the cobalt oxide.
• By checking electrodes used after one day, two days……until used out in
1 M NaOH solution, a simple conclusion could be drawn that crystal
89
cobalt oxide was reduced to metal Co and Co(OH)2 and then changed
into amorphous phase. Reduction reaction also happened to copper
oxide to form metal Cu. Amorphous Co formation and its trap in the spinel
structure are the most important features of the electrode material which
allow Ti/Cu0.3Co2.7O4 to function as anode and also cathode for water
electrolysis with a prolonged service life.
6.2 Recommendations for Future Work
Due to time limitation, many challenges should have been but could not be
tackled. Thus, further study is necessary. Specifically:
• Continue to investigate the reason of amorphous cobalt formation and it

trap in the structure.
• Although Ti/CuxCo3-xO4 electrodes could be applied in water electrolysis

for more than 1,000 h under accelerated service life test, this kind of
electrode required the solution pH near 14. It is still necessary to search
for another electrode material that can perform well under various pH
conditions.
• Electrochemical treatment of anionic inorganic toxins in solution. Anodic

oxidation has also been used to destroy toxic inorganic species in solution,
with the most common and important example being cyanide oxidation
from electroplating, surface finishing, and gold mining operation. The
general reaction mechanism has been known for a very long time as
below:
CN-+2OH-→CNO-+H2O+2e- (6.1)
Since Ti/CuxCo3-xO4 electrodes could resist high pH, it can be considered
as an appropriate candidate for anodic oxidation of cyanide.
90
• Cathodic removal of toxic metal ions from solution. Cathodic
electrochemistry is one of the largest industrial areas for inorganic
electrochemistry (along with the production of chlorine/caustic for pulp
and paper industry). It is known now that Ti/CuxCo3-xO4 electrode is a fine
choice for cathode and has the ability to resist metal ion poisoning. Thus,
this electrode may have a good performance in cathodic electrochemistry
industry.
91
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Fabrication of High Quality One Material Anode

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Fabrication of High Quality One Material Anode

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Fabrication of High Quality

One Material Anode and Cathode

The Hong Kong University of Science and Technology

in Partial Fulfilment of the Requirements for

the Degree of Master of Philosophy

in the Environmental Engineering Program

December 2008, Hong Kong

Copyright © by Jingshu JIA 2008

I would like to express my thanks to the technicians in the Department of

I would like to thank my friends outside HKUST, including Mr. Guanghui

Finally, I would like to thank my parents for their unconditional love,

Figure 2.1 Schematic diagram of the experimental apparatus

Environmental Engineering Program

The Hong Kong University of Science and Technology

The Ti/CuxCo3-xO4 electrodes were characterized by different techniques such

For decades electrochemical technologies have contributed successfully to

Electroflotation, one of the environmental protection wastewater treatment

In an electrofloatation (EF) process, pollutants adhered onto tiny bubbles of

To solve these problems, it is proposed to find a DSA-based electrode that can

• Tolerating chlorides and metal ions. The service life of platinum or

• Reducing the cost from mal-operation. Anode material is usually more

• Saving electricity cost. The most conventional cathode materials used

With the background of research as introduced above, the research objectives of

2.1 Introduction of Electrochemistry

Electrochemistry is the branch of chemistry concerned with the interrelation of

Modern electrochemistry presents itself as a strongly diversified field, which one

Applied electrochemistry can provide valuable cost efficient and environmentally

The main advantages of electrochemical processes are as follows (Macdonald

• Versatility: Direct or indirect oxidation and reduction, phase separation,

Since electrochemical reactions take place at the interface of an electronic

2.2 Electrode Fabrication Methods

2.2.1 Thermal Decomposition Method

2.2.2 Sol-gel Method

The sol-gel process is a wet-chemical technique (Chemical Solution Deposition)

2.2.3 Electrostatic Spray Deposition (ESD)

Figure 2.1 Schematic diagram of the experimental apparatus used for

HEMB is known as an effective means of preparing nonequilibrium and

2.2.5 Chemical Vapor Deposition (CVD)

CVD has been a powerful technique in synthesizing film-structured materials with

Electrochemistry principle involves redox reactions (shorthand for

Electrochemical reactions have many applications, but those electrochemical

Electrolytic industrial processes for metals include the production of metals

2.4 Electrochemical Technology in Environmental Application

Electrochemical technology has contributed successfully to environmental

The performance of an electroflotation system is affected by the pollutant

Treatment type EF DAF IF Settling

Specific electricity consumption 30–50 50–60 100–150 50–100

Treatment time (min) 10–20 30–40 30–40 100–120

Sludge volume as percent of 0.05–0.1 0.3–0.4 3–5 7–10

Suspended solids removal 99–99. 5 90–95 85–90 90–95

In wastewater treatment, flotation is an indispensable process for the separation

In electroflotation, the useful small O2 and H2 bubbles are generated on an anode

OH- – 2e- → ½ O2 + ½ H2O on an anode (2.1)

High stability, high electrical efficiency electrodes for electroflotation play a

2.5.2 Electrodes for O2 Evolution

2.5.2.1 Graphite, PbO2 and Pt

The most common non-consumable anode materials are normally Graphite,

The DSAs are the most important anodes nowadays in electrochemical

a) Ruthenium oxide based electrode (RuOx)

c) Cobalt oxide based electrode (Co3O4)

2.5.3 Electrodes for H2 Evolution

2.5.3.1 Metals and Alloys

a) Ruthenium oxide based electrodes (RuOx)

b) Iridium oxide based electrode (IrOx)