This document summarizes the synthesis, characterization, and evaluation of various IrO2-based binary metal oxide electrocatalysts for the oxygen evolution reaction. IrO2, IrxRu1-xO2, IrxSnx-1O2 and IrxTax-1O2 (where x is between 1 and 0.7) were synthesized via an adapted Adams fusion method. X-ray diffraction and electron microscopy showed the materials formed nanocrystalline solid solutions. Electrochemical testing found that adding RuO2, SnO2, or Ta2O5 to IrO2 improved its catalytic performance for oxygen evolution. Specifically, Ir0.7Ru0.3O2 exhibited the best
IrO2 as an anodic electrocatalyst for the oxygen evolution reaction (OER) in solid polymer electrolyte (SPE)
electrolysers was synthesised by adapting the Adams fusion method. Optimisation of the IrO2 electrocatalyst was achieved
by varying the synthesis duration (0.5 – 4 hours) and temperature (250 - 500°C). The physical properties of the
electrocatalysts were characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and
x-ray diffraction (XRD). Electrochemical characterisation of the electrocatalysts toward the OER was evaluated by
chronoamperometry (CA). CA analysis revealed the best electrocatalytic activity towards the OER for IrO2 synthesised
for 2 hours at 350oC which displayed a better electrocatalytic activity than the commercial IrO2 electrocatalyst used in this
study. XRD and TEM analyses revealed an increase in crystallinity and average particle size with increasing synthesis
duration and temperature which accounted for the decreasing electrocatalytic activity. At 250°C the formation of an active
IrO2 electrocatalyst was not favoured.
IrO2 as an anodic electrocatalyst for the oxygen evolution reaction (OER) in solid polymer electrolyte (SPE)
electrolysers was synthesised by adapting the Adams fusion method. Optimisation of the IrO2 electrocatalyst was achieved
by varying the synthesis duration (0.5 – 4 hours) and temperature (250 - 500°C). The physical properties of the
electrocatalysts were characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and
x-ray diffraction (XRD). Electrochemical characterisation of the electrocatalysts toward the OER was evaluated by
chronoamperometry (CA). CA analysis revealed the best electrocatalytic activity towards the OER for IrO2 synthesised
for 2 hours at 350oC which displayed a better electrocatalytic activity than the commercial IrO2 electrocatalyst used in this
study. XRD and TEM analyses revealed an increase in crystallinity and average particle size with increasing synthesis
duration and temperature which accounted for the decreasing electrocatalytic activity. At 250°C the formation of an active
IrO2 electrocatalyst was not favoured.
Electrochemical study of anatase TiO2 in aqueous sodium-ion electrolytesRatnakaram Venkata Nadh
In this paper, a basic electro-analytical study on the behavior of anatase TiO2 in aqueous NaOH has been presented using cyclic voltammetry technique (CV). The study has explored the possibility of using TiO2 as anode material for ARSBs in presence of 5 M NaOH aqueous electrolyte. CV profiles show that anatase TiO2 exhibits reversible sodium ion insertion/de-insertion reactions. CV studies of TiO2 anode in aqueous sodium electrolytes at different scan rate shows that the Na+ ion insertion reaction at the electrode is diffusion controlled with a resistive behavior. Proton insertion from aqueous sodium electrolytes into TiO2 cannot be ruled out. To confirm the ion inserted and de-inserted, CV studies are done at different concentration of NaOH and it is found that at lower concentrations of NaOH, proton insertion process competes with Na+ ion insertion process and as the concentration increases, the Na+ ion insertion process becomes the predominant electrode reaction making it suitable anode materials for aqueous sodium batteries in 5 M NaOH.
Effects of Precipitation pH Values on the Electrochemical Properties of β-Nic...iosrjce
IOSR Journal of Applied Chemistry (IOSR-JAC) is a double blind peer reviewed International Journal that provides rapid publication (within a month) of articles in all areas of applied chemistry and its applications. The journal welcomes publications of high quality papers on theoretical developments and practical applications in Chemical Science. Original research papers, state-of-the-art reviews, and high quality technical notes are invited for publications.
Direct Synthesis Carbon/Metal Oxide Composites for Electrochemical Capacitors...drboon
This paper deals with the study of the carbon/metal oxide composites synthesis for electrochemical capacitor electrode material. Transition metal salts, such as FeCl3 and TiCl3 act as activator in the synthesis of activated carbon from gelam wood sawdust (Melaleuca cajuputi Powell) which also have the functions as substrates for the composites. The surface functionalities of activated carbons were modified using oxidative treatments. The changes on crystallography and surface functionalities were analyzed based on XRD and FTIR data. The electrical conductivities and electrochemical properties were determined using kelvin and cyclic voltammetry methods, respectively. FTIR analyses showed that the activation and oxidation treatments affected their surface functionalities. The XRD analyses showed that oxidative treatments also affected carbons crystallite. The electrical conductivities and electrochemical properties were influenced by their crystallite and surface functionalities. The shape of the cyclic voltammograms varied according to the changes on the surface functionalities and on the metals loading. TEM analyses indicated the existence of nanoparticles metal oxides in the carbon samples.
Corrosion Inhibition of Carbon Steel In Sulfuric Acid by Sodium CaprylateIJERA Editor
The interaction of a sodium salt of octanoic acid, sodium caprylate (SC), with a carbon steel (CS) surface was
investigated, using range of experimental techniques. It was shown that SC acts as a good CS general corrosion
inhibitor, yielding a maximum corrosion inhibition efficiency of 77%. This high inhibition efficiency is
maintained even at higher temperatures. It was determined that SC inhibits both partial corrosion reactions, and
can thus be considered to be a mixed-type inhibitor. The adsorption of SC on the CS surface was described by
the Langmuir adsorption isotherm. It was found that this process is spontaneous, irreversible and driven by the
entropy gain. The CS surface morphology was studied by SEM and it was demonstrated that SC is a very
effective general corrosion inhibitor of CS. This also was confirmed by contact angle measurements which
showed that the CS surface became more hydrophobic when the SC was added to the solution.
Maiyalagan,Performance of carbon nanofiber supported pd ni catalysts for elec...kutty79
Carbon nanofibers (CNF) supported Pd–Ni nanoparticles have been prepared by chemical reduction
with NaBH4 as a reducing agent. The Pd–Ni/CNF catalysts were characterized by X-ray diffraction
(XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical
voltammetry analysis. TEM showed that the Pd–Ni particles were quite uniformly distributed on the
surface of the carbon nanofiber with an average particle size of 4.0 nm. The electro-catalytic activity of
the Pd–Ni/CNF for oxidation of ethanol was examined by cyclic voltammetry (CV). The onset potential
was 200mV lower and the peak current density four times higher for ethanol oxidation for Pd–Ni/CNF
compared to that for Pd/C. The effect of an increase in temperature from 20 to 60 ◦C had a great effect on
increasing the ethanol oxidation activity
Corrosion Inhibition of Carbon Steel In Sulfuric Acid by Sodium CaprylateIJERA Editor
The interaction of a sodium salt of octanoic acid, sodium caprylate (SC), with a carbon steel (CS) surface was
investigated, using range of experimental techniques. It was shown that SC acts as a good CS general corrosion
inhibitor, yielding a maximum corrosion inhibition efficiency of 77%. This high inhibition efficiency is
maintained even at higher temperatures. It was determined that SC inhibits both partial corrosion reactions, and
can thus be considered to be a mixed-type inhibitor. The adsorption of SC on the CS surface was described by
the Langmuir adsorption isotherm. It was found that this process is spontaneous, irreversible and driven by the
entropy gain. The CS surface morphology was studied by SEM and it was demonstrated that SC is a very
effective general corrosion inhibitor of CS. This also was confirmed by contact angle measurements which
showed that the CS surface became more hydrophobic when the SC was added to the solution.
Electrochemical study of anatase TiO2 in aqueous sodium-ion electrolytesRatnakaram Venkata Nadh
In this paper, a basic electro-analytical study on the behavior of anatase TiO2 in aqueous NaOH has been presented using cyclic voltammetry technique (CV). The study has explored the possibility of using TiO2 as anode material for ARSBs in presence of 5 M NaOH aqueous electrolyte. CV profiles show that anatase TiO2 exhibits reversible sodium ion insertion/de-insertion reactions. CV studies of TiO2 anode in aqueous sodium electrolytes at different scan rate shows that the Na+ ion insertion reaction at the electrode is diffusion controlled with a resistive behavior. Proton insertion from aqueous sodium electrolytes into TiO2 cannot be ruled out. To confirm the ion inserted and de-inserted, CV studies are done at different concentration of NaOH and it is found that at lower concentrations of NaOH, proton insertion process competes with Na+ ion insertion process and as the concentration increases, the Na+ ion insertion process becomes the predominant electrode reaction making it suitable anode materials for aqueous sodium batteries in 5 M NaOH.
Effects of Precipitation pH Values on the Electrochemical Properties of β-Nic...iosrjce
IOSR Journal of Applied Chemistry (IOSR-JAC) is a double blind peer reviewed International Journal that provides rapid publication (within a month) of articles in all areas of applied chemistry and its applications. The journal welcomes publications of high quality papers on theoretical developments and practical applications in Chemical Science. Original research papers, state-of-the-art reviews, and high quality technical notes are invited for publications.
Direct Synthesis Carbon/Metal Oxide Composites for Electrochemical Capacitors...drboon
This paper deals with the study of the carbon/metal oxide composites synthesis for electrochemical capacitor electrode material. Transition metal salts, such as FeCl3 and TiCl3 act as activator in the synthesis of activated carbon from gelam wood sawdust (Melaleuca cajuputi Powell) which also have the functions as substrates for the composites. The surface functionalities of activated carbons were modified using oxidative treatments. The changes on crystallography and surface functionalities were analyzed based on XRD and FTIR data. The electrical conductivities and electrochemical properties were determined using kelvin and cyclic voltammetry methods, respectively. FTIR analyses showed that the activation and oxidation treatments affected their surface functionalities. The XRD analyses showed that oxidative treatments also affected carbons crystallite. The electrical conductivities and electrochemical properties were influenced by their crystallite and surface functionalities. The shape of the cyclic voltammograms varied according to the changes on the surface functionalities and on the metals loading. TEM analyses indicated the existence of nanoparticles metal oxides in the carbon samples.
Corrosion Inhibition of Carbon Steel In Sulfuric Acid by Sodium CaprylateIJERA Editor
The interaction of a sodium salt of octanoic acid, sodium caprylate (SC), with a carbon steel (CS) surface was
investigated, using range of experimental techniques. It was shown that SC acts as a good CS general corrosion
inhibitor, yielding a maximum corrosion inhibition efficiency of 77%. This high inhibition efficiency is
maintained even at higher temperatures. It was determined that SC inhibits both partial corrosion reactions, and
can thus be considered to be a mixed-type inhibitor. The adsorption of SC on the CS surface was described by
the Langmuir adsorption isotherm. It was found that this process is spontaneous, irreversible and driven by the
entropy gain. The CS surface morphology was studied by SEM and it was demonstrated that SC is a very
effective general corrosion inhibitor of CS. This also was confirmed by contact angle measurements which
showed that the CS surface became more hydrophobic when the SC was added to the solution.
Maiyalagan,Performance of carbon nanofiber supported pd ni catalysts for elec...kutty79
Carbon nanofibers (CNF) supported Pd–Ni nanoparticles have been prepared by chemical reduction
with NaBH4 as a reducing agent. The Pd–Ni/CNF catalysts were characterized by X-ray diffraction
(XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical
voltammetry analysis. TEM showed that the Pd–Ni particles were quite uniformly distributed on the
surface of the carbon nanofiber with an average particle size of 4.0 nm. The electro-catalytic activity of
the Pd–Ni/CNF for oxidation of ethanol was examined by cyclic voltammetry (CV). The onset potential
was 200mV lower and the peak current density four times higher for ethanol oxidation for Pd–Ni/CNF
compared to that for Pd/C. The effect of an increase in temperature from 20 to 60 ◦C had a great effect on
increasing the ethanol oxidation activity
Corrosion Inhibition of Carbon Steel In Sulfuric Acid by Sodium CaprylateIJERA Editor
The interaction of a sodium salt of octanoic acid, sodium caprylate (SC), with a carbon steel (CS) surface was
investigated, using range of experimental techniques. It was shown that SC acts as a good CS general corrosion
inhibitor, yielding a maximum corrosion inhibition efficiency of 77%. This high inhibition efficiency is
maintained even at higher temperatures. It was determined that SC inhibits both partial corrosion reactions, and
can thus be considered to be a mixed-type inhibitor. The adsorption of SC on the CS surface was described by
the Langmuir adsorption isotherm. It was found that this process is spontaneous, irreversible and driven by the
entropy gain. The CS surface morphology was studied by SEM and it was demonstrated that SC is a very
effective general corrosion inhibitor of CS. This also was confirmed by contact angle measurements which
showed that the CS surface became more hydrophobic when the SC was added to the solution.
Recent progress in non platinum counter electrode materials for dye sensitize...Science Padayatchi
Dye-sensitized solar cells (DSSCs) have gained increasing attention
with regard to photovoltaic devices, because of their low
cost and simple fabrication methods; they are mostly investigated
in indoor light-harvesting and portable applications. The
focus has been on three main parameters of photovoltaic devices,
that is, lifetime, and cost effectiveness. A DSSC consists of
four prominent components including a photoanode, a photosensitizer,
a redox electrolyte, and a counter electrode. The
counter electrode is a crucial component, in which triiodide is
reduced to iodide by electrons flowing through the external
circuit. An effective approach to improve the performance of
a counter electrode is to enhance the power conversion efficiency
and to reduce the cost of the device. Platinum-coated
conducting glass electrodes give the best performance, but
their high cost and the scarcity of platinum restricts large-scale
application in DSSCs. This has prompted researchers to develop
low-costing platinum-free electrodes for DSSCs. In this
review, we focus mainly on counter electrode materials for the
electrocatalytic redox reaction for the I¢/I¢
3 electrolyte, and
apart from this, other counter electrode materials for iodinefree
redox electrolytes are discussed. Different counter electrode
materials are highlighted in different categories such as
carbon materials, conducting polymers, oxide and sulfide materials,
transition-metal nitrides and carbides, and composite
materials. The stability of counter electrodes in DSSCs is also
presented.
Recent progress in non platinum counter electrode materials for dye sensitize...Science Padayatchi
Dye-sensitized solar cells (DSSCs) have gained increasing attention
with regard to photovoltaic devices, because of their low
cost and simple fabrication methods; they are mostly investigated
in indoor light-harvesting and portable applications. The
focus has been on three main parameters of photovoltaic devices,
that is, lifetime, and cost effectiveness. A DSSC consists of
four prominent components including a photoanode, a photosensitizer,
a redox electrolyte, and a counter electrode. The
counter electrode is a crucial component, in which triiodide is
reduced to iodide by electrons flowing through the external
circuit. An effective approach to improve the performance of
a counter electrode is to enhance the power conversion efficiency
and to reduce the cost of the device. Platinum-coated
conducting glass electrodes give the best performance, but
their high cost and the scarcity of platinum restricts large-scale
application in DSSCs. This has prompted researchers to develop
low-costing platinum-free electrodes for DSSCs. In this
review, we focus mainly on counter electrode materials for the
electrocatalytic redox reaction for the I¢/I¢
3 electrolyte, and
apart from this, other counter electrode materials for iodinefree
redox electrolytes are discussed. Different counter electrode
materials are highlighted in different categories such as
carbon materials, conducting polymers, oxide and sulfide materials,
transition-metal nitrides and carbides, and composite
materials. The stability of counter electrodes in DSSCs is also
presented.
A new technique to measure oxygen reduction kinetics underneath coatings using hydrogen permeation from the back side. Huge step towards characterising buried interface reactivity.
Inhibition, kinetic and thermodynamic effects of new Azo derivatives on iron ...Al Baha University
This investigation is designed to apply an advanced kinetic-thermodynamic model on the experimental data obtained from acidic and alkaline corrosion of iron using mono- and bis-azo dyes as corrosion inhibitors. The inhibition properties of the tested azo dyes on corrosion of iron in HNO3 and NaOH media were analyzed by gravimetric, thermometric and polarization measurements. The three studied methods gave consistent results. Polarization study showed that all the inhibitors are mixed type in acidic, act mainly as cathodic in alkaline solution. The synthesized azo dye derivatives exhibit good inhibition properties, obeys the Frumkin adsorption isotherm. The large values of the change in the standard free energy of adsorption (∆Goads), equilibrium constant (Kads) and binding constant (Kb) revealed that the reactions proceed spontaneously and result in highly efficient physisorption mechanism and stronger electrical interaction between the double layer existing at the phase boundary and the adsorbing molecules. The inhibition efficiency depends on the number of adsorption oxygen sites (OH and OMe groups), their charge density and π-electron clouds. The inhibition efficiency evaluated via theoretical methods was well accorded with reported experimental ones, following the same order as: -naphthyl- ligand > -naphthyl>p-anisdine>p-toluidine >o-toluidine >m-toluidine derivative. This research might provide a theoretical inhibition performance evaluation approach for homologous inhibitors.
IJERA (International journal of Engineering Research and Applications) is International online, ... peer reviewed journal. For more detail or submit your article, please visit www.ijera.com
IJERA (International journal of Engineering Research and Applications) is International online, ... peer reviewed journal. For more detail or submit your article, please visit www.ijera.com
We all have good and bad thoughts from time to time and situation to situation. We are bombarded daily with spiraling thoughts(both negative and positive) creating all-consuming feel , making us difficult to manage with associated suffering. Good thoughts are like our Mob Signal (Positive thought) amidst noise(negative thought) in the atmosphere. Negative thoughts like noise outweigh positive thoughts. These thoughts often create unwanted confusion, trouble, stress and frustration in our mind as well as chaos in our physical world. Negative thoughts are also known as “distorted thinking”.
Synthetic Fiber Construction in lab .pptxPavel ( NSTU)
Synthetic fiber production is a fascinating and complex field that blends chemistry, engineering, and environmental science. By understanding these aspects, students can gain a comprehensive view of synthetic fiber production, its impact on society and the environment, and the potential for future innovations. Synthetic fibers play a crucial role in modern society, impacting various aspects of daily life, industry, and the environment. ynthetic fibers are integral to modern life, offering a range of benefits from cost-effectiveness and versatility to innovative applications and performance characteristics. While they pose environmental challenges, ongoing research and development aim to create more sustainable and eco-friendly alternatives. Understanding the importance of synthetic fibers helps in appreciating their role in the economy, industry, and daily life, while also emphasizing the need for sustainable practices and innovation.
How to Make a Field invisible in Odoo 17Celine George
It is possible to hide or invisible some fields in odoo. Commonly using “invisible” attribute in the field definition to invisible the fields. This slide will show how to make a field invisible in odoo 17.
The Roman Empire A Historical Colossus.pdfkaushalkr1407
The Roman Empire, a vast and enduring power, stands as one of history's most remarkable civilizations, leaving an indelible imprint on the world. It emerged from the Roman Republic, transitioning into an imperial powerhouse under the leadership of Augustus Caesar in 27 BCE. This transformation marked the beginning of an era defined by unprecedented territorial expansion, architectural marvels, and profound cultural influence.
The empire's roots lie in the city of Rome, founded, according to legend, by Romulus in 753 BCE. Over centuries, Rome evolved from a small settlement to a formidable republic, characterized by a complex political system with elected officials and checks on power. However, internal strife, class conflicts, and military ambitions paved the way for the end of the Republic. Julius Caesar’s dictatorship and subsequent assassination in 44 BCE created a power vacuum, leading to a civil war. Octavian, later Augustus, emerged victorious, heralding the Roman Empire’s birth.
Under Augustus, the empire experienced the Pax Romana, a 200-year period of relative peace and stability. Augustus reformed the military, established efficient administrative systems, and initiated grand construction projects. The empire's borders expanded, encompassing territories from Britain to Egypt and from Spain to the Euphrates. Roman legions, renowned for their discipline and engineering prowess, secured and maintained these vast territories, building roads, fortifications, and cities that facilitated control and integration.
The Roman Empire’s society was hierarchical, with a rigid class system. At the top were the patricians, wealthy elites who held significant political power. Below them were the plebeians, free citizens with limited political influence, and the vast numbers of slaves who formed the backbone of the economy. The family unit was central, governed by the paterfamilias, the male head who held absolute authority.
Culturally, the Romans were eclectic, absorbing and adapting elements from the civilizations they encountered, particularly the Greeks. Roman art, literature, and philosophy reflected this synthesis, creating a rich cultural tapestry. Latin, the Roman language, became the lingua franca of the Western world, influencing numerous modern languages.
Roman architecture and engineering achievements were monumental. They perfected the arch, vault, and dome, constructing enduring structures like the Colosseum, Pantheon, and aqueducts. These engineering marvels not only showcased Roman ingenuity but also served practical purposes, from public entertainment to water supply.
The Art Pastor's Guide to Sabbath | Steve ThomasonSteve Thomason
What is the purpose of the Sabbath Law in the Torah. It is interesting to compare how the context of the law shifts from Exodus to Deuteronomy. Who gets to rest, and why?
Instructions for Submissions thorugh G- Classroom.pptxJheel Barad
This presentation provides a briefing on how to upload submissions and documents in Google Classroom. It was prepared as part of an orientation for new Sainik School in-service teacher trainees. As a training officer, my goal is to ensure that you are comfortable and proficient with this essential tool for managing assignments and fostering student engagement.
How to Create Map Views in the Odoo 17 ERPCeline George
The map views are useful for providing a geographical representation of data. They allow users to visualize and analyze the data in a more intuitive manner.
Model Attribute Check Company Auto PropertyCeline George
In Odoo, the multi-company feature allows you to manage multiple companies within a single Odoo database instance. Each company can have its own configurations while still sharing common resources such as products, customers, and suppliers.
1. Int. J. Electrochem. Sci., 7 (2012) 12064 - 12077
International Journal of
ELECTROCHEMICAL
SCIENCE
www.electrochemsci.org
Synthesis, Characterisation and Evaluation of IrO2 Based
Binary Metal Oxide Electrocatalysts for Oxygen Evolution
Reaction
C. Felix, T. Maiyalagan*, S. Pasupathi*, B. Bladergroen, V. Linkov
South African Institute for Advanced Materials Chemistry (SAIAMC), University of the Western
Cape, Modderdam Road, Bellville 7535, Cape Town, South Africa
*
E-mail: spasupathi@uwc.ac.za; maiyalagan@gmail.com
Received: 13 June 2012 / Accepted: 29 September 2012 / Published: 1 December 2012
IrO2, IrxRu1-xO2, IrxSnx-1O2 and IrxTax-1O2 (1 ≥ x ≥ 0.7) were synthesized, characterised and evaluated
as electrocatalysts for the oxygen evolution reaction in solid polymer electrolyte electrolysers. The
electrocatalysts were synthesised by adapting the Adams fusion method. The physical properties of the
electrocatalysts were characterised by scanning electron microscopy, transmission electron microscopy
and x-ray diffraction. Electrochemical activity of the electrocatalysts toward the oxygen evolution
reaction was evaluated by cyclic voltammetry and chronoamperometry. X-ray diffraction revealed no
phase separation when RuO2 or SnO2 was introduced into the IrO2 lattice suggesting that solid
solutions were formed. Transmission electron microscope analysis revealed nanosize particles for all
synthesised metal oxides. Crystallinity increased with the addition of RuO2 and SnO2 while a
suppression of crystal growth was observed with the addition of Ta2O5 to IrO2. Chronoamperometry
revealed that the addition of all the secondary metal oxides to IrO2 resulted in improved catalytic
performance. Ir0.7Ru0.3O2 was identified as the most promising electrocatalyst for the oxygen evolution
reaction.
Keywords: Adams fusion method, Anodic electrocatalyst, Oxygen evolution reaction, Solid polymer
electrolyte, Water electrolysis.
1. INTRODUCTION
Solid polymer electrolyte (SPE) or commonly known as proton exchange membrane (PEM)
electrolysers have in recent years received considerable interest as a production method for carbon free
hydrogen [1 - 3]. SPE electrolysers are well suited for water electrolysis using intermittent power
sources and have been identified by the European Commission as a key technology to transform
2. Int. J. Electrochem. Sci., Vol. 7, 2012
12065
renewable electricity into hydrogen and oxygen [4]. The main drawback at present is the high cost
associated with the SPE electrolyser components such as the expensive precious metal electrocatalysts
and proton conducting membranes [5, 6]. One way to reduce the cost of the SPE electrolyser is by
improving the specific performance and durability of the noble metal electrocatalysts. The oxygen
evolution electrode (anode) is the greatest source of overpotential of the system at typical operating
current density [2, 6] therefore the anodic electrocatalyst needs to be highly stable and active under the
operating conditions [7]. IrO2 is commonly employed as the anodic electrocatalyst as it exhibits a high
corrosion resistance to the oxygen evolution reaction (OER) in a strong acidic environment [7, 8]. IrO2
is scarce and very expensive [9], adding significantly to the cost of the SPE electrolyser system. Since
there is still no non-metal electrocatalyst with satisfactory activity and durability, it becomes important
to improve both the activity and durability of the IrO2 electrocatalyst. The most common method of
enhancing the electrochemical properties of the IrO2 electrocatalyst is by insertion of other metal
oxides into the IrO2 lattice. In this study, IrO2, IrxRu1-xO2, IrxSnx-1O2 and IrxTax-1O2 (1 ≥ x ≥ 0.7) were
synthesised and characterised as suitable anodic electrocatalysts for the SPE electrolyser. RuO2 is
known to be the most active towards the OER but suffers from instability, and should thus be stabilised
with another metal oxide such as IrO2 or SnO2 [10, 11]. Corrosion of Ru proceeds via RuO4 and is
directly coupled to oxygen evolution via this common intermediate. The stabilisation of Ru by Ir has
been explained on the basis of shifted oxidation potentials and surface segregation [12]. IrO2 thus
stabilises RuO2 by preventing its oxidation to the soluble RuO4 [13]. Ir-Ru mixed oxides are known to
have superior catalytic and stability properties with respect to Ru-Ti mixed oxide electrodes [14]. Ta is
a well known addition to the dimensionally stable anode (DSA) electrodes and Ir-Ta oxides have been
suggested to be an efficient catalyst for the OER in acidic media due to the high activity and corrosion
resistance [2]. The IrO2-Ta2O5 system as DSAs is a promising catalyst in various electrochemical
industries, such as cleaning of waste water and electrowinning (electro-extraction) of metals, where
oxygen evolution is the main anodic reaction. However Ta2O5 is mainly added to improve the service
life of IrO2, which is the active and most expensive component [15]. IrO2-Ta2O5 with the composition
of 70 % IrO2 and 30% Ta2O5 has been previously verified to be the best combination in binary metal
oxide systems in present commercial applications [16]. Sn was selected on the basis of its high
chemical and mechanical stability as well as its lower cost than the expensive noble metals [17]. The
Adams fusion method was adapted to synthesise the Ir based metal oxides and the electrocatalytic
activities were evaluated by cyclic voltammetry (CV) and chronoamperometry (CA). Physical
characterisation was performed by scanning electron microscope (SEM), transmission electron
microscope (TEM) and x-ray diffraction (XRD).
2. EXPERIMENTAL DETAILS
2.1 Preparation of the catalyst
The Adams fusion method, first described by R. Adams and R.L. Shriner [18], entails the
fusion of the metal chloride precursor with NaNO3 in air at elevated temperatures. The method has
3. Int. J. Electrochem. Sci., Vol. 7, 2012
12066
since been used to synthesise various noble metal oxides [15, 17-19]. H2IrCl6 (SA precious metals,
South Africa), RuCl3, SnCl2.2H2O and TaCl5 (Alfa Aesar, Johnson Matthey) were used as catalyst
precursors to synthesise the electrocatalysts. The catalyst precursor(s) were dissolved in 10 ml
isopropanol (Alfa Aesar, Johnson Matthey) until a metal concentration of 3.5 x 10 -2 M was achieved
and magnetically stirred for 90 minutes. For each type of binary metal oxide system the second metal
(Sn, Ru or Ta) was added in a concentration of 5–30 mol % to Ir. Five grams of finely ground NaNO3
(Holpro Fine Chemicals, South Africa) was added to the solution, which was then further stirred for 30
minutes. The mixture was then dried in an oven for 30 minutes. The dried catalyst precursor/salt
mixture was then reacted in a furnace for 120 minutes at 350 °C. No additional annealing step
followed to limit the sintering of the nanosize particles. The obtained metal oxide was cooled and
washed with ultrapure water to remove the unreacted NaNO3. The final step was to dry the metal oxide
in an oven for 120 minutes at 100 °C.
2.2 Preparation of the working electrode
A predetermined size of Ti mesh (Bekinit K.K, Japan) was etched and cleaned by boiling in
oxalic acid (NT Laboratory Supplies) for 12 minutes. Catalyst inks were prepared by mixing together
the synthesised metal oxides, 5 wt% Nafion solution (Aldrich) and ultrapure water in a ratio of 1:6:2.
A measured volume of isopropanol was added to serve as dispersion medium. The mixture was
ultrasonically dispersed for 30 minutes. An airbrush with N2 propulsion was used to spray the catalyst
ink (1 mg cm-2) onto the pre-treated Ti mesh. The catalyst ink was thoroughly dried between each
layer sprayed to prevent agglomeration of the electrocatalytic particles. Spraying of the catalyst layer
was followed by spraying a Nafion layer (1 mg cm-2). The working electrode was cut out with a punch
and had an area of 0.785 cm2.
2.3 Physical characterisation
Physical phases and structures of the electrocatalysts were characterised by X-ray diffraction
(XRD) employing the Bruker AXS D8 Advance diffractometer using Cu K radiation (λ = 1.5406 Å)
operating at 40 kV and 40 mA. Scanning electron micrographs were obtained with the Hitachi X-650
SEM using GENESIS software, working at 25 keV. Transmission electron micrographs were obtained
using a Tecnai G2 F20 X-Twin Mat200 kV Field Emission TEM, operating at 200 kV.
2.4 Electrochemical characterisation
Electrochemical analyses were performed in a standard three-electrode cell at 25 oC and
atmospheric pressure. The Ti mesh working electrode (as described in earlier), a 3M Ag/AgCl
reference electrode, a Pt mesh counter electrode and a 0.5 M H2SO4 electrolyte solution was used.
Autolab potentiostat PGSTAT20 (Eco-Chemie) was used for CV and CA analyses to evaluate the
electrocatalytic activity of the synthesised electrocatalysts towards the OER. The electrolyte solution
4. Int. J. Electrochem. Sci., Vol. 7, 2012
12067
was purged with N2 for 30 minutes before performing electrochemical measurements. CV was
performed by cycling the potential from -0.2 to +1.2 V at a potential sweep rate of 50 mV s-1. CA was
performed by stepping the potentials from 1.2 to 1.6 V and measuring the current (mA) response as a
function of time. Each potential step was performed for 30 minutes. All potentials are reported versus
the 3M Ag/AgCl electrode.
3. RESULTS AND DISCUSSION
3.1 Physical characterisation
5. Int. J. Electrochem. Sci., Vol. 7, 2012
12068
Figure 1. XRD patterns of (a) IrO2 (b) Ir0.7Ru0.3O2 (c) Ir0.9Sn0.1O2 and (d) Ir0.8Ta0.2Ox.
Fig. 1 shows the XRD patterns of IrO2 and the best performing electrocatalysts (established by
CA analysis) of the three metal oxide combinations i.e. Ir0.7Ru0.3O2, Ir0.9Sn0.1O2 and Ir0.8Ta0.2Ox. The
XRD analysis of IrO2 (Fig. 1a) revealed a rutile oxide characterised by an amorphous phase which is
known to consist of smaller particles. Calculated from the 101 phase using the Scherrer formula, the
average particle size was estimated to be 3.5 nm. No metallic Ir was observed. The XRD analysis of
Ir0.7Ru0.3O2 (Fig. 1b) revealed a crystalline structure assigned to tetragonal rutile. Sharper peaks were
observed in comparison to pure IrO2 which indicates an increase in the particle size. The single peaks
observed at the 110 and 101 phases (2θ = 28° and 35° respectively) suggests that Ir 0.7Ru0.3O2 is a solid
6. Int. J. Electrochem. Sci., Vol. 7, 2012
12069
solution of IrO2 and RuO2. This observation is consistent with other reports [8, 9, and 13]. The addition
of RuO2 to IrO2 resulted in an increase in the 110 phase (a stable surface of IrO2) which may lead to a
synergistic effect. Although it is known that IrO2 and RuO2 can form stable solid solutions, the
presence of multiple rutile phases should not be ruled out. The Hume–Rothery theory states that it is
possible to form a continuous solid solution of IrO2 and RuO2, where Ru4+ and Ir4+ share the same site
on the cationic sub-lattice of a tetragonal (rutile-like) phase [20]. The higher degree of crystallisation
observed for Ir0.7Ru0.3O2 in comparison to pure IrO2 may be attributed to the fact that RuO2 crystallises
at a lower temperature than IrO2 [21]. Calculated from the 110 and 101 phases using the Scherrer
formula, the average particle size for Ir0.7Ru0.3O2 was estimated at 11 nm. The presence of metallic Ir
and Ru was not observed.
Figure 2. SEM images of (a) IrO2 (b) Ir0.7Ru0.3O2 (c) Ir0.9Sn0.1O2 and (d) Ir0.8Ta0.2Ox.
7. Int. J. Electrochem. Sci., Vol. 7, 2012
12070
XRD analysis of Ir0.9Sn0.1O2 (Fig. 1c) revealed a rutile-type oxide with single peaks observed at
the 110 and 101 phases (2θ = 28° and 35° respectively) which suggests that Ir0.9Sn0.1O2 is a solid
solution of IrO2 and SnO2. The addition of SnO2 to IrO2 resulted in an increase in the 110 phase (a
stable surface of IrO2) which may lead to a synergistic effect. Mayousse et al. [9] also observed the
formation of a solid solution between IrO2 and SnO2. They suggested that IrO2 and SnO2 crystallised in
the same tetragonal structure due to the comparable atomic radii of Ir and Sn. However the presence of
two phases should not be ruled out. Marshall et al. [22] used profiling of the XRD patterns and
suggested that the XRD patterns were a mixture of two highly dispersed rutile oxide phases. The
presence of multiple phases and the lack of a single solid solution phase were suggested to arise from
the poor interaction of the precursors during the initial stages of the reaction. It was assumed that SnO 2
formed first since there is a significant difference in ∆Gf0 for IrO2 and SnO2 (-510 kJ mol-1 [23] and 186.5 kJ mol-1 [24], respectively). Calculated from the 110 and 101 phases using the Scherrer formula,
the average particle size for Ir0.9Sn0.1O2 was estimated at 6.5 nm. The presence of metallic Ir and Sn
was not observed.
XRD analysis of Ir0.8Ta0.2Ox (Fig. 1d) revealed a slight decrease in the 110 phase of IrO2 and a
slight increase in the 002 (one of the non-close-packed planes of the Ir atom) phase which is consistent
with what is reported in the literature [25]. This could be explained by the stabilisation effect that Ta
has on the Ir component in the non-close-packed plane [14]. XRD analysis further revealed mainly an
amorphous phase which is consistent with the results of Di Blasi et al [26]. Calculated from 101 phase
using the Scherrer formula, the average particle size for Ir0.8Ta0.2Ox was estimated at 3 nm. The
addition of Ta2O5 is known to suppress the crystallisation of IrO2 [15]. Ta was found to be present in
the +5 oxidation state; consistent to what was reported previously [2]. The presence of metallic Ir and
Ta was not observed.
Fig. 2 shows the SEM images of IrO2 and the best performing electrocatalysts (established by
CA analysis) of the three metal oxide combinations i.e. Ir0.7Ru0.3O2, Ir0.9Sn0.1O2 and Ir0.8Ta0.2Ox.
Particle formation and sizes could not be defined from the SEM images. The SEM image of IrO2 (Fig.
2a) shows micrometer size flake shaped aggregates whereas Ir0.7Ru0.3O2 (Fig. 2b), Ir0.9Sn0.1O2 (Fig. 2c)
and Ir0.8Ta0.2Ox (Fig. 2d) exhibited sheet like porous morphology. From the SEM images, it appears
that the addition of the secondary metal oxides to IrO2 resulted in larger aggregate sizes.
Fig. 3 shows the TEM images of IrO2 and the best performing electrocatalysts (established by
CA analysis) of the three metal oxide combinations i.e. Ir0.7Ru0.3O2, Ir0.9Sn0.1O2 and Ir0.8Ta0.2Ox. TEM
analysis of IrO2 (Fig. 3a) revealed an amorphous phase consisting of nanoparticles with an average
size of about 4.5 nm. TEM analysis of Ir0.7Ru0.3O2 (Fig. 3b) revealed an amorphous phase consisting of
smaller particles and a crystalline phase consisting of larger pin shaped particles of up to 80 nm in
length. The larger pin shaped particles formed due to the crystallisation of RuO2 as was revealed by
XRD. TEM analysis of Ir0.9Sn0.1O2 (Fig. 3c) revealed an amorphous phase consisting of smaller
particles and a crystalline phase consisting of larger needle shaped particles of up to 50 nm in length.
The larger needle shaped particles formed due to the crystallisation of SnO2 as was revealed by XRD.
From literature [22, 27], a slight increase in particle size was observed as the SnO2 content was
increased. The slight increase in particle size can be expected since the slightly larger Sn 4+ ions (0.083
nm) are substituting the smaller Ir4+ ions (0.077 nm) in the IrO2 lattice [28]. TEM analysis of
8. Int. J. Electrochem. Sci., Vol. 7, 2012
12071
Ir0.8Ta0.2Ox (Fig. 3d) revealed uniformly distributed nanosize particles with an average size of 3.5 nm.
The most important enhancing effect that the addition of Ta2O5 to IrO2 has is mainly related to the
reduction of the particle size [15].
Figure 3. TEM images of (a) IrO2 (b) Ir0.7Ru0.3O2 (c) Ir0.9Sn0.1O2 and (d) Ir0.8Ta0.2Ox.
3.2 Electrochemical characterisation
Fig. 4 shows the CV analysis for IrO2 and the best performing electrocatalysts (as established
by CA analysis) of the three metal oxide combinations i.e. Ir0.7Ru0.3O2, Ir0.9Sn0.1O2 and Ir0.8Ta0.2Ox.
The potential was cycled from -0.2 to +1.2 V (vs. 3M Ag/AgCl electrode) at a potential sweep rate of
50 mV s-1 in 0.5M H3SO4 solution. The voltammetric curve for IrO2 (Fig. 4a) shows two peaks at
about 0.4 and 1 V which are located in the redox transition region [5]. The peaks at 0.4 and 1V have
9. Int. J. Electrochem. Sci., Vol. 7, 2012
12072
been assigned to redox couples Ir (III)/Ir (IV) and Ir (IV)/Ir (VI), respectively. There is a lack of
symmetry along the potential axis especially in the region of the Ir (IV)/Ir (VI) redox couple which is
probably due to sluggish electrode kinetics.
Figure 4. Cyclic voltammograms of (a) IrO2 (b) Ir0.7Ru0.3O2 (c) Ir0.9Sn0.1O2 and (d) Ir0.8Ta0.2Ox at 50
mVs-1.
Furthermore the peaks are broad and not well depicted suggesting the existence of a variety of
active surface sites with different formal potentials which is consistent with an amorphous state of IrO2
[29]. The voltammetric curve for Ir0.7Ru0.3O2 (Fig. 4b) shows a positive potential shift for the redox
transition region in comparison to pure IrO2. The peak at about 0.6 and 0.95V was assigned to the
redox transition couples of the Ru(III)/Ru(IV) and Ru(IV)/Ru(VI) respectively. The voltammogram
displays reversible charge transfer transition in the O2 evolution region which suggests an
10. Int. J. Electrochem. Sci., Vol. 7, 2012
12073
improvement in electrode kinetics in comparison to pure IrO2. At about -0.1V there is a noticeable
peak due to hydrogen adsorption which is commonly associated with the presence of a metallic species
since hydrogen is not known to easily adsorb onto an oxide surface [29]. However, no metallic Ir or Ru
was observed with XRD analysis. The voltammetric curve for Ir0.9Sn0.1O2 (Fig. 4c) exhibits a shape
similar to that of pure IrO2 with a positive potential shift of the redox transition region which is
observed between 0.65 and 1.1V. The peak at about 0.65V can be assigned to the Ir(III)/Ir(IV) couple
since the electrode response is strongly dominated by the Ir component [27]. The voltammogram
shows good reversibility in the O2 evolution region suggesting improved electrode kinetics in
comparison to pure IrO2. The voltammetric curve for Ir(0.8)Ta(0.2)Ox (Fig. 4d) displays two peaks at 0.7
and 1.1V. The peak at about 0.7V is attributed to the Ir(III)/Ir(IV) couple which suggests that the
surface electrochemistry is governed by the active component of IrO2 [30]. The voltammogram shows
good reversibility in the O2 evolution region suggesting improved electrode kinetics in comparison to
pure IrO2. CV was also used to investigate the electrochemical activities of the oxides which are
related to the number of active sites accessible to the electrolyte solution [31]. The anodic charge, qa,
due to double layer charging and surface redox transitions, is proportional to the active site surface
concentration [32].
Figure 5. Chronoamperometric measurements of IrO2 and IrxRu1-xO2 (1 ≥ x ≥ 0.7) at 1.6 V.
The qa for the electrodes was obtained by integration of the voltammetric curves in the range
between H2 and O2 gas evolution. The qa values for IrO2, Ir0.7Ru0.3O2, Ir0.9Sn0.1O2 and Ir0.8Ta0.2Ox are
144, 185, 180 and 274 mC cm-2, respectively. The mixed oxides show higher qa than for pure IrO2
indicating that Ru, Sn and Ta have a positive effect on the active area of the mixed oxide electrodes. JM Hu et al. [33] observed that the voltammetric charge significantly varies with the Ta composition
and that 20 mol % Ta addition shows a significantly higher charge value than that of pure IrO 2. The
11. Int. J. Electrochem. Sci., Vol. 7, 2012
12074
higher qa for Ir0.8Ta0.2Ox may also be due to the smaller particle sizes as was revealed by TEM and
XRD. De Pauli et al. [34] suggested that the sharp decrease in charge value as the electrode surface
composition reached 100 mol % IrO2 was due to diminution or a reduction of the surface area.
Fig. 5 shows the CA analysis of the IrxRu1-xO2 (1 ≥ x ≥ 0.7) electrocatalysts performed at 1.6 V
for 30 minutes. CA revealed the best electrocatalytic activity towards the OER for Ir 0.7Ru0.3O2.
Electrocatalytic activity towards the OER increased as the RuO2 content was increased. This
observation is consistent with an improvement in the oxide activity due to the larger exchange current
density of RuO2 compared to that IrO2 [2]. The catalytic activity of Ir0.7Ru0.3O2 was significantly
higher than that of pure IrO2. The addition of RuO2 to IrO2 was reported to result in a significant
reduction in the overpotential [9]. The addition of RuO2 of up to 80 mol% was also reported to yield an
electrocatalyst with high electrochemical activity while displaying good stability under the OER [8].
The combination of RuO2 and IrO2 could thus facilitate a reduction in the required electrocatalyst
loading as well as a direct material cost reduction considering that Ir is more expensive than Ru.
Figure 6. Chronoamperometric measurements of IrO2 and IrxSnx-1O2 (1 ≥ x ≥ 0.7) at 1.6 V.
Fig. 6 shows the CA analysis of the IrxSnx-1O2 (1 ≥ x ≥ 0.7) electrocatalysts performed at 1.6 V
for 30 minutes. CA revealed the best electrocatalytic activity towards the OER for Ir 0.9Sn0.1O2. A
significant increase in electrocatalytic activity was observed as a Sn content of 10 mol% was reached
which is consistent with a higher qa value obtained from CV for Ir0.9Sn0.1O2 as compared to pure IrO2.
Further addition of Sn resulted in a rapid decrease in the oxide performance. However, CA analysis
still revealed an improved performance for all IrO2-SnO2 electrocatalysts in comparison to pure IrO2.
12. Int. J. Electrochem. Sci., Vol. 7, 2012
12075
Xu et al. [1] reported similar behavior for their RuO2-SnO2 electrocatalysts where the catalytic activity
initially increased followed by a dramatic decrease as the Sn content was increased. Marshall et al.
[27] reported a 10 – 15% decrease in the total active area for SnO2 contents of 20 – 30 mol% but also
observed a better cell performance for Ir0.8Sn0.2O2 as compared to pure IrO2 at 25°C [11]. Xu et al. [35]
observed that at low SnO2 contents the IrO2 particles were well dispersed but at higher SnO2 contents
the active surface area of IrO2 decreased due to an increase in the average particle size.
Figure 7. Chronoamperometric measurements of IrO2 and IrxTax-1O2 (1 ≥ x ≥ 0.7) at 1.6 V.
Fig. 7 shows the CA analysis of the IrxTax-1O2 (1 ≥ x ≥ 0.7) electrocatalysts performed at 1.6 V
for 30 minutes. The best catalytic activity towards the OER was observed for Ir0.8Ta0.2Ox. An increase
in electrocatalytic activity was observed as the Ta content was increased up to 20 mol% followed by a
decrease in electrocatalytic activity as the Ta content reached 30 mol %. The addition of Ta2O5 to IrO2
was reported to increase the resistivity by 2 orders of magnitude by the time the composition reached
Ir0.7Ta0.3Ox, due to the low electronic conductivity of Ta2O5 [2]. The catalytic activity for Ir0.7Ta0.3Ox
was still slightly higher than that of pure IrO2. It was previously suggested that an improved active
surface area can be obtained when there is a proper ratio of Ir to Ta [36]. A similar trend in
performance was reported by Hu et al. [33] however they observed a maximum current response at 30
mol% Ta content. Furthermore, a higher cell resistance was observed for the Ir-Ta oxides in
comparison to other Ir based metal oxides [26]. The improved electrocatalytic activity observed by the
addition of Ta2O5 to IrO2 was probably as a result of the smaller particle sizes (revealed by XRD and
TEM) and increased active surface sites (revealed by CV).
13. Int. J. Electrochem. Sci., Vol. 7, 2012
12076
4. CONCLUSIONS
Electrocatalysts based on IrO2 were successfully synthesised and characterised. CA analyses
have shown that the addition of secondary metal oxides (RuO2, SnO2 and Ta2O5) to IrO2, improved the
catalytic activity of the oxide towards the OER. Ir0.7Ru0.3O2, while displaying a slightly lower catalytic
activity than Ir(0.9)Sn(0.1)O2, proved to be the most promising electrocatalyst for the OER since no
decrease in catalytic activity was observed as the RuO2 content was increase up to 30 mol%. This
suggests that even better catalytic activity may be achieved with even higher contents of RuO 2. The
addition of SnO2 and Ta2O2 was limited to 10 and 20 mol% respectively. CA proved to be a useful
technique for the electrochemical characterisation of the electrocatalysts. TEM and XRD were useful
in relating the physical structure of the electrocatalysts to the electrochemical activity. Particle sizes
were found to be of nanometer scale for all the synthesised electrocatalysts thus rendering the Adams
fusion method a relatively simple and quick method for directly producing metal oxides suitable as
electrocatalysts for the SPE electrolyser. The combination of various metal oxides can be considered a
viable approach to address the high cost and efficiency issues facing the present SPE electrolyser
technology.
ACKNOWLEDGEMENTS
This work was supported by the South African Department of Science and Technology through the
Technology Implementation Agency (TIA) project number T70600 (SPE Electrolyser).
References
1.
2.
3.
4.
5.
6.
7.
W. Xu, J. Tayal, S. Basu, K. Scott, Int. J. Hydrogen Energy, 36 (2011) 14796.
A.T. Marshall, S. Sunde, M. Tsypkin, R. Tunold, Int. J. Hydrogen Energy, 32 (2007) 2320.
T. Maiyalagan, S. Pasupathi, Mater. Sci. Forum, 657 (2010) 143.
C. Xu, L. Ma, J. Li, W. Zhao, Z. Gan, Int. J. Hydrogen Energy, (2011) 1.
J. Cheng, H. Zhang, H. Ma, H. Zhong, Y. Zou, Electrochim. Acta, 55 (2010) 1855.
S. Song, H. Zhang, X. Ma, Z. Shao, R.T. Baker, B. Yi, Int. J. Hydrogen Energy, 33 (2008) 4955.
S. Siracusano, V. Baglio, A. Stassi, R. Ornelas, V. Antonucci, A.S. Arico, Int. J. Hydrogen Energy,
36 (2011) 7822.
8. J. Cheng, H. Zhang, G. Chen, Y. Zhang, Electrochim. Acta, 54 (2009) 6250.
9. E. Mayousse, F. Maillard, F. Fouda-Onana, O. Sicardy, N. Guillet, Int. J. Hydrogen Energy, 36
(2011) 10474.
10. A.Marshall, B. Børresen, G. Hagen, M. Tsypkin, R. Tunold, Energy, 32 (2007) 431.
11. A.Marshall, B. Børresen, G. Hagen, S. Sunde, M. Tsypkin, and R. Tunold, Russian J.
Electrochem., 42 (10) (2006) 1134.
12. R. Kötz, S. Stucki, Electrochim. Acta, 31 (10) (1986) 1311.
13. W. Xu, K. Scott, S. Basu, J. Power Sources, 196 (2011) 8918.
14. C. Angelinetta, S. Trasatti, Mater. Chem. Phys., 22 (1989) 231.
15. E. Rasten, Electrocatalysis in water electrolysis with solid polymer electrolyte, PhD. Thesis,
Norwegian University of Science and technology (2001).
16. J.M. Hu, H.M. Meng, J.Q. Zhang, C.N. Cao, Corrosion Sci., 44 (2002) 1655.
17. Y. Zhang, C. Wang, Z. Mao, N. Wang, Mater. Lett., 61 (2007) 1205.
18. R. Adams, R.L. Shriner, J. Am. Chem. Soc., 45 (1923) 2171.