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Recently, there has been a growing demand for electrode materials to serve as electrochemical capacitors (EC). It has been an important issue to come up with environment friendly electric power sources to reduce pollution caused by combustion engines of automotive systems. Even though conventional battery systems and fuel cells supply high energy, they lack the high specific power that would be required for hybrid power sources. The ECs can fill the gap between conventional capacitors and batteries. / Carbon nanotubes (CNTs), discovered by Iijima in 1991, attracted great attention in recent years for their unique properties, such as mesoporous character, excellent conductivity, moderate to high specific surface area as well as chemical and mechanical stability. These properties of CNTs make them useful in a wide of range applications including electrode materials for EC applications. / The preparation of CNT electrodes is accomplished by either pasting them onto metallic current collectors with the use of binder materials such as PVDF or growing them from deposited metal nanoparticles on substrates such as graphite paper. The deposition of metal nanoparticles is achieved via sputtering techniques or lengthy electrochemical deposition methods. The aim of this research was to simplify the preparation step by growing CNTs directly on metallic substrates and to study the relationship between surface area and electrochemical capacitance of CNTs. CNTs were produced on metal-alloy grids via chemical vapor deposition (CVD) of acetylene (C2H2). The physical characterization of the samples was achieved by Field Emission Scanning Electron Microscopy (FE-SEM), Raman spectroscopy and Single point BET surface area. The electrochemical performance of the samples was evaluated by cyclic voltammetry (CV) in a three electrode electrochemical cell with 1M sulfuric acid (H2SO4) solution as the electrolyte.

This thesis presents a study of three electrochemical methods applied to the fragmentation of proteins. Direct electrochemical oxidation at graphite electrodes, production of hydroxyl radicals on lead dioxide electrodes and electro-Fenton methods were each investigated as methods for fragmenting proteins. A key objective of this project was to achieve specific fragmentation, meaning that fragmentation would only occur at defined sites on each protein molecule and that this process may provide a new pathway to producing useful protein fragments. Protein fragments produced by electrochemical means were detected using mass spectroscopy and gel electrophoresis techniques. Direct electrochemical oxidation of the target proteins was studied at a graphite rod electrode in a solution containing acetonitrile, water and formic acid. β-lactoglobulin fragmentation was detected by mass spectroscopy, but fragmentation did not occur to an extent where fragments were observable by gel electrophoresis. It was evident that most of the electrolysis products appear to arise from non-cleavage oxidation reactions. The use of lead dioxide electrodes to generate hydroxyl radicals was thoroughly investigated in this work. For the first time, specific fragmentation of proteins has been achieved by direct electrochemical generation of hydroxyl radicals on the electrode surface. The pH and the chemical composition of the protein solutions were found have a strong influence on the extent of fragmentation. Electro-Fenton chemistry was conducted on a woven carbon fibre electrode. The electrode successfully reduced dissolved oxygen to produce hydrogen peroxide and regenerated Fe(II) from Fe(III). Cell conditions were optimized for applied current, method of oxygen delivery and cell division. The Fenton reaction between hydrogen peroxide and Fe(II) produced hydroxyl radicals that were able to specifically fragment proteins. It was not possible to increase the concentration of these protein fragments by increasing the hydrogen peroxide concentration, as the fragmentation products were also further fragmented. Electrochemical protein fragmentation was achieved in all three electrochemical systems, however the most promising results were achieved by electrochemical generation of hydroxyl radicals on a lead dioxide electrode. This work has the potential to become a fast and cost effective method for the fragmentation of proteins required for nutrition and medical purposes or for use in protein identification analysis with mass spectroscopy.

With increasing emphasis on renewable energy sources and efficient energy use, energy storage devices, and in particular electrochemical storage devices, are becoming more prevalent. In order to interface batteries to systems, converters are used to maintain the desired voltage, current or power. In this thesis, we explore the response of the battery to commonly seen current waveforms to understand the impact of the converter on the battery. An electrochemical model of the electrode-electrolyte is studied to first understand its operating principles and then to pinpoint the causes of the observed battery response. A circuit was built to test the response of the battery to current waveforms. Experiments consisting of constant current, triangular and sinusoidal currents of varying frequency and ripple currents, and pulsed currents were conducted. Using electrochemical principles, an explanation of the results is presented along with the impact of the experimental results on converter design specifications.

Electrochemical capacitors (ECs) have drawn much attention owing to their fast charging/discharging rate, and long lifetime up to millions of cycles. Applications of EC range from large scale transportation to miniaturized electronics. The research reported herein explores the development of an economical process for the synthesis of high performance electrode material for high power ECs. A two stage synthesis process which consists of electroplating of molybdenum oxide followed by thermal nitridation was developed. X-ray diffraction and X-ray photoelectron spectroscopy revealed the material to be Mo oxide with nitrogen substitution, Moz(O,N). In a three electrode system, the Moz(O,N) electrodes showed capacitance as high as 16 mF/cm2. Symmetric EC cells achieved state of the art time constant of 100 ms. Ultrahigh power ECs were demonstrated for the first time using Moδ(O,N) electrodes and SiWA-H3PO4-PVA electrolyte, achieving with 10 ms time constant one of the lowest time constants reported for EC.

With increasing emphasis on renewable energy sources and efficient energy use, energy storage devices, and in particular electrochemical storage devices, are becoming more prevalent. In order to interface batteries to systems, converters are used to maintain the desired voltage, current or power. In this thesis, we explore the response of the battery to commonly seen current waveforms to understand the impact of the converter on the battery. An electrochemical model of the electrode-electrolyte is studied to first understand its operating principles and then to pinpoint the causes of the observed battery response. A circuit was built to test the response of the battery to current waveforms. Experiments consisting of constant current, triangular and sinusoidal currents of varying frequency and ripple currents, and pulsed currents were conducted. Using electrochemical principles, an explanation of the results is presented along with the impact of the experimental results on converter design specifications.

Electrochemical capacitors (ECs) have drawn much attention owing to their fast charging/discharging rate, and long lifetime up to millions of cycles. Applications of EC range from large scale transportation to miniaturized electronics. The research reported herein explores the development of an economical process for the synthesis of high performance electrode material for high power ECs. A two stage synthesis process which consists of electroplating of molybdenum oxide followed by thermal nitridation was developed. X-ray diffraction and X-ray photoelectron spectroscopy revealed the material to be Mo oxide with nitrogen substitution, Moz(O,N). In a three electrode system, the Moz(O,N) electrodes showed capacitance as high as 16 mF/cm2. Symmetric EC cells achieved state of the art time constant of 100 ms. Ultrahigh power ECs were demonstrated for the first time using Moδ(O,N) electrodes and SiWA-H3PO4-PVA electrolyte, achieving with 10 ms time constant one of the lowest time constants reported for EC.

Ionic liquids (ILs) were studied as solvents for electrochemical reactions with the intent to devise metallurgical processes for Al, Mg and Ti that are less energy intensive and operate at lower temperatures than current industrial practice. Tetra-alkyl phosphonium ILs are on the low end of the IL cost spectrum and are regarded as understudied compared with imidazolium and pyridinium ILs. They are also known to be more thermally stable. The density, viscosity and conductivity of the phosphonium ILs and metal salt-IL mixtures were measured. The conductivity of the phosphonium ILs tested were found to be roughly an order of magnitude lower than imidazolium ILs; this is attributed to the relatively large cation size and localized charge. Linear density-temperature functions are presented. The viscosity and conductivity temperature relationship was modeled using the Vogel-Tamman-Fulcher (VTF) equation. The electrochemical window of A10341'14,6,6,610 was studied on a Pt substrate over a wide range of A1C13 concentrations using cyclic voltammetry (CV). It was found that the tetra-alkyl phosphonium cation is on the order of 800 mV more electrochemically stable than the 1-ethyl-3-methyl imidazolium (EMI+). Cathodic and anodic polarization of Al in A1C13-[P14,6,6,6]C1 (Xmc13 = 0.67) was studied at temperatures ranging from 347 to 423 K. The Butler-Volmer equation was fitted to the plots by varying the kinetic parameters. The cathodic reaction was found to be diffusion limited and the anodic reaction is limited by passivation at lower temperatures. The overpotential required for electrodissolution of Al was found to be higher than for electrodeposition. Aluminium was electrodeposited using both an electrowinning setup (chlorine evolution anode reaction) and electrorefining setup (Al dissolution anode reaction). The deposits were characterized in terms of morphology, current efficiency and power consumption. A variety of deposit morphologies were observed ranging from smooth, to spherical to dendritic, and in some cases, the IL was occluded in the deposit. The current efficiency and power consumption were negatively impacted by the presence of H2O and HCl present in the as-received ILs and by C12(g) generated by the anode reaction in the case of the electrowinning setup. HC1 was removed by cyclic polarization or corrosion of pure Al, resulting in current efficiencies above 90%. Aluminium was electrodeposited using the electrorefining setup with anode-cathode spacing of 2 mm at power consumption as low as 0.6 kWhr/kg-Al. This is very low compared with industrial Al electrorefining and Al electroplating using the National Bureau of Standards bath, which require 15-18 kWhr/kg-Al and 18 kWhr/kg-Al, respectively. However, due to low solution conductivity the power consumption increases significantly with increased anode-cathode spacing. Titanium tetrachloride was found to be soluble in [P14,6,6,6]Cl and increases the conductivity of the solution. Attempts to reduce the Ti(IV) included corrosion of titanium metal, corrosion of magnesium metal powder and cathodic polarization. Despite a few attempts, the electro-deposition of Ti was not observed. At this point, titanium electrodeposition from phosphonium based ILs does not appear feasible.

A series of 2,6- and 3,5-ethynylpyridyl compounds and their cobalt clusters have been prepared and analysed in Chapter 2, in order to study through-space and through-bond interactions between the ethynyl arms. Bidentate N- donor ligands, such as bipyridine and o-phenanthroline with alkyne functionality have been used extensively as building blocks for a wide range of molecular materials, but monodentate ethynylpyridyls have received less attention. The results showed that while there is no orbital restriction on a RC[triple bond]C-n-[pi]�cc-C[triple bond]CR through-bond interaction in 2,6-ethynylpyridyls, no significant interaction exists. Nevertheless, there are intramolecular interactions as manifested in the distortions which occur in the solid state structure of the compounds and the lability of the diphenylphosphine methane (dppm) moieties in the oxidised Co₂(CO)₄dppm species. Polymerisation by Sonogashira coupling between dibromo pyridines or diiodo ferrocene and ethynyl pyridines resulted in only oligomeric fractions that could be separated. The thesis also reports the synthesis and characterization of some novel naphthalimide monomers with acrylic and allyl headgroups. The naphthalimide moiety is substituted in the 4-position with various functionalities. This is presented in detail in Chapter 3 of the thesis. The monomers� structure is the following: [illustration omitted] wherein: A may be a polymerizable group (methacrylate or allyl), which includes a spacer entity (aliphatic or aromatic); B is selected from an ethenyl or ethynyl linked organometallic group, a halogen and/or an amine (i.e. bromo, ethynylferrocene, ethenylferrocene, trimethylsilylethynyl, nitro, piperidine and ethenylpiperidine). The acrylic monomers were synthesized by coupling 4-bromo-1,8-naphthalic anhydride with an amino alcohol to give an imide, which then was coupled with methacryloyl chloride to provide the methacrylate. Functionalization in the 4-position of the naphthalimide moieties was achieved by Sonogashira and Heck coupling reactions with for example ethynylferrocene, trimethylsilyl acetylene, vinylferrocene. For the allyl monomers synthesis, a reaction between allyl amine and 4-Bromo-naphthalic anhydride provided 4-bromo-naphthalimido allyl, which was then functionalized by further Sonogashira and Heck coupling reactions. The monomers were polymerised and copolymerised with other widely used comonomers, such as methyl methacrylate, methyl acrylate, styrene, vinyl carbazole and acrylonitrile. The polymerisation processes and the full analyses of the (co)polymers are described in Chapter 4. Free radical polymerisation, FRP, initiated by azo bisisobutyronitrile, AIBN at elevated temperature was the main technique employed for making the (co)polymers. Atom Transfer Radical Polymerisation, ATRP was conducted for some monomers although the results were inconclusive (the yields were low, under 50%, but the molecular weight distributions were quite narrow, PDI�s <1.7). Heck coupling polymerisation was performed for the bromo- substituted methacrylic and allyl monomers and supplied colorful, well-defined polymeric materials, with low polymerisation degrees. All polymers were analyzed by HPLC, NMR, UV-VIS, IR, electrochemistry and fluorescence. The (co)polymers made by FRP had various molecular masses (Mn = 3000- 90.000), whereas the polydispersities were PDI = 1.4- 4.6. Most of the (co)polymers were fluorescent and had good thermal and electrochemical properties. Potential applications of the polymers have been suggested and relevant literature background in the field is provided in both Chapters 1 and 4. The monomers/ polymers are stable compounds (no special storage conditions required) and can act as good candidates for potential applications in light emitting devices, as resins/ binders for coating materials, in the dyes and pigment industry and also for manufacturing of conducting polymers and/or composite materials.