| Summary: | <p>This thesis primarily focuses on the electrochemical properties of the H<sub>2</sub>/H<sup>+</sup> redox couple, at various metallic electrodes in room temperature ionic liquids. Initially, a comprehensive overview of room temperature ionic liquids, RTILs, compared to conventional organic solvents is presented which identifies their favourable properties and applications, followed by a second chapter describing the basic theory of electrochemistry. A third chapter presents the general experimental reagents, instruments and measurements used in this thesis. The results presented in this thesis are summarized in six further chapters and shown as follows.</p> <p>(1) Hydrogenolysis, hydrogen loaded palladium electrodes by electrolysis of H[NTf<sub>2</sub>] in a RTIL [C<sub>2</sub>mim][NTf<sub>2</sub>].</p> <p>(2) Palladium nanoparticle-modified carbon nanotubes for electrochemical hydrogenolysis in RTILs.</p> <p>(3) Electrochemistry of hydrogen in the RTIL [C<sub>2</sub>mim][NTf<sub>2</sub>]: dissolved hydrogen lubricates diffusional transport. </p> <p>(4) The hydrogen evolution reaction in a room temperature ionic liquid: mechanism and electrocatalyst trends.</p> <p>(5) The formal potentials and electrode kinetics of the proton_hydrogen couple in various room temperature ionic liquids.</p> <p>(6) The electroreduction of benzoic acid: voltammetric observation of adsorbed hydrogen at a Platinum microelectrode in room temperature ionic liquids.</p> <p>The first two studies show electrochemically formed adsorbed H atoms at a metallic Pt or Pd surface can be used for clean, efficient, safe electrochemical hydrogenolysis of organic compounds in RTIL media. The next study shows the physicochemical changes of RTIL properties, arising from dissolved hydrogen gas. The last three studies looked at the electrochemical properties of H<sub>2</sub>/H<sup>+</sup> redox couple at various metallic electrodes over a range of RTILs vs a stable Ag/Ag<sup>+</sup> reference couple, using H[NTf<sub>2</sub>] and benzoic acid as proton sources. The kinetic and thermodynamic mechanisms of some reactions or processes are the same in RTILs as in conventional organic or aqueous solvents, but other remarkably different behaviours are presented. Most importantly significant constants are seen for platinum, gold and molybdenum electrodes in term of the mechanism of proton reduction to form hydrogen.</p>
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