Surface and materials electrochemistry: adsorption, reduction, oxidation, and corrosion phenomena

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OBJECTIVES AND APPROACH. I propose experimental and theoretical studies on the adsorption of prochiral/chiral organic molecules on achiral/chiral Pt(hkl) electrodes, and the mechanism and kinetics of their electrocatalytic hydrogenation (ECH). I will perform T-dependent studies and will determine the surface coverage of hydrogen (H), anions (AN), and organic molecules (ORG). I will determine thermodynamic state functions for H and ORG adsorption. The products of ECH, their yields, and enantiomeric excesses will be examined using vapor-phase chromatography, nuclear magnetic resonance, and circular dichromism. I will investigate the under-potential deposition (UPD) of Ag and Cu on Pt(hkl), Au(hkl) and Rh(hkl) electrodes. The surface coverage of Ag and Cu will be examined by application of electrochemical techniques. I will conduct T-dependent cyclic-voltammetry (CV) studies and perform theoretical data analysis to determine the substrate-adsorbate bond energy. I will analyze the influence of electrochemical interface on the interfacial bonding of metals. I will investigate the biocorrosion and biocompatibility of colored passive layers on titanium-molybdenum alloy (TMA) and nickel-titanium alloy (NiTi) in simulated body fluids. I will also study the adsorption of model proteins on these materials using complementary physical and analytical techniques.SIGNIFICANCE. The outcome of this research will provide molecular-level understanding of electrochemical reactions and will shed light on interfacial thermodynamics. It will explain the adsorption of prochiral/chiral organic molecules on achiral/chiral surfaces in relation to their mutual geometry and size. It will explain the metal-metal bonding in nanometric layers prepared by electrochemical techniques and their adhesion to various substrates under electrochemical conditions. The study on passive layers on TMA and NiTi will facilitate the preparation of new materials of enhanced biocompatibility and reduced biocorrosion in simulated body fluids. The cross-disciplinary research will train HQP that will enter the Canadian job market.