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

目标和方法。对前手性/手性有机分子在非手性/手性铂(HKL)电极上的吸附及其电催化加氢(ECH)的机理和动力学进行了实验和理论研究。我将进行与T相关的研究，并确定氢(H)、阴离子(AN)和有机分子(ORG)的表面覆盖率。我将确定H和ORG吸附的热力学状态函数。环氧乙烷的产物、它们的产率和对映体过量将用气相色谱、核磁共振和圆二色谱进行检测。我将研究银和铜在铂(Hkl)、Au(Hkl)和Rh(Hkl)电极上的欠电位沉积(UPD)。将应用电化学技术检测银和铜的表面覆盖率。我将进行依赖于T的循环伏安法(CV)研究，并进行理论数据分析，以确定底物-吸附键能。我将分析电化学界面对金属界面结合的影响。研究钛钼合金(TMA)和镍钛合金(NiTi)彩色钝化层在模拟体液中的生物腐蚀和生物相容性。我还将使用补充的物理和分析技术来研究模型蛋白质在这些材料上的吸附。意义。这项研究的结果将提供对电化学反应的分子水平的理解，并将揭示界面热力学。它将解释前手性/手性有机分子在非手性/手性表面上的吸附与它们的相互几何和尺寸的关系。它将解释用电化学技术制备的纳米层中的金属-金属键合，以及在电化学条件下它们与不同衬底的结合。对TMA和NiTi上钝化层的研究将有助于制备具有更高生物相容性和减少模拟体液中生物腐蚀的新材料。这项跨学科研究将培养将进入加拿大就业市场的HQP。

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.