Electrode Potential Dependence of Elementary Reaction Steps in Electrocatalysis: Development of Ab Initio Methodology and Applications

电催化基本步骤的计算研究形成了分析和表面化学计划支持的这一研究项目的重点。阿尔弗雷德·B·安德森教授在凯斯韦斯特的研究小组将从头算量子力学计算应用于研究电化学界面上的电子和质子转移。用密度泛函相关校正方法研究了氧在铂电极表面的四电子还原反应以及水和羟基对CO的氧化作用。强调了基本反应步骤对电极电位的依赖关系，并与Case WESTERN合作者进行的实验研究进行了比较。为了了解对电催化和燃料电池设计至关重要的电极反应的详细微观机理，使用量子化学计算确定了电极表面分子过程的动力学和能量路径。该项目在分析和表面化学计划的支持下，解决了这些微观反应机理的问题。凯斯韦斯特大学的安德森教授的团队研究了氧的还原和一氧化碳的氧化，作为这些电催化过程的重要模型系统。来自这些研究的信息将对燃料电池和电催化系统的设计和工程有用。

Calculational studies of the elementary steps of electrocatalysis form the focus of this research project supported in the Analytical and Surface Chemistry Program. Professor Alfred B. Anderson's research group at Case Western applies ab initio quantum mechanical calculations to the study of electron and proton transfer at the electrochemical interface. Density functional correlation corrected methods are used to examine the four electron reduction of oxygen to water and the oxidation of CO by water and hydroxyl at the platinum electrode surface. The electrode potential dependence of the fundamental reaction steps is emphasized, and comparisons with experimental studies carried out by collaborators at Case Western are included.In order to understand the detailed microscopic mechanism of electrode reactions important to electrocatalysis and fuel cell design, quantum chemical calculations are used to determine the kinetic and energetic pathways for molecular processes on the electrode surface. This project, supported by the Analytical and Surface Chemistry Program, addresses these questions of microscopic reaction mechanism. Professor Anderson's group at Case Western examines the reduction of oxygen and the oxidation of CO as important model systems for these electrocatalytic processes. Information from these studies will be useful in the design and engineering of fuel cell and electrocatalytic systems.