CAREER: Molecular Engineering of Catalytic Surface Chemistry Through First-Principles Simulation

摘要提案标题：基于第一性原理模拟的催化表面化学分子工程提案编号：CTS-9702762首席研究员：马修·神经研究所：弗吉尼亚大学，夏洛茨维尔密度泛函理论、过渡态理论和蒙特卡罗模拟相结合，研究金属表面的化学反应机理。特别是在Au促进的Pd催化剂上合成乙酸乙烯酯的研究。这一反应在塑料行业具有重要意义。一些基本问题，如表面结构和吸附氧的影响，还没有完全了解。从金属团簇结构和组成、吸附成键、氧覆盖和可能的途径等方面对这种选择氧化化学进行了分析。用密度泛函方法计算了中间体的吸附和势垒，用TST计算了可能步骤的本征动力学，用MC模拟计算了宏观动力学。能量学和动力学的实验验证包括在超高压下的程序升温脱附以及在超高压和常压条件下的反应，这项工作将由杜邦的合作者进行。在教育层面，该研究所将加强计算化学领域的化学工程课程。将为本科生和研究生开发两门新的计算化学课程，以及一门用于工业的分子建模课程。

ABSTRACT Proposal Title: Molecular Engineering of Catalytic Surface Chemistry Through First-Principles Simulation Proposal Number: CTS-9702762 Principal Investigator: Matthew Neurock Institution: University of Virginia, Charlottesville Density functional theory (DFT), transition state theory (TST), and Monte Carlo simulation (MC), are combined to study the mechanism of chemical reactions on metal surfaces. In particular, this proposal is focused on the synthesis of vinyl acetate on Au-promoted Pd catalyst. The reaction is of relevance in the plastics industry. Some fundamental issues, such as the effects of surface structure and adsorbed oxygen, are not completely understood. This selective oxidation chemistry is analyzed in terms of metal cluster structure and composition, adsorbate bonding, oxygen coverage and possible pathways. Energetics of adsorption and energy barriers of intermediate formation are calculated with DFT, intrinsic kinetics of the many possible steps are computed from TST, and macroscopic kinetics are calculated from MC simulations. The experimental validation of energetics and kinetics involves temperature-programmed desorption at UHV and reaction both at UHV and ambient pressure conditions, in work to be carried out by collaborators at DuPont. At the educational level, the PI will strengthen the chemical engineering curriculum in the area of computational chemistry. Two new courses in computational chemistry for undergraduate and graduate students and a course in molecular modeling for industry will be developed.