"Kinetics and Mechanism of Selective Oxidation of Cyclic andLinear Alkenes on Metal Surfaces"

这项工作旨在了解环烯的非均相选择氧化和氧加成反应以及直链烯烃在选定的金属表面(主要是银)上的选择氧化的动力学和机理。它包括对反应产物的鉴定和在富氧和贫氧条件下反应选择性的测定；确定每个产物形成的速率决定步骤，以及每个步骤的活化能和指前因子；反应中间体的鉴定，以及从反应物到产物的基本断键和成键过程的细节的澄清。这项研究采用了超高真空技术的组合，包括程序升温反应光谱和振动光谱；在某些情况下，同步辐射技术被用来帮助确定吸附的几何形状。正在研究的系统构成了一些商品和特种化学过程的基础，在这些过程中，对有害副产品的选择性和最小化对商业成功至关重要。这项工作应该为这些过程中的设计改进和控制提供有价值的指导。

This work is directed toward understanding the kinetics and mechanisms of heterogeneous selective oxidation of cycle alkenes and of oxygen-addition reactions and selective oxidation of linear alkenes on selected metal surfaces, principally silver. It includes the identification of reaction products and determination of reaction selectivity under oxygen-rich and oxygen-lean conditions; the determination of the rate-determining step in the formation of each product, and of the activation energy and preexponential factor for each such steps; the identification of reaction intermediates, and the clarification of the details of the elementary bond-breaking and bond-forming processes leading from reactant to product. The study employs a combination of ultrahigh-vacuum techniques including temperature-programmed reaction spectroscopy and vibrational spectroscopy; in some cases, synchrotron radiation techniques are used to assist in the determination of adsorbate geometries. The systems under study form the basis of a number of commodity and specialty chemical processes in which selectivity and minimization of deleterious byproducts are crucial to commercial success. This work should provide valuable guidance for design improvements and control in these processes.