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.
