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

“环状和直链烯烃在金属表面选择性氧化的动力学和机理”

• 批准号: 9005135
• 负责人: Robert Madix
• 金额: $ 32.5万
• 依托单位: Stanford University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-07-01 至 1993-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9005135&HistoricalAwards=false
• 关键词: Kinetics; Mechanism; Selective; Oxidation; Cyclic

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.

这项工作是针对了解动力学和 多相选择性氧化循环机理 烯烃和氧加成反应和选择性 直链烯烃在所选金属表面上的氧化， 主要是银。 它包括确定 反应产物和反应选择性的测定 在富氧和贫氧条件下; 形成中的速率决定步骤的确定 每个产品，以及活化能和指前 每个步骤的因子;反应的识别 中间体，并澄清的细节， 基本的键断裂和键形成过程， 从反应物到产物 该研究采用了以下组合： 超高真空技术，包括程序升温 反应光谱和振动光谱;在某些情况下， 在某些情况下，同步辐射技术被用来帮助 吸附物几何形状的测定。 正在研究的系统构成了一些 商品和特种化学工艺， 有害副产物的选择性和最小化， 商业成功的关键。 这项工作应提供 对设计改进和控制有价值的指导， 流程.