晶格氧催化丙烷脱氢活性位的理论识别及其机理研究

项目名称： 晶格氧催化丙烷脱氢活性位的理论识别及其机理研究

项目编号： No.21203250

项目类型： 青年科学基金项目

立项/批准年度： 2013

项目学科： 物理化学

项目作者： 傅惠

作者单位： 中国石油大学（华东）

项目金额： 24万元

中文摘要： 丙烷脱氢制丙烯是石化资源优化利用的重要反应，近年来因丙烯下游产品的快速发展而得到广泛关注，开发高效的丙烷脱氢催化剂成为国内外研究热点。目前由于对该反应催化剂的活性位认识不够、反应历程存在争论等问题，在催化剂的研制上往往缺乏主动性。本课题拟采用DFT和周期性超元胞模型研究负载型氧化物催化剂上的丙烷氧化脱氢反应机理，识别不同类型晶格氧的作用，讨论催化脱氢和过度氧化的活性位在产物选择性方面的关系。模拟活性组分在金属氧化物表面的分散形态，找出载体酸碱性与分散形式的关系，通过几何效应、电子效应来分析和解释活性位的本质。系统研究反应过程中的中间产物或过渡态在不同活性位上的吸附-反应规律，推断催化剂上烷烃氧化脱氢的反应网络和控速步骤，明确决定目标产物选择性的关键步骤；从原子水平深入认识表面化学微观过程和载体催化角色，系统研究催化材料对催化剂活性和选择性的影响,为开发丙烷氧化脱氢催化剂提供理论层面的指导。

中文关键词： 钒；氧化脱氢；二氧化钛；钼；密度泛函

英文摘要： Dehydrogenation of propane to propylene is one of the important reactions of petrochemical resources optimization. In recent years, due to the rapid development of downstream products of propylene, it received extensive attention. The development of efficient propane dehydrogenation catalyst has become a hot research subject. At present due to the not enough awareness of reaction catalyst active sites, debatable problems of reaction course, the preparation of catalyst is often lack of initiative. In this project, using the DFT and periodic super cell model, we will research the oxidative dehydrogenation of propane mechanism on supported oxide catalysts, identify the role of different types of lattice oxygen, and discuss the relationship with respect to the catalytic dehydrogenation and excessive oxidation of the active site in the product selectivity. Simulate dispersion of active component on the surface of the metal oxide, find out the relationship between acid-base properties of support and dispersion forms, through the geometric effects, electronic effects to analyze and explain the nature of active sites. Systematically study the adsorption and reaction rules of the transition state or intermediate in different active sites during the reaction process, infer the oxidative dehydrogenation reaction network an

英文关键词： vanadium；oxidative dehydrogenation；titania oxide；molybdenum；density functional theory