Heterogeneous epoxidation of alkenes containing allylic hydrogen on Cu-based catalysts

含烯丙基氢烯烃在铜基催化剂上的多相环氧化

• 批准号: 22032621
• 负责人: Professorin Dr. Swetlana Schauermann
• 金额: --
• 依托单位: Yusuf Hamied Department of Chemistry
• 依托单位国家: 德国
• 项目类别: Research Fellowships
• 财政年份: 2005
• 资助国家: 德国
• 起止时间: 2004-12-31 至 2006-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/22032621?language=en
• 关键词: Heterogeneous; epoxidation; alkenes; containing; allylic

Heterogeneous epoxidation of allylic alkenes represents a demanding task, since the easy abstraction of labile allylic hydrogen triggers total combustion of the alkene and prevents selective oxidation. Recently, it was shown that copper is intrinsically much more selective than widely used silver for both alkene epoxidation in general and for the difficult case of allylic alkenes in particular. The present project aims at an understanding of the microscopic mechanisms of allylic alkenes epoxidation on well-defined Cu single crystal surfaces and a connection of these mechanisms with the reactivity and selectivity of Cu-based supported catalysts operated under practical conditions. The main focus of this study will lie on investigation of the role of structural parameters such as alkene adsorption geometry, vicinity of the olefinic double bond and of the allylic hydrogen to the surface, the microscopic structure of the catalyst surface etc. in the activity and selectivity towards epoxidation. Additionally, possible alternative epoxidation pathways will be investigated, which do not include a common step of alkene oxidation with atomic oxygen. The experiments will be carried out in the group of Prof. Lambert (University of Cambridge, England).

烯丙基烯烃的多相环氧化是一项艰巨的任务，因为不稳定的烯丙基氢的容易提取会引发烯烃的完全燃烧并防止选择性氧化。最近，研究表明，对于一般的烯烃环氧化和特别是烯丙基烯烃的困难情况，铜本质上比广泛使用的银更具选择性。本项目旨在了解明确的铜单晶表面上烯丙基烯烃环氧化的微观机制，并将这些机制与实际条件下运行的铜基负载催化剂的反应性和选择性联系起来。本研究的主要重点将在于研究结构参数（例如烯烃吸附几何形状、烯属双键和表面烯丙氢的附近、催化剂表面的微观结构等）在环氧化活性和选择性中的作用。此外，还将研究可能的替代环氧化途径，其中不包括用原子氧氧化烯烃的常见步骤。实验将在Lambert教授（英国剑桥大学）的小组中进行。