基于有机-无机杂化构筑金属卟啉基材料及其仿生催化烯烃环氧化

金属卟啉模拟酶催化烯烃环氧化因其反应条件温和、产物选择性高等优点而受到广泛关注，但其活性和循环使用稳定性还有待提高。根据前期研究工作，基于金属卟啉电子结构的调控和反应微环境的设计，通过有机-无机杂化的方法制备新型金属卟啉-无机基底杂化催化剂可提高催化活性并在循环使用中保持稳定的催化性能。进一步通过对照实验证明金属卟啉与无机基底间存在较强的相互作用，但其具体协同机制尚未明确。. 拟利用原位表征、动力学分析和理论计算等手段，系统研究金属卟啉与无机基底之间的相互作用，并详细探讨该作用对金属卟啉电子结构和高价金属氧代物形成过程、催化剂精细结构及形成机理、和金属卟啉与无机基底的结合作用等方面的影响。进而关联其催化性能，阐明活性与循环稳定性的主要影响因素，从分子/原子水平上认识该催化体系作用机理和构效关系，为新型高效模拟酶催化剂的产业化应用奠定理论和实验基础。

Epoxidation of olefins catalyzed by metalloporphyrins has been widely concerned for its mild reaction conditions and high selectivity. However, it is urgent to improve the catalytic performance, including activity and stability. According to the previous works, based on the mediation of the metalloporphyrin electronic structure and design of the reaction micro-environment, the catalysts of metalloporphyrins-inorgnic substrates prepared with orgnic-inorgnic hybrid method showed excellent catalytic activity and stability even after several runs. Further experimental studies proved there was strong interaction between metalloporphyrin and inorganic substrates. But the synergistic mechanisms are not clear. .By in situ characterizations, kinetic analysis and theoretical calculations, the interaction between metalloporphyrins and inorganic substrates will be investigated systematically, including a) the electronic structure of metalloporphyrins and the formation of high-valent metal oxo intermediates, b) the fine structure of the catalysts and its formation mechanism, and c) the tight linkage between metalloporphyrins and inorganic substrates. Associated with the catalytic performance, key factors that influence the catalytic activity and stability will be clarified and the catalytic mechanism and structure-activity relationship will be elucidated from the level of molecules/atoms. The project is expected to provide theory and technology basis for the industrial applications of the novel mimetic enzyme catalysts.