【作者】 常欢； 于艳敏； 佘远斌；

【Author】 Huan Chang;Y.M. Yu;Y.B. She;Department of Chemistry and Chemical Engineering,College of Environmental and Energy Engineering,Beijing University of Technology;

【机构】 北京工业大学环境与能源工程学院化学化工系；

【摘要】 金属卟啉能模拟生物氧化酶(如单加氧酶细胞色素P-450、血红蛋白、肌红蛋白)在温和条件下活化分子氧,并实现有机物的催化氧化。考察金属卟啉与氧气之间的相互作用是金属卟啉作为仿生催化剂研究过程中的关键步骤,对阐明金属卟啉的催化性能具有重要的意义[1,2]。本文采用密度泛函理论方法研究了具有不同中心金属离子(Fe、Co、Mn、Cu、Zn)的金属卟啉(如图1)与氧气之间的相互作用,并对其所形成络合物的稳定结构进行考察。结果发现,中心金属离子为易变价金属的铁卟啉,钴卟啉和锰卟啉均和氧气之间以配位键相结合,且相互作用较强,对氧气分子的活化程度较高。而中心金属离子为不易变价金属的铜卟啉和锌卟啉则和氧气之间未形成配位键,相互作用较弱,对氧气分子的活化能力较弱。更多还原

【Abstract】 The interaction between the metalloporphyrin and dioxygen is the key step in biomimetic catalytic process. The interaction between metalloporphyrin and dioxygen was studied using density functional theory, and the stable structure of the complex was investigated. The results show that iron porphyrin, cobalt porphyrin and manganese porphyrin combined dioxygen with coordination bond, which have a strong interaction and a higher degree of activation for oxygen molecule. The interaction between copper porphyrin, zinc porphyrin and dioxygen is weak, and there is no coordination bond between them.更多还原