氧分子的活化与还原:从金属蛋白酶的模拟到燃料电池电催化剂的应用

项目名称： 氧分子的活化与还原:从金属蛋白酶的模拟到燃料电池电催化剂的应用

项目编号： No.21271072

项目类型： 面上项目

立项/批准年度： 2013

项目学科： 数理科学和化学

项目作者： 刘劲刚

作者单位： 华东理工大学

项目金额： 80万元

中文摘要： 氧分子的活化还原不管在生命过程中还是在能量转换体系如燃料电池中都是一个非常重要的化学反应过程，也是人们广泛研究的热点课题。用模型化合物来模拟金属蛋白酶活性中心的结构与性能，能为解开金属蛋白酶对小分子氧的活化机理提供化学模型证据，并对氧分子仿生还原催化剂的设计与应用发挥指导性的作用。本项目基于含血红素金属蛋白酶的活性中心结构，设计制备一系列含铁卟啉的模型化合物，通过各种光谱学和电化学方法研究氧分子与模型化合物的键合、还原性质。本研究旨在为血红素蛋白酶及细胞色素c氧化酶对氧分子的活化过程中出现的涉及O-O键断裂的各种难观察到的关键瞬态中间体提供相应的化学模型证据;为燃料电池设计优化新型仿生氧分子还原催化剂。该项目的成功实施将在基础研究方面进一步推动生物大分子对小分子氧的活化还原机理的理解；在应用基础研究方面将扩大仿生氧分子还原催化剂在燃料电池贱金属电催化剂上的进一步应用。

中文关键词： 金属蛋白酶；化学模型；氧还原反应；燃料电池；电催化剂

英文摘要： The oxygen activation/reduction reaction is one of the most important reactions in both life processes and in energy converting systems such as fuel cells, and it has recently being an extensively studied research area. Biomimetic models which resemble the active site of heme-containing enzymes may provide chemical evidence for the clarification of dioxygen activation mechanisms, and may aid to guide the design of biomimetic oxygen reduction reaction (ORR) catalysts for potential applications as well. This proposal will design and prepare a serial of iron porphyrin or heme-copper complexes as chemical models of the active site of heme-containing enzymes including the terminal enzyme of respiratory chain, cytochrome c oxidase. The O2-binding and activation by these model compounds will be investigated by various spectroscopic and electrochemical methods. The objectives of this proposal will be to further clarify the mechanism of O2-binding and activation catalyzed by cytochrome c oxidase, esp.to demonstrate the key transient intermediates that relating to the O-O bonding cleavage; to provide the spectroscopic evidence of different kinds of one-electron reduced heme-dixoygen adducts relating to the intermediates generated by heme-containing enzymes during their different activation pathways; and to design and opti

英文关键词： Metalloenzymes；Chemical Models；oxygen reduction reaction；Fuel Cells；Electrocatalyst