共面双核金属卟啉作为燃料电池高效氧还原电催化剂的合成及性能研究

项目名称： 共面双核金属卟啉作为燃料电池高效氧还原电催化剂的合成及性能研究

项目编号： No.20871082

项目类型： 面上项目

立项/批准年度： 2009

项目学科： 金属学与金属工艺

项目作者： 任奇志

作者单位： 上海交通大学

项目金额： 30万元

中文摘要： 共面双核金属卟啉对氧气的4电子还原能力近年来引起了广泛的关注，但其作为燃料电池电催化剂的研究却鲜有报导。本项目拟合成系列新型共面双核金属卟啉作为燃料电池的高效氧还原电催化剂,研究其高效4电子催化分子氧还原的机理、活性中心结构与双卟啉空间构象之间关系，提供新途径以解决目前燃料电池非贵金属电催化剂面临的难题：催化分子氧还原主要进行2电子反应，产物为易破坏催化剂结构的过氧化氢，导致催化活性低，稳定性不佳。研究内容包括：系列新型金属双卟啉(连接方式为离子对、柔性共价键及刚性共轭键)的合成；碳载电催化剂的制备；半电池及全电池电化学性能的测试；双卟啉空间构象的量化计算；催化机理及活性中心的研究。重点考察双卟啉中金属活性中心的协同效应及配位环境对分子氧-双卟啉之间吸附、活化及O-O键断裂的影响，分析活性中心结构，探讨催化氧还原机理。将对寻找高效非贵金属电催化剂，推动燃料电池的发展和产业化有重大意义。

中文关键词： 共面双核金属卟啉; 氧还原; 电催化剂; 催化活性; 燃料电池

英文摘要： The investigation of cofacial metallodiporphyrins which can catalyze four electron oxygen reduction reaction presents a major challenge in current chemical research. The corresponding application as electrocatalyst of fuel cell has been seldom reported. In this research, a new series of cofacial metalloporphyrin dimers will be synthesized and as efficient oxygen reaction reduction electro catalyst of fuel cell; The relationship among the catalytic mechanism, catalytic active center structure and the steric conformation of porphyrin dimers will be investigated in detail; Trying to provide a new way to serve the main drawbacks for current non-noble ectrocalysts in fuel cell: 1) two electron oxygen reduction reaction; 2) the unfavored H2O2 product, which can easily destroy the catalyst structure; 3) lower catalytic activity and catalytic stability. The research content will include following aspects: 1) the synthesis and characterization of new series of cofacial metalloporphyrin dimers, linked by ion pairs, flexible covalently chains and rigid cojugated chains respectively; 2) preparation of carbon supported porphyrin electrocatalysts; 3) the examination of the performance of half and single cell using carbon supported porphyrins as cathodic oxygen reduction catalyst; 4) the quantum calculation of the steric conformation of porphyrin dimers, the investigation of the catalytic mechanism and the catalytic active center. This research will be great useful for searching and investigating the efficient non-noble electro catalysts and for the development and the commercialization for fuel cells which have been recognized as environmentally friendly and highly efficient energy-converting devices.

英文关键词： cofacial dimeric metalloporphyrin; oxygen reduction; electrocatalyst; catalytic activity; fuel cell