基于双核Schiff碱配合物固载的MOFs的构筑与催化性能开发

项目名称： 基于双核Schiff碱配合物固载的MOFs的构筑与催化性能开发

项目编号： No.21201064

项目类型： 青年科学基金项目

立项/批准年度： 2013

项目学科： 无机化学

项目作者： 程爱玲

作者单位： 华东师范大学

项目金额： 25万元

中文摘要： 金属-有机框架 (MOFs) 材料在多相催化领域具有很高的理论研究价值和广阔的应用开发前景。将配合物均相催化剂直接固载到MOFs中，是构筑高性能MOFs多相催化材料的有效策略。然而，材料骨架的弱稳定性和开放性多孔结构的易穿插性制约了这一合成策略的拓展，应对这些挑战的关键是催化功能导向的高稳定性"金属配体"的设计合成。基于双核Schiff碱(大环)配合物的稳定性、拟酶活性和羧基的多齿桥联特性，本项目设计含上述配合物功能单元的羧酸配体，构筑双金属活性中心固载的新型MOFs材料。在结构研究的基础上，开展材料对儿茶酚、环己醇等氧化反应的催化性能研究，探讨材料骨架结构、双金属活性中心结构(包括金属离子种类)、抗衡阴离子等与催化性能之间的构效关系，探索双金属协同参与的多相催化机理，为优化材料性能和开发新型高效的多相仿生催化材料奠定理论基础。

中文关键词： 金属-有机骨架；表面修饰；催化；离子交换；吸附

英文摘要： Metal-organic frameworks (MOFs) have attracted tremendous attention because of their unique properties as heterogeneous catalysts. Among many strategies for synthesizing MOF-based catalyst, an attractive and straightforward approach is to directly incorporate the well-defined metal compexes into the frameworks ('metalloligand'), examples include M-salen, M-porphyrin and Ti-BINOLate complexes. Given their high stability and excellent biomimetic catalytic properties, bimetalic schiff base macrocyclic complexes should also be potential building blocks for catalytically active MOFs. With this perspective, we aim to construct and characterize the heterogeneous biomimetic catalytic properties of the functional MOFs based on the bimetalic schiff base macrocyclic complexes. The main topics of this project are as follows: Contructing novel catalytic MOFs using the well-defined bimetalic schiff base complexes as building blocks; Evaluating the heterogeneous catalytic activity and selectivity of the MOFs in the given model reaction, such as the oxidation of catechol and cyclohexanol; Exploring the relationships between structures (including the channel environment, the bimetalic center and the charge ligands) and the catalytic properites in MOFs; Elucidating the reaction mechanism of heterogeneous catalysis. The above r

英文关键词： metal-organic frameworks；ligand modification；catalysis；ion exchange；absorption