基于双核Schiff碱配合物固载的MOFs的构筑与催化性能开发

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 research may establish an important theoretical foundation for fine-tuning the catalytic properties of MOFs, especially in heterogeneous biomimetic catalysis.

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。

金属-有机框架 (MOFs) 材料因具有结构可测、孔道内表面易于修饰等优点，在选择性吸附与存储、催化等领域具有很高的理论研究价值和广阔的应用开发前景，近年来逐渐成为化学及材料领域的研究热点。本项目旨在通过配体修饰策略在孔道内壁引入活性基团，提高MOFs材料的选择性吸附性能和催化性能，研究内容涉及两个方面：1.利用金属配体策略，将活性salen配合物引入MOFs孔道内部，由于中间产物溶解性较差且易形成内盐，本部分合成条件仍在探索。2.利用配体修饰策略，选用含双功能基团的H2NSBPDC为桥联配体，构筑了系列多孔MOFs材料（配合物1-5），探讨了材料的离子交换性质和吸附性质，部分研究内容已整理成文，2篇待发表，1篇正在整理。后续研究将在配体上引入碱性基团，开发MOFs材料在CO2吸附及碱催化领域的应用。本项目的研究为活性MOFs的构筑及性能开发奠定了一定的理论和实验基础。