可金属修饰的Keggin型缺位多酸基MOFs的设计合成及催化性质研究

The design and synthesis of novel structure, high catalytic performance of MOFs is a hot research field of Inorganic Coordination Chemistry and Materials Science, and also an effective method for the development of new catalysts. Using vacant Keggin-type polyoxometalates as building blocks, N-heterocycle-containing zwitterions as bridging ligands and transition metals or rare earth metals acting as assembly nodes,the new MOFs will be synthesized by the routine synthetic reaction or hydrotherml/solvothermal, which can achieve the modification of the active metals via ion exchage or coordination adsorption, in order to develop their catalytic properties. With a suitble modle reaction, the catalytic activities of the compounds will be clarified on the level of the molecular structure. The mechanism of interaction between the active sites and the substrates will be explored in depth. The relationship among active sites, structural characteristics and catalytic properties will be revealed, thus guiding the design and synthesis of MOFs and the development of highly active catalysts and the modulation and improvement of the catalytic performance. This work has important theoretical significance upon the design, synthesis and application for the functional MOFs, and a great of practical value for the further study on catalytic application of MOFs and the synthesis of a new-style, high-efficient catalysts.

设计合成具有新颖结构，高效催化活性的MOF材料是无机配位化学及材料科学的热点研究领域，也是开发新型催化剂的一种有效方法。 本课题以Keggin型缺位多酸阴离子为功能构筑单元，以含氮杂环两性离子化合物为桥联配体，以过渡金属或稀土金属为组装节点，采用溶液法或水/溶剂热法合成新的MOF化合物，并采用离子交换、配位吸附等方法实现活性金属对材料骨架的修饰，以此开发其催化性能。通过筛选适当的模板反应，研究化合物的催化性质，在结构水平上阐明合成化合物的催化活性，探讨活性中心与催化底物的作用机制，揭示化合物的组成结构与其催化活性的关系，进一步指导MOF材料的设计合成，实现对高效催化剂的开发及对其催化性能的调节和改善。 本研究对于功能MOF材料的设计、合成方法及应用开发有重要的理论意义，对于进一步研究MOF材料催化应用，合成新型、高效催化剂具有重要的实际意义。