有机溶剂分子和多酸阴离子协同导向的多孔POMOFs材料的设计合成与催化性能研究

Polyoxometalates (POMs)-based metal-organic frameworks (POMOFs) have become an important and crossed branch of polyoxometalate chemistry and coordination chemistry. In this project, by playing the structure-directing role of the organic solvents and the synergistic template role of POMs, three kinds of organic ligands [(polyamide)pyridines/polyazoles, phenathroline derivatives and N-containing polycarboxylates] were employed as the main ligands to assemble with transition/rare earth metals under the solvothermal conditions, aiming at constructing the porous POMOFs and combining the POMs with the MOFs. The effect of the organic solvents on the construction and size of the pores of target POMOFs will be explored by tuning the sizes and category of the organic solvents as well as the ratio of the mixed organic solvents. The effects of the coordination groups /orientation /length /rigidity /flexibility of the organic ligands and the structure/size/charge of the POMs on the architectures of the target porous POMOFs will be investigated. The assembly rules will be summarized to realize the controllable synthesis of the POMOFs. The intrinsic relation between the structures and the properties will be explored by systematically investigating the catalysis and photocatalysis properties of the target POMOFs. This project is very important due to the potential application of the porous POMOFs in the fields of catalysis on organic synthesis and photocatalysis degrade on the organic polluters.

多酸(POMs)基金属有机骨架（POMOFs）是多酸化学与配位化学领域发展的一个重要新方向。本项目拟利用有机溶剂分子的结构导向作用，同时充分发挥多酸的协同模板作用，以多酰胺多吡啶/多唑、菲啰啉衍生物及多种含氮羧酸为主要配体，在溶剂热条件下与过渡/稀土金属进行配位组装，来构筑多孔POMOFs配合物，实现POMs与MOFs的有机结合；通过调控有机溶剂分子的种类、尺寸及混合溶剂比例，探索有机溶剂分子对孔道形成和尺寸的影响；通过调节有机配体的配位基团、配位取向、长度和刚/柔韧性及多酸的结构、尺寸、电荷等，研究上述因素对目标多孔POMOFs结构的影响，总结其组装规律，实现该类POMOFs功能配合物的可控合成；对所合成POMOFs材料的催化、光催化性能进行系统研究，探索结构与性能之间的关系。本项目对扩展多孔POMOFs材料在催化有机合成以及光催化降解有机污染物等领域的应用具有重要的意义。

本项目中设计合成6类氮杂环有机配体：柔性/半刚性的双吡啶-双酰胺、柔性双吡嗪-双酰胺、不对称吡啶/吡嗪-多唑单酰胺、吡啶/吡嗪-酰胺羧酸、柔性和刚性的双咪唑双酰胺、其他刚性吡啶-多唑配体、双吡啶-四唑配体，并将其在溶剂热条件下与多金属氧酸盐及过渡金属进行配位组装，构筑了一系列结构新颖的带有不同孔道的多酸(POMs)基金属有机骨架(POMOFs)配合物。并通过元素分析、红外光谱、热重分析、单晶X射线衍射以及粉末X射线衍射等进行了结构表征。通过调控有机溶剂分子的种类、尺寸及混合溶剂比例，探索了有机溶剂分子对孔道形成和尺寸的影响；通过调节有机配体的配位基团、配位取向、长度和刚/柔韧性及多酸的结构、尺寸、电荷等，研究上述因素对目标多孔POMOFs结构的影响，总结其组装规律，实现该类POMOFs功能配合物的可控合成；对所合成POMOFs材料的电催化、光催化性能进行系统研究，初步探索了结构与性能之间的关系。本项目对扩展多孔POMOFs材料在电催化、吸附和光催化材料等领域的应用具有重要的意义。