多酸模板剂导向多孔框架晶态材料的可控合成及其环境友好催化研究

Research and development of environmentally friendly catalysts is an important research field in catalytic chemistry. Polyoxometalates (POMs) as green catalysts exhibit high activity and good selectivity. Therefore, the catalytic study for the POMs has attracted considerable attention of researchers. The one-step hydrothermal synthetic method with POMs as the template provides a feasible platform for the preparation of the framework crystalline state materials with high stability, good recyclability and uniform dispersion. This project will mainly focus on the design, synthesis and catalytic study of the framework crystalline state catalysts modulated by POMs. We try to reduce electronegativity of the designed macrocyclic polycarboxylic acid ligands through coordination of the metal cations with central macrocycle. Then, we will attempt to perform controllable synthesis of POMs-templated metal-organic framework crystalline catalysts. Catalytic performances of esterification and oxidation desulfurization will be intensively studied using the POMs-templated metal-organic framework materials. Crystalline catalysts with high activity and good recyclability will be achieved via catalytic study. The relationship between the catalytic activity and structure of the catalysts will be eluciated. Finally, we will try to controllably assemble POMs-templated metal-organic framework crystalline catalysts.

环境友好型高效催化剂的研究与开发是催化化学研究的重要方向，多酸作为绿色催化剂具有催化活性高、选择性好等优点，从而受到了研究者们的广泛关注。以多酸作为模板剂的一步水热法为制备稳定性高、循环性好、分散均匀的框架晶态催化剂提供了可行的平台。本课题主要着眼于多酸模板剂导向的框架晶态材料的设计合成与催化研究这两个前沿方向。利用设计合成的中心含氮大环可以与金属离子配位的大环多羧酸配体来降低羧酸质子化后的负电性，从而实现以杂多酸为模板剂导向的金属-有机框架晶态催化剂的可控合成。深入探究以杂多酸为模板剂的金属-有机框架晶态材料的催化酯化反应和催化氧化脱硫性能，筛选出具有高活性和高循环性的催化剂。阐明催化活性和循环使用性与催化剂结构之间的内在联系，尝试杂多酸模板剂导向的高效型金属-有机框架晶态催化剂的定向组装。

多酸催化剂具有催化活性高和选择性好等优点，多酸模板剂法为制备稳定性高、分散均匀、循环性好的金属-有机框架晶态催化剂提供了可行的合成策略。本课题以多酸模板剂导向的金属-有机框架晶态材料的设计合成与环境友好催化研究为出发点，设计合成了系列含氮大环配体，以多酸作为模板剂通过一步溶剂热法制备了系列多酸模板剂导向的金属-有机框架晶态材料。合成过程中考察了配体及多酸的类型等因素对多酸模板剂导向的金属-有机框架晶态材料制备的影响，优化了目标框架晶态催化剂制备的影响因素。通过单晶X-射线衍射对制备的多酸模板剂导向的金属-有机框架晶态材料的结构进行了测定，并做了相应的表征。探究了多酸模板剂导向的金属-有机框架晶态材料的催化氧化脱硫等性能，考察了催化剂对不同底物的催化活性及其循环使用性，探究了多酸框架晶态催化剂结构与催化氧化脱硫等性能之间的关系。