多酸基金属-有机限域体系的构筑及其催化多组分耦合反应性能研究

The development of environment-friendly catalysts and multicomponent catalytic system with high efficiency is of great theoretical and practical significance for achieving the production from simple materials to high value-added chemicals. Considering the key issues of the atomic economy of the light-driven proton reduction from water-splitting and the additional oxidizing agent needed during the oxidative cyclization process forming quinazolinone, in this project, the complementary coupling reactions of oxidative cyclization and water-splitting proton reduction have been designed, which the left oxygen after proton reduction could be regarded as oxidizing source for the oxidative cyclization and the given electron in oxidation process as the electron donor for the proton reduction. Utilizing the assembly strategy, the POMs-based metal-organic bifunctional catalyst, combining oxidative activity and redox active centers within one catalyst, has been constructed. The well-designed confined pocket could regard as molecular flask as well, providing the ideal platform for the catalytic coupling reactions. This coupling reaction achieves the clean conversion in this filed without adding additional oxidizing agent and avoiding the forming of useless products in a greener and high-efficient route.

发展高效、环境友好的新型催化剂和多组分耦合催化体系，实现由简单原料出发到高附加值化学品的制备，具有重要的理论和现实意义。本项目针对光解水质子还原半反应的原子经济性，以及氧化环化制备喹唑啉酮必须外加氧化剂等关键问题，将“互补型”氧化环化与水分解还原过程相耦合，水分解还原产氢后所剩的氧可为氧化环化过程的氧源，同时氧化反应中的给电子过程可为水分解反应提供所需电子。利用可控的自组装策略，构建兼具氧化催化以及水分解催化活性中心的多酸基金属-有机限域体系作为耦合反应双功能催化剂，并且其限域空腔作为分子反应器为催化反应提供场地，最终实现无外加氧化剂参与及无用副产物生成的绿色、高效转化过程。

本项目紧紧围绕金属-有机限域超分子体系的构筑及其识别、催化等性能调控这一目标展开执行。按计划逐步对有机配体设计与合成、金属-有机限域分子的构筑、超分子行为及性能等探究等研究工作。目前已合成得到约10余种有机配体及多酸基配体，并采用溶剂热和溶剂扩散法制备了一系列空腔结构与活性中心协同、高活性、高稳定性的限域笼状化合物，对它们进行了单晶结构测定和系统的表征。建立起较为完善的功能测试平台，对其荧光发射、紫外吸收、电化学、质子导电等性能进行系统探究，总结了功能位点调控与催化性能之间的规律。除此之外，将孤立的限域体系延展到三维骨架材料领域、或者多酸类化合物体系中，实现其特异性识别、催化等方面的应用。