多级孔有机聚合物多相催化剂用于低浓度CO2环加成转化的研究

Facile elimination and transformation of low concentration CO2 is of great significance for the practical utilization. However, most of the works are still focuse on the adsorption of CO2 with low concentration, the chemical fixation of the low concentration CO2 is still a challenge. The cycloaddition of CO2 with epoxides to form cyclocarbonates using heterogeneous catalysts under mild and co-catalysts free conditions have attracted numerous attentions recently. In this project, a series of porous organic polymers based heterogeneous catalysts will be constructed through a free radical copolymerization method from the vinyl functionalized metal-organic complexes and the vinyl functionalized ionic liquids decorated with polar groups (such as hydroxyl, carboxyl, amino, etc.), which will serve as Lewis acid and Lewis base central in the coupling of CO2 with epoxides respectively. The catalytic activity of the resulted heterogeneous catalysts in the cycloaddition of low concentration CO2 with epoxides will further be studied under mild and co-catalysts free conditions. It is mentionable that the introduction of polar groups in the polymer materials can efficiently enhance the adsorption and enrichment of CO2 in the low concentration, while the fine combination of ionic liquids and metal organic complexes can provide efficient acid and base active centers for the cycloaddition of CO2 under mild conditions. At last, the in-situ IR spectroscopy and DFT calculation will be used to determine the reaction pathway and reaction mechanism of the cycloaddition reaction of CO2 under low concentration, and the corresponding structure-property relationship will be constructed furthermore. Obviously, those results will sure to provide guidance for the green transformation of low concentration CO2 in the future.

实现低浓度CO2的消除与转化在工业生产中有着重要的意义，但目前实现低浓度CO2的有效转化仍是一个难点。本项目拟以CO2与环氧化物的环加成转化为研究对象，通过乙烯基功能化的金属有机配合物与极性基团（如羟基、羧基、氨基等）修饰的乙烯基功能化离子液体自由基共聚合的方法，构建环加成转化所需的路易斯酸、碱中心复合的多级孔有机聚合物，并研究其在温和、无共催化剂、低浓度条件CO2环加成转化生成环碳酸酯反应中的催化活性。采用原位红外和理论计算等方法研究反应历程和反应机理，构建相应的构效关系。值得一提的是，本项目中极性基团修饰的离子液体一方面可以有效增强目标聚合物对CO2的吸附与富集，同时又可以与金属有机配合物协同作用，提供CO2环加成转化反应所需的路易斯碱性和酸性活性中心，使得高效实现低浓度CO2的转化成为可能。因此，本项目为实现低浓度CO2的消除提供了一种新的可能途径与方法。

实现聚合物材料的精准构筑和设计是材料领域的研究热点之一。在本项目中我们通过有机合成的手段，定向合成了一系列乙烯基功能化的离子液体和乙烯基功能化的金属有机配合物，分别采用自由基共聚和分级后修饰构建等手段，构建了一系列兼具路易斯酸中心和碱中心的多孔有机聚合物双功能多相催化剂，实现了不同催化活性中心在分子水平的结合，并研究了它们在常温、无共催化剂、低浓度CO2条件下的CO2与环氧化物的环加成转化生成环碳酸酯反应中的应用，对它们的相关反应机理进行探索，建立了相应的构效关系。在此基础上，我们进一步发展了多种功能化离子液体多孔有机聚合物，实现了多相催化剂的精准构筑，并系统研究了它们在低浓度CO2条件下的环加成转化中的应用。此外，鉴于多孔有机聚合物的可设计性，我们也拓展了系列聚合物在酸性污染特别是在SO2气体吸附分离上的应用研究。通过本项目的实施，为具有特定结构和用途的聚合物材料的创制提供了理论指导。