含咪唑鎓的有机多孔材料的制备与性能研究

This proposal aims to design and prepare various imidazole- or imidazolium-containing conjugated organic building blocks with linear, planar and three-dimensional structure, and then cross-link these building blocks through efficient carbon−nitrogen (N-alkylation) or carbon−carbon bond-forming reaction (condensation or polymerization) to produce imidazolium-based polymeric materials with infinite nanoporous network structure. By varying the size, length and type of the core units in the organic conjugated building blocks, the porosity parameters of the obtained imidazolium-based organic porous materials, such as specific surface area, pore size and pore size distruction can be tuned to fulfill the size-fit concept between the pore size of the polymeric materials and the dimater of canbon dioxide molecule. Alternatively, varying the density of the imidazolium moieties and the counter anions in the skeletons of the organic porous materials will enhance the interaction between the pore surface of the imidazolium-based organic porous material and carbon dioxide molecules. This above two approaches based on the basic concepts of supramolecular chemistry can effectively improve the carbon dioxide sorption uptake capacity and sorption selectivity of the novel ionic organic porous materials. The sustainable preparation procedures, desorption behaviors, the regeneration conditions, and catalytic carbon dioxide conversion of the imidazolium-based organic porous materials will establish a solid base of developing practical smart carbon dioxide sorbents with high uptake capacity and sorption selectivity and catalytic conversion potentials. Furthermore, it will be beneficial to the improvement of the living environment of mankind and the human survival in the closed space in the submarines and spacecraft cabins.

拟设计合成线形、平面形和三维结构的含有咪唑端基或咪唑鎓的多种有机共轭建筑块，通过高效的碳−氮(N-烷基化)或碳−碳(缩合或聚合)成键反应，将它们连接起来，形成具有纳米孔道结构的含有咪唑鎓的无限网络结构。通过调节建筑块核心单元的大小、长度和类型等，可有效调控所制备材料的孔道结构和比表面积、孔容与孔径分布等孔隙参数，以期达到有机多孔材料的孔道与二氧化碳分子的尺寸匹配。通过多孔材料骨架中咪唑鎓基团的密度及对阴离子的改变，增强含咪唑鎓的有机多孔材料孔道表面与二氧化碳分子之间的相互作用力。此二途径基于超分子化学的基本概念，可有效提高此类新颖的离子型有机多孔材料对二氧化碳的吸附容量与选择性。经济可持续型制备、吸脱附与再生条件的探索以及对所吸附的二氧化碳的催化转化，为开发实用化的二氧化碳吸储与催化转化复合材料奠定基础，将对大气环境的改善、海洋潜艇与太空舱封闭空间内人员生存质量的提高，具有非常重要的意义。

项目设计合成了线形、平面形和三维结构的含有咪唑端基或咪唑鎓的多种有机共轭建筑块，通过高效的碳–氮(N-烷基化)或碳–碳(缩合或聚合)成键反应，直接形成具有纳米孔道结构的含有咪唑鎓等阳离子的无限网络结构，或者通过后修饰的方法将阳离子基团引入多孔网络结构中获得阳离子型有机多孔材料。1) 所获得的阳离子型有机多孔材料对气体分子、阴离子染料及含金属的阴离子，为水系的污染治理、放射性核废料的处理提供了新型的吸附剂材料。2) 制备出含有咪唑鎓的聚合物复合膜，基于其结构特征，可以通过溶剂处理，达到可控分离水油的性能。3) 通过催化基团的引入，获得具有催化基团的有机多孔聚合物材料，作为多相催化剂，对化学转化、光还原二氧化碳等反应表现出很好的性能，同时具有易于回收利用的特点。4) 通过功能性对阴离子的引入，探索了有机多孔材料作为全固态电解质，应用于储能器件中，表面出良好的性能。本项目从阳离子型有机多孔材料对二氧化碳的吸附、阴离子的吸附、到催化转化等，为开发实用化的二氧化碳吸储与催化转化复合材料奠定基础，将对能源与环境领域的可持续性发展，具有非常重要的意义。