高稳定性孔性配位聚合物在能源气体分离的研究

孔性配位聚合物，以其可控的结构，较高的比表面积,特殊的认知能力等特点，受到全球范围化学家、材料学家的广泛关注，也将成为"清洁能源气体存储和低能耗混和能源气体分离"的重要平台，但是材料的水稳定性是目前尚待解决的关键难题。本项目拟基于运用唑类和多酸配体连接子，引入疏水基团和高价金属节点的策略，利用增强配位键能力和遮挡配位键等方法，从而实现控制搭建高水稳定，且兼具高分离性能的孔性配位聚合物材料。同时，系统研究不同疏水基团，配位点位置，孔洞类型和尺寸，气体扩散效率等因素与多孔材料稳定性和分离性能的关系，为制备具有自主创新的孔性材料提供科学依据和技术支持。

Recently, a new class of designable and robust porous materials, porous coordination polymers (PCPs) or metal organic frameworks (MOFs), have demonstrated significant promise for energy gas adsorption and separation because of their chemical tailorability, which results in high BET surface areas and specific recognition ability for components in the gas mixture. Because of the theoretically limitless possibilities in assembling organic linkers and metal or cluster connectors, a large number of structures have been reported,but a few of them show show outstanding storage and selectivity for small hydrocarbons. This is mainly due to their similar physical and chemical properties, which lead to the difficulty for adsorption-based separation. However, among these few structures, their rather low hydrothermal and chemical stabilities, compared with zeolites, further limit their usage in moist and chemical environments. Therefore, candidate PCPs with high separation capability and enhanced stability in air, water, and acidic and basic media for energy gas separation are urgently needed. To overcome these issues, our strategy is to employ the trivalent ion and rigid azole-carboxylic ligand with hydrophobic group to construct porous frameworks. Because of the high coordination number of metal, zeolite-framework, and also the protected coordination bond by hydrophobic group may enhance the water stability of the framework. Meanwhile, it is very important to explore the relationship between the stability and adsorption/separation performance that will influenced by the the position of the hydrophobic group, cooprative tuned pore type/size and the framework topology. Overall, our work will provide a scientic support for finding the porous materilas with independent creation.