离子液体介质调控合成功能型微孔-介孔有机聚合物材料及其催化CO2转化研究

CO2 is an abundant C1 resource, and its utilization as feedstock has been paid worldwide attention. The development of functionalized porous polymeric materials has provided broad opportunity for CO2 utilization. The project focuses on CO2 activation and chemical conversion into value-added chemicals (including formic acid, methanol, (C2+)-acids/alcohols, benzaldehydes, carboxylic acids and their derivatives), to construct reaction media composed of ionic liquids/water (organic solvents or compressed CO2), design various reaction pathways and realize controllable synthesis of micro- and mesoporous organic polymeric materials functionalized with "CO2-philic" groups (nitrogen/phosphine containing groups or ionic ones). New progress will be made aboute regulating the structures and morphologies of materials by reaction medium; In addition, bifunctional catalysts will be prepared via immobilizing transition metal complex/nanoparticles onto the as-prepared polymers; Investigate the CO2 adsorption capacity, activation and catalytic activity of the resultant materials, and ultimately realize efficient CO2 conversion under mild conditions; Uncover the synergistic effects between the functionalities within the backbone, metal catalytic center and porosity nature, and get deeper insight of physical, chemical and catalytic characterization of the porous organic polymers. The project is related to the multidisciplinary overlap of physical, organic and material chemistry. It is expected to make a series of important achievements, and establish reliable scientific basis for CO2 utilization. Hence, it has important theoretical significance and practical value.

CO2是储量丰富的可再生C1资源，其资源化利用是国内外普遍关注的重大课题。功能型聚合物孔材料为CO2的资源化利用提供了广阔的发展空间。本项目针对CO2活化转化为高附加值化学品（包括甲酸/醇、长链酸/醇、苯甲醛、羧酸及其衍生物等），构建离子液体/水（有机溶剂或压缩CO2）反应介质体系，采用多种反应路线，调控合成兼具微孔-介孔结构、富含亲CO2基团（氮/膦功能化、离子型）的有机聚合物材料；在认识介质体系调控材料结构形貌方面取得新进展；对所得聚合物材料进行金属功能化，获得多功能聚合物基催化材料；研究催化材料吸附、活化和催化CO2转化的性能，实现温和条件下CO2的催化转化；揭示催化材料的骨架官能团、金属中心及孔结构的协同作用机制，以期获得对材料构效关系的新认识。项目研究涉及物理化学、有机化学、材料科学的交叉渗透，有望获得一批重要成果，为CO2资源化利用奠定科学基础，具有重要的科学意义和实用价值。

功能型多孔有机聚合物具有广泛用途，发展其绿色制备方法具有重要意义。本项目通过使用新的反应单体、发展绿色合成路径等方式，设计合成了多种功能型多孔有机聚合物，将其应用于CO2和MeOH等绿色C1资源的催化转化，揭示了其构效关系。主要内容和创新结果如下：在水相体系中，无模板剂、无催化剂条件下，发展了基于芳基铵盐与芳香醛的聚合反应制备亚胺功能化的介孔有机聚合物（Imine-POP）的新方法；基于Sonogashira-Hagihara交叉偶联反应，通过孟加拉红与1,4-二乙炔基苯反应制备了孟加拉红官能化的多孔有机聚合物（RB-POP）；基于酸性红87分子（EosinY）与芳香炔的偶联反应，制备了EosinY功能化的多孔共轭有机聚合物（PEosinY）；构建H2O和离子液体（IL）绿色溶剂体系，基于芳香胺与二甲氧基甲烷的聚合反应，设计合成了Tröger碱功能化的介孔有机合物材料（Meso-TBPs）；针对有机胺中N-H键的甲基化反应，以甲醇为甲基化试剂，建立了由钴盐（如Co(acac)2）、四齿膦配体P(CH2CH2PPh2)3和磷酸钾构成的钴催化体系；针对C(sp3)−H 和C(sp2)-H的甲基化反应，以甲醇作为甲基化试剂，构建了Co(BF4)2·6H2O/PP3/K3CO3催化系统，系统研究了对芳基烷基酮、芳乙腈和吲哚C-H键甲基化的催化性能；构建了[Co]/PP3/碱/溶剂催化体系，系统研究了对有机胺与二氧化碳参与的甲基化/甲酰化反应的催化性能；构建RhI3或者RhI3/Pd(dppp)Cl2、三苯基膦催化体系，首次以二氧化碳为碳基试剂在氢气、乙酸酐和三乙胺存在下，实现芳碘和芳溴的甲酰化反应。本项目取得了一系列创新性研究成果，发表SCI论文18篇，培养博士生2名。