构建多活性位点的单组分金属卤化物@吡啶/咪唑多孔有机框架用于CO_(2)的高效吸收与催化  

Constructing the One-component Metal Halide@Pyridine/Imidazole Porous Organic Frameworks with Multiple Active Sites for Highly Efficient CO_(2) Adsorption and Catalysis

作　　者：刘方旺 王建花 于明月 张莉[1] 张倩[1] 孟建华 高庆平[1] 江津河 LIU Fangwang;WANG Jianhua;YU Mingyue;ZHANG Li;ZHANG Qian;MENG Jianhua;GAO Qingping;JIANG Jinhe(Huanbohai Green Chemical Application Technology Collaborative Innovation Center,College of Chemical Engineering,Weifang Vocational College,Weifang 262737,Shandong,China;College of Chemical Engineering and Environmental Engineering,Weifang University,Weifang 261061,Shandong,China)

机构地区：[1]潍坊职业学院化学工程学院,环渤海绿色化工应用技术协同创新中心,山东潍坊262737 [2]潍坊学院化学化工与环境工程学院,山东潍坊261061

出　　处：《材料导报》2024年第15期283-292,共10页Materials Reports

基　　金：国家自然科学基金(51541205);潍坊市科学技术发展计划项目(2022GX020);潍坊职业学院博士基金项目。

摘　　要：定向设计的多孔有机框架被认为是提高CO_(2)捕集与利用效率的优异纳米材料。本研究通过ZnCl_(2)催化的氰基离子热聚合反应以及合成后修饰法构建了一系列多活性位点的单组分金属卤化物@吡啶/咪唑多孔有机框架材料(M@PIPOFs),并详细探讨了不同单体浓度和聚合温度对材料结构及性能的影响。作为具有较高比表面积、多层次孔隙结构的多相催化材料,M@PIPOFs同时含有丰富的氢键供体基团、Lewis酸/碱基团和亲核基团,在吸收CO_(2)以及催化CO_(2)与环氧化物耦合制备环状碳酸酯方面表现出极好的性能。结果表明,该类材料对CO_(2)的吸附性能较强,在273 K、100 kPa CO_(2)压力下吸附量最高,为3093μmol/g。考察了M@PIPOFs结构和反应条件对其催化性能的影响,结果表明,单组分1.0ZnI_(2)@PIPOF-400-30材料具有最高的催化性能。其能够在无溶剂、无助催化剂的条件下,高活性、高选择性地催化CO_(2)与含有不同终端基团的环氧化物耦合,并以88%~98%的收率生成相对应的环状碳酸酯。此外,该M@PIPOFs催化剂回收简单,具有持久的高稳定性和催化活性。最后,基于对M@PIPOFs材料的表征和催化数据分析,提出了一种可行的多活性位点单组分催化机理。本研究希望能够为后续高效多相催化体系的设计、开发提供参考。Porous organic frameworks designed directionally have been regarded as the promising nano-materials for improving the efficiency of CO_(2) capture and utilization.In this work,a series of one-component metal halide@pyridine/imidazole porous organic frameworks(M@PIPOFs)with multiple active sites were fabricated via ZnCl_(2)-catalyzed cyano ionothermal polymerization and post-synthesis decoration,meanwhile,the influences of different monomer concentration and polymerization temperature on the material structure performance were discussed in detail.As the heterogeneous catalytic materials with a high specific surface area and hierarchical pore structure,M@PIPOFs also contained abundant hydrogen bond donors,Lewis acid/base groups and nucleophilic groups,which exhibited excellent performance in absorbing CO_(2) and catalyzing the coupling of CO_(2) and epoxides into cyclic carbonates.The data indicated that these materials showed the slightly higher CO_(2) adsorption capacity,and the highest uptake capacity of 3093μmol/g was afforded at 273 K and 100 kPa CO_(2) pressure.The effects of M@PIPOFs structure and reaction conditions on the catalytic performance were investigated,the results revealed the single-component 1.0ZnI_(2)@PIPOF-400-30 had the highest catalytic performance.It could catalyze the coupling reaction of CO_(2) and epoxides containing different terminal groups with high activity and selectivity under solvent/cocatalyst-free condition,and achieve the corresponding cyclic carbonate with the 88%—98%yield.Moreover,the M@PIPOFs catalysts could be simply separated with durable high stability and activity.Finally,based on the characterization and catalytic data analysis of M@PIPOFs,a feasible one-component catalytic mechanism with multiple active sites was proposed,which hoped this research could provide a refe-rence for the subsequent design and development of highly efficient heterogeneous catalytic systems.

关 键 词：二氧化碳 单组分多相催化剂 耦合反应 环状碳酸酯 多孔有机框架 

分 类 号：TQ203.2[化学工程—有机化工]