共轭微孔聚合物-碳纳米管混合基质膜的可控成核生长与PM/CO_(2)同步捕集机理  

Controlled Nucleation Growth and Mechanism of Simultaneous Capture of PM and CO_(2)in Conjugated Microporous Polymer-Carbon Nanotube Mixed Matrix Membranes

作　　者：徐明伟 杨尚学 刘冠林 汪少振 王存民 李佳琪 李湘 张一帆[3] 张明明[4] 何新建[2] 徐欢 XU Mingwei;YANG Shangxue;LIU Guanlin;WANG Shaozhen;WANG Cunmin;LI Jiaqi;LI Xiang;ZHANG Yifan;ZHANG Mingming;HE Xinjian;XU Huan(School of Safety Engineering,Beijing Institute of Petrochemical Technology,Beijing 102617,China;School of Safety Engineering,China University of Mining and Technology,Xuzhou 221116,China;School of Materials Science and Physics,China University of Mining and Technology,Xuzhou 221116,China;China Academy of Safety Science and Technology,Beijing 100012,China)

机构地区：[1]北京石油化工学院安全工程学院,北京102617 [2]中国矿业大学安全工程学院,徐州221116 [3]中国矿业大学材料与物理学院,徐州221116 [4]中国安全生产科学研究院,北京100012

出　　处：《高等学校化学学报》2025年第4期123-132,共10页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:52404195,52003292,52174222);国家重点研发计划项目(批准号:2023YFC3011704);北京市教委科技面上项目(批准号:KM202310017002);中国矿业大学研究生创新计划项目(批准号:2024WLKXJ143,2024WLJCRCZL272,2024WLKXJ140);中央高校基本科研业务费专项资金(批准号:2024-10958,2024-10967);江苏省研究生科研与实践创新计划项目(批准号:KYCX24_2917,SJCX24_1403,KYCX24_2914);国家能源集团科技攻关项目(批准号:E210100285)资助。

摘　　要：混合基质膜(MMMs)通过将聚合物的优点与有机/无机填料相结合来提高吸附和分离性能.共轭微孔聚合物(CMPs)具有层次化的多孔结构和丰富的杂原子吸附位点,能够在复杂的环境中实现高效、稳定的气体吸附和分离.本文构建了碳纳米管(CNTs)网络支撑CMPs膜,该膜以具有三维网络结构的CNTs为柔性基底,以具有分级多孔结构和丰富杂原子吸附位点的CMPs为吸附活性层,旨在解决制备过程中多孔聚合物自成膜难的问题.所制备的CMP-CNTs膜保留了CNTs的三维网络结构和CMPs的分级多孔结构,在高效吸附颗粒物(PM)和分离二氧化碳/氮气(CO_(2)/N_(2))的同时显著降低了渗透阻力.在酸碱环境中,CMP-CNTs对PM3.0的拦截效率超过99.9%.孔隙性质测试结果表明,CMP-CNTs具有与气体分子动力学直径相似的尺寸特征和由氮和氧杂原子引起的极性诱导环境,因此具有优异的CO_(2)/N_(2)分离能力.CMP-CNTs对CO_(2)/N_(2)混合组分的选择性高达119[273 K,1.0 bar(1 bar=0.1 MPa)].本文将CMPs同轴共价接枝在CNTs表面形成核壳结构的混合基质膜,这种将多孔聚合物和柔性基底优势互补的加工方法表现出设计灵活性和工艺普适性.Mixed matrix membranes(MMMs)are extensively utilized to enhance adsorption and separation performance by integrating the advantageous properties of polymers with organic and inorganic fillers.Conjugated microporous polymers(CMPs),characterized by their hierarchical porous structure and abundant heteroatom adsorption sites,demonstrate efficient and stable gas adsorption and separation capabilities in complex environments.Herein,we constructed a CMPs membrane supported by a carbon nanotubes(CNTs)network,utilizing three-dimensional network structured CNTs as a flexible substrate and CMPs with hierarchical porous structures and abundant heteroatom adsorption sites as the adsorptive active layer,aiming to address the challenge of self-membrane formation in porous polymers during the preparation process.The fabricated CMP-CNTs membrane retains the threedimensional reticulated structure of CNTs and the hierarchical porous structure of CMPs,ensuring efficient adsorption and separation of particulate matter(PM)and carbon dioxide/nitrogen(CO_(2)/N_(2))while significantly reducing permeation resistance.In acidic and alkaline environments,the interception efficiency of CMP-CNTs for PM3.0 exceeds 99.9%.The pore property characterization indicate that CMP-CNTs have dimensional characteristics similar to the molecular dynamic diameter of gases and a polar-induced environment caused by nitrogen and oxygen heteroatoms,giving them excellent CO_(2)/N_(2)separation capacity.The selectivity of CMP-CNTs for the CO_(2)/N_(2)mixture reaches an impressive value of 119 at 273 K and 1.0 bar(1 bar=0.1 MPa).This study proposes an MMM formed by coaxially covalently grafting CMPs onto the surface of CNTs to create a core-shell structure,thus demonstrating a processing approach that leverages the complementary advantages of porous polymers and flexible substrates,showcasing design flexibility and process universality.

关 键 词：混合基质膜 同轴共价接枝 核壳结构 酸碱耐受性 颗粒物/CO_(2)同步捕集 

分 类 号：O631[理学—高分子化学]