中空纳米纤维内部生长金属有机框架柔性复合膜的制备与表征  

Preparation and characterization of flexible composite membranes with MOFs grown inside hollow nanofiber

作　　者：郑凯[1] 周全 杨帆[1] 任瑞鹏[1] 吕永康[1] ZHENG Kai;ZHOU Quan;YANG Fan;REN Ruipeng;LYU Yongkang(State Key Laboratory of Clean and Efficient Coal Utilization,College of Chemistry and Chemical Engineering,Taiyuan University of Technology,Taiyuan 030024,China)

机构地区：[1]太原理工大学化学与化工学院省部共建煤基能源清洁高效利用国家重点实验室,太原030024

出　　处：《复合材料学报》2025年第3期1622-1632,共11页Acta Materiae Compositae Sinica

基　　金：国家自然科学基金(21707098)。

摘　　要：基于金属有机框架(MOFs)的柔性复合膜材料在气体分离、污染物吸附、药物可控释放等领域具有重要的作用。利用同轴静电纺丝技术,在聚偏氟乙烯(PVDF)的高分子溶液中添加有机配体2-甲基咪唑(2-mI)作为外壳纺丝液,在甘油中添加锌离子作为内芯纺丝液,制备得到的核壳结构纳米纤维进行水热反应。在内芯甘油溶解形成中空结构的同时,锌离子向外扩散接触到外壳高分子层内表面的有机配体,在中空纳米纤维(HNFs)内部原位生成了MOF晶体ZIF-8,得到了ZIF-8@HNFs柔性复合膜材料。同时研究了金属盐与有机配体的不同比例、水热生长时间和温度对中空纳米纤维内部生长ZIF-8的影响。最佳金属盐与有机配体的摩尔比为1∶40,65℃水热生长4 h。采用XRD、SEM、FTIR、TGA和氮气吸附-脱附实验等对ZIF-8@HNFs柔性复合膜的结构和性能进行了表征。结果表明:ZIF-8原位生长在中空纳米纤维内部,负载量为3.351wt%,ZIF-8@HNFs复合材料的比表面积为38.189 m^(2)/g、孔体积为0.204 cm^(3)/g、孔径分布在4.678 nm和7.573 nm,并且可以耐受200℃高温、多次弯折和纯水、碱液的浸泡4 h依旧保持结构的稳定性。而ZIF-8本身在酸性条件下会发生解离的特性,使得ZIF-8@HNFs柔性复合膜材料在污染物吸附-解吸、药物可控释放等领域具有潜在的应用价值。The flexible composite membranes materials based on metal organic frameworks(MOFs)play a significant role in many fields such as gas separation,pollutant removal and controlled drug release system.Utilizing coaxial electrospinning technology,the composite nanofibers of core-shell structure was prepared by mixing organic ligand 2-methylimidazole(2-mI)in polyvinylidene fluoride(PVDF)polymer solution as shell spinning solution,and adding zinc ion to glycerol as core spinning solution.With hydrothermal synthesis,the glycerol in the core layer dissolves to form a hollow structure,while the zinc ion diffuses outward and contacts the organic ligands on the inner surface of the polymer shell layer at the same time.The in-situ growth of ZIF-8 MOF crystals inside PVDF hollow nanofibers(HNFs)were obtained as the ZIF-8@HNFs flexible composite membrane material.The effect of different metal salt and ligand proportions,different hydrothermal growth time and temperature on the formation of ZIF-8 in HNFs were studied.The molar ratio of zinc ion and 2-mI ligand was 1∶40,and the hydrothermal growth condition was at 65℃for 4 h with water as solvent,which proved to be the optimal preparation circumstance.The structure and performance of ZIF-8@HNFs were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),Fourier transform infrared spectroscopy(FTIR),thermogravimetry analysis(TGA)and the nitrogen adsorption-desorption test,etc.The results indicated that the ZIF-8 crystals were in-situ synthesized and loaded inside the PVDF HNFs with 3.351%content.The Brunner-Emmet-Teller measurements(BET)surface area was 38.189 m^(2)/g,the pore volume was 0.204 cm^(3)/g and the pore size distribution were at 4.678 nm and 7.573 nm.Furthermore,the ZIF-8@HNFs still maintains its structural stability after being treated with 200℃high temperature,multiple bending and soaking with water or alkali solution for 4 h.The characteristic of ZIF-8 that itself can dissociate under acidic conditions,which makes the ZIF-8@HNFs flexible com

关 键 词：同轴静电纺丝 中空纳米纤维 金属有机框架 ZIF-8 原位生长 

分 类 号：TQ340.64[化学工程—化纤工业] TQ342[一般工业技术—材料科学与工程] TB332