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中空纳米纤维内部生长MOFs的柔性复合膜的制备与表征

郑凯 周全 杨帆 任瑞鹏 吕永康

郑凯, 周全, 杨帆, 等. 中空纳米纤维内部生长MOFs的柔性复合膜的制备与表征[J]. 复合材料学报, 2024, 42(0): 1-11.
引用本文: 郑凯, 周全, 杨帆, 等. 中空纳米纤维内部生长MOFs的柔性复合膜的制备与表征[J]. 复合材料学报, 2024, 42(0): 1-11.
ZHENG Kai, ZHOU Quan, YAN Fan, et al. Preparation and characterization of flexible composite membranes with MOFs grown inside hollow nanofiber[J]. Acta Materiae Compositae Sinica.
Citation: ZHENG Kai, ZHOU Quan, YAN Fan, et al. Preparation and characterization of flexible composite membranes with MOFs grown inside hollow nanofiber[J]. Acta Materiae Compositae Sinica.

中空纳米纤维内部生长MOFs的柔性复合膜的制备与表征

基金项目: 国家自然科学基金 (No. 21707098)
详细信息
    通讯作者:

    周 全,博士,讲师,硕士生导师,研究方向为环境功能材料和纳米复合材料 E-mail: zhouquan@tyut.edu.cn

  • 中图分类号: TQ340.64; TQ342; TB332

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

Funds: National Natural Science Foundation of China (No. 21707098)
  • 摘要: 基于金属有机框架 (Metal organic frameworks, 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 (Polyvinylidene fluoride, PVDF) 的高分子溶液中添加有机配体2-甲基咪唑 (2-Methylimidazole, 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 (Hollow nanofibers, 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物质的量比为1∶40,65℃水热生长4 h。采用XRD、SEM、FT-IR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3.351%,ZIF-8@HNFs复合材料的比表面积为38.189 m2/g、孔体积为0.204 cm3/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。

     

  • 图  1  ZIF-8@中空纳米纤维(HNFs)复合膜的制备流程图

    Figure  1.  Flow chart of preparation of ZIF-8@Hollow nanofibers(HNFs) composite membranes

    图  2  ZIF-8粉末、HNFs和ZIF-8@HNFs复合膜的XRD图谱

    Figure  2.  XRD patterns of ZIF-8 powder, HNFs and ZIF-8@HNFs composite membranes

    图  3  锌离子与2-甲基咪唑的摩尔比分别为1∶10、1∶20和1∶40时制备的ZIF-8@HNFs复合膜的XRD图谱

    Figure  3.  XRD patterns of ZIF-8@HNFs composite membranes synthesized by adding different molar ratios of zinc ions and 2-methylimidazole: 1∶10, 1∶20 and 1∶40

    图  4  水热反应温度分别为45℃、65℃和85℃时生长4 h制备的ZIF-8@HNFs复合膜的XRD图谱

    Figure  4.  XRD patterns of ZIF-8@HNFs composite membranes synthesized by different hydrothermal growth temperature at 45℃, 65℃ and85℃ for 4 h

    图  5  水热反应时间分别为2 h、4 h、8 h和12 h时在65℃制备的ZIF-8@HNFs复合膜的XRD图谱

    Figure  5.  XRD patterns of ZIF-8@HNFs composite membranes synthesized by different hydrothermal growth time for 2 h, 4 h, 8 h and 12 h at 65℃

    图  6  不同制备条件下ZIF-8@HNFs复合膜的SEM图

    Figure  6.  SEM images of ZIF-8@HNFs composite nanofiber membranes under different preparation conditions

    图  7  ZIF-8@HNFs复合膜的EDS能谱图 (氟、碳、锌和氮):(a) 大范围的纳米纤维膜;(b) 放大的单根纳米纤维

    Figure  7.  EDS maps of ZIF-8@HNFs composite membranes (F, C, Zn and N): (a) wide scale elemental mapping of nanofiber membranes; (b) enlarged elemental mapping of single nanofiber

    图  8  锌离子与2-甲基咪唑的摩尔比为1∶10、1∶20和1∶40时制备的ZIF-8@HNFs复合膜的FT-IR图

    Figure  8.  FT-IR spectra of ZIF-8@HNFs composite membranes synthesized by adding different molar ratios of zinc ions and 2-methylimidazole: 1∶10, 1∶20 and 1∶40

    图  9  ZIF-8粉末(a)和ZIF-8@HNFs复合膜(b)的水接触角照片

    Figure  9.  Water contact angle photos of ZIF-8 powder (a) and ZIF-8@HNFs composite membranes (b)

    图  10  ZIF-8粉末、HNFs和ZIF-8@HNFs复合膜的TGA 曲线

    Figure  10.  Thermogravimetry curves of ZIF-8 powder, HNFs and ZIF-8@HNFs composite membrane

    图  11  不同温度处理后ZIF-8@HNFs复合膜的XRD图谱

    Figure  11.  XRD patterns of ZIF-8@HNFs composite membranes treated by different temperature

    图  12  ZIF-8粉末、HNFs和ZIF-8@HNFs复合膜的N2吸附-脱附曲线(a)和孔径分布(b)

    Figure  12.  N2 adsorption-desorption curves (a) and pore size distribution (b) of ZIF-8 powder, HNFs and ZIF-8@HNFs composite membranes

    图  13  ZIF-8@HNFs复合膜:(a)尺寸和(b)质量;柔性测试:(c)对折、(d)弯曲和(e)缠绕

    Figure  13.  ZIF-8@HNFs composite membranes: (a) Size and (b) Mass; Flexibility testing: (c) Folding, (d) Bending and (e) Wrapping

    图  14  ZIF-8@HNFs复合膜经过水、酸性环境和碱性环境洗涤4 h后的XRD图谱

    Figure  14.  XRD patterns of ZIF-8@HNFs composite membranes after washing 4 h in water, acidic and alkaline conditions

    表  1  ZIF-8粉末、HNFs和ZIF-8@HNFs复合膜的吸附性能数据

    Table  1.   Adsorption performance of ZIF-8 powder, HNFs and ZIF-8@HNFs composite membranes

    Sample SBET/(m2·g−1) Pore Volume/(cm3·g−1) Pore size/nm
    ZIF-8@HNFs 38.189 0.204 4.678, 7.573
    HNFs 32.708 0.169 4.678, 7.838
    ZIF-8 484.327 0.273 0.926
    Notes: SBET is the specific surface area calculated by the Brunner-Emmet-Teller (BET) method.
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  • 收稿日期:  2024-03-26
  • 修回日期:  2024-04-24
  • 录用日期:  2024-04-27
  • 网络出版日期:  2024-05-29

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