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ZIF-67@PDA/含氟聚酰亚胺混合基质膜的制备及其气体分离性能

李金岭 赖石清 刘婵娟 吴伟莲 倪靖 黄孝华 周立

李金岭, 赖石清, 刘婵娟, 等. ZIF-67@PDA/含氟聚酰亚胺混合基质膜的制备及其气体分离性能[J]. 复合材料学报, 2022, 40(0): 1-9
引用本文: 李金岭, 赖石清, 刘婵娟, 等. ZIF-67@PDA/含氟聚酰亚胺混合基质膜的制备及其气体分离性能[J]. 复合材料学报, 2022, 40(0): 1-9
Jinling LI, Shiqing LAI, Chanjuan LIU, Weilian WU, Jing NI, Xiaohua HUANG, Li ZHOU. Preparation of ZIF-67@PDA/fluorine-containing polyimide mixed matrix membrane and gas separation performance[J]. Acta Materiae Compositae Sinica.
Citation: Jinling LI, Shiqing LAI, Chanjuan LIU, Weilian WU, Jing NI, Xiaohua HUANG, Li ZHOU. Preparation of ZIF-67@PDA/fluorine-containing polyimide mixed matrix membrane and gas separation performance[J]. Acta Materiae Compositae Sinica.

ZIF-67@PDA/含氟聚酰亚胺混合基质膜的制备及其气体分离性能

基金项目: 国家自然科学基金资助项目(51963007,52003064),广西自然科学基金资助项目(2020 GXNSFAA159006,2021 GXNSFAA075016)和桂林市科学研究与技术开发计划(2020010906)
详细信息
    通讯作者:

    黄孝华,教授,研究方向为聚合物基复合材料 E-mail:huangxiaohua@glut.edu.cn

  • 中图分类号: TB332

Preparation of ZIF-67@PDA/fluorine-containing polyimide mixed matrix membrane and gas separation performance

  • 摘要: 金属有机框架材料(MOF)/聚合物混合基质膜(MMMs)通过结合MOF的分子筛效应和聚合物基质成本较低、加工性能好、机械强度高的特征,使其在气体分离领域展现出巨大的应用前景。然而由于MOF在聚合物基体中存在分散性差问题,极大地限制了其应用。采用溶剂热法合成金属框架材料ZIF-67,并通过溶液氧化法在ZIF-67表面修饰聚多巴胺(PDA)层制备ZIF-67@PDA纳米多孔材料。以(ODA-6FDA)型含氟聚酰亚胺(FPI)为基体,ZIF-67和ZIF-67@PDA为填料,制备不同质量分数的ZIF-67/FPI和ZIF-67@PDA/FPI。通过FT-IR、WAXD、TGA、SEM、比表面和孔径分布分析仪、气体渗透仪等测试对MMMs的结构和性能进行表征并测试了N2、O2、CO2、He四种气体的渗透性。结果表明,经聚多巴胺修饰后的纳米微孔材料ZIF-67在聚合物基体中的能均匀分散并为气体分子的通过提供快速通道,且表现出良好的热稳定性。ZIF-67@PDA对CO2具有良好的亲和性,这有利于提高CO2/N2选择性。当ZIF-67@PDA负载量为10%时,MMMs的CO2渗透性和CO2/N2选择性协同增加,和纯FPI膜相比分别增加了131%、50%,MMMs表现出良好的气体分离性能。

     

  • 图  1  ZIF-67(a)和ZIF-67@聚多巴胺(PDA) (b)的SEM图像

    Figure  1.  SEM images of ZIF-67 (a) and ZIF-67@ polydopamine (PDA) (b)

    图  2  ZIF-67和ZIF-67@PDA N2吸脱附等温曲线

    Figure  2.  N2 adsorption-desorption isotherms of ZIF-67 and ZIF-67@PDA

    图  3  ZIF-67和ZIF-67@PDA的WAXD曲线

    Figure  3.  XRD curves of ZIF-67 and ZIF-67@PDA

    图  4  PDA、ZIF-67和ZIF-67@PDA的FT-IR曲线

    Figure  4.  FT-IR curves of PDA、ZIF-67 and ZIF-67@PDA

    图  5  ZIF-67和ZIF-67@PDA的热重曲线

    Figure  5.  TGA curves of ZIF-67 and ZIF-67@PDA

    图  6  含氟聚酰亚胺(FPI),ZIF-67/FPI 和 ZIF-67@PDA/FPI混合基质膜的WAXD谱图

    Figure  6.  WAXD curves of fluorinated polyimide (FPI),ZIF-67/FPI and ZIF-67@PDA/FPI composite film

    图  7  FPI,ZIF-67(10)/FPI和ZIF-67@PDA (10)/FPI的热重及微商热重曲线

    Figure  7.  TGA and DTG curves of FPI, ZIF-67(10)/FPI and ZIF-67@PDA(10)/FPI

    图  8  FPI及其混合基质膜的DSC曲线

    Figure  8.  DSC curves of FPI and composite film

    图  9  ZIF-67/FPI (a,b和c)和ZIF-67@PDA/FPI (d,e和f) SEM图像

    Figure  9.  SEM images of ZIF-67/FPI (a,b and c) and ZIF-67@PDA/FPI (d,e and f)

    图  10  FPI及其混合基质膜在35℃和4 bar下的气体渗透性和选择性:(a)(c)ZIF-67/FPI 混合基质膜;(b)(d) ZIF-67@PDA/FPI

    Figure  10.  Gas permeability and selectivity for FPI and its composite film at 35℃ and 4 bar: (a)(c) ZIF-67/FPI composite film; (b)(d) ZIF-67@PDA/FPI composite film

    表  1  FPI,ZIF-67/FPI和ZIF-67@PDA/FPI的热性能

    Table  1.   Thermal performance of FPI, ZIF-67/FPI and ZIF-67@PDA/FPI

    SampleT10%/℃Vmax/(%·℃−1)Residual mass/%
    FPI514.20.3446.53
    ZIF-67(10)/FPI440.40.3441.04
    ZIF-67@PDA(10)/FPI378.30.3137.35
    Notes: T10%—Onset decomposition temperature at 10% mass loss recorded by TGA at a heating rate of 10℃/min in N2. Vmax—Maximum decomposition rate.
    下载: 导出CSV

    表  2  FPI、ZIF-67/FPI和ZIF67@PDA/FPI复合膜的气体分离数据

    Table  2.   FPI、ZIF-67/FPI和ZIF67@PDA/FPI composite membranes for gas separation

    SamplePermeability/BarrersIdeal Selectivity
    N2O2CO2HeCO2/N2He/N2
    FPI0.843.6012.138.014.545.2
    ZIF-67(5)/FPI1.315.5024.665.218.949.7
    ZIF-67(10)/FPI1.806.5029.1869.717.1641.0
    ZIF-67(15)/FPI3.208.8640.088.012.527.5
    ZIF-67@PDA(5)/FPI1.034.0023.854.623.153.0
    ZIF-67@PDA(10)/FPI1.295.8028.065.021.754.0
    ZIF-67@PDA(15)/FPI1.796.6034.669.020.638.5
    Note: 1 Barrer=1×10−10cm3·cm·cm−2·s−1·cmHg−1
    下载: 导出CSV

    表  3  将这项工作中获得的气体分离性能与报告的MMMs进行比较

    Table  3.   Comparison of gas separation performance achieved in this work with those of reported MMMs

    Membrane typesPCO2α(CO2/N2)Testing conditionsRef.
    SO3H-MCM-41/SPEEK21.022.925℃, 10 Barrer[31]
    ZIF-8/PI27.913.625℃, 4 Barrer[32]
    LDH/MPI24.212.125℃, 1 Barrer[33]
    Cu3(BTC)2/MPI27.219.025℃, 1 Barrer33
    ZIF-67(10)/FPI29.217.235℃, 4 BarrerThis work
    ZIF-67@PDA(10)/FPI28.021.735℃, 4 BarrerThis work
    Note: 1 Barrer=1×10−10cm3·cm·cm−2·s−1·cmHg−1; PCO2—Gas permeability coefficient of carbon dioxide; α(CO2/N2)—Gas selectivity of CO2/N2.
    下载: 导出CSV
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  • 收稿日期:  2022-01-13
  • 录用日期:  2022-03-26
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  • 网络出版日期:  2022-04-18

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