Volume 40 Issue 2
Feb.  2023
Turn off MathJax
Article Contents
LI Jinling, LAI Shiqing, LIU Chanjuan, et al. Preparation of ZIF-67@PDA/fluorine-containing polyimide mixed matrix membrane and gas separation performance[J]. Acta Materiae Compositae Sinica, 2023, 40(2): 950-958. doi: 10.13801/j.cnki.fhclxb.20220406.001
Citation: LI Jinling, LAI Shiqing, LIU Chanjuan, et al. Preparation of ZIF-67@PDA/fluorine-containing polyimide mixed matrix membrane and gas separation performance[J]. Acta Materiae Compositae Sinica, 2023, 40(2): 950-958. doi: 10.13801/j.cnki.fhclxb.20220406.001

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

doi: 10.13801/j.cnki.fhclxb.20220406.001
Funds:  Natural Science Foundation of China (51963007; 52003064); Natural Science Foundation of Guangxi (2020 GXNSFAA159006; 2021 GXNSFAA075016); Project of Department of Science and Technology of Guilin (2020010906)
  • Received Date: 2022-01-13
  • Accepted Date: 2022-03-26
  • Rev Recd Date: 2022-03-14
  • Available Online: 2022-04-07
  • Publish Date: 2023-02-15
  • Metal-organic framework (MOF)/polymer mixed matrix membranes (MMMs) have shown great promising application in gas separation fields by combining the features of MOF with molecular sieving effect and polymer matrix with lower cost, better processing properties, and high mechanical strength. However, their applications are greatly limited due to MOF poor dispersity in polymer matrix. The metal frame material ZIF-67 was synthesized by solvothermal method, and the polydopamine (PDA) layer was modified on the surface of ZIF-67 by solution oxidation to prepare ZIF-67@PDA nano-porous materials. The ZIF-67/FPI composite membrane and ZIF-67@PDA/FPI composite membrane with different mass fraction were prepared by using 4, 4'-oxydianiline-2, 2'-(hexafluoroisopropylidene)diphthalic anhydride (ODA-6FDA) fluorinated polyimide (FPI) as matrix and ZIF-67 and ZIF-67@PDA as fillers. The structure and properties of MMMs were characterized by FTIR, WAXD, TGA, SEM, specific surface and pore size distribution analyzer, gas permeant, and the permeability of four gases including N2, O2, CO2, and He was tested. The results show that the nanomicro porous material ZIF-67 modified with polydopamine can disperse uniformly in the polymer matrix and provides fast channels for the passage of gas molecules, and exhibits good thermal stability. ZIF-67@PDA has a good affinity for CO2, which is beneficial to improve the CO2/N2 selectivity. When the ZIF-67@PDA loading is 10wt%, the CO2 permeability and CO2/N2 selectivity of MMMs increases by 131% and 50% respectively compared with pure FPI membrane, and MMMs show good gas separation performance.


  • loading
  • [1]
    崔晓萍, 朱光明, 刘文元. 纳米Al2O3/聚酰亚胺复合薄膜的介电与力学性能[J]. 复合材料学报, 2016, 33(11):2419-2425.

    CUI Xiaoping, ZHU Guangming, LIU Wenyuan. Dielectric and mechanical properties of nano Al2O3/polyimide composite film[J]. Acta Materiae Compositae Sinica,2016,33(11):2419-2425(in Chinese).
    ROBESON L M. The upper bound revisited[J]. Journal of Membrane Science,2008,320(1-2):390-400. doi: 10.1016/j.memsci.2008.04.030
    牛红超. 新型含氟聚酰亚胺的合成及其气体分离性能研究[D]. 桂林: 桂林理工大学, 2020.

    NIU Hongchao. Synthesis of novel fluoropolyimide and its gas separation performance[D]. Guilin: Guilin University of Technology, 2020(in Chinese).
    薛佳佳. 原位制备MOFs/PI混合基质膜及其气体分离性能研究[D]. 大连: 大连理工大学, 2020.

    XUE Jiajia. Study on in situ preparation of MOFs/PI hybrid matrix membranes and their gas separation performance[D]. Dalian: Dalian University of Technology, 2020(in Chinese).
    王天琦, 肖国勇, 鲁云华, 等. 镧系金属有机骨架/聚酰亚胺复合材料的制备及其性能[J]. 复合材料学报, 2018, 35(11):2927-2934.

    WANG Tianqi, XIAO Guoyong, LU Yunhua, et al. Preparation and properties of lanthanide metal organic skeleton/polyimide composites[J]. Acta Materiae Compositae Sinica,2018,35(11):2927-2934(in Chinese).
    YANG Q P, LI L J, TAN W Q, et al. Exceptional high selectivity of hydrogen/methane separation on a phosphonate-based MOF membrane with exclusion of methane molecules[J]. Chemical Communications,2017,53(70):9797-9800. doi: 10.1039/C7CC05486F
    KRAUSE S, BON V, SENKOVSKA I, et al. A pressure-amplifying framework material with negative gas adsorption transitions[J]. Nature,2016,532(7599):348-352. doi: 10.1038/nature17430
    文桂林, 李莹, 张红星, 等. 离子液体/金属-有机骨架复合材料制备方法、理论计算及应用研究进展[J]. 复合材料学报, 2021, 38(2):298-314.

    WEN Guilin, LI Ying, ZHANG Hongxing, et al. Research progress on preparation method, theoretical calculation and application of ionic liquid/metal-organic skeleton composites[J]. Acta Materiae Compositae Sinica,2021,38(2):298-314(in Chinese).
    PENG Y, LI Y, BAN Y, et al. Two-dimensional metal-organic framework nano sheets for membrane-based gas separation[J]. Angewandte Chemie-International Edition,2017,56(33):9757-9761. doi: 10.1002/anie.201703959
    IU Z, CUI X, PHAM T, et al. A MOF-based ultra-strong acetylene nano-trap for highly efficient C2H2/CO2 separation[J]. Angewandte Chemie-International Edition,2021,133(10):5343-5348. doi: 10.1002/ange.202016225
    WANG Z B, KNEBEL A, GROSJEAN S, et al. Tunable molecular separation by nanoporous membranes[J]. Nature Communications,2016,7:13872. doi: 10.1038/ncomms13872
    LI L, LIN R B, KRISHNA R, et al. Flexible-robust metal-organic framework for efficient removal of propyne from propylene[J]. Journal of the American Chemical Society,2017,139(23):7733-7736. doi: 10.1021/jacs.7b04268
    TAN L L, ZHU Y, LONG H, et al. Pillar [n] arene-based supramolecular organic frameworks with high hydrocarbon storage and selectivity[J]. Chemical Communications,2017,53(48):6409-6412. doi: 10.1039/C7CC03638H
    LIN R J, GE L, HOU L, et al. Mixed matrix membranes with strengthened MOFs/polymer interfacial interaction and improved membrane performance[J]. ACS Applied Materials & Interfaces,2014,6(8):5609-5618.
    RODENAS T, LUZ I, PRIETO G, et al. Metal-organic framework nano sheets in polymer composite materials for gas separation[J]. Nature Materials,2015,14(1):48-55. doi: 10.1038/nmat4113
    王钰淇. 多孔材料改性聚二甲基硅氧烷/聚醚酰亚胺复合膜用于气体分离的研究[D]. 北京: 北京化工大学, 2015.

    WANG Yuqi. Study on the use of polydimethylsiloxane/polyetherimide composite membrane for gas separation with porous materials[D]. Beijing: Beijing University of Chemical Technology, 2015(in Chinese).
    BARANKOVA E, TAN X, VILLALOBOS L F, et al. A metal chelating porous polymeric support: The missing link for a defect-free metal-organic framework composite membrane[J]. Angewandte Chemie-International Edition,2017,56(11):2965-2968. doi: 10.1002/anie.201611927
    廉玉姣, 王永洪, 张新儒, 等. N2优先渗透ZIF-8复合膜的制备及其CO2捕集[J]. 化工学报, 2019, 70(9):3573-3581.

    LIAN Yujiao, WANG Yonghong, ZHANG Xinru, et al. Preparation of N2-priority permeation ZIF-8 composite membrane and its CO2 capture[J]. CIESC Journal,2019,70(9):3573-3581(in Chinese).
    BACHMAN J E, SMITH Z P, LI T, et al. Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal-organic framework nanocrystals[J]. Nature Materials,2016,15(8):845-849. doi: 10.1038/nmat4621
    FENG X, CARREON M A. Kinetics of transformation on ZIF-67 crystals[J]. Journal of Crystal Growth,2015,418:158-162. doi: 10.1016/j.jcrysgro.2015.02.064
    MRIDUSMITA B, BISHNUPADA M. Synthesis, characterization and CO2 separation performance of novel PVA/PG/ZIF-8 mixed matrix membrane[J]. Journal of Membrane Science,2019,572:198-209. doi: 10.1016/j.memsci.2018.11.001
    MESHKAT S, KALIAGUINE S, RODRIGUE D. Comparison between ZIF-67 and ZIF-8 in Pebax® MH-1657 mixed matrix membranes for CO2 separation[J]. Separation and Purification Technology,2020,235:116150. doi: 10.1016/j.seppur.2019.116150
    YANG Y W, DENG F, ZAN J, et al. Core-shell-structured ZIF-8@PDA-HA with controllable zinc ion release and superior bioactivity for improving a poly-L-lactic acid scaffold[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(4): 1814-1825.
    YING C T, HUA C Z. Self-templating synthesis of hollow spheres of MOFs and their derived nanostructures[J]. Chemical Communications,2016,52(77):11591-11594. doi: 10.1039/C6CC05699G
    SALIBA D, AMMAR M, RAMMAL M, et al. Crystal growth of ZIF-8, ZIF-67, and their mixed-metal derivatives[J]. Jour-nal of the American Chemical Society,2018,140(5):1812-1823. doi: 10.1021/jacs.7b11589
    CHEN M, DONG L, WU X, et al. Multi-functional polydopamine coating: Simultaneous enhancement of interfacial adhesion and CO2 separation performance of mixed matrix membranes[J]. New Journal of Chemistry,2016,40(11):9148-9159. doi: 10.1039/C6NJ02013E
    ANJUM M W, VERTRLE F, KHAN A L, et al. Modulated UiO-66-based mixed-matrix membranes for CO2 separation[J]. ACS Applied Materials & Interfaces,2015,7(45):25193-25201.
    SHIN J E, LEE S K, CHO Y H, et al. Effect of PEG-MEA and graphene oxide additives on the performance of Pebax®1657 mixed matrix membranes for CO2 separation[J]. Journal of Membrane Science,2019,572:300-308. doi: 10.1016/j.memsci.2018.11.025
    XING Y W, WEI L, HONG W, et al. Nanoporous ZIF-67 embedded polymers of intrinsic microporosity membranes with enhanced gas separation performance[J]. Journal of Membrane Science,2018,548:309-318. doi: 10.1016/j.memsci.2017.11.038
    WANG Z, WANG D, ZHANG S, et al. Interfacial design of mixed matrix membranes for improved gas separation performance[J]. Advanced Materials,2016,28(17):3399-3405. doi: 10.1002/adma.201504982
    KHAN A L, KLAYSAM C, GAHLAUT A, et al. SPEEK and functionalized mesoporous MCM-41 mixed matrix membranes for CO2 separations[J]. Journal of Materials Che-mistry,2012,22:20057-20064. doi: 10.1039/c2jm34885c
    朱娜娜, 李越, 高会元. PI/ZIF-8杂化膜的制备及CO2/N2分离性能研究[J]. 功能材料, 2016, 47(4):4099-4104. doi: 10.3969/j.issn.1001-9731.2016.04.020

    ZHU Nana, LI Yue, GAO Huiyuan. Preparation of PI/ZIF-8 hybrid membrane and separation performance of CO2/N2[J]. Functional Materials,2016,47(4):4099-4104(in Chinese). doi: 10.3969/j.issn.1001-9731.2016.04.020
    龚金华, 王臣辉, 卞子君, 等. 多孔材料表面修饰聚酰亚胺非对称混合基质膜对CO2/N2和CO2/CH4的气体分离[J]. 物理化学学报, 2015, 31(10):1963-1970. doi: 10.3866/PKU.WHXB201508282

    GONG Jinhua, WANG Chenhui, BIAN Zijun, et al. Gas separation of CO2/N2 and CO2/CH4 by polyimide asymmetric mixed matrix membrane modified on porous material surface[J]. Journal of Physical Chemistry,2015,31(10):1963-1970(in Chinese). doi: 10.3866/PKU.WHXB201508282
  • 加载中


    通讯作者: 陈斌, bchen63@163.com
    • 1. 

      沈阳化工大学材料科学与工程学院 沈阳 110142

    1. 本站搜索
    2. 百度学术搜索
    3. 万方数据库搜索
    4. CNKI搜索

    Figures(10)  / Tables(4)

    Article Metrics

    Article views (1609) PDF downloads(69) Cited by()
    Proportional views


    DownLoad:  Full-Size Img  PowerPoint