表面修饰在MOF薄膜制备中的应用

doi:10.16085/j.issn.1000-6613.2017.04.021

摘要/Abstract

摘要： 综述了近几年表面修饰手段在金属-有机骨架（MOF）薄膜制备中的应用研究进展。MOF材料由于具有结构可设计、孔道尺寸可调且可功能化等特点，在气体分离膜领域具有极大的应用价值。制备连续致密MOF膜的关键是解决MOF与基底之间的界面结合问题。表面修饰可改善基底表面的物理化学性质，增强MOF与基底之间的相互作用力。本文从有机分子修饰、无机化合物修饰和MOF晶种修饰三方面入手，介绍修饰手段在MOF薄膜制备中的应用研究进展。其中，着重阐述了不同修饰手段的修饰机理，分析了修饰手段对MOF薄膜的制备及其气体分离性能的影响。研究表明，MOF的种类繁多且成膜过程复杂，有时单一的修饰手段无法制备高质量的MOF薄膜。因此，文中指出根据MOF和基底的性质，选择不同的修饰手段结合使用将是MOF薄膜制备的一个重要发展方向。

关键词: 金属-有机骨架, 膜, 制备, 表面修饰, 气体分离

Abstract: This review summarizes the recent research progress of surface modification methods for the preparation of metal-organic framework(MOF) thin films. MOF,featured by designable structures,tunable pore sizes and functions and so on,is considered as attractive membrane material for gas separation. Forming interfacial interaction between the MOF crystals and substrates is the key to fabricate a continuous and compact MOF film. Surface modifications can improve the physical/chemical properties of the substrates and enhance the interaction force between MOF crystals and substrates. In this review,three main surface modification methods for the preparation of MOF thin films are highlighted,including organic molecular modification,inorganic compound modification,and MOF seed modification. Particularly,the modification mechanisms of different modification methods are emphasized,and the influences of the modification methods on the preparation and gas separation performance of MOF thin films are analyzed. Due to the diversity of MOF and complexity of the film formation,single modification can't always produce dense and uniform MOF membrane. Therefore,we propose that it will be an important development direction for the preparation of MOF films to combine different modification methods according to the properties of the MOF and the substrate.

Key words: metal-organic framework, film, preparation, surface modification, gas separation

中图分类号:

TQ016.1

秦茜, 孙玉绣, 王乃鑫, 谢亚勃, 李建荣. 表面修饰在MOF薄膜制备中的应用[J]. 化工进展, 2017, 36(04): 1306-1315.

QIN Xi, SUN Yuxiu, WANG Naixin, XIE Yabo, LI Jianrong. Surface modifications for preparation of MOF thin films[J]. Chemical Industry and Engineering Progress, 2017, 36(04): 1306-1315.

参考文献

[1] LI H L,EDDAOUDI M,O'KEEFFE M,et al. Design and synthesis of an exceptionally stable and highly porous metal-organic framework[J]. Nature,1999,402(6759):276-279.
[2] 侯丹丹,刘大欢,杨庆元,等. 金属-有机骨架材料在气体膜分离中的研究进展[J]. 化工进展,2015,34(8):2907-2915. HOU D D,LIU D H,YANG Q Y,et al. Progress of metal-organic framework-based membranes for gas separation[J]. Chem. Ind. Eng. Prog.,2015,34(8):2907-2915.
[3] 郭瑞梅,白金泉,张恒,等. 金属-有机骨架(MOFs)材料在催化氧化反应中的应用[J]. 化学进展,2016,28(2/3):232-243. GUO R M,BAI J Q,Z H,et al. Metal-organic frameworks for catalytic oxidation[J]. Prog. Chem.,2016,28(2/3):232-243.
[4] 周健,谢林华,豆义波,等. MOFs基材料在超级电容器中的应用[J]. 化工进展,2016,35(9):2830-2838. ZHOU J,XIE L H,DOU Y B,et al. MOFs-based materials for supercapacitor[J]. Chem. Ind. Eng. Prog.,2016,35(9):2830-2838.
[5] KESKIN S,KIZILEL S. Biomedical applications of metal organic frameworks[J]. Ind. Eng. Chem. Res.,2011,50(4):1799-1812.
[6] HERMES S,SCHRÖDER F,CHELMOWSKI R,et al. Selective nucleation and growth of metal-organic open framework thin films on patterned COOH/CF₃-terminated self-assembled monolayers on Au(111)[J]. J. Am. Chem. Soc.,2005,127(40):13744-13745.
[7] GASCON J,AGUADO S,KAPTEIJN F. Manufacture of dense coatings of Cu₃(BTC)₂(HKUST-1)on α-alumina[J]. Microporous Mesoporous Mater.,2008,113(1/2/3):132-138.
[8] YOO Y,JEONG H K. Rapid fabrication of metal organic framework thin films using microwave-induced thermal deposition[J]. Chem. Commun.,2008,21(1):2441-2443.
[9] LIU Y Y,NG Z,KHAN E A,et al. Synthesis of continuous MOF-5 membranes on porous α-alumina substrates[J]. Microporous Mesoporous Mater.,2009,118(1/2/3):296-301.
[10] SHAH M,MCCARTHY M C,SACHDEVA S,et al. Current status of metal-organic framework membranes for gas separations:promises and challenges[J]. Ind. Eng. Chem. Res.,2012,51(5):2179-2199.
[11] 董献堆,陆君涛,查全性. 巯基化合物自组装单分子层的研究进展[J]. 电化学,1995,1(3):248-258. DONG X D,LU J T,CHA Q X. Self-assembled monolayers:preparation,properties and application[J]. Electrochemistry,1995,1(3):248-258.
[12] BIEMMI E,SCHERB C,BEIN T. Oriented growth of the metal organic framework Cu₃(BTC)₂(H₂O)₃·xH₂O tunable with functionalized self-assembled monolayers[J]. J. Am. Chem. Soc.,2007,129(26):8054-8055.
[13] SCHERB C,SCHÖDEL A,BEIN T. Directing the structure of metal-organic frameworks by oriented surface growth on an organic monolayer[J]. Angew. Chem. Int. Ed.,2008,47(31):5777-5779.
[14] 沈玺,高雅男,徐政. 硅烷偶联剂的研究与应用[J]. 上海生物医学工程,2006,26(1):14-17. SHEN X,GAO Y N,XU Z. Research and application of silane coupling agents[J]. Shanghai J. Biomed. Eng.,2006,26(1):14-17.
[15] HUANG A S,DOU W,CARO J. Steam-stable zeolitic imidazolate framework ZIF-90 membrane with hydrogen selectivity through covalent functionalization[J]. J. Am. Chem. Soc.,2010,132(44):15562-15564.
[16] HUANG A S,CHEN Y F,WANG N Y,et al. A highly permeable and selective zeolitic imidazolate framework ZIF-95 membrane for H₂/CO₂ separation[J]. Chem. Commun.,2012,48(89):10981-10983.
[17] HOU J W,SUTRISNA P D,ZHANG Y T,et al. Formation of ultrathin,continuous metal-organic framework membranes on flexible polymer substrates[J]. Angew. Chem. Int. Ed.,2016,55(12):3947-3951.
[18] KIDA K,FUJITA K,SHIMADA T,et al. Layer-by-layer aqueous rapid synthesis of ZIF-8 films on a reactive surface[J]. Dalton Trans.,2013,42(31):11128-11135.
[19] TANAKA S,SHIMADA T,FUJITA K,et al. Seeding-free aqueous synthesis of zeolitic imidazolate framework-8 membranes:how to trigger preferential heterogeneous nucleation and membrane growth in aqueous rapid reaction solution[J]. J. Membr. Sci.,2014,472(1):29-38.
[20] LEE H,DELLATORE S M,MILLER W M,et al. Mussel-inspired surface chemistry for multifunctional coatings[J]. Science,2007,318(5849):426-430.
[21] LIU Q,WANG N Y,CARO J,et al. Bio-inspired polydopamine:a versatile and powerful platform for covalent synthesis of molecular sieve membranes[J]. J. Am. Chem. Soc.,2013,135(47):17679-17682.
[22] HUANG A S,LIU Q,WANG N Y,et al. Highly hydrogen permselective ZIF-8 membranes supported on polydopamine functionalized macroporous stainless-steel-nets[J]. J. Mater. Chem. A,2014,2(22):8246-8251.
[23] WANG N Y,LIU Y,QIAO Z W,et al. Polydopamine-based synthesis of a zeolite imidazolate framework ZIF-100 membrane with high H₂/CO₂ selectivity[J]. J. Mater. Chem. A,2015,3(8):4722-4728.
[24] BEN T,LU C J,PEI C Y,et al. Polymer-supported and free-standing metal-organic framework membrane[J]. Chem. Eur. J.,2012,18(33):10250-10253.
[25] LI W B,YANG Z H,ZHANG G L,et al. Stiff metal-organic framework-polyacrylonitrile hollow fiber composite membranes with high gas permeability[J]. J. Mater. Chem. A,2014,2(7):2110-2118.
[26] LI W B,MENG Q,ZHANG C Y,et al. Metal-organic framework/PVDF composite membranes with high H₂ permselectivity synthesized by ammoniation[J]. Chem. Eur. J.,2015,21(19):7224-7230.
[27] SHAMSAEI E,LOW Z X,LIN X C,et al. Rapid synthesis of ultrathin,defect-free ZIF-8 membranes via chemical vapour modification of a polymeric support[J]. Chem. Commun.,2015,51(57):11474-11477.
[28] GUO Y,MAO Y Y,HU P,et al. Self-confined synthesis of HKUST-1 membranes from CuO nanosheets at room temperature[J]. Chemistry Select,2016,1(1):108-113.
[29] ZHANG X F,LIU Y G,LI S H,et al. New membrane architecture with high performance:ZIF-8 membrane supported on vertically aligned ZnO nanorods for gas permeation and separation[J]. Chem. Mater.,2014,26(5):1975-1981.
[30] LI W B,MENG Q,LI X N,et al. Non-activation ZnO array as a buffering layer to fabricate strongly adhesive metal-organic framework/PVDF hollow fiber membranes[J]. Chem. Commun.,2014,50(68):9711-9713.
[31] SUN Y X,YANG F,WEI Q,et al. Oriented nano-microstructure-assisted controllable fabrication of metal-organic framework membranes on nickel foam[J]. Adv. Mater.,2016,28(12):2374-2381.
[32] EVANS D G,SLADE R C T. Structural aspects of layered double hydroxides[J]. Struct. Bond.,2006,119(1):1-87.
[33] LIU Y,WANG N Y,PAN J H,et al. In situ synthesis of MOF membranes on ZnAl-CO₃ LDH buffer layer-modified substrates[J]. J. Am. Chem. Soc.,2014,136(41):14353-14356.
[34] LIU Y,PAN J H,WANG N Y,et al. Remarkably enhanced gas separation by partial self-conversion of a laminated membrane to metal-organic frameworks[J]. Angew. Chem. Int. Ed.,2015,54(10):3028-3032.
[35] MAO Y Y,LI J W,CAO W,et al. Pressure-assisted synthesis of HKUST-1 thin film on polymer hollow fiber at room temperature toward gas separation[J]. ACS Appl. Mater. Interfaces,2014,6(6):4473-4479.
[36] MAO Y Y,LI J W,CAO W,et al. General incorporation of diverse components inside metal-organic framework thin films at room temperature[J]. Nat. Commun.,2014,5(1):5532-5540.
[37] LI J W,CAO W,MAO Y Y,et al. Zinc hydroxide nanostrands:unique precursors for synthesis of ZIF-8 thin membranes exhibiting high size-sieving ability for gas separation[J]. CrystEngComm,2014,16(42):9788-9791.
[38] VENNA S R,CARREON M A. Highly permeable zeolite imidazolate framework-8 membranes for CO₂/CH₄ separation[J]. J. Am. Chem. Soc.,2010,132(1):76-78.
[39] TAO K,KONG C L,CHEN L. High performance ZIF-8 molecular sieve membrane on hollow ceramic fiber via crystallizing-rubbing seed deposition[J]. Chem. Eng. J.,2013,220(1):1-5.
[40] GE L,ZHOU W,DU A J,et al. Porous polyethersulfone-supported zeolitic imidazolate framework membranes for hydrogen separation[J]. J. Phys. Chem. C,2012,116(24):13264-13270.
[41] PAN Y C,LI T,LESTARI G,et al. Effective separation of propylene/propane binary mixtures by ZIF-8 membranes[J]. J. Membr. Sci.,2012,390/391(1):93-98.
[42] LI Y S,LIANG F Y,BUX H,et al. Molecular sieve membrane:supported metal-organic framework with high hydrogen selectivity[J]. Angew. Chem. Int. Ed.,2010,49(3):548-551.
[43] GUERRERO V V,YOO Y,MCCARTHY M C,et al. HKUST-1 membranes on porous supports using secondary growth[J]. J. Mater. Chem.,2010,20(19):3938-3943.
[44] TAO K,CAO L J,LIN Y C,et al. A hollow ceramic fiber supported ZIF-8 membrane with enhanced gas separation performance prepared by hot dip-coating seeding[J]. J. Mater. Chem. A,2013,1(42):13046-13049.
[45] HU Y X,DONG X L,NAN J P,et al. Metal-organic framework membranes fabricated via reactive seeding[J]. Chem. Commun.,2011,47(2):737-739.
[46] NAN J P,DONG X L,WANG W J,et al. Formation mechanism of metal-organic framework membranes derived from reactive seeding approach[J]. Microporous Mesoporous Mater.,2012,155(1):90-98.
[47] HUANG K,LIU S N,LI Q Q,et al. Preparation of novel metal-carboxylate system MOF membrane for gas separation[J]. Sep. Purif. Technol.,2013,119(1):94-101.
[48] YOO Y,LAI Z P,JEONG H K. Fabrication of MOF-5 membranes using microwave-induced rapid seeding and solvothermal secondary growth[J]. Microporous Mesoporous Mater.,2009,123(1/2/3):100-106.
[49] KWON H T,JEONG H K. Highly propylene-selective supported zeolite-imidazolate framework(ZIF-8) membranes synthesized by rapid microwave-assisted seeding and secondary growth[J]. Chem. Commun.,2013,49(37):3854-3856.
[50] KWON H T,JEONG H K,LEE A S,et al. Heteroepitaxially grown zeolitic imidazolate framework membranes with unprecedented propylene/propane separation performances[J]. J. Am. Chem. Soc.,2015,137(38):12304-12311.