金属-有机骨架材料在气体膜分离中的研究进展

doi:10.16085/j.issn.1000-6613.2015.08.001

摘要/Abstract

摘要： 金属-有机骨架材料(metal-organic frameworks,MOF)由于具有高比表面积、大孔隙率、功能性孔道结构以及种类多样性等特征,在储气、分离、催化、载药和光学等领域受到重视。其中,制备纯MOF膜或基于MOF的混合基质膜(mixed matrix membranes,MMMs)并用于气体分离,被认为具有潜在的应用前景。目前为止,实验合成的MOF材料种类已有两万种,为了快速筛选出合适的MOF材料作为膜材料,计算化学的方法可以极大地缩减MOF膜的研究周期,并有助于指导实验合成高效膜分离材料。本文分别从计算和实验两方面介绍了MOF膜在气体分离中的研究进展,分析表明,MOF膜的研究总体上向功能性更强、稳定性更高的方向发展,但是利用计算方法建立MOF膜的构效关系还存在一定的难度。因此,建立MOF膜的结构与性能表征的新概念、新方法,并利用MOF膜的结构-性能关系指导实验合成高稳定性、低成本的膜材料将是未来MOF膜的发展方向。

关键词: 金属-有机骨架材料膜, 气体分离, 计算化学

Abstract: Metal-organic frameworks (MOF) have potential applications in gas storage, separation, catalysis, drug delivery and optical devices due to their large surface area and free volume, adjustable pore surface and various structures. Among them, gas separation using MOF membranes and MOF-based mixed-matrix membranes (MMM) is considered as one of the most promising applications. So far, a large number of MOF have been synthesized in experiment. Computational chemistry, as a complement to experimental study, provides a convenient approach to screen the MOF candidates in a large scale and shortens the design and research period. This paper reviewed recent research progress in computational and experimental works on MOF-based membranes, which are mainly focused on the development of membranes with more abundant functionality and higher stability. However, it is still a great challenge to build the structure-property relationship using the computational chemistry method. Therefore, more efforts should be made to develop new concepts and methods to estimate the structure and performance of MOF membranes, and then to design membrane materials with high stability and low cost in the future.

Key words: metal-organic framework membranes, gas separation, computational chemistry

中图分类号:

TQ013.1

侯丹丹, 刘大欢, 阳庆元, 仲崇立. 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(08): 2907-2915.

HOU Dandan, LIU Dahuan, YANG Qingyuan, ZHONG Chongli. Progress of metal-organic framework-based membranes for gas separation[J]. Chemical Industry and Engineering Progree, 2015, 34(08): 2907-2915.

参考文献

[1] Zornoza B, Tellez C, Coronas J, et al. Metal organic framework based mixed matrix membranes: An increasingly important field of research with a large application potential[J]. Microporous Mesoporous Mater., 2013, 166: 67-78.
[2] Robeson L M. Correlation of separation factor versus permeability for polymeric membranes[J]. J. Membr. Sci., 1991, 62(2): 165-185.
[3] Yaghi O M, O'Keeffe M, Ockwig N W, et al. Reticular synthesis and the design of new materials[J]. Nature, 2003, 423(6941): 705-714.
[4] Li J R, Sculley J, Zhou H C. Metal-organic frameworks for separations[J]. Chem. Rev., 2011, 112(2): 869-932.
[5] Zhang R, Ji S, Wang N, et al. Coordination-driven in situ self-assembly strategy for the preparation of metal-organic framework hybrid membranes[J]. Angew. Chem. Int. Ed., 2014, 53(37): 9775-9779.
[6] 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.
[7] 曹发. 金属-有机骨架材料膜的制备及其气体分离性能的研究[D]. 北京: 北京化工大学, 2012.
[8] 吴栋. 金属-有机骨架材料吸附分离和膜分离性能研究[D]. 北京: 北京化工大学, 2013.
[9] 阳庆元, 刘大欢, 仲崇立. 金属-有机骨架材料的计算化学研究[J]. 化工学报, 2009, 60(4): 805-819.
[10] Jeazet H B T, Staudt C, Janiak C. Metal-organic frameworks in mixed-matrix membranes for gas separation[J]. Dalton Trans., 2012, 41(46): 14003-14027.
[11] Keskin S, Sholl D S. Assessment of a metal-organic framework membrane for gas separations using atomically detailed calculations: CO₂, CH₄, N₂, H₂ mixtures in MOF-5[J]. Ind. Eng. Chem. Res., 2008, 48(2): 914-922.
[12] Keskin S, Liu J, Johnson J K, et al. Atomically detailed models of gas mixture diffusion through Cu-BTC membranes[J]. Microporous Mesoporous Mater., 2009, 125(1): 101-106.
[13] Atci E, Erucar I, Keskin S. Adsorption and transport of CH₄, CO₂, H₂ mixtures in a bio-MOF material from molecular simulations[J]. J. Phys. Chem. C, 2011, 115(14): 6833-6840.
[14] Liu J, Keskin S, Sholl D S, et al. Molecular simulations and theoretical predictions for adsorption and diffusion of CH₄/H₂ and CO₂/CH₄ mixtures in ZIFs[J]. J. Phys. Chem. C, 2011, 115(25): 12560-12566.
[15] Keskin S. Atomistic simulations for adsorption, diffusion, and separation of gas mixtures in zeolite imidazolate frameworks[J]. J. Phys. Chem. C, 2010, 115(3): 800-807.
[16] Watanabe T, Keskin S, Nair S, et al. Computational identification of a metal organic framework for high selectivity membrane-based CO₂/CH₄ separations: Cu(hfipbb)(H₂hfipbb)_0.5[J]. Phys. Chem. Chem. Phys., 2009, 11(48): 11389-11394.
[17] Atci E, Keskin S. Understanding the potential of zeolite imidazolate framework membranes in gas separations using atomically detailed calculations[J]. J. Phys. Chem. C, 2012, 116(29): 15525-15537.
[18] Keskin S. High CO₂ selectivity of a microporous metal-imidazolate framework: A molecular simulation study[J]. Ind. Eng. Chem. Res., 2011, 50(13): 8230-8236.
[19] Hertäg L, Bux H, Caro J, et al. Diffusion of CH₄ and H₂ in ZIF-8[J]. J. Membr. Sci., 2011, 377(1): 36-41.
[20] Krishna R, van Baten J M. In silico screening of metal-organic frameworks in separation applications[J]. Phys. Chem. Chem. Phys., 2011, 13(22): 10593-10616.
[21] Wu D, Maurin G, Yang Q, et al. Computational exploration of a Zr-carboxylate based metal-organic framework as a membrane material for CO₂ capture[J]. J. Mater. Chem. A, 2014, 2(6): 1657-1661.
[22] Ozturk T N, Keskin S. Computational screening of porous coordination networks for adsorption and membrane-based gas separations[J]. J. Phys. Chem. C, 2014, 118(25): 13988-13997.
[23] Keskin S. Comparing performance of CPO and IRMOF membranes for gas separations using atomistic models[J]. Ind. Eng. Chem. Res., 2010, 49(22): 11689-11696.
[24] Haldoupis E, Nair S, Sholl D S. Efficient calculation of diffusion limitations in metal organic framework materials: A tool for identifying materials for kinetic separations[J]. J. Am. Chem. Soc., 2010, 132(21): 7528-7539.
[25] Gurdal Y, Keskin S. Atomically detailed modeling of metal organic frameworks for adsorption, diffusion, and separation of noble gas mixtures[J]. Ind. Eng. Chem. Res., 2012, 51(21): 7373-7382.
[26] Thornton A W, Dubbeldam D, Liu M S, et al. Feasibility of zeolitic imidazolate framework membranes for clean energy applications[J]. Energy Environ. Sci., 2012, 5(6): 7637-7646.
[27] Keskin S, Sholl D S. Selecting metal organic frameworks as enabling materials in mixed matrix membranes for high efficiency natural gas purification[J]. Energy Environ. Sci., 2010, 3(3): 343-351.
[28] Erucar I, Keskin S. Screening metal-organic framework-based mixed-matrix membranes for CO₂/CH₄ separations[J]. Ind. Eng. Chem. Res., 2011, 50(22): 12606-12616.
[29] Erucar I, Keskin S. Computational screening of metal organic frameworks for mixed matrix membrane applications[J]. J. Membr. Sci., 2012, 407-408: 221-230.
[30] Yilmaz G, Keskin S. Molecular modeling of MOF and ZIF-filled MMMs for CO₂/N₂ separations[J]. J. Membr. Sci., 2014, 454: 407-417.
[31] 仲崇立, 刘大欢, 阳庆元. 金属-有机骨架材料的构效关系及设计[M]. 北京: 科学出版社, 2013.
[32] Huang A, Bux H, Steinbach F, et al. Molecular-sieve membrane with hydrogen permselectivity: ZIF-22 in LTA topology prepared with 3-aminopropyltriethoxysilane as covalent linker[J]. Angew. Chem. Int. Ed., 2010, 49(29): 4958-4961.
[33] Huang A, Chen Y, Wang N, 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.
[34] Huang A, 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.
[35] 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.
[36] Liu Y, Zeng G, Pan Y, et al. Synthesis of highly c-oriented ZIF-69 membranes by secondary growth and their gas permeation properties[J]. J. Membr. Sci., 2011, 379(1-2): 46-51.
[37] Zhang C, Xiao Y, Liu D, et al. A hybrid zeolitic imidazolate framework membrane by mixed-linker synthesis for efficient CO₂ capture[J]. Chem. Commun., 2012, 49(6): 600-602.
[38] Nan J, Dong X, Wang W, et al. Step-by-step seeding procedure for preparing HKUST-1 membrane on porous α-alumina support[J]. Langmuir, 2011, 27(8): 4309-4312.
[39] 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.
[40] Hermes S, Zacher D, Baunemann A, et al. Selective growth and MOCVD loading of small single crystals of MOF-5 at alumina and silica surfaces modified with organic self-assembled monolayers[J]. Chem. Mater., 2007, 19(9): 2168-2173.
[41] Yoo Y, Lai Z, Jeong H K. Fabrication of MOF-5 membranes using microwave-induced rapid seeding and solvothermal secondary growth[J]. Microporous Mesoporous Mater., 2009, 123(1): 100-106.
[42] Liu 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(1-3): 296-301.
[43] Bux H, Liang F, Li Y, et al. Zeolitic imidazolate framework membrane with molecular sieving properties by microwave-assisted solvothermal synthesis[J]. J. Am. Chem. Soc., 2009, 131(44): 16000-16001.
[44] Li Y S, Bux H, Feldhoff A, et al. Controllable synthesis of metal-organic frameworks: From MOF nanorods to oriented MOF membranes[J]. Adv. Mater., 2010, 22(30): 3322-3326.
[45] Bux H, Feldhoff A, Cravillon J, et al. Oriented zeolitic imidazolate framework-8 membrane with sharp H₂/C₃H₈ molecular sieve separation[J]. Chem. Mater., 2011, 23(8): 2262-2269.
[46] Huang A, Wang N, Kong C, et al. Organosilica-functionalized zeolitic imidazolate framework ZIF-90 membrane with high gas-separation performance[J]. Angew. Chem. Int. Ed., 2012, 51(42): 10551-10555.
[47] Huang A, Caro J. Covalent post-functionalization of zeolitic imidazolate framework ZIF-90 membrane for enhanced hydrogen selectivity[J]. Angew. Chem. Int. Ed., 2011, 50(21): 4979-4982.
[48] Dong X, Huang K, Liu S, et al. Synthesis of zeolitic imidazolate framework-78 molecular-sieve membrane: Defect formation and elimination[J]. J. Mater. Chem., 2012, 22(36): 19222-19227.
[49] Huang K, Dong Z, Li Q, et al. Growth of a ZIF-8 membrane on the inner-surface of a ceramic hollow fiber via cycling precursors[J]. Chem. Commun., 2013, 49(87): 10326-10328.
[50] Bux H, Chmelik C, van Baten J M, et al. Novel MOF-membrane for molecular sieving predicted by IR-diffusion studies and molecular modeling[J]. Adv. Mater., 2010, 22(42): 4741-4743.
[51] Cao F, Zhang C, Xiao Y, et al. Helium recovery by a Cu-BTC metal-organic framework membrane[J]. Ind. Eng. Chem. Res., 2012, 51(34): 11274-11278.
[52] Gao H, Hu Y, Xuan Y, et al. Large-scale nanoshaping of ultrasmooth 3D crystalline metallic structures[J]. Science, 2014, 346(6215): 1352-1356.
[53] Zhang X, Liu Y, Kong L, et al. A simple and scalable method for preparing low-defect ZIF-8 tubular membranes[J]. J. Mater. Chem. A, 2013, 1(36): 10635-10638.
[54] Zhang F, Zou X, Gao X, et al. Hydrogen selective NH₂-MIL-53 (Al) MOF membranes with high permeability[J]. Adv. Funct. Mater., 2012, 22(17): 3583-3590.
[55] Zornoza B, Seoane B, Zamaro J M, et al. Combination of MOFs and zeolites for mixed-matrix membranes[J]. Chem. Phys. Chem., 2011, 12(15): 2781-2785.
[56] Zornoza B, Martinez-Joaristi A, Serra-Crespo P, et al. Functionalized flexible MOFs as fillers in mixed matrix membranes for highly selective separation of CO₂ from CH₄ at elevated pressures[J]. Chem. Commun., 2011, 47(33): 9522-9524.
[57] Car A, Stropnik C, Peinemann K V. Hybrid membrane materials with different metal-organic frameworks (MOFs) for gas separation[J]. Desalination, 2006, 200(1-3): 424-426.
[58] Sorribas S, Zornoza B, Téllez C, et al. Mixed matrix membranes comprising silica-(ZIF-8) core-shell spheres with ordered meso-microporosity for natural-and bio-gas upgrading[J]. J. Membr. Sci., 2014, 452: 184-192.
[59] Perez E V, Balkus K J, Ferraris J P, et al. Mixed-matrix membranes containing MOF-5 for gas separations[J]. J. Membr. Sci., 2009, 328(1-3): 165-173.
[60] Ordonez M J C, Balkus K J, Ferraris J P, et al. Molecular sieving realized with ZIF-8/Matrimid mixed-matrix membranes[J]. J. Membr. Sci., 2010, 361(1-2): 28-37.
[61] Zhang Y, Musselman I H, Ferraris J P, et al. Gas permeability properties of Matrimid Membranes® containing the metal-organic framework Cu-BPY-HFS[J]. J. Membr. Sci., 2008, 313(1-2): 170-181.
[62] Shahid S, Nijmeijer K. High pressure gas separation performance of mixed-matrix polymer membranes containing mesoporous Fe (BTC)[J]. J. Membr. Sci., 2014, 459: 33-44.
[63] Yang T, Xiao Y, Chung T S. Poly-/metal-benzimidazole nano-composite membranes for hydrogen purification[J]. Energy Environ. Sci., 2011, 4(10): 4171-4180.
[64] Song Q, Nataraj S K, Roussenova M V, et al. Zeolitic imidazolate framework (ZIF-8) based polymer nanocomposite membranes for gas separation[J]. Energy Environ. Sci., 2012, 5(8): 8359-8369.
[65] Guo X, Huang H, Ban Y, et al. Mixed matrix membranes incorporated with amine-functionalized titanium-based metal-organic framework for CO₂/CH₄ separation[J]. J. Membr. Sci., 2015.478: 130-139.
[66] Xiao Y, Guo X, Huang H, et al. Synthesis of MIL-88B (Fe)/Matrimid mixed-matrix membranes with high hydrogen permselectivity[J]. RSC Adv., 2015, 5(10): 7253-7259.
[67] Ma J, Ying Y, Yang Q, et al. Mixed-matrix membranes containing functionalized porous metal-organic polyhedrons for the effective separation of CO₂/CH₄ mixture[J]. Chem. Commun., 2015, 51(20): 4249-4251.
[68] Li T, Pan Y, Peinemann K V, et al. Carbon dioxide selective mixed matrix composite membrane containing ZIF-7 nano-fillers[J]. J. Membr. Sci., 2013, 425: 235-242.
[69] Thompson J A, Chapman K W, Koros W J, et al. Sonication-induced Ostwald ripening of ZIF-8 nanoparticles and formation of ZIF-8/polymer composite membranes[J]. Microporous Mesoporous Mater., 2012, 158: 292-299.
[70] Yang T, Chung T S. High performance ZIF-8/PBI nano-composite membranes for high temperature hydrogen separation consisting of carbon monoxide and water vapor[J]. Int. J. Hydrogen Energy, 2013, 38(1): 229-239.
[71] Askari M, Chung T S. Natural gas purification and olefin/paraffin separation using thermal cross-linkable co-polyimide/ZIF-8 mixed matrix membranes[J]. J. Membr. Sci., 2013, 444: 173-183.
[72] Zhang C, Dai Y, Johnson J R, et al. High performance ZIF-8/6FDA-DAM mixed matrix membrane for propylene/propane separations[J]. J. Membr. Sci., 2012, 389: 34-42.
[73] Dai Y, Johnson J R, Karvan O, et al. Ultem®/ZIF-8 mixed matrix hollow fiber membranes for CO₂/N₂ separations[J]. J. Membr. Sci., 2012, 401: 76-82.
[74] Bae T H, Lee J S, Qiu W, et al. A high performance gas separation membrane containing submicrometer-sized metal-organic framework crystals[J]. Angew. Chem. Int. Ed., 2010, 49(51): 9863-9866.
[75] Yang T, Chung T S. Room temperature synthesis of ZIF-90 nanocrystals and the derived nano-composite membranes for hydrogen separation[J]. J. Mater. Chem. A, 2013, 1(19): 6081-6090.
[76] Rodenas T, Luz I, Prieto G, et al. Metal-organic framework nanosheets in polymer composite materials for gas separation[J]. Nat. Mater., 2015, 14(1): 48-55.
[77] Cao L, Tao K, Huang A, et al. A highly permeable mixed matrix membrane containing CAU-1-NH₂ for H₂ and CO₂ separation[J]. Chem. Commun., 2013, 49(76): 8513-8515.
[78] Hu J, Cai H, Ren H, et al. Mixed-matrix membrane hollow fibers of Cu₃(BTC)₂ MOF and polyimide for gas separation and adsorption[J]. Ind. Eng. Chem. Res., 2010, 49(24): 12605-12612.