一类新型镁材料——镁基金属有机骨架材料

doi:10.16085/j.issn.1000-6613.2017-2174

摘要/Abstract

摘要： 镁基金属有机骨架材料（Mg-MOFs）是近年来逐渐受到关注的一类新型功能材料，其种类与结构多样化，使其在很多领域中展现出了潜在的应用价值，为镁资源的开发利用开拓了一个新的领域。本文从Mg-MOFs的种类、特点、制备方法、应用以及稳定性5个方面展开论述。详细阐述了Mg-MOFs在催化、药物缓释、光学材料、气体储存、气体吸附和分离等方面的应用，着重介绍了Mg-MOFs的储氢能力和对二氧化碳的吸附能力及对不同混合物的选择分离能力。提出了今后Mg-MOFs的研究重点：优化Mg-MOFs的制备条件，降低制备难度及成本；选择新的配体源及溶剂，开发具有结构稳定、高比表面积、功能多样的Mg-MOFs，扩大其在气体吸附与选择性分离方向的应用；将Mg-MOFs应用于复合材料中，拓宽其应用范围。

关键词: 镁基金属有机骨架材料, 羧酸配体, 储氢, 分离

Abstract: Magnesium based metal organic frameworks (Mg-MOFs), as a new kind of functional material, have recently drawn much research attention. Due to the diversified specie and structures, Mg-MOFs have shown potential applications in many fields, which provide a new research area for the development and utilization of magnesium resources. Five aspects on Mg-MOFs are discussed in this article, including the main types, characteristics, preparation method, applications and stability. The applications of Mg-MOFs in catalysis, drug delivery, optical properties, gas storage, adsorption and separation are elaborated, and the capacities of hydrogen storage, carbon dioxide adsorption and selective uptake are presented emphatically. In addition, the prospects and challenges in the future are pointed out. For instance:optimizing the preparation conditions of Mg-MOFs to reduce the process difficulty and costs; selecting new ligands and solvent to prepare Mg-MOFs of high surface area, developing varieties of functional Mg-MOFs with structural stability to expand their applications in gas adsorption and separation, and applying Mg-MOFs to the composite materials to extend their application range.

Key words: magnesium based metal organic frameworks (Mg-MOFs), ligands of carboxylic acid, storage hydrogen gas, separation

中图分类号:

O6-1

韩森建, 王海增. 一类新型镁材料——镁基金属有机骨架材料[J]. 化工进展, 2018, 37(09): 3437-3445.

HAN Senjian, WANG Haizeng. A new material of magnesium complexes——magnesium based metal organic frameworks[J]. Chemical Industry and Engineering Progress, 2018, 37(09): 3437-3445.

参考文献

[1] BI S F, CUI X M. The exploitation and comprehensive utilization of magnesium resources in Salt Lakes of China[J]. Acta Geologica Sinica, 2014, 88(s1):294-295.
[2] HUANG Y L, GONG Y N, JIANG L, et al. A unique magnesium-based 3D MOF with nanoscale cages and temperature dependent selective gas sorption properties[J]. Chemical Communications, 2013, 49(17):1753.
[3] KITAGAWA S, KITAURA R, NORO S. Functional porous coordination polymers[J]. Angewandte Chemie International Edition, 2004, 43(18):2334-2375.
[4] 张所瀛, 刘红, 刘朋飞, 等. 金属有机骨架材料在CO₂/CH₄吸附分离中的研究进展[J]. 化工学报, 2014, 65(5):1563-1570. ZHANG S Y, LIU H, LIU P F, et al. Progress of adsorption-based CO₂/CH₄ separation by metal organic frameworks[J]. CIESC Journal, 2014, 65(5):1563-1570.
[5] HORCAJADA P, CHALATI T, SERRE C, et al. Porous metal-organic-framework nanoscale carriers as a potential platform for drug delivery and imaging[J]. Nature Materials, 2010, 9(2):172-178.
[6] COTE A P, SHIMIZU G K. Coordination solids via assembly of adaptable components:systematic structural variation in alkaline earth organosulfonate networks[J]. Chemistry:A European Journal, 2010, 9(21):5361-5370.
[7] DINCA M, LONG J R. Strong H₂ binding and selective gas adsorption within the microporous coordination solid Mg₃(O₂ C-C₁₀ H₆-CO₂)₃[J]. Journal of the American Chemical Society, 2005, 127(26):9376-9377.
[8] XIE Y M, WU J H. A trinuclear magnesium based metal-organic framework with self-penetrated rob topology[J]. Inorganica Chimica Acta, 2014, 412:15-19.
[9] BISWAS A, KIM M B, KIM S Y, et al. A novel 3-D microporous magnesium-based metal-organic framework with open metal sites[J]. RSC Advances, 2016, 6(85):81485-81490.
[10] LIU Y, CHEN Y P, LIU T F, et al. Selective gas adsorption and unique phase transition properties in a stable magnesium metal-organic framework constructed from infinite metal chains[J]. CrystEngComm, 2013, 15(45):9688-9693.
[11] SENKOVSKA I, KASKEL S. Solvent-induced pore-size adjustment in the metal-organic framework[Mg₃ (ndc)₃ (dmf)₄] (ndc=naphthalenedicarboxylate)[J]. European Journal of Inorganic Chemistry, 2006(22):4564-4569.
[12] CHAEMCHUEN Somboon, 周奎, 姚宸, 等. 碱性金属修饰金属有机骨架材料MOF-5吸附位点及其常态下分离二氧化碳/甲烷的应用[J].应用化学, 2015, 32(5):552-556. CHAEMCHUEN S, ZHOU K, YAO C, et al. Alkali-metal tuning of adsorption sites in metal organic frameworks MOF-5 for carbon dioxide/methane separation at ambient conditions[J]. Chinese Journal of Applied Chemistry, 2015, 32(5):552-556.
[13] MALLICK A, SAHA S, PACHFULE P, et al. Selective CO₂ and H₂ adsorption in a chiral magnesium-based metal organic framework (Mg-MOF) with open metal sites[J]. Journal of Materials Chemistry, 2010, 20(41):9073-9080.
[14] MAZAJ M, CELIC T B, MALI G, et al. Control of the crystallization process and structure dimensionality of Mg-benzene-1,3,5-tricarboxylates by tuning solvent composition[J]. Crystal Growth & Design, 2013, 13(8):3825-3834.
[15] GUO Y, FENG X, HAN T, et al. Tuning the luminescence of metal-organic frameworks for detection of energetic heterocyclic compounds[J]. Journal of the American Chemical Society, 2014, 136(44):15485-15488.
[16] MAO H, XU J, HU Y, et al. The effect of high external pressure on the structure and stability of MOF α-Mg₃ (HCOO)₆ probed by in situ Raman and FT-IR spectroscopy[J]. Journal of Materials Chemistry A, 2015, 3(22):11976-11984.
[17] YANG D A, CHO H Y, KIM J, et al. CO₂ capture and conversion using Mg-MOF-74 prepared by a sonochemical method[J]. Energy & Environmental Science, 2012, 5(4):6465-6473.
[18] VIERTELHAUS M, ANSON C E, DR A K P. Solvothermal synthesis and crystal structure of one-dimensional chains of anhydrous zinc and magnesium formate[J]. Zeitschrift für Anorganische und Allgemeine Chemie, 2005, 631(12):2365-2370.
[19] MALLICK A, SAHA S, PACHFULE P, et al. Structure and gas sorption behavior of a new three dimensional porous magnesium formate[J]. Inorganic Chemistry, 2011, 50(4):1392-1401.
[20] STEIN I, RUSCHEWITZ U. Mechanochemical synthesis of new coordination polymers with acetylenedicarboxylate as bridging ligand[J]. Zeitschrift für Anorganische und Allgemeine Chemie, 2010, 636(2):400-404.
[21] KAM K C, YOUNG K L M, CHEETHAM A K. Chemical and structural diversity in chiral magnesium tartrates and their racemic and meso analogues[J]. Crystal Growth & Design, 2007, 7(7):1522-1532.
[22] GRIRRANE A, PASTOR A, ALVAREZ E, et al. Magnesium dicarboxylates:first structurally characterized oxydiacetate and thiodiacetate magnesium complexes[J]. Inorganic Chemistry Communications, 2005, 8(5):453-456.
[23] DIETZEL P D C, BLOM R, FJELLVAG H. Base-induced formation of two magnesium metal-organic framework compounds with a bifunctional tetratopic ligand[J]. European Journal of Inorganic Chemistry, 2008, 2008(23):3624-3632.
[24] ROOD J A, NOLL B C, HENDERSON K W. Cubic networks and 36 tilings assembled from isostructural trimeric magnesium aryldicarboxylates[J]. Main Group Chemistry, 2006, 5(1):21-30.
[25] DAVIES R P, LESS R J, LICKISS P D, et al. Framework materials assembled from magnesium carboxylate building units[J]. Dalton Transactions, 2007, 24(24):2528-2535.
[26] WILLIAMS C A, BLAKE A J, WILSON C, et al. Novel metal-organic frameworks derived from group Ⅱ metal cations and aryldicarboxylate anionic ligands[J]. Crystal Growth & Design, 2008, 8(3):911-922.
[27] HE Y, SHANG J, ZHAO Q, et al. A comparative study on conversion of porous and non-porous metal-organic frameworks(MOFs) into carbon-based composites for carbon dioxide capture[J]. Polyhydron, 2016, 120:30-35.
[28] GURUNATHA K L, UEMURA K, MAJI T K. Temperature-and stoichiometry-controlled dimensionality in a magnesium 4,5-imidazoledicarboxylate system with strong hydrophilic pore surfaces[J]. Inorganic Chemistry, 2008, 47(15):6578-6580.
[29] BOHNSACK A M, IBARRA I A, HATFIELD P W, et al. High capacity CO₂ adsorption in a Mg(Ⅱ)-based phosphine oxide coordination material[J]. Chemical Communications, 2011, 47(17):4899-4901.
[30] BANERJEE R, MALLICK A, GARAI B, et al. Solid state organic amine detection in a photochromic porous metal organic framework[J]. Chemical Science, 2015, 6(2):1420-1425.
[31] INGLESON M J, BARRIO J P, BACSA J, et al. Magnesium borohydride confined in a metal-organic framework:a preorganized system for facile arene hydroboration[J]. Angewandte Chemie, 2009, 48(11):2012-2016.
[32] PLATEROPRATS A E, IGLESIAS M, SNEJKO N, et al. From coordinatively weak ability of constituents to very stable alkaline-earth sulfonate metal-organic frameworks[J]. Crystal Growth & Design, 2011, 11(5):1750-1758.
[33] VALERIO C C, MUNOZ HERN A NDEZ M A, GREVY J M. Reactivity of Zn(Ⅱ), Mg(Ⅱ) and Al(Ⅲ) chlorides with a phosphinimine ligand:new tetrameric inverse crown ether structures[J]. Dalton Transactions, 2010, 39(28):6441-6448.
[34] DENG H, GRUNDER S, CORDOVA K E, et al. Large-pore apertures in a series of metal-organic frameworks[J]. Science, 2012, 336(6084):1018-1023.
[35] WITMAN M, LING S, ANDERSON S, et al. In silico design and screening of hypothetical MOF-74 analogs and their experimental synthesis[J]. Chemical Science, 2016, 7(9):6263-6272.
[36] BRITT D, FURUKAWA H, WANG B, et al. Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites[J]. Proceedings of the National Academy of Sciences of the United States of America, 2009, 106(49):20637-20640.
[37] SACCOCCIA B, BOHNSACK A M, WAGGONER N W, et al. Separation of p-divinylbenzene by selective room-temperature adsorption inside Mg-CUK-1 prepared by aqueous microwave synthesis[J]. Angewandte Chemie, 2015, 54(18):5394-5398.
[38] SAHA D, SEN R, MAITY T, et al. Porous magnesium carboxylate framework:synthesis, X-ray crystal structure, gas adsorption property and heterogeneous catalytic aldol condensation reaction[J]. Dalton Transactions, 2012, 41(24):7399-7408.
[39] LIU D, LIU X, LIU Y, et al. Host-guest interaction dictated selective adsorption and fluorescence quenching of a luminescent lightweight metal-organic framework toward liquid explosives[J]. Dalton Transactions, 2014, 43(40):15237-15244.
[40] REMY T, PETER S A, PERRE S V D, et al. Selective dynamic CO₂ separations on Mg-MOF-74 at low pressures:a detailed comparison with 13X[J]. Journal of Physical Chemistry C, 2013, 117(18):9301-9310.
[41] VERYASOV G, HARINAGA U, MATSUMOTO K, et al. Crystallographic insight into the Mg²⁺ coordination mode and N(SO₂CF₃)^2- anion conformation in Mg[N(SO₂CF₃)₂]₂ and its adducts[J]. European Journal of Inorganic Chemistry, 2017(7):1087-1099.
[42] PELI G, MASCIOCCHI N, GARLASCHELLI L, et al. Synthesis, structure and thermal behaviour of two magnesium complexes containing the 1,4-bis(5-tetrazolyl)benzene ligand[J]. Inorganica Chimica Acta, 2009, 362(12):4630-4634.
[43] SON W J, KIM J, AHN W S. Sonochemical synthesis of MOF-5[J]. Chemical Communications, 2008, 47:6336-6338.
[44] TAHMASIAN A, MORSALI A, SANG W J. Sonochemical syntheses of a one-dimensional Mg(Ⅱ) metal-organic framework:a new precursor for preparation of MgO one-dimensional nanostructure[J]. Journal of Nanomaterials, 2013(3):1-7.
[45] 吴兆锋.若干镁基金属有机框架化合物的合成与表征[D].衡阳:南华大学, 2014. WU Z F. The synthesis and characterization of some magnesium metal-organic framework[D]. Hengyang:University of South China, 2014.
[46] MCDONALD T M, LEE W R, MASON J A, et al. Capture of carbon dioxide from air and flue gas in the alkylamine-appended metal-organic framework mmen-Mg₂ (dobpdc)[J]. Journal of the American Chemical Society, 2012, 134(16):7056-7065.
[47] KIM J, KIM S N, JANG H G, et al. CO₂ cycloaddition of styrene oxide over MOF catalysts[J]. Applied Catalysis A:General, 2013, 453(6):175-180.
[48] PHAM T, FORREST K A, FALCAO E H, et al. Exceptional H₂ sorption characteristics in a Mg²⁺ -based metal-organic framework with small pores:insights from experimental and theoretical studies[J]. Physical Chemistry Chemical Physics, 2016, 18(3):1786-1796.
[49] SUKSAENGRAT P, AMORNKITBAMRUNG V, SREPUSHARAWOOT P, et al. Density functional theory study of hydrogen adsorption in a Ti-decorated Mg-based metal-organic framework-74[J]. ChemPhySchem:A European Journal of Chemical Physics & Physical Chemistry, 2016, 17(6):879-884.
[50] LIN Q, WU T, ZHENG S T, et al. A chiral tetragonal magnesiumcarboxylate framework with nanotubular channels[J]. Chemical Communications, 2011, 47(43):11852.
[51] DIETZEL P D, GEORGIEV P A, ECKERT J, et al. Interaction of hydrogen with accessible metal sites in the metal-organic frameworks M₂ (dhtp)(CPO-27-M; M=Ni, Co, Mg)[J]. Chemical Communications, 2010, 46(27):4962-4964.
[52] WU H, ZHOU W, YILDIRIM T. High-capacity methane storage in metal-organic frameworks M₂ (dhtp):the important role of open metal sites[J]. Journal of the American Chemical Society, 2009, 131(13):4995-5000.
[53] LI Y P, ZHANG L J, JI W J. Synthesis, characterization, crystal structure of magnesium compound based 3,3',5,5'-azobenzentetracarboxylic acid and application as high-performance heterogeneous catalyst for cyanosilylation[J]. Journal of Molecular Structure, 2017, 1133:607-614.
[54] BAO Z, YU L, REN Q, et al. Adsorption of CO₂ and CH₄ on a magnesium-based metal organic framework[J]. Journal of Colloid & Interface Science, 2011, 353(2):549-556.
[55] 姜宁, 邓志勇, 王公应, 等.金属有机框架材料的制备及其在吸附分离CO₂ 中的应用[J].化学进展, 2014,26(10):1645-1654. JIANG N, DENG Z Y, WANG G Y, et al. Preparation of metal-organic frameworks and application for CO₂ adsorption and separation[J]. Progress in Chemistry, 2014, 26(10):1645-1654.
[56] HU J, SUN T, LIU X, et al. Rationally tuning the separation performances of[M₃ (HCOO)₆] frameworks for CH₄/N₂ mixtures via metal substitution[J]. Microporous & Mesoporous Materials, 2016, 225:456-464.
[57] XU J, YU Y, LI G, et al. A porous magnesium metal-organic framework showing selective adsorption and separation of nitrile guest molecules[J]. RSC Advances, 2016, 6(106):104451-104455.
[58] DOUVALI A, TSIPIS A C, ELISEEVA S V, et al. Turn-on luminescence sensing and real-time detection of traces of water in organic solvents by a flexible metal-organic framework[J]. Angewandte Chemie, 2015, 54(5):1651-1656.
[59] ZHAI L, ZHANG W W, ZUO J L, et al. Simultaneous observation of ligand-based fluorescence and phosphorescence within a magnesiumbased CP/MOF at room temperature[J]. Dalton Transactions, 2016, 45(30):11935-11938.
[60] 乔智威, 李理波, 周健.生物相容性金属-有机骨架材料负载药物的分子模拟[J].高等学校化学学报, 2014, 35(12):2638-2644. QIAO Z W, LI L B, ZHOU J. Molecular simulations of biocompatible metal-organic frameworks for drug carrier application[J]. Chemical Journal of Chinese Universities, 2014, 35(12):2638-2644.