柔性金属有机骨架材料(MOFs)用于气体吸附分离

doi:10.16085/j.issn.1000-6613.2016.06.020

摘要/Abstract

摘要： 柔性金属有机骨架材料(MOFs)具有高度有序的网络结构与可变形的骨架,其骨架结构会对外界的温度、压力及客体分子的刺激产生独特的结构响应。近几年来,柔性MOFs在气体吸附、气体分离、传感等领域显示出巨大的应用潜力。截至目前,研究者们对柔性MOFs的研究仅局限于对其结构形变的机理解释,而缺乏对柔性MOFs应用于相关化工过程的性能研究。本文着重对近年来柔性MOFs在气体吸附分离领域的研究进展进行了综述,并详细地分析了柔性MOFs结构与其气体吸附分离性能之间的构效关系。通过分子模拟结合实验,讨论了柔性MOFs结构对气体分子的平衡吸附与动力学扩散的影响。分析表明,设计合成具有良好吸附选择性与扩散性能的柔性MOFs是其应用于绿色、高效气体分离过程的重要发展方向。

关键词: 柔性金属有机骨架, 吸附, 分离, 天然气, 碳氢化合物

Abstract: Flexible metal-organic frameworks(MOFs)have both highly ordered coordination network and cooperative structural transformability. Their strutures can respond to temperature,pressure,guest adsorption/desorption,and other external stimuli. In recent years,flexible MOFs has showed great potential in gas adsorption,gas separation and sensing. However,most reports on flexible MOFs are limited to the mechanism study on structural transformation,while their applications on chemical industry has been insufficiently investigated. In this review,emphasis is given on the recent progress in the gas adsorption and separation on flexible MOFs. And the relationships between adsorption/separation properties and framework features are detailed analyzed. In addition to the experimental aspect,theoretical investigations of adsorption equilibrium and diffusion dynamics via molecular simulations are also briefly reviewed. Therefore,more efforts should be made to design and synthesis new flexible MOFs with highly adsorption selectivity and diffusion properties for green and efficient gas separation process.

Key words: flexible metal-organic frameworks, adsorption, separation, natural gas, hydrocarbons

中图分类号:

TQ028.1

李立博, 王勇, 王小青, 陈杨, 杨江峰, 李晋平 . 柔性金属有机骨架材料(MOFs)用于气体吸附分离[J]. 化工进展, 2016, 35(06): 1794-1803.

LI Libo, WANG Yong, WANG Xiaoqing, CHEN Yang, YANG Jiangfeng, LI Jinping. Selective gas adsorption and separation in flexible metal-organic frameworks[J]. Chemical Industry and Engineering Progree, 2016, 35(06): 1794-1803.

参考文献

[1] LI J R,SCULLEY J,ZHOU H C,et al. Metal-organic frameworks for separations[J]. Chem. Rev.,2012,112(2):869-932.
[2] FURUKAWA H,CORDOVA K E,KEEFFE M O',et al. The chemistry and applications of metal-organic frameworks[J]. Science,2013,341(6149):974.
[3] SLATER A G,COOPER A I. Function led design of new porous materials[J]. Science,2015,348(6238):988.
[4] LI M,LI D,KEEFFE M O' ,et al. Topological analysis of metal-organic frameworks with polytopic linkers and/or multiple building units and the minimal transitivity principle[J]. Chem. Rev.,2014,114(2):1343-1370.
[5] KITAGAWA S,KITAURA R,NORO S I. Functional porous coordination polymers[J]. Angew. Chem. Int. Ed.,2004,43:2334-2375.
[6] HORIKE S,SHIMOMURA S,KITAGAWA S. Soft porous crystals[J]. Nat. Chem.,2009,1:695-704.
[7] SAKATA Y,FURUKAWA S,KITAGAWA S. Shape-memory nanopores induced in coordination frameworks by crystal downsizing[J]. Science,2013,339(6116):193-196.
[8] SCHNEEMANN A,BON V,SCHWEDLER I,et al. Flexible metal-organic frameworks[J]. Chem. Soc. Rev.,2015,43(16):6062-6096.
[9] KRENO L E,LEONG K,FARHA O K,et al. Metal-organic framework materials as chemical sensors[J]. Chem. Rev.,2012,112:1105-1125.
[10] LI L B,WANG Y,YANG J F,et al. Targeted capture and pressure/temperature-responsive separation in flexible metal-organic frameworks[J]. J. Mater. Chem. A,2015,3:22574-22583.
[11] LOISEAU T,SERRE C,HUGUENARD C,et al. A rationale for the large breathing of the porous aluminum terephthalate (MIL-53) upon hydration[J]. Chem. Eur. J.,2004,10:1373-1382.
[12] MILLANGE F,GUILLOU N,WALTON R I,et al. Effect of the nature of the metal on the breathing steps in MOFs with dynamic frameworks[J]. Chem. Commun.,2008(39):4732-4734.
[13] MILLANGE F,SERRE C,FÉREY G. Synthesis,structure determination and properties of MIL-53as and MIL-53ht:the first Cr^III hybrid inorganic-organic microporous solid:Cr^III(OH)·{O₂C—C₆H₄—CO₂}·{HO₂C—C₆H₄—CO₂H}_x[J]. Chem. Commun.,2002(8):822-823.
[14] SERRE C,MILLANGE F,THOUVENOT C,et al. Very large breathing effect in the first nanoporous chromium(III)-based solids:MIL-53 or Cr^III(OH)·{O₂C—C₆H₄—CO₂}·{HO₂C-C₆H₄-CO₂H}_x H₂O_y[J]. J. Am. Chem. Soc.,2002,124(45):13519-13526.
[15] MOWAT J P S,SEYMOUR V R,GRIFFIN J M,et al. A novel structural form of MIL-53 observed for the scandium analogue and its response to temperature variation and CO₂ adsorption[J]. Dalton Trans.,2012,41:3937-3941.
[16] VOLKRINGER C,LOISEAU T,GUILLOU N,et al. XRD and IR structural investigations of a particular breathing effect in the MOF-type gallium terephthalate MIL-53(Ga)[J]. Dalton Trans.,2009(12):2241-2249.
[17] ANOKHINA E V,VOUGO-ZANDA M,WANG X,et al. In(OH)BDC·0.75BDCH₂, a hybrid inorganic-organic vernier structure[J]. J. Am. Chem. Soc.,2005,127(43):15000-15001.
[18] BOUSQUET D,COUDERT F X,FOSSATI A G J,et al. Adsorption induced transitions in soft porous crystals:an osmotic potential approach to multistability and intermediate structures[J]. J. Chem. Phys.,2013,138:174706.
[19] COUDERT F X,BOUTIN A,FUCHS A H,et al. Adsorption deformation and structural transitions in metal-organic frameworks: from the unit cell to the crystal[J]. J. Phys. Chem. Lett.,2013,4(19):3198-3205.
[20] MELLOT-DRAZNIEKS C,SERRE C,SURBLE S,et al. Very large swelling in hybrid frameworks:a combined computational and powder diffraction study[J]. J. Am. Chem. Soc.,2005,127(46):16273-16278.
[21] SURBLE S,SERRE C,MELLOT-DRAZNIEKS C,et al. A new isoreticular class of metal-organic-frameworks with the MIL-88 topology[J]. Chem. Commun.,2006(3):284-286.
[22] SEO J,MATSUDA R,SAKAMOTO H,et al. A pillared-layer coordination polymer with a rotatable pillar acting as a molecular gate for guest molecules[J]. J. Am. Chem. Soc.,2009,131(35):12792-12800.
[23] KONDO A,NOGUCHI H,OHNISHI S,et al. Novel expansion/shrinkage modulation of 2D layered MOF triggered by clathrate formation with CO₂ molecules[J]. Nano Letter,2006,6(11):2581-2584.
[24] SERVICE R F. Stepping on the gas[J]. Science,2014,346(6209):538-541.
[25] YEH S. An empirical analysis on the adoption of alternative fuel vehicles: the case of natural gas vehicles[J]. Energy Policy,2007,35(11):5865-5875.
[26] WHYATT G A. Issues Affecting adoption of natural gas fuel in light- and heavy-duty vehicles[R]. No. PNNL-19745,US Department of Energy,2010.
[27] WEGRZYN J,GUREVICH M. Adsorbent storage of natural gas[J]. Appl. Energy,1996,55(2):71-83.
[28] MAKAL T A,LI J R,LU W,et al. Methane storage in advanced porous materials[J]. Chem. Soc. Rev.,2012,41:7761-7779.
[29] HE Y B,ZHOU W,QIAN G D,et al. Methane storage in metal-organic frameworks[J]. Chem. Soc. Rev.,2014,43:5657-5678.
[30] PENG Y,KRUNGLEVICIUTE V,ERYAZICI I,et al. Methane storage in metal-organic frameworks:current records,surprise findings,and challenges[J]. J. Am. Chem. Soc.,2013,135(32):11887-11894.
[31] MASON J A,VEENSTRA M,LONG J R. Evaluating metal-organic frameworks for natural gas storage[J]. Chem. Sci.,2014,5:32-51.
[32] MASON J A,OKTAWIEC J,TAYLOR M K,et al. Methane storage in flexible metal-organic frameworks with intrinsic thermal management[J]. Nature,2015,527:357-361.
[33] INUBUSHI Y,HORIKE S,FUKUSHIMA T,et al. Modification of flexible part in Cu²⁺ interdigitated framework for CH₄/CO₂ separation[J]. Chem. Commun.,2010,46:9229-9231.
[34] CHEN B L,MA S,ZAPATA F,et al. Rationally designed micropores within a metal-organic framework for selective sorption of gas molecules[J]. Inorg. Chem.,2007,46(4):1233-1236.
[35] TRUNG T K,TRENS P,TANCHOUX N,et al. Hydrocarbon adsorption in the flexible metal organic frameworks MIL-53(Al,Cr)[J]. J. Am. Chem. Soc.,2008,130(50):16926-16932.
[36] HE Y B,XIANG S,CHEN B L. A microporous hydrogen-bonded organic framework for highly selective C₂H₂/C₂H₄ separation at ambient temperature[J]. J. Am. Chem. Soc.,2011,133(37):14570-14573.
[37] MATSUDA R,KITAURA R,KITAGAWA S,et al. Highly controlled acetylene accommodation in a metal-organic microporous material[J]. Nature,2005,436:238-241.
[38] BERGH J van den,GUCUYENER C,PIDKO E A,et al. Understanding the anomalous alkane selectivity of ZIF-7 in the separation of light alkane/alkene mixtures[J]. Chem. Eur. J.,2011,17(32):8832-8840.
[39] RABONE J,YUE Y F,CHONG S Y,et al. An adaptable peptide-based porous material[J]. Science,2010,329:1053-1057.
[40] MAES M,SCHOUTEDEN S,HIRAI K,et al. Liquid phase separation of polyaromatics on [Cu₂(BDC)₂(dabco)][J]. Langmuir,2011,27(15):9083-9087.
[41] MAJI T K,MOSTAFA G,MATSUDA R,et al. Guest-induced asymmetry in a metal-organic porous solid with reversible single-crystal-to-single-crystal structural transformation[J]. J. Am. Chem. Soc.,2005,127(49):17152-17153.
[42] LI J R,SCULLEY J,ZHOU H C. Metal-organic frameworks for separations[J]. Chem. Rev.,2012,112:869-932.
[43] LI L B,YANG J F,ZHAO Q,et al. One-dimensional interpenetrated coordination polymers showing step gas sorption properties[J]. CrystEngComm.,2013,15:1689-1692.
[44] SATO H,KOSAKA W,MATSUDA R,et al. Self-accelerating CO sorption in a soft nanoporous crystal[J]. Science,2014,343:167-170.
[45] HIJIKATA Y,HORIKE S,Sugimoto M,et al. Pore design of two-dimensional coordination polymers toward selective adsorption[J]. Inorg. Chem.,2013,52(7):3634-3642.
[46] NORO S I,HIJIKATA Y,INUKAI M,et al. Highly selective CO₂ adsorption accompanied with low-energy regeneration in a two-dimensional Cu(II) porous coordination polymer with inorganic fluorinated PF^6– anions[J]. Inorg. Chem.,2012,52(1):280-285.
[47] INUBUSHI Y,HORIKE S,FUKUSHIMA T,et al. Modification of flexible part in Cu²⁺ interdigitated framework for CH₄/CO₂ separation[J]. Chem. Commun.,2010,46:9229-9231.
[48] GOMEZ L F,ZACHARIA R,BÉNARD P,et al. Simulation of binary CO₂/CH₄ mixture breakthrough profiles in MIL-53 (Al)[J]. J. Nanomater.,2015:439382. DOI:10.1155/2015/439382.
[49] COUCK S,DENAYER J F M,BARON G V,et al. An amine-functionalized MIL-53 metal-organic framework with large separation power for CO₂ and CH₄[J]. J. Am. Chem. Soc.,2009,131(18):6326-6327.
[50] SRINIVAS G,TRAVIS W,FORD J,et al. Nanoconfined ammonia borane in a flexible metal-organic framework Fe–MIL-53: clean hydrogen release with fast kinetics[J]. J. Mater. Chem. A,2013,1:4167-4172.
[51] MA Q,YANG Q,GHOU A,et al. Guest-modulation of the mechanical properties of flexible porous metal-organic frameworks[J]. J. Mater. Chem. A,2014,2:9691-9698.
[52] LI L B,WANG Y,YANG J F,et al. Targeted capture and pressure/temperature-responsive separation in flexible metal-organic frameworks[J]. J. Mater. Chem. A,2015,3:22574-22583.
[53] BLOCH E D,QUEEN W L,KRISHNA R,et al. Hydrocarbon separations in a metal-organic framework with open iron(II) coordination sites[J]. Science,2012,335(6076):1606-1610.
[54] LOU W L,YANG J F,LI L B,et al. Adsorption and separation of CO₂ on Fe(II)-MOF-74: effect of the open metal coordination site[J]. J. Solid State Chem.,2014,213:224-228.
[55] HE Y B,ZHOU W,KRISHNA R,et al. Microporous metal-organic frameworks for storage and separation of small hydrocarbons[J]. Chem. Commun.,2012,48:11813-11831.
[56] HE Y B,KRISHNA R,CHEN B L. Metal-organic frameworks with potential for energy-efficient adsorptive separation of light hydrocarbons[J]. Energy Environ. Sci.,2012,5:9107-9120.
[57] BAE Y,LEE C Y,KIM K C,et al. High propene/propane selectivity in isostructural metal-organic frameworks with high densities of open metal sites[J]. Angew. Chem. Int. Ed.,2012,51(8):1857-1860.
[58] LI L B,KRISHNA R,WANG Y,et al. Exploiting the gate opening effect in a flexible MOF for selective adsorption of propyne from C1/C2/C3 hydrocarbons[J]. J. Mater. Chem. A,2016,4:751-755.
[59] OBENHAUS F,DROSTE W,NEUMEISTER J B. Ullman's encyclopedia of industrial chemistry; electronic release[M]. Weinheim:Wiley-VCH,2012.
[60] BERGH J van den,GUCUYENER C,PIDKO E A,et al. Understanding the anomalous alkane selectivity of ZIF-7 in the separation of light alkane/alkene mixtures[J]. Chem. Eur. J.,2011,17:8832-8840.
[61] PAN L,OLSON D H,CIEMNOLONSKI L R,et al. Zeolitic imidazolate frameworks for kinetic separation of propane and propene[J]. Angew. Chem. Int. Ed.,2006,45(4):616-635.
[62] ALAERTS L,MAES M,VEEN van der,et al. Metal-organic frameworks as high-potential adsorbents for liquid-phase separations of olefins,alkylnaphthalenes and dichlorobenzenes[J]. Phys. Chem. Chem. Phys.,2009,11:2903-2911.
[63] MENDES P A P,HORCAJADA P,RIVES S,et al. A complete separation of hexane isomers by a functionalized flexible metal organic framework[J]. Adv. Funct. Mater.,2014,24:7666-7673.
[64] BAREA E,MONTORO C,NAVARRO J A R. Toxic gas removal—metal-organic frameworks[J]. Chem. Soc. Rev.,2014,43:5419-4530.
[65] YANAI N,UEMURA T,INOUE M,et al. Guest-to-host transmission of structural changes for stimuli-responsive adsorption property[J]. J. Am. Chem. Soc.,2012,134(10):4501-4504.
[66] YANAI N,KITAYAMA K,HIJIKATA Y,et al. Gas detection by structural variations of fluorescent guest molecules in a flexible porous coordination polymer[J]. Nature Mater.,2011,10:787- 793.
[67] CHEN Y,LI L B,YANG J Y,et al. Reversible flexible structural changes in multidimensional MOFs by guest molecules (I₂,NH₃) and thermal stimulation[J]. J. Solid State Chem.,2015,226:114-119.
[68] LI L B,WANG Y,YANG J F,et al. Functionalized metal-organic frameworks for the efficient removal of low concentrations of ammonia[J]. ChemPlusChem.,2016,81(2):222-228.