Progress of metal-organic frameworks for selective gas storage,adsorption and separation

doi:10.16085/j.issn.1000-6613.2017-0392

Abstract

Abstract: Metal-organic frameworks(MOFs)are widely studied in gas adsorption and separation for their inherent advantages,including high specific surface area,high porosity,tunable pore sizes,structural diversity,open metal sites and easy chemical modifications. This review focused on recent research progress of MOFs in the storage of H₂ and CH₄ and in the separation of CO₂/N₂ and light hydrocarbons,etc. It is pointed that the properties of gas adsorption and separation in MOFs are affected by various parameters such as specific surface area,porosity,the central metal ions,π-π stacking/interactions,organic ligands,etc. Rational design and functionalization on MOFs are effective methods to improve their adsorption and separation properties. To achieve the practical application of MOFs,more efforts should be taken to improve the stability and reduce the cost.

Key words: metal-organic frameworks, adsorption, separation, hydrogen, carbon dioxide, light hydrocarbons

摘要： 金属有机骨架（MOFs）由于具有大比表面积、高孔隙率、可调孔径、结构多样、开放的金属位点和化学可修饰性等诸多优点而被广泛用于气体的吸附分离研究。本文对近年来MOFs在气体存储、吸附分离领域的研究进展进行了综述，讨论了不同MOFs对氢气、甲烷的存储性能和存储机理及对二氧化碳、低碳烃等的分离性能和吸附机理，指出MOFs材料的比表面积、孔结构、金属位点、π-π键合作用、可修饰基团等是影响不同MOFs吸附分离过程的重要参数。有目的的功能化改性是提高MOFs材料选择性吸附分离性能的有效方法，但目前仍普遍存在存储吸附性能不够、稳定性不强、成本过高等问题，只有解决这些问题才能使MOFs大量从实验室走向工业化。

关键词: 金属有机骨架, 吸附, 分离, 氢, 二氧化碳, 低碳烃

CLC Number:

TQ028.1

ZHENG Lijun, GONG Qihan, LI Xuejing, ZHU Qingyun. Progress of metal-organic frameworks for selective gas storage,adsorption and separation[J]. Chemical Industry and Engineering Progress, 2017, 36(11): 4116-4123.

郑丽君, 龚奇菡, 李雪静, 朱庆云. 金属有机骨架用于气体存储、吸附分离的研究进展[J]. 化工进展, 2017, 36(11): 4116-4123.

References

[1] LI H,EDDAOUDI M,KEEFE M O,et al. Design and synthesis of an exceptionally stable and highly porous metal-organic framework[J]. Nature,1999,402:276-279.
[2] FURUKAWA H,MULLER U,YAGHI O M. "Heterogeneity within Order" in metal-organic frameworks[J]. Angew. Chem. Int. Ed.,2015,54:3417-3430.
[3] GAMAGE N-D H,MCDONALD K A,MATZGER A J. MOF-5-polystyrene:direct production from monomer,improved hydrolytic stability,and unique guest adsorption[J]. Angew. Chem.,2016,128:12278-12282.
[4] TEO H W B,CHAKRABORTY A,KAYAL S. Evaluation of CH₄ and CO₂ adsorption on HKUST-1 and MIL-101(Cr) MOFs employing Monte Carlo simulation and comparison with experimental data[J]. Applied Thermal Engineering,2017,110:891-900.
[5] WANG H L,ZHU Q L,ZOU R Q,et al. Metal-organic frameworks for energy applications[J]. Chem. Rev.,2017,2(1):52-80.
[6] LIN Y C,KONG C L,ZHANG Q J,et al. Metal-organic frameworks for carbon dioxide capture and methane storage[J]. Adv. Energy Master.,2017,7.DOI:10.1002/aenm.201601451.
[7] FURUKAWA H,KO N,GO Y B,et al. Ultrahigh porosity in metal-organic frameworks[J].Science,2010,329:424-428.
[8] MIHALY J J,ZELLER M,GENNA D T. Ion-directed synthesis of indium-derived 2,5-thiophenedicarboxylate metal-organic frameworks:tuning framework dimensionality[J]. Cryst. Growth Des.,2016,16(3):1550-1558
[9] SUN M P,PARK H J,PRASAD T K,et al. Hydrogen storage in metal-organic frameworks[J]. Chem. Rev.,2012,112(2):782-835.
[10] YAN Y,BLAKE A J,LEWIS W,et al. Modifying cage structures in metal-organic polyhedral frameworks for H₂ storage[J]. Chem. Eur. J.,2011,17:11162-11170.
[11] LI Y W,YANG R T. Significantly enhanced hydrogen storage in metal-organic frameworks via spillover[J]. J. Am. Chem. Soc.,2006,128:726-727.
[12] USDRIVE.Target explanation document:onboard hydrogen storage for light-duty fuel cell vehicles[EB/OL].[2015-5].http://go.nature.com/EHHdZ5.
[13] HE Y B,ZHOU W,CHEN G D,et al. Methane storage in metal-organic frameworks[J]. Chem. Soc. Rev.,2014,43:5657-5678.
[14] 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.,2013,135:11887-11894.
[15] KLEIN N,SENKOVSKA I,GEDRICH K,et al. A mesoporous metal-organic framework[J]. Angew. Chem. Int. Ed. Eng.,2009,48(52):9954-9957.
[16] LI B,WEN H M,WANG H,et al. A porous metal-organic framework with dynamic pyrimidine groups exhibiting record high methane storage working capacity[J]. J. Am. Chem. Soc.,2014,136(17):6207-6210.
[17] MASON J A,OKTAWIEC J,TAYLOR M K,et al. Methane storage in inflexible metal-organic frameworks with intrinsic thermal management[J]. Nature,2015,527:357-361.
[18] 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]. Proc. Natl. Acad. Sci. USA,2009,106:20637-20640.
[19] LI B,ZHANG Z J,LI Y,et al. Enhanced binding affinity,remarkable selectivity,and high capacity of CO₂ by dual functionalization of a rht-type metal-organic framework[J]. Angew. Chem. Int. Ed.,2012,51:1412-1415.
[20] PACHFUEL P,CHEN Y F,JIANG J W,et al. Experimental and computational approach of understanding the gas adsorption in amino functionalized interpenetrated metal organic frameworks (MOFs)[J]. J. Mater. Chem.,2011,21:17737-17745.
[21] DUAN J G,YANG Z,BAI J,et al. Highly selective CO₂ capture of an agw-type metal-organic framework with inserted amides:experimental and theoretical studies[J]. Chem. Commun.,2012,48:3058-3060.
[22] LING Y,YANG F L,DENG M L,et al. Novel iso-reticular Zn(ii)metal-organic frameworks constructed by trinuclear-triangular and paddle-wheel units:synthesis,structure and gas adsorption[J]. Dalton Trans.,2012,41:4007-4011.
[23] ZHOU X P,LI M,LIU J,et al. Gyroidal metal-organic frameworks[J]. J. Am. Chem. Soc.,2012,134:67-70
[24] LU W,YUAN D,MAKALl T A,et al. A highly porous and robust(3,3,4)-connected metal-organic framework assembled with a 90 degrees bridging-angle embedded octacarboxylate ligand[J]. Angew Chem. Int. Ed.,2012,51:1580-1584.
[25] CHOI H-S,SUH M P. Highly selective CO₂ capture in flexible 3D coordination polymer networks[J]. Angew. Chem.,2009,48(37):6865-6869.
[26] ZHENG B,YANG Z,BAI J,et al. High and selective CO₂ capture by two mesoporous acylamide-functionalized rht-type metal-organic frameworks[J]. Chem. Commun.,2012,48(56):7025-7027.
[27] YUAN B Z,MA D Y,WANG X,et al. A microporous,moisture-stable,and amine-functionalized metal-organic framework for highly selective separation of CO₂ from CH₄[J]. Chem. Commun.,2012,48:1135-1137.
[28] MILLWARD A R,YAGHI O M. Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room temperature[J]. J. Am. Chem. Soc.,2005,127:17998-17999.
[29] 颜星,李永生,杨杰. 金属有机骨架化合物在CO₂捕集中的研究进展[J]. 天然气化工·C1化学与化工,2016,41(1):68-74. YAN X,LI Y S,YANG J. Research progress in CO₂ capture by metal organic frameworks[J]. Nature Gas Chemical Industry,2016,41(1):68-74.
[30] ZHANG Z J,ZHAO Y G,GONG Q H,et al. MOFs for CO₂ capture and separation from flue gas mixtures:the effect of multifunctional sites on their adsorption capacity and selectivity[J]. Chem. Comm.,2013,49:653-661.
[31] HAO H H,REALI R S,SMITH D A,et al. Highly selective CO₂ capture by a flexible microporous metal-organic framework(MMOF)material[J]. Chem.:Eur. J.,2010,16(17):13951-13954.
[32] LONG P,DAVID H O,LAUREN R,et al. Separation of hydrocarbons with a microporous metal-organic framework[J]. Angew. Chem. Int. Ed.,2006,45:616-619.
[33] PERALTA D,CHAPLAIS G,MASSERON A S.Comparison of the behavior of metal organic frameworks and zeolites for hydrocarbon separations[J]. J. Am. Chem. Soc.,2012,134:8115-8126.
[34] 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(48):7666-7673.
[35] HERM Z R,WIERS B M,MASON J A,et al. Separation of hexane isomers in a metal-organic framework with triangular channels[J]. Science,2013,340(6135):960-964.
[36] 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,2012,335:1606-1610.
[37] LI K H,OLSON D H,DEIDEL J,et al. Zeolitic imidazolate frameworks for kinetic separation of propane and propene[J]. J. Am. Chem. Soc.,2009,131(30):10368-10369.
[38] 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.
[39] OBENHAUS F,DROSTE W,NEUMEISTER J B. Ullman's encyclopedia of industrial chemistry; electronic release[M]. Weinheim:Wiley-VCH,2012.
[40] BERGH J van de,GUCUYENER C,PIDKE E A,et al. Understanding the anomalous alkane selectivity of ZIF-7 in the separation of light alkane/alkene mixtures[J]. Chem. Int. Ed.,2011,17:8832-8840.
[41] 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.,2016,4:751-755.
[42] 侯丹丹,刘大欢,阳庆元,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]. Chemical Industry and Engineering Progress,2015,34(8):2907-2915.
[43] BAHRI M,HAGHIGHAT F,KAZEMIAN H,et al. A comparative study on metal organic frameworks for indoor environment application:adsorption evaluation[J]. Chem. Eng. J.,2017,313:711-723.
[44] 贾雪莹,阚爱婷,朱丽君,等. 羧酸配体金属有机骨架材料在吸附脱硫领域的应用进展[J]. 石油化工,2016,45(4):491-500. JIA X Y,HAN A T,ZHU L J,et al. Progresses in metal-organic framework materials based on carboxylate ligands for adsorption desulfurization[J]. Petrochemical Technology,2016,45(4):491-500.
[45] HUANG Z H,LIU G Q,KANG F Y. Glucose-promoted Zn-based metal-organic framework/graphene oxide composites for hydrogen sulfi de removal[J]. Appl. Mater. Interfaces,2012,4(9):4942-4947.
[46] 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.
[47] YAMAGIWA H,SATO S,FUKAWA T,et al.Detection of volatile organic compounds by weight -detectable sensors coated with metal organic frameworks[J].Scientific Reports,2014,4:6247-6251.
[48] 李立博,王勇,王小青,等. 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(6):1794-1803. LI L B,WANG Y,WANG X Q,et al. Selective gas adsorption and separation in flexible metal-organic frameworks[J]. Chemical Industry and Engineering Progress,2016,35(6):1794-1803.
[49] CHEN Y F,HAN S,CAO S J,et al. Roll-to-roll production of metal-organic framework coatings for particulate matter removal[J]. Advanced Materials,2017,29(15):1606221.