Molecular design of metal-organic frameworks with different metal ligands for bio-methane separation

doi:10.3969/j.issn.0438-1157.2014.05.024

Abstract

Abstract: The adsorption and separation capabilities of metal-organic frameworks (MOFs) for CO₂ and CH₄ gas mixtures were studied by grand canonical Monte Carlo (GCMC) simulations. Three sub-families (M-MOF-74, M-MIL-53 and [M(atz)(bdc)_0.5]) (M=Mg, Co, Ni, Zn, Al, Cr) MOFs with different metal ligands were investigated. Simulation results showed that the CO₂ adsorption capability of Mg-MOF-74 exceeded the others at high pressures; both amine functionalized [Zn(atz)(bdc)_0.5] and [Co(atz)(bdc)_0.5] MOFs had superior CO₂ separation performance at low pressures. The radial distribution functions and the overlapping snapshots of CO₂ adsorption showed that in each sub-family of MOFs, different metal ligands affected their CO₂ adsorption configuration and resulted in their different adsorption and separation capabilities. This work could provide some guidance for the design and development of new high performance MOFs for CO₂ and CH₄ separation.

Key words: molecular simulation, metal-organic framework, adsorption, separation, bio-methanePPT

摘要： 采用巨正则Monte Carlo法（GCMC），对CH₄ /CO₂混合气体体系基于金属-有机骨架材料（MOFs）的吸附分离进行了模拟研究。吸附分离材料涉及3个系列（M-MOF-74、M-MIL-53和[M（atz）（bdc）_0.5]）（M=Mg，Co，Ni，Zn，Al，Cr）不同金属配位的8种MOF材料。研究表明，Mg-MOF-74的CO₂吸附性能在高压下优于其他材料；在低压时，拥有大量氨基官能团的[Zn（atz）（bdc）_0.5]和[Co（atz）（bdc）_0.5]材料有更高效的CO₂分离性能。通过径向分布函数和CO₂吸附构型快照重叠图进一步分析发现，各个系列材料不同金属配位对CO₂吸附构型的影响造成了材料吸附分离性能有较大的不同。研究结果能够为实验上设计和开发新型高效CO₂和CH₄吸附分离MOFs材料提供启发。

关键词: 分子模拟, 金属-有机骨架材料, 吸附, 分离, 生物甲烷

CLC Number:

TQ013
O647.3

QIAO Zhiwei, YANG Rendang, WANG Haihui, ZHOU Jian. Molecular design of metal-organic frameworks with different metal ligands for bio-methane separation[J]. CIESC Journal, DOI: 10.3969/j.issn.0438-1157.2014.05.024.

乔智威, 杨仁党, 王海辉, 周健. 面向生物甲烷分离的不同金属配位金属-有机骨架材料的分子设计[J]. 化工学报, DOI: 10.3969/j.issn.0438-1157.2014.05.024.

References 30

[1]	Liu Chang(刘畅),Lu Xiaohua(陆小华). Carbon reduction pattern in China: comparison of CCS and biomethane route[J]. CIESC Journal(化工学报), 2012, 63(1): 1-6
[2]	Wu D, Wang C, Liu B, Liu D, Yang Q, Zhong C. Large-scale computational screening of metal-organic frameworks for CH4/H2 separation[J]. AIChE J., 2012, 58(7): 2078-2084
[3]	Qiao Z, Wu Y, Li X, Zhou J. Molecular simulation on the separation of water/ethanol azeotropic mixture by poly (vinyl alcohol) membrane[J]. Fluid Phase Equilib., 2011, 302(1): 14-20
[4]	Lu L, Lu X, Chen Y, Huang L, Shao Q, Wang Q. Monte Carlo simulation of adsorption of binary and quaternary alkane isomers mixtures in zeolites: effect of pore size and structure[J]. Fluid. Phase Equilibr., 2007, 259(2): 135-145
[5]	Fairen-Jimenez D, Colón Y J, Farha O, Bae Y S, Hupp J T, Snurr R Q. Understanding excess uptake maxima for hydrogen adsorption isotherms in frameworks with rht topology[J]. Chem. Commun., 2012, 48: 10496-10498
[6]	Caskey S R, Wong-Foy A G, Matzger A J. Dramatic tuning of carbon dioxide uptake via metal substitution in a coordination polymer with cylindrical pores[J]. J. Am. Chem. Soc., 2008, 130(33): 10870-10871
[7]	Mueller U, Schubert M, Teich F, Puetter H, Schierle-Arndt K, Pastre J. Metal-organic frameworks-prospective industrial applications[J]. J. Mater. Chem., 2006, 16(7): 626-636
[8]	Dietzel P D C, Besikiotis V, Blom R. Application of metal-organic frameworks with coordinatively unsaturated metal sites in storage and separation of methane and carbon dioxide[J]. J. Mater. Chem., 2009, 19(39): 7362-7370
[9]	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
[10]	Alaerts L, Maes M, van der Veen M A, Jacobs P A, De Vos D E. Metal-organic frameworks as high-potential adsorbents for liquid-phase separations of olefins, alkylnaphthalenes and dichlorobenzenes [J]. Phys. Chem. Chem. Phys., 2009, 11(16): 2903- 2911
[11]	Horcajada P, Serre C, Vallet-Regí M, Sebban M, Taulelle F, Férey G. Metal-organic frameworks as efficient materials for drug delivery[J]. Angew. Chem., 2006, 118(36): 6120-6124
[12]	Yazayd?n A O, Snurr R Q, Park T H, Koh K, Liu J, LeVan M D, Benin A I, Jakubczak P, Lanuza M, Galloway D B, Low J J, Willis R R. Screening of metal-organic frameworks for carbon dioxide capture from flue gas using a combined experimental and modeling approach[J]. J. Am. Chem. Soc., 2009, 131(51): 18198-18199
[13]	Yang Qingyuan(阳庆元),Liu Dahuan(刘大欢),Zhong Chongli(仲崇立). Computational study of metal-organic frameworks[J]. CIESC Journal(化工学报), 2009, 60(4): 805-819
[14]	Zhu Y, Zhou J, Hu J, Liu H, Hu Y. Computer simulation of gas adsorption in modified COF-108: the impregnation of C60 into COF-108[J]. Mol. Simulat., 2012, 38(7): 595-603
[15]	Dietzel P D C, Morita Y, Blom R, Fjellvåg H. An in situ high-temperature single-crystal investigation of a dehydrated metal-organic framework compound and field-induced magnetization of one-dimensional metal-oxygen chains[J]. Angew. Chem., 2005, 117(39): 6512-6516
[16]	Dietzel P D C, Panella B, Hirscher M, Blom R, Fjellvåg H. Hydrogen adsorption in a nickel based coordination polymer with open metal sites in the cylindrical cavities of the desolvated framework[J]. Chem. Commun., 2006(9): 959-961
[17]	Serre C, Millange F, Thouvenot C, Noguès M, Marsolier G, Louër D, Férey G. Very large breathing effect in the first nanoporous chromium(Ⅲ)-based solids: MIL-53 or CrⅢ(OH)·{O2C-C6H4-CO2}· {HO2C-C6H4-CO2H} x·H2Oy[J]. J. Am. Chem. Soc., 2002, 124(45): 13519-13526
[18]	Loiseau T, Serre C, Huguenard C, Fink G, Taulelle F, Henry M, Bataille T, Férey G. A rationale for the large breathing of the porous aluminum terephthalate (MIL-53) upon hydration[J]. Chem. Eur. J., 2004, 10(6): 1373-1382
[19]	Liu B, Zhao R, Yang G, Hou L, Wang Y Y, Shi Q Z. Two isostructural amine-functionalized 3D self-penetrating microporous MOFs exhibiting high sorption selectivity for CO2[J]. Cryst. Eng. Comm., 2013, 15: 2057-2060
[20]	Mayo S L, Olafson B D, Goddard W A. Dreiding: a generic force field for molecular simulations[J]. J. Phys. Chem., 1990, 94(26): 8897-8909
[21]	Rappe A K, Casewit C J, Colwell K S, Goddard Iii W A, Skiff W M. UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations[J]. J. Am. Chem. Soc., 1992, 114(25): 10024-10035
[22]	Breneman C M, Wiberg K B. Determining atom-centered monopoles from molecular electrostatic potentials. The need for high sampling density in formamide conformational analysis[J]. J. Comput. Chem., 1990, 11(3): 361-373
[23]	Lee C, Yang W, Parr R G. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density[J]. Phys. Rev. B, 1988, 37(2): 785-789
[24]	Becke A D. Density-functional thermochemistry(Ⅲ): The role of exact exchange [J]. J. Chem. Phys., 1993, 98: 5648-5652
[25]	Goodbody S J, Watanabe K, MacGowan D, Walton J P R B, Quirke N. Molecular simulation of methane and butane in silicalite[J]. J. Chem. Soc., Faraday Trans., 1991, 87(13): 1951-1958
[26]	Potoff J J, Siepmann J I. Vapor-liquid equilibria of mixtures containing alkanes, carbon dioxide, and nitrogen[J]. AIChE J., 2001, 47(7): 1676-1682
[27]	Wilmer C E, Farha O K, Bae Y S, Hupp J T, Snurr R Q. Structure-property relationships of porous materials for carbon dioxide separation and capture[J]. Energy Environ. Sci., 2012, 5: 9849-9856
[28]	Qiao Z, Zhou J, Lu X. Designing new amine functionalized metal-organic frameworks for carbon dioxide/methane separation[J]. Fluid Phase Equilibr., 2014, 362: 342-348
[29]	Zhu Y, Zhou J, Hu J, Liu H. The effect of grafted amine group on the adsorption of CO2 in MCM-41: a molecular simulation[J]. Catal. Today, 2012, 194(1): 53-59
[30]	Xu Q, Liu D, Yang Q, Zhong C, Mi J. Li-modified metal-organic frameworks for CO2/CH4 separation: a route to achieving high adsorption selectivity[J]. J. Mater. Chem., 2010, 20(4): 706-714