Abstract
The porous MIL-47 material shows a selective adsorption behavior for para-, ortho-, and meta-isomers of xylenes, making the material a serious candidate for separation applications. The origin of the selectivity lies in the differences in interactions (energetic) and confining (entropic). This paper investigates the xylene–framework interactions and the xylene–xylene interactions with quantum mechanical calculations, using a dispersion-corrected density functional and periodic boundary conditions to describe the crystal. First, the strength and geometrical characteristics of the optimal xylene–xylene interactions are quantified by studying the pure and mixed pairs in gas phase. An extended set of initial structures is created and optimized to sample as many relative orientations and distances as possible. Next, the pairs are brought in the pores of MIL-47. The interaction with the terephthalic linkers and other xylenes increases the stacking energy in gas phase (-31.7 kJ/mol per pair) by roughly a factor four in the fully loaded state (-58.3 kJ/mol per xylene). Our decomposition of the adsorption energy shows various trends in the contributing xylene–xylene interactions. The absence of a significant difference in energetics between the isomers indicates that entropic effects must be mainly responsible for the separation behavior.
Published as part of the special collection of articles celebrating theoretical and computational chemistry in Belgium.
Electronic supplementary materialThe online version of this article (doi:10.1007/s00214-012-1234-7) contains supplementary material, which is available to authorized users.
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References
Férey G (2008) Hybrid porous solids: past, present, future. Chem Soc Rev 37:191–214
Long JR, Yaghi OM (2009) The pervasive chemistry of metalorganic frameworks. Chem Soc Rev 38:1213–1214
Perry JJ, Perman JA, Zaworotko MJ (2009) Design and synthesis of metal-organic frameworks using metal-organic polyhedra as supermolecular building blocks. Chem Soc Rev 38:1400–1417
Eddaoudi M, Kim J, Rosi N, Vodak D, Wachter J, O’Keeffe M, Yaghi OM (2002) Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 295:469–472
Férey G, Serre C, Devic T, Maurin G, Jobic H, Llewellyn PL, De Weireld G, Vimont A, Daturi M, Chang JS (2011) Why hybrid porous solids capture greenhouse gases? Chem Soc Rev 40:550–562
Meek ST, Greathouse JA, Allendorf MD (2011) Metal-organic frameworks: a rapidly growing class of versatile nanoporous materials. Adv Mater 23:249–267
Tranchemontagne DJ, Mendoza-Cortes JL, O’Keeffe M, Yaghi OM (2009) Secondary building units, nets and bonding in the chemistry of metal-organic frameworks. Chem Soc Rev 38:1257– 1283
Alaerts L, Kirschhock CEA, Maes M, van der Veen MA, Finsy V, Depla A, Martens JA, Baron GV, Jacobs PA, Denayer JEM, De Vos DE (2007) Selective adsorption and separation of xylene isomers and ethylbenzene with the microporous vanadium(IV) terephthalate MIL-47. Angew Chem Int Edit 46:4293–4297
Finsy V, Verelst H, Alaerts L, De Vos D, Jacobs PA, Baron GV, Denayer JFM (2008) Pore-filling-dependent selectivity effects in the vapor-phase separation of xylene isomers on the metalorganic framework MIL-47. J Am Chem Soc 130:7110–7118
Vermoortele F, Maes M, Moghadam PZ, Lennox MJ, Ragon F, Boulhout M, Biswas S, Laurier KGM, Beurroies I, Denoyel R, Roeffaers M, Stock N, Düren T, Serre C, De Vos DE (2011) p-xylene-selective metal–organic frameworks: a case of topology- directed selectivity. J Am Chem Soc 133:18526–18529
Fritz Ullmann’s encyclopedia of industrial chemistry, 6th edn. In: Electronic release, 2000
Barthelet K, Marrot J, Riou D, Férey G (2002) A breathing hybrid organic-inorganic solid with very large pores and high agnetic characteristics. Angew Chem Int Edit 41:281
Grimme S (2006) Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J Comput Chem 27:1787–1799
Grimme S, Antony J, Schwabe T, Muck-Lichtenfeld C (2007) Density functional theory with dispersion corrections for supramolecular structures, aggregates, and complexes of (bio)organic molecules. Org Biomol Chem 5:741–758
Schwabe T, Grimme S (2008) Theoretical thermodynamics for large molecules: walking the thin line between accuracy and computational cost. Acc Chem Res 41:569–579
Liu B, Smit B (2009) Comparative molecular simulation study of CO2/N2 and CH4/N2 separation in zeolites and metal—organic frameworks. Langmuir 25:5918–5926
Ramsahye NA, Maurin G, Bourrelly S, Llewellyn PL, Devic T, Serre C, Loiseau T, Férey G (2007) Adsorption of CO2 in metal organic frameworks of different metal centres: grand Canonical Monte Carlo simulations compared to experiments. Adsorpt J Int Adsorpt Soc 13:461–467
Rosenbach N, Jobic H, Ghoufi A, Salles F, Maurin G, Bourrelly S, Llewellyn PL, Devic T, Serre C, Férey G (2008) Quasi- lastic neutron scattering and molecular dynamics study of methane diffusion in metal organic frameworks MIL-47(V) and MIL- 53(Cr). Angew Chem Int Edit 47:6611–6615
Salles F, Jobic H, Maurin G, Koza MM, Llewellyn PL, Devic T, Serre C, Férey G (2008) Experimental evidence supported by simulations of a very high H-2 diffusion in metal organic framework materials. Phys Rev Lett 100(24):245901
Castillo JM, Vlugt TJH, Calero S (2009) Molecular simulation study on the separation of xylene isomers in MIL-47 metal— organic frameworks. J Phys Chem C 113:20869–20874
Wang S, Yang Q, Zhong C (2008) Adsorption and separation of binary mixtures in a metal-organic framework Cu-BTC: a computational study. Sep Purif Technol 60:30–35
Hamon L, Llewellyn PL, Devic T, Ghoufi A, Clet G, Guillerm V, Pirngruber GD, Maurin G, Serre C, Driver G, Beek WV, Jolimaître E, Vimont A, Daturi M, Férey GR (2009) Co-adsorption and separation of CO2–CH4 mixtures in the highly flexible MIL- 53(Cr) MOF. J Am Chem Soc 131:17490–17499
Gallo M, Glossman-Mitnik D (2009) Fuel gas storage and separations by Metal—organic frameworks: simulated adsorption isotherms for H2 and CH4 and their equimolar mixture. J Phys Chem C 113:6634–6642
Pan L, Olson DH, Ciemnolonski LR, Heddy R, Li J (2006) Separation of hydrocarbons with a microporous metal-organic framework. Angew Chem Int Edit 45:616–619
Vanduyfhuys L, Verstraelen T, Vandichel M, Waroquier M, Van Speybroeck V (2012) Ab initio parametrized force field of the metal-organic framework MIL-53(Al) for use in molecular simulations including lattice dynamics. J Chem Theory Comput (submitted)
Sinnokrot MO, Sherrill CD (2003) Unexpected substituent effects in face-to-face p-stacking interactions. J Phys Chem A 107:8377– 8379
Sinnokrot MO, Sherrill CD (2004) Highly accurate coupled cluster potential energy curves for the benzene dimer: sandwich, T-shaped, and parallel-displaced configurations. J Phys Chem A 108:10200–10207
Sinnokrot MO, Sherrill CD (2004) Substituent effects in p–p interactions: sandwich and T-shaped configurations. J Am Chem Soc 126:7690–7697
Alaerts L, Maes M, Jacobs PA, Denayer JFM, De Vos DE (2008) Activation of the metal-organic framework MIL-47 for selective adsorption of xylenes and other difunctionalized aromatics. Phys Chem Chem Phys 10:2979–2985
Cremer D, Pople JA (1975) General definition of ring puckering coordinates. J Am Chem Soc 97:1354–1358
Car R, Parrinello M (1985) Unified approach for molecular dynamics and density-functional theory. Phys Rev Lett 55:2471– 2474
Becke AD (1988) Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A 38:3098
Vanderbilt D (1990) Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Phys Rev B 41:7892
Verstraelen T, Van Speybroeck V, Waroquier M (2008) ZEOBUILDER: a GUI toolkit for the construction of complex molecular structures on the nanoscale with building blocks. J Chem Inf Model 48:1530–1541
Gu J, Wang J, Leszczynski J, Xie Y, Schaefer HF (2008) Chem Phys Lett 459:164
McGaughey GB, Gagne M, Rappe AK (1998) J Biol Chem 273:15458
Morgado C, Vincent MA, Hillier IH, Shan X (2007) Phys Chem Chem Phys 9:448
Pavone M, Rega N, Barone V (2008) Chem Phys Lett 452:333
Piacenza M, Grimme S (2004) J Comput Chem 25:83
Podeszwa R, Bukowski R, Szalewicz K (2006) J Phys Chem A 110:10345
Waller MP, Robertazzi A, Platts JA, Hibbs DE, Williams PA (2006) J Comput Chem 27:491
Zhao Y, Truhlar DG (2005) Phys Chem Chem Phys 7:2701
Zhao Y, Truhlar DG (2006) J Chem Theory Comput 2:1009
Lee EC, Hong BH, Lee JY, Kim JC, Kim D, Kim Y, Tarakeshwar P, Kim KS (2005) Substituent effects on the edge-to-face aromatic interactions. J Am Chem Soc 127:4530–4537
Raju RK, Bloom JWG, An Y, Wheeler SE (2011) Substituent effects on non-covalent interactions with aromatic rings: insights from computational chemistry. ChemPhysChem 12:3116–3130
Hohenstein EG, Duan JN, Sherrill CD (2011) Origin of the surprising enhancement of electrostatic energies by electron-donating substituents in substituted sandwich benzene dimers. J Am Chem Soc 133:13244–13247
De Moor BA, Ghysels A, Reyniers M-F, Van Speybroeck V, Waroquier M, Marin GB (2011) Normal mode analysis in zeolites: toward an efficient calculation of adsorption entropies. J Chem Theory Comput 7:1090–1101
Van der Mynsbrugge J, Hemelsoet K, Vandichel M, Waroquier M, Van Speybroeck V (2012) An efficient approach for the computational study of alcohol and nitrile adsorption in H-ZSM- 5. J Phys Chem C 116:5499–5508
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Ghysels, A. et al. (2014). Host–guest and guest–guest interactions between xylene isomers confined in the MIL-47(V) pore system. In: Champagne, B., Deleuze, M., De Proft, F., Leyssens, T. (eds) Theoretical Chemistry in Belgium. Highlights in Theoretical Chemistry, vol 6. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-41315-5_4
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DOI: https://doi.org/10.1007/978-3-642-41315-5_4
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