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Host-guest and guest-guest interactions between xylene isomers confined in the MIL-47(V) pore system

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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.
Keywords
Separation, METAL-ORGANIC FRAMEWORKS, DENSITY-FUNCTIONAL THEORY, Xylenes, MIL-47, DFT-D, Adsorption, PI-STACKING INTERACTIONS, NONCOVALENT INTERACTIONS, BENZENE DIMER, SELECTIVE ADSORPTION, MOLECULAR-DYNAMICS, SEPARATION, SANDWICH

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Chicago
Ghysels, An, Matthias Vandichel, Toon Verstraelen, Monique A van der Veen, Dirk E De Vos, Michel Waroquier, and Veronique Van Speybroeck. 2012. “Host-guest and Guest-guest Interactions Between Xylene Isomers Confined in the MIL-47(V) Pore System.” Theoretical Chemistry Accounts 131 (7).
APA
Ghysels, A., Vandichel, M., Verstraelen, T., van der Veen, M. A., De Vos, D. E., Waroquier, M., & Van Speybroeck, V. (2012). Host-guest and guest-guest interactions between xylene isomers confined in the MIL-47(V) pore system. THEORETICAL CHEMISTRY ACCOUNTS, 131(7).
Vancouver
1.
Ghysels A, Vandichel M, Verstraelen T, van der Veen MA, De Vos DE, Waroquier M, et al. Host-guest and guest-guest interactions between xylene isomers confined in the MIL-47(V) pore system. THEORETICAL CHEMISTRY ACCOUNTS. 2012;131(7).
MLA
Ghysels, An, Matthias Vandichel, Toon Verstraelen, et al. “Host-guest and Guest-guest Interactions Between Xylene Isomers Confined in the MIL-47(V) Pore System.” THEORETICAL CHEMISTRY ACCOUNTS 131.7 (2012): n. pag. Print.
@article{2979575,
  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.},
  articleno    = {1234},
  author       = {Ghysels, An and Vandichel, Matthias and Verstraelen, Toon and van der Veen, Monique A and De Vos, Dirk E and Waroquier, Michel and Van Speybroeck, Veronique},
  issn         = {1432-881X},
  journal      = {THEORETICAL CHEMISTRY ACCOUNTS},
  keyword      = {Separation,METAL-ORGANIC FRAMEWORKS,DENSITY-FUNCTIONAL THEORY,Xylenes,MIL-47,DFT-D,Adsorption,PI-STACKING INTERACTIONS,NONCOVALENT INTERACTIONS,BENZENE DIMER,SELECTIVE ADSORPTION,MOLECULAR-DYNAMICS,SEPARATION,SANDWICH},
  language     = {eng},
  number       = {7},
  pages        = {13},
  title        = {Host-guest and guest-guest interactions between xylene isomers confined in the MIL-47(V) pore system},
  url          = {http://dx.doi.org/10.1007/s00214-012-1234-7},
  volume       = {131},
  year         = {2012},
}

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