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Theoretical Chemistry in Belgium pp 35–47Cite as

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

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Part of the book series: Highlights in Theoretical Chemistry ((HITC,volume 6))

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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Author information

Authors and Affiliations

  1. Center for Molecular Modeling, Quantum Chemistry-Molecular Modeling Alliance, Ghent University, Technologiepark 903, 9052, Ghent, Belgium

    An Ghysels, Matthias Vandichel, Toon Verstraelen, Michel Waroquier & Veronique Van Speybroeck

  2. Centre for Surface Chemistry and Catalysis, KU Leuven, Kasteelpark Arenberg 23, 3001, Heverlee, Belgium

    Monique A. van der Veen & Dirk E. De Vos

Authors
  1. An Ghysels
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  2. Matthias Vandichel
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  3. Toon Verstraelen
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  4. Monique A. van der Veen
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  5. Dirk E. De Vos
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  6. Michel Waroquier
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  7. Veronique Van Speybroeck
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Corresponding authors

Correspondence to An Ghysels or Veronique Van Speybroeck .

Editor information

Editors and Affiliations

  1. Laboratory of Theoretical Chemistry, University of Namur, Namur, Belgium

    Benoît Champagne

  2. Research Group of Theoretical Chemistry and Molecular Modeling, Hasselt University, Diepenbeek, Belgium

    Michael S. Deleuze

  3. Faculteit Wetenschappen, Free University of Brussels, Brussels, Belgium

    Frank De Proft

  4. Laboratory of Crystal Engineering Inst.of Condensed Matter and Nanoscience, Catholic University of Louvain, Louvain-La-Neuve, Belgium

    Tom Leyssens

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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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