Host-guest and guest-guest interactions between xylene isomers confined in the MIL-47(V) pore system
- Author
- An Ghysels (UGent) , Matthias Vandichel (UGent) , Toon Verstraelen (UGent) , Monique A van der Veen, Dirk E De Vos, Michel Waroquier (UGent) and Veronique Van Speybroeck (UGent)
- Organization
- 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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Citation
Please use this url to cite or link to this publication: http://hdl.handle.net/1854/LU-2979575
- MLA
- Ghysels, An, et al. “Host-Guest and Guest-Guest Interactions between Xylene Isomers Confined in the MIL-47(V) Pore System.” THEORETICAL CHEMISTRY ACCOUNTS, vol. 131, no. 7, 2012, doi:10.1007/s00214-012-1234-7.
- 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). https://doi.org/10.1007/s00214-012-1234-7
- Chicago author-date
- 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). https://doi.org/10.1007/s00214-012-1234-7.
- Chicago author-date (all authors)
- 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). doi:10.1007/s00214-012-1234-7.
- 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).
- IEEE
- [1]A. Ghysels et al., “Host-guest and guest-guest interactions between xylene isomers confined in the MIL-47(V) pore system,” THEORETICAL CHEMISTRY ACCOUNTS, vol. 131, no. 7, 2012.
@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}},
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}},
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://doi.org/10.1007/s00214-012-1234-7}},
volume = {{131}},
year = {{2012}},
}
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