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Efficient approach for the computational study of alcohol and nitrile adsorption in H-ZSM-5

Jeroen Van der Mynsbrugge UGent, Karen Hemelsoet UGent, Matthias Vandichel UGent, Michel Waroquier UGent and Veronique Van Speybroeck UGent (2012) JOURNAL OF PHYSICAL CHEMISTRY C. 116(9). p.5499-5508
abstract
Since many industrially important processes start with the adsorption of guest molecules inside the pores of an acidic zeolite catalyst, a proper estimate of the adsorption enthalpy is of paramount importance. In this contribution, we report ab initio calculations on the adsorption of water, alcohols, and nitriles at the bridging Bronsted sites of H-ZSM-5, using both cluster and periodic models to account for the zeolite environment. Stabilization of the adsorption complexes results from hydrogen bonding between the guest molecule and the framework, as well as from embedding, i.e., van der Waals interactions with the pore walls. Large-cluster calculations with different DFT methods, in particular B3LYP(-D), PBE(-D), M062X(-D), and omega B97X-D, are tested for their ability to reproduce the experimental heats of adsorption available in the literature (J. Phys. Chem. B 1997, 101, 3811-3817). A proper account of dispersion interactions is found to be crucial to describe the experimental trend across a series of adsorbates of increasing size, i.e., an increase in adsorption enthalpy by 10-15 kJ/mol for each additional carbon atom. The extended-cluster model is shown to offer an attractive alternative to periodic simulations on the entire H-ZSM-5 unit cell, resulting in virtually identical final adsorption enthalpies. Comparing calculated stretch frequencies of the zeolite acid sites and the adsorbate functional groups with experimental IR data additionally confirms that the cluster approach provides an appropriate representation of the adsorption complexes.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
INITIO MOLECULAR-DYNAMICS, DENSITY-FUNCTIONAL THEORY, TOTAL-ENERGY CALCULATIONS, DER-WAALS COMPLEXES, SURFACE COMPLEXES, DISPERSION CORRECTIONS, AB-INITIO, ACIDIC ZEOLITES, ZSM-5 ZEOLITES, WAVE BASIS-SET
journal title
JOURNAL OF PHYSICAL CHEMISTRY C
J. Phys. Chem. C
volume
116
issue
9
pages
5499 - 5508
Web of Science type
Article
Web of Science id
000301315700028
JCR category
MATERIALS SCIENCE, MULTIDISCIPLINARY
JCR impact factor
4.814 (2012)
JCR rank
26/239 (2012)
JCR quartile
1 (2012)
ISSN
1932-7447
DOI
10.1021/jp2123828
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
2082545
handle
http://hdl.handle.net/1854/LU-2082545
date created
2012-04-10 08:56:18
date last changed
2013-03-08 00:30:42
@article{2082545,
  abstract     = {Since many industrially important processes start with the adsorption of guest molecules inside the pores of an acidic zeolite catalyst, a proper estimate of the adsorption enthalpy is of paramount importance. In this contribution, we report ab initio calculations on the adsorption of water, alcohols, and nitriles at the bridging Bronsted sites of H-ZSM-5, using both cluster and periodic models to account for the zeolite environment. Stabilization of the adsorption complexes results from hydrogen bonding between the guest molecule and the framework, as well as from embedding, i.e., van der Waals interactions with the pore walls. Large-cluster calculations with different DFT methods, in particular B3LYP(-D), PBE(-D), M062X(-D), and omega B97X-D, are tested for their ability to reproduce the experimental heats of adsorption available in the literature (J. Phys. Chem. B 1997, 101, 3811-3817). A proper account of dispersion interactions is found to be crucial to describe the experimental trend across a series of adsorbates of increasing size, i.e., an increase in adsorption enthalpy by 10-15 kJ/mol for each additional carbon atom. The extended-cluster model is shown to offer an attractive alternative to periodic simulations on the entire H-ZSM-5 unit cell, resulting in virtually identical final adsorption enthalpies. Comparing calculated stretch frequencies of the zeolite acid sites and the adsorbate functional groups with experimental IR data additionally confirms that the cluster approach provides an appropriate representation of the adsorption complexes.},
  author       = {Van der Mynsbrugge, Jeroen and Hemelsoet, Karen and Vandichel, Matthias and Waroquier, Michel and Van Speybroeck, Veronique},
  issn         = {1932-7447},
  journal      = {JOURNAL OF PHYSICAL CHEMISTRY C},
  keyword      = {INITIO MOLECULAR-DYNAMICS,DENSITY-FUNCTIONAL THEORY,TOTAL-ENERGY CALCULATIONS,DER-WAALS COMPLEXES,SURFACE COMPLEXES,DISPERSION CORRECTIONS,AB-INITIO,ACIDIC ZEOLITES,ZSM-5 ZEOLITES,WAVE BASIS-SET},
  language     = {eng},
  number       = {9},
  pages        = {5499--5508},
  title        = {Efficient approach for the computational study of alcohol and nitrile adsorption in H-ZSM-5},
  url          = {http://dx.doi.org/10.1021/jp2123828},
  volume       = {116},
  year         = {2012},
}

Chicago
Van der Mynsbrugge, Jeroen, Karen Hemelsoet, Matthias Vandichel, Michel Waroquier, and Veronique Van Speybroeck. 2012. “Efficient Approach for the Computational Study of Alcohol and Nitrile Adsorption in H-ZSM-5.” Journal of Physical Chemistry C 116 (9): 5499–5508.
APA
Van der Mynsbrugge, J., Hemelsoet, K., Vandichel, M., Waroquier, M., & Van Speybroeck, V. (2012). Efficient approach for the computational study of alcohol and nitrile adsorption in H-ZSM-5. JOURNAL OF PHYSICAL CHEMISTRY C, 116(9), 5499–5508.
Vancouver
1.
Van der Mynsbrugge J, Hemelsoet K, Vandichel M, Waroquier M, Van Speybroeck V. Efficient approach for the computational study of alcohol and nitrile adsorption in H-ZSM-5. JOURNAL OF PHYSICAL CHEMISTRY C. 2012;116(9):5499–508.
MLA
Van der Mynsbrugge, Jeroen, Karen Hemelsoet, Matthias Vandichel, et al. “Efficient Approach for the Computational Study of Alcohol and Nitrile Adsorption in H-ZSM-5.” JOURNAL OF PHYSICAL CHEMISTRY C 116.9 (2012): 5499–5508. Print.