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Isobutene Protonation in H-FAU, H-MOR, H-ZSM-5, and H-ZSM-22

Cuong Manh Nguyen UGent, Bart De Moor UGent, Marie-Françoise Reyniers UGent and Guy Marin UGent (2012) JOURNAL OF PHYSICAL CHEMISTRY C. 116(34). p.18236-18249
abstract
Kinetics and thermodynamics of isobutene protonation in H-FAU, H-MOR., H-ZSM-5, and H-ZSM-22 have been studied in a temperature range of 300-800 K, combining PW91-D//PW91 periodic density functional :theory calculations with statistical thermodynamics. At temperatures relevant for industrial zeolite-catalyzed processes (500-800 K), the tert-butyl carbenium ions more stable than the tert-butoxy in H-MOR, H-ZSM-5, and H-ZSM-22. Entropy contributions govern the standard Gibbs free energy stability of the chemisorbed intermediates. Due to the absence of a C-O covalent bond, formation of the tert-butyl carbenium ion is accompanied by a lower entropy :Loss and, consequently, has a higher stability than the tert-butoxy in H-MOB., H-ZSM-5, and H-ZSM-22. At 800 K, the protonation toward tert-butoxy in H-FAU, H-MOB, and H-ZSM-5 and to the tert-butyl carbenium ion in H-ZSM-22 is 5 to 7 orders of magnitude faster than the protonation toward isobutoxy. Among the four zeolites, the lowest activation energy is found in H-ZSM-22.
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, GENERALIZED GRADIENT APPROXIMATION, TOTAL-ENERGY CALCULATIONS, AUGMENTED-WAVE METHOD, ELASTIC BAND METHOD, TERT-BUTYL CATION, HYDROCARBON CONVERSION, CATALYTIC CRACKING, ZEOLITE FRAMEWORK, ACIDIC ZEOLITES
journal title
JOURNAL OF PHYSICAL CHEMISTRY C
J. Phys. Chem. C
volume
116
issue
34
pages
18236 - 18249
Web of Science type
Article
Web of Science id
000308120000030
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/jp304081k
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
3010153
handle
http://hdl.handle.net/1854/LU-3010153
date created
2012-10-09 16:37:00
date last changed
2012-10-12 10:16:59
@article{3010153,
  abstract     = {Kinetics and thermodynamics of isobutene protonation in H-FAU, H-MOR., H-ZSM-5, and H-ZSM-22 have been studied in a temperature range of 300-800 K, combining PW91-D//PW91 periodic density functional :theory calculations with statistical thermodynamics. At temperatures relevant for industrial zeolite-catalyzed processes (500-800 K), the tert-butyl carbenium ions more stable than the tert-butoxy in H-MOR, H-ZSM-5, and H-ZSM-22. Entropy contributions govern the standard Gibbs free energy stability of the chemisorbed intermediates. Due to the absence of a C-O covalent bond, formation of the tert-butyl carbenium ion is accompanied by a lower entropy :Loss and, consequently, has a higher stability than the tert-butoxy in H-MOB., H-ZSM-5, and H-ZSM-22. At 800 K, the protonation toward tert-butoxy in H-FAU, H-MOB, and H-ZSM-5 and to the tert-butyl carbenium ion in H-ZSM-22 is 5 to 7 orders of magnitude faster than the protonation toward isobutoxy. Among the four zeolites, the lowest activation energy is found in H-ZSM-22.},
  author       = {Nguyen, Cuong Manh and De Moor, Bart and Reyniers, Marie-Fran\c{c}oise and Marin, Guy},
  issn         = {1932-7447},
  journal      = {JOURNAL OF PHYSICAL CHEMISTRY C},
  keyword      = {INITIO MOLECULAR-DYNAMICS,GENERALIZED GRADIENT APPROXIMATION,TOTAL-ENERGY CALCULATIONS,AUGMENTED-WAVE METHOD,ELASTIC BAND METHOD,TERT-BUTYL CATION,HYDROCARBON CONVERSION,CATALYTIC CRACKING,ZEOLITE FRAMEWORK,ACIDIC ZEOLITES},
  language     = {eng},
  number       = {34},
  pages        = {18236--18249},
  title        = {Isobutene Protonation in H-FAU, H-MOR, H-ZSM-5, and H-ZSM-22},
  url          = {http://dx.doi.org/10.1021/jp304081k},
  volume       = {116},
  year         = {2012},
}

Chicago
Nguyen, Cuong Manh, Bart De Moor, Marie-Françoise Reyniers, and Guy Marin. 2012. “Isobutene Protonation in H-FAU, H-MOR, H-ZSM-5, and H-ZSM-22.” Journal of Physical Chemistry C 116 (34): 18236–18249.
APA
Nguyen, C. M., De Moor, B., Reyniers, M.-F., & Marin, G. (2012). Isobutene Protonation in H-FAU, H-MOR, H-ZSM-5, and H-ZSM-22. JOURNAL OF PHYSICAL CHEMISTRY C, 116(34), 18236–18249.
Vancouver
1.
Nguyen CM, De Moor B, Reyniers M-F, Marin G. Isobutene Protonation in H-FAU, H-MOR, H-ZSM-5, and H-ZSM-22. JOURNAL OF PHYSICAL CHEMISTRY C. 2012;116(34):18236–49.
MLA
Nguyen, Cuong Manh, Bart De Moor, Marie-Françoise Reyniers, et al. “Isobutene Protonation in H-FAU, H-MOR, H-ZSM-5, and H-ZSM-22.” JOURNAL OF PHYSICAL CHEMISTRY C 116.34 (2012): 18236–18249. Print.