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Theoretical study of the adsorption of C1-C4 primary alcohols in H-ZSM-5

Cuong Manh Nguyen UGent, Marie-Françoise Reyniers UGent and Guy Marin UGent (2010) PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 12(32). p.9481-9493
abstract
The adsorption of C1-C4 primary alcohols at the Al12-O24(H)-Si12 intersection site in H-ZSM-5 is investigated using periodic density functional theory (DFT) calculations and adding a damped interatomic potential to the DFT results to account for dispersive van der Waals interactions (DFT-D). A good agreement between predicted and experimentally available adsorption enthalpies for C1-C3 alcohols is obtained. The effect of the H-ZSM-5 framework is sampled for adsorption of the C1-C4 alcohols in the straight and the zigzag channel. A variety of possible geometries, including hydrogen-bonded (physisorbed) and protonated (chemisorbed) complexes, are located as stable minima indicating that the potential energy surface connecting them is broad and very shallow. Experimental infrared (IR) spectra of the C1-C4 alcohols are interpreted based on harmonic frequency calculations for the most stable physisorbed and chemisorbed complexes. The stability of the adsorbed alcohols is governed by an interplay between their intrinsic basicity, van der Waals dispersive interactions and steric constraints exerted by the zeolite framework. In essence, steric constraints destabilize local hydrogen bonding and/or Coulomb alcohol-Bronsted acid site interactions while dispersive van der Waals interactions enhance the stability of physisorbed and chemisorbed complexes. Due to the prevalence of van der Waals interactions over steric constraints, C1-C4 alcohols adsorb preferentially in the more compact zigzag channel than in the straight channel. Both the physisorption and chemisorption energies increase linearly with 13 to 15 kJ mol(-1) per carbon atom in the straight and the zigzag channel, respectively.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
zeolites, adsorption, periodic DFT, alcohols, PORE CONFINEMENT, CATALYTIC DEHYDRATION, METHANOL ADSORPTION, AMORPHOUS ALUMINOSILICATE, ZEOLITE ZSM-5, AB-INITIO, MOLECULAR-SIEVES, HOST FORCE-FIELD, BRONSTED ACID SITES, DENSITY-FUNCTIONAL THEORY
journal title
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Phys. Chem. Chem. Phys.
volume
12
issue
32
pages
9481 - 9493
Web of Science type
Article
Web of Science id
000280708400044
JCR category
PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
JCR impact factor
3.453 (2010)
JCR rank
4/31 (2010)
JCR quartile
1 (2010)
ISSN
1463-9076
DOI
10.1039/c000503g
project
HPC-UGent: the central High Performance Computing infrastructure of Ghent University
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
978305
handle
http://hdl.handle.net/1854/LU-978305
date created
2010-06-15 11:50:16
date last changed
2013-09-17 10:47:55
@article{978305,
  abstract     = {The adsorption of C1-C4 primary alcohols at the Al12-O24(H)-Si12 intersection site in H-ZSM-5 is investigated using periodic density functional theory (DFT) calculations and adding a damped interatomic potential to the DFT results to account for dispersive van der Waals interactions (DFT-D). A good agreement between predicted and experimentally available adsorption enthalpies for C1-C3 alcohols is obtained. The effect of the H-ZSM-5 framework is sampled for adsorption of the C1-C4 alcohols in the straight and the zigzag channel. A variety of possible geometries, including hydrogen-bonded (physisorbed) and protonated (chemisorbed) complexes, are located as stable minima indicating that the potential energy surface connecting them is broad and very shallow. Experimental infrared (IR) spectra of the C1-C4 alcohols are interpreted based on harmonic frequency calculations for the most stable physisorbed and chemisorbed complexes. The stability of the adsorbed alcohols is governed by an interplay between their intrinsic basicity, van der Waals dispersive interactions and steric constraints exerted by the zeolite framework. In essence, steric constraints destabilize local hydrogen bonding and/or Coulomb alcohol-Bronsted acid site interactions while dispersive van der Waals interactions enhance the stability of physisorbed and chemisorbed complexes. Due to the prevalence of van der Waals interactions over steric constraints, C1-C4 alcohols adsorb preferentially in the more compact zigzag channel than in the straight channel. Both the physisorption and chemisorption energies increase linearly with 13 to 15 kJ mol(-1) per carbon atom in the straight and the zigzag channel, respectively.},
  author       = {Nguyen, Cuong Manh and Reyniers, Marie-Fran\c{c}oise and Marin, Guy},
  issn         = {1463-9076},
  journal      = {PHYSICAL CHEMISTRY CHEMICAL PHYSICS},
  keyword      = {zeolites,adsorption,periodic DFT,alcohols,PORE CONFINEMENT,CATALYTIC DEHYDRATION,METHANOL ADSORPTION,AMORPHOUS ALUMINOSILICATE,ZEOLITE ZSM-5,AB-INITIO,MOLECULAR-SIEVES,HOST FORCE-FIELD,BRONSTED ACID SITES,DENSITY-FUNCTIONAL THEORY},
  language     = {eng},
  number       = {32},
  pages        = {9481--9493},
  title        = {Theoretical study of the adsorption of C1-C4 primary alcohols in H-ZSM-5},
  url          = {http://dx.doi.org/10.1039/c000503g},
  volume       = {12},
  year         = {2010},
}

Chicago
Nguyen, Cuong Manh, Marie-Françoise Reyniers, and Guy Marin. 2010. “Theoretical Study of the Adsorption of C1-C4 Primary Alcohols in H-ZSM-5.” Physical Chemistry Chemical Physics 12 (32): 9481–9493.
APA
Nguyen, C. M., Reyniers, M.-F., & Marin, G. (2010). Theoretical study of the adsorption of C1-C4 primary alcohols in H-ZSM-5. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 12(32), 9481–9493.
Vancouver
1.
Nguyen CM, Reyniers M-F, Marin G. Theoretical study of the adsorption of C1-C4 primary alcohols in H-ZSM-5. PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 2010;12(32):9481–93.
MLA
Nguyen, Cuong Manh, Marie-Françoise Reyniers, and Guy Marin. “Theoretical Study of the Adsorption of C1-C4 Primary Alcohols in H-ZSM-5.” PHYSICAL CHEMISTRY CHEMICAL PHYSICS 12.32 (2010): 9481–9493. Print.