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Catalytic decomposition of formic acid on oxide catalysts - III. IOM model approach to bimolecular mechanism

Borowiak, LA; Jamroz, MH and Larsson, Ragnar LU (2000) In Journal of Molecular Catalysis A: Chemical 152(1-2). p.121-132
Abstract
In our previous paper [M.A. Borowiak, M.H. Jamroz, R. Larsson, J. Mol. Catal. A: Chem., 139 (1999) 97], an impulse-oscillation model (IOM) was used for a time description of catalytic acts in the reactions of catalytic decomposition of formic acid on oxide catalysts for unimolecular mechanism. In this paper: the bimolecular mechanism were modelled for the same reactions. The results of IOM calculation show the increase of the Selectivity of choice of the dehydrogenation path, in comparison to the unimolecular mechanism. The highest increase is for monodentate or bridged forms of adsorbed formats ions (the selectivity 60% in comparison to 42% for the unimolecular mechanism). The OCO bending mode in formate and the O-H surface stretching... (More)
In our previous paper [M.A. Borowiak, M.H. Jamroz, R. Larsson, J. Mol. Catal. A: Chem., 139 (1999) 97], an impulse-oscillation model (IOM) was used for a time description of catalytic acts in the reactions of catalytic decomposition of formic acid on oxide catalysts for unimolecular mechanism. In this paper: the bimolecular mechanism were modelled for the same reactions. The results of IOM calculation show the increase of the Selectivity of choice of the dehydrogenation path, in comparison to the unimolecular mechanism. The highest increase is for monodentate or bridged forms of adsorbed formats ions (the selectivity 60% in comparison to 42% for the unimolecular mechanism). The OCO bending mode in formate and the O-H surface stretching modes are not so important in the bimolecular mechanism as in unimolecular one. The conclusion can be explained from the point of view of the postulated [H. Onishi, T. Aruga, Y. Iwasawa, J. Am. Chem. Sec. 115 (1993) 10460; H. Onishi, T. Aruga, Y. Iwasawa, J. Catal. 146 (1994) 557; H. Onishi, Y. Iwasawa, Chem. Phys. Lett, 226(1994) 111; Y. Iwasawa, Stud. Surf. Sci. Catal. 101 (1996)21] mechanism which does not need strong deformation of OCO bond system and used as a source of acid proton from formic acid and not from surface hydroxyl group on catalyst. The best ranges of wavenumbers for the considered in IOM modes for the dehydrogenation reaction are proposed. (C) 2000 Elsevier Science B.V. All rights reserved. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
catalytic decomposition, formic acid, oxide catalysts
in
Journal of Molecular Catalysis A: Chemical
volume
152
issue
1-2
pages
121 - 132
publisher
Elsevier
external identifiers
  • wos:000085805200014
  • scopus:0034163378
ISSN
1381-1169
DOI
10.1016/S1381-1169(99)00271-X
language
English
LU publication?
yes
id
9e2beb19-cfc4-4b43-8474-5d97fa8cf7eb (old id 3917089)
date added to LUP
2013-07-03 10:45:07
date last changed
2017-01-01 06:43:06
@article{9e2beb19-cfc4-4b43-8474-5d97fa8cf7eb,
  abstract     = {In our previous paper [M.A. Borowiak, M.H. Jamroz, R. Larsson, J. Mol. Catal. A: Chem., 139 (1999) 97], an impulse-oscillation model (IOM) was used for a time description of catalytic acts in the reactions of catalytic decomposition of formic acid on oxide catalysts for unimolecular mechanism. In this paper: the bimolecular mechanism were modelled for the same reactions. The results of IOM calculation show the increase of the Selectivity of choice of the dehydrogenation path, in comparison to the unimolecular mechanism. The highest increase is for monodentate or bridged forms of adsorbed formats ions (the selectivity 60% in comparison to 42% for the unimolecular mechanism). The OCO bending mode in formate and the O-H surface stretching modes are not so important in the bimolecular mechanism as in unimolecular one. The conclusion can be explained from the point of view of the postulated [H. Onishi, T. Aruga, Y. Iwasawa, J. Am. Chem. Sec. 115 (1993) 10460; H. Onishi, T. Aruga, Y. Iwasawa, J. Catal. 146 (1994) 557; H. Onishi, Y. Iwasawa, Chem. Phys. Lett, 226(1994) 111; Y. Iwasawa, Stud. Surf. Sci. Catal. 101 (1996)21] mechanism which does not need strong deformation of OCO bond system and used as a source of acid proton from formic acid and not from surface hydroxyl group on catalyst. The best ranges of wavenumbers for the considered in IOM modes for the dehydrogenation reaction are proposed. (C) 2000 Elsevier Science B.V. All rights reserved.},
  author       = {Borowiak, LA and Jamroz, MH and Larsson, Ragnar},
  issn         = {1381-1169},
  keyword      = {catalytic decomposition,formic acid,oxide catalysts},
  language     = {eng},
  number       = {1-2},
  pages        = {121--132},
  publisher    = {Elsevier},
  series       = {Journal of Molecular Catalysis A: Chemical},
  title        = {Catalytic decomposition of formic acid on oxide catalysts - III. IOM model approach to bimolecular mechanism},
  url          = {http://dx.doi.org/10.1016/S1381-1169(99)00271-X},
  volume       = {152},
  year         = {2000},
}