Monomer formation model versus chain growth model of the Fischer-Tropsch reaction

Rutger A. Van Santen, Albert J. Markvoort, Minhaj Ghouri, Peter A J Hilbers, Emiel J M Hensen

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

One of the great challenges in molecular heterogeneous catalysis is to model selectivity of a heterogeneous catalytic reaction based on first principles. Molecular kinetics simulations of the Fischer-Tropsch reaction, which converts synthesis gas into linear hydrocarbons, demonstrate the need for microkinetics approaches that do not make a priori choices of rate controlling steps. A key question pertaining to this reaction, in which hydrocarbons are formed through consecutive insertion of adsorbed CHx monomers into adsorbed growing hydrocarbon chains, is whether the CO consumption rate depends on the rate of the CHx insertion polymerization process. Microkinetic theory of this heterogeneous catalytic reaction based on quantum-chemical data is used to deduce expressions for the CO consumption rate and chain growth parameter α in the two limiting cases where chain growth rate is fast compared to the formation of CHx (monomer formation limit) or where the reverse relation holds (chain growth limit). The conventional assumptions that CHx formation is rate controlling and that change in CO coverage due to reaction is negligible lead to substantial overestimation of the rate of CO consumption. It appears that intermediate reactivity of the catalytic reaction center, with neither too low nor too high activation energies for C-O bond cleavage, and low reagent gas pressure lead to such monomer formation limiting type behavior, whereas maximum rate of CO consumption is found when chain growth rate is limiting.

Original languageEnglish
Pages (from-to)4488-4504
Number of pages17
JournalJournal of Physical Chemistry C
Volume117
Issue number9
DOIs
Publication statusPublished - 7 Mar 2013
Externally publishedYes

Fingerprint

Carbon Monoxide
monomers
Monomers
Hydrocarbons
Catalyst selectivity
Synthesis gas
Catalysis
Activation energy
hydrocarbons
Polymerization
Kinetics
insertion
Gases
synthesis gas
catalysis
gas pressure
reagents
cleavage
polymerization
reactivity

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Surfaces, Coatings and Films
  • Physical and Theoretical Chemistry

Cite this

Van Santen, R. A., Markvoort, A. J., Ghouri, M., Hilbers, P. A. J., & Hensen, E. J. M. (2013). Monomer formation model versus chain growth model of the Fischer-Tropsch reaction. Journal of Physical Chemistry C, 117(9), 4488-4504. https://doi.org/10.1021/jp310245m

Monomer formation model versus chain growth model of the Fischer-Tropsch reaction. / Van Santen, Rutger A.; Markvoort, Albert J.; Ghouri, Minhaj; Hilbers, Peter A J; Hensen, Emiel J M.

In: Journal of Physical Chemistry C, Vol. 117, No. 9, 07.03.2013, p. 4488-4504.

Research output: Contribution to journalArticle

Van Santen, Rutger A. ; Markvoort, Albert J. ; Ghouri, Minhaj ; Hilbers, Peter A J ; Hensen, Emiel J M. / Monomer formation model versus chain growth model of the Fischer-Tropsch reaction. In: Journal of Physical Chemistry C. 2013 ; Vol. 117, No. 9. pp. 4488-4504.
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