Mechanism and microkinetics of the Fischer-Tropsch reaction

R. A. Van Santen, A. J. Markvoort, I. A W Filot, Minhaj Ghouri, E. J M Hensen

Research output: Contribution to journalArticle

107 Citations (Scopus)

Abstract

The increasing availability of quantum-chemical data on surface reaction intermediates invites one to revisit unresolved mechanistic issues in heterogeneous catalysis. One such issue of particular current interest is the molecular basis of the Fischer-Tropsch reaction. Here we review current molecular understanding of this reaction that converts synthesis gas into longer hydrocarbons where we especially elucidate recent progress due to the contributions of computational catalysis. This perspective highlights the theoretical approach to heterogeneous catalysis that aims for kinetic prediction from quantum-chemical first principle data. Discussion of the Fischer-Tropsch reaction from this point of view is interesting because of the several mechanistic options available for this reaction. There are many proposals on the nature of the monomeric single C atom containing intermediate that is inserted into the growing hydrocarbon chain as well as on the nature of the growing hydrocarbon chain itself. Two dominant conflicting mechanistic proposals of the Fischer-Tropsch reaction that will be especially compared are the carbide mechanism and the CO insertion mechanism, which involve cleavage of the C-O bond of CO before incorporation of a CHx species into the growing hydrocarbon chain (the carbide mechanism) or after incorporation into the growing hydrocarbon chain (the CO insertion mechanism). The choice of a particular mechanism has important kinetic consequences. Since it is based on molecular information it also affects the structure sensitivity of this particular reaction and hence influences the choice of catalyst composition. We will show how quantum-chemical information on the relative stability of relevant reaction intermediates and estimates of the rate constants of corresponding elementary surface reactions provides a firm foundation to the kinetic analysis of such reactions and allows one to discriminate between the different mechanistic options. The paper will be concluded with a short perspective section dealing with the needs for future research. Many of the current key questions on the physical chemistry as well as computational study of heterogeneous catalysis relate to particular topics for further research on the fundamental aspects of Fischer-Tropsch catalysis.

Original languageEnglish
Pages (from-to)17038-17063
Number of pages26
JournalPhysical Chemistry Chemical Physics
Volume15
Issue number40
DOIs
Publication statusPublished - 28 Oct 2013
Externally publishedYes

Fingerprint

Hydrocarbons
Catalysis
catalysis
Carbon Monoxide
hydrocarbons
Reaction intermediates
Surface reactions
Kinetics
Carbides
reaction intermediates
Physical Chemistry
carbides
surface reactions
Physical chemistry
proposals
insertion
kinetics
Synthesis gas
Rate constants
synthesis gas

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Van Santen, R. A., Markvoort, A. J., Filot, I. A. W., Ghouri, M., & Hensen, E. J. M. (2013). Mechanism and microkinetics of the Fischer-Tropsch reaction. Physical Chemistry Chemical Physics, 15(40), 17038-17063. https://doi.org/10.1039/c3cp52506f

Mechanism and microkinetics of the Fischer-Tropsch reaction. / Van Santen, R. A.; Markvoort, A. J.; Filot, I. A W; Ghouri, Minhaj; Hensen, E. J M.

In: Physical Chemistry Chemical Physics, Vol. 15, No. 40, 28.10.2013, p. 17038-17063.

Research output: Contribution to journalArticle

Van Santen, RA, Markvoort, AJ, Filot, IAW, Ghouri, M & Hensen, EJM 2013, 'Mechanism and microkinetics of the Fischer-Tropsch reaction', Physical Chemistry Chemical Physics, vol. 15, no. 40, pp. 17038-17063. https://doi.org/10.1039/c3cp52506f
Van Santen, R. A. ; Markvoort, A. J. ; Filot, I. A W ; Ghouri, Minhaj ; Hensen, E. J M. / Mechanism and microkinetics of the Fischer-Tropsch reaction. In: Physical Chemistry Chemical Physics. 2013 ; Vol. 15, No. 40. pp. 17038-17063.
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