Construction of a mechanistic model of Fischer-Tropsch synthesis on Ni(1 1 1) and Co(0 0 0 1) surfaces

David J. Klinke, Linda J. Broadbelt*

*Corresponding author for this work

Research output: Contribution to journalConference articlepeer-review

47 Scopus citations

Abstract

Tools for computer generation of reaction mechanisms were extended to handle heterogeneous catalytic reactions. Development of these generic capabilities was carried out by constructing a detailed kinetic model of Fischer-Tropsch synthesis on Ni(1 1 1) and Co(0 0 1) surfaces. To estimate rate constants during automatic mechanism generation for heterogeneous catalytic reactions, linear free energy relationships were applied using heat of reaction as the reactivity index, and theoretical approaches were used to estimate activation energies and preexponential factors. Calculation of heats of reaction involving surface species presented special challenges due to unknown heats of adsorption for many adsorbates. This problem was addressed by estimating heats of adsorption using a phenomenological approach which relates the chemisorption energy of multiatomic species to that of adatoms. To provide a basis set of values for adsorbed species on Ni(1 1 1) and Co(0 0 0 1) surfaces, the binding energies of key intermediates were calculated using an ab initio method developed for periodic systems. The energetics obtained were used in an automatically constructed reaction mechanism describing Fischer-Tropsch synthesis via carbene polymerization. The model predictions for Ni(1 1 1) and Co(0 0 0 1) surfaces successfully captured product selectivities observed experimentall over nickel and cobalt catalysts.

Original languageEnglish (US)
Pages (from-to)3379-3389
Number of pages11
JournalChemical Engineering Science
Volume54
Issue number15-16
DOIs
StatePublished - Jul 1 1999
EventProceedings of the 1998 15th International Symposium on Chemical Reaction Engineering, ISCRE 15 - Newport Beach, CA, USA
Duration: Sep 13 1998Sep 16 1998

Keywords

  • Automatic mechanism generation
  • Cobalt
  • Fischer-Tropsch synthesis
  • Microkinetic model
  • Nickel
  • Single crystal

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Industrial and Manufacturing Engineering

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