First-principles study of oxygenates on Co surfaces in Fischer-Tropsch synthesis

J. Cheng, Peijun Hu, P. Ellis, S. French, G. Kelly, C.M. Lok

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76 Citations (Scopus)


Extensive density function theory calculations are performed to study the mechanism of the formation of aldehyde and alcohol on Co surfaces in Fischer-Tropsch synthesis, a challenging issue in heterogeneous catalysis. Three possible pathways for the production of formaldehyde and methanol on flat and stepped Co(0001) surfaces are investigated: (i) CO + 4H -> CHO + 3H -> CH2O + 2H -> CH3O + H -> CH3OH; (ii) CO + 4H -> COH + 3H -> CHOH + 2H -> CH2OH + H -> CH3OH; and (iii) the coupling reactions of CH2 + O -> CH2O and CH3 + OH -> CH3OH. It is found that these pathways are generally favored at step sites, and the preferred mechanism is pathway (i) via CHO. Furthermore, the three traditional chain growth mechanisms in Fischer-Tropsch synthesis are semi quantitatively compared and discussed. Our results suggest that the two mechanisms involving oxygenate intermediates (the CO-insertion and hydroxycarbene mechanisms) are less important than the carbene mechanism in the production of long chain hydrocarbons. However, the CO-insertion mechanism may be responsible for the production of long-chain oxygenates.
Original languageEnglish
Pages (from-to)9464-9473
Number of pages10
JournalJournal of Physical Chemistry C
Volume112 (25)
Issue number25
Publication statusPublished - 26 Jun 2008

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • General Energy


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