A quantitative determination of reaction mechanisms from density functional theory calculations: Fischer-Tropsch synthesis on flat and stepped cobalt surfaces

Jun Cheng, Xue-Qing Gong, P. Hu, C. Martin Lok, Peter Ellis, Sam French

Research output: Contribution to journalArticle

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Abstract

We systematically investigated the mechanism of the C-1 + C-1 coupling reactions using density functional theory. The activation energies of C-1 + C-1 coupling and carbon hydrogenation reactions on both flat and stepped surfaces were calculated and analyzed. Moreover, the coverages of adsorbed C-1 species were estimated, and the reaction rates of all possible C-1 + C-1 coupling pathways were quantitatively evaluated. The results suggest that the reactions of CH2 + CH2 and CH3 + C at steps are most likely to be the key C-1 + C-1 coupling steps in FT synthesis on Co catalysts. The reactions of C-2 + C-1 and C-3 + C-1 coupling also were studied; the results demonstrate that in addition to the pathways of RCH + CH2 and RCH2 + C, the coupling of RC + C and RC + CH also may contribute to the chain growth after C-1. (C) 2008 Elsevier Inc. All rights reserved.

Original languageEnglish
Pages (from-to)285-295
Number of pages11
JournalJournal of Catalysis
Volume254
Issue number2
Early online date11 Feb 2008
DOIs
Publication statusPublished - 10 Mar 2008

Keywords

  • Fischer-tropsch
  • DFT
  • Co
  • mechanism
  • C-C coupling
  • electron-energy-loss
  • carbon-monoxide
  • AB-initio
  • methane decomposition
  • rate coefficients
  • CO dissociation
  • metal-surfaces
  • chain growth
  • catalysts
  • CO(0001)

Cite this

A quantitative determination of reaction mechanisms from density functional theory calculations : Fischer-Tropsch synthesis on flat and stepped cobalt surfaces. / Cheng, Jun; Gong, Xue-Qing; Hu, P.; Lok, C. Martin; Ellis, Peter; French, Sam.

In: Journal of Catalysis, Vol. 254, No. 2, 10.03.2008, p. 285-295.

Research output: Contribution to journalArticle

Cheng, Jun ; Gong, Xue-Qing ; Hu, P. ; Lok, C. Martin ; Ellis, Peter ; French, Sam. / A quantitative determination of reaction mechanisms from density functional theory calculations : Fischer-Tropsch synthesis on flat and stepped cobalt surfaces. In: Journal of Catalysis. 2008 ; Vol. 254, No. 2. pp. 285-295.
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abstract = "We systematically investigated the mechanism of the C-1 + C-1 coupling reactions using density functional theory. The activation energies of C-1 + C-1 coupling and carbon hydrogenation reactions on both flat and stepped surfaces were calculated and analyzed. Moreover, the coverages of adsorbed C-1 species were estimated, and the reaction rates of all possible C-1 + C-1 coupling pathways were quantitatively evaluated. The results suggest that the reactions of CH2 + CH2 and CH3 + C at steps are most likely to be the key C-1 + C-1 coupling steps in FT synthesis on Co catalysts. The reactions of C-2 + C-1 and C-3 + C-1 coupling also were studied; the results demonstrate that in addition to the pathways of RCH + CH2 and RCH2 + C, the coupling of RC + C and RC + CH also may contribute to the chain growth after C-1. (C) 2008 Elsevier Inc. All rights reserved.",
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T2 - Fischer-Tropsch synthesis on flat and stepped cobalt surfaces

AU - Cheng, Jun

AU - Gong, Xue-Qing

AU - Hu, P.

AU - Lok, C. Martin

AU - Ellis, Peter

AU - French, Sam

PY - 2008/3/10

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N2 - We systematically investigated the mechanism of the C-1 + C-1 coupling reactions using density functional theory. The activation energies of C-1 + C-1 coupling and carbon hydrogenation reactions on both flat and stepped surfaces were calculated and analyzed. Moreover, the coverages of adsorbed C-1 species were estimated, and the reaction rates of all possible C-1 + C-1 coupling pathways were quantitatively evaluated. The results suggest that the reactions of CH2 + CH2 and CH3 + C at steps are most likely to be the key C-1 + C-1 coupling steps in FT synthesis on Co catalysts. The reactions of C-2 + C-1 and C-3 + C-1 coupling also were studied; the results demonstrate that in addition to the pathways of RCH + CH2 and RCH2 + C, the coupling of RC + C and RC + CH also may contribute to the chain growth after C-1. (C) 2008 Elsevier Inc. All rights reserved.

AB - We systematically investigated the mechanism of the C-1 + C-1 coupling reactions using density functional theory. The activation energies of C-1 + C-1 coupling and carbon hydrogenation reactions on both flat and stepped surfaces were calculated and analyzed. Moreover, the coverages of adsorbed C-1 species were estimated, and the reaction rates of all possible C-1 + C-1 coupling pathways were quantitatively evaluated. The results suggest that the reactions of CH2 + CH2 and CH3 + C at steps are most likely to be the key C-1 + C-1 coupling steps in FT synthesis on Co catalysts. The reactions of C-2 + C-1 and C-3 + C-1 coupling also were studied; the results demonstrate that in addition to the pathways of RCH + CH2 and RCH2 + C, the coupling of RC + C and RC + CH also may contribute to the chain growth after C-1. (C) 2008 Elsevier Inc. All rights reserved.

KW - Fischer-tropsch

KW - DFT

KW - Co

KW - mechanism

KW - C-C coupling

KW - electron-energy-loss

KW - carbon-monoxide

KW - AB-initio

KW - methane decomposition

KW - rate coefficients

KW - CO dissociation

KW - metal-surfaces

KW - chain growth

KW - catalysts

KW - CO(0001)

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SN - 0021-9517

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ER -