Hydrogenation of CO to Methanol on Ni(110) through Subsurface Hydrogen

Adam P. Ashwell, Wei Lin, Michelle S. Hofman, Yuxin Yang, Mark A Ratner, Bruce E. Koel, George C Schatz

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Abstract

We present a combined theoretical and experimental study of CO hydrogenation on a Ni(110) surface, including studies of the role of gas-phase atomic hydrogen, surface hydrogen, and subsurface hydrogen reacting with adsorbed CO. Reaction mechanisms leading both to methane and methanol are considered. In the reaction involving surface or subsurface hydrogen, we investigate four possible pathways, using density functional theory to characterize the relative energetics of each intermediate, including the importance of further hydrogenation versus C-O bond breaking, where the latter may lead to methane production. The most energetically favorable outcome is the production of methanol along a pathway involving the sequential hydrogenation of CO to a H3CO∗ intermediate, followed by a final hydrogenation to give methanol. In addition, we find that subsurface hydrogen noticeably alters reaction barriers, both passively and through the energy released by diffusion to the surface. Indeed, the effective reaction barriers are even lower than for CO methanolation on Cu(211) and Cu(111) than for Ni(110). In studies of gas-phase H atoms impinging on a CO-adsorbed Ni(110) surface, Born-Oppenheimer molecular dynamics simulations show that direct impact of H is unlikely to result in hydrogenation of CO. This means that Eley-Rideal or hot-atom mechanisms are not important; thus, thermal reactions involving subsurface hydrogen are the primary reaction mechanisms leading to methanol. Finally, we demonstrate experimentally for the first time the production of methanol and formaldehyde from CO hydrogenation on Ni(110) and confirm the role of subsurface hydrogen in the mechanism of this reaction.

Original languageEnglish
Pages (from-to)17582-17589
Number of pages8
JournalJournal of the American Chemical Society
Volume139
Issue number48
DOIs
Publication statusPublished - Dec 6 2017

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Hydrogenation
Carbon Monoxide
Methanol
Hydrogen
Methane
Gases
Atoms
Surface reactions
Molecular Dynamics Simulation
Formaldehyde
Density functional theory
Molecular dynamics
Theoretical Models
Hot Temperature
Computer simulation

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Hydrogenation of CO to Methanol on Ni(110) through Subsurface Hydrogen. / Ashwell, Adam P.; Lin, Wei; Hofman, Michelle S.; Yang, Yuxin; Ratner, Mark A; Koel, Bruce E.; Schatz, George C.

In: Journal of the American Chemical Society, Vol. 139, No. 48, 06.12.2017, p. 17582-17589.

Research output: Contribution to journalArticle

Ashwell, Adam P. ; Lin, Wei ; Hofman, Michelle S. ; Yang, Yuxin ; Ratner, Mark A ; Koel, Bruce E. ; Schatz, George C. / Hydrogenation of CO to Methanol on Ni(110) through Subsurface Hydrogen. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 48. pp. 17582-17589.
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