CO 2 hydrogenation to formic acid on Ni(110)

Guowen Peng, S. J. Sibener, George C Schatz, Manos Mavrikakis

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

Hydrogen (H) in the subsurface of transition-metal surfaces exhibits unique reactivity for heterogeneously catalyzed hydrogenation reactions. Here, we explore the potential of subsurface H for hydrogenating carbon dioxide (CO 2) on Ni(110). The energetics of surface and subsurface H reacting with surface CO 2 to form formate, carboxyl, and formic acid on Ni(110) is systematically studied using self-consistent, spin-polarized, periodic density functional theory (DFT-GGA-PW91) calculations. We show that on Ni(110), CO 2 can be hydrogenated to formate by surface H. However, further hydrogenation of formate to formic acid by surface H is hindered by a larger activation energy barrier. The relative energetics of hydrogenation barriers is reversed for the carboxyl-mediated route to formic acid. We suggest that the energetics of subsurface H emerging to the surface is suitable for providing the extra energy needed to overcome the barrier to formate hydrogenation. CO 2 hydrogenation to formic acid could take place on Ni(110) when subsurface H is available to react with CO 2. Additional electronic-structure based dynamic calculations would be needed to elucidate the detailed reaction paths for these transformations.

Original languageEnglish
Pages (from-to)1050-1055
Number of pages6
JournalSurface Science
Volume606
Issue number13-14
DOIs
Publication statusPublished - Jul 2012

Fingerprint

formic acid
Formic acid
Carbon Monoxide
Hydrogenation
hydrogenation
formates
acids
Hydrogen
Energy barriers
metal surfaces
carbon dioxide
emerging
Discrete Fourier transforms
reactivity
transition metals
Electronic structure
Transition metals
Density functional theory
routes
Carbon dioxide

Keywords

  • Carbon dioxide
  • Carboxyl
  • Density functional calculations
  • Formate
  • Hydrogenation
  • Nickel
  • Subsurface hydrogen

ASJC Scopus subject areas

  • Surfaces and Interfaces
  • Condensed Matter Physics
  • Materials Chemistry
  • Surfaces, Coatings and Films

Cite this

Peng, G., Sibener, S. J., Schatz, G. C., & Mavrikakis, M. (2012). CO 2 hydrogenation to formic acid on Ni(110). Surface Science, 606(13-14), 1050-1055. https://doi.org/10.1016/j.susc.2012.02.027

CO 2 hydrogenation to formic acid on Ni(110). / Peng, Guowen; Sibener, S. J.; Schatz, George C; Mavrikakis, Manos.

In: Surface Science, Vol. 606, No. 13-14, 07.2012, p. 1050-1055.

Research output: Contribution to journalArticle

Peng, G, Sibener, SJ, Schatz, GC & Mavrikakis, M 2012, 'CO 2 hydrogenation to formic acid on Ni(110)', Surface Science, vol. 606, no. 13-14, pp. 1050-1055. https://doi.org/10.1016/j.susc.2012.02.027
Peng, Guowen ; Sibener, S. J. ; Schatz, George C ; Mavrikakis, Manos. / CO 2 hydrogenation to formic acid on Ni(110). In: Surface Science. 2012 ; Vol. 606, No. 13-14. pp. 1050-1055.
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