CO 2 hydrogenation to formic acid on Ni(110)

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

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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

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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