Selective decomposition of formic acid on molybdenum carbide: A new reaction pathway

David W. Flaherty, Sean P. Berglund, C. Buddie Mullins

Research output: Contribution to journalArticlepeer-review

Abstract

Selective decomposition of formic acid is important as a prototype to study selective bond cleavage of oxygenates. We demonstrate that carbon-modified Mo(1 1 0), C-Mo(1 1 0), is up to 15 times more selective for the dehydrogenation of formic acid than Mo(1 1 0). Reflection absorption infrared spectroscopy (RAIRS) indicates that carbidic carbon blocks active sites for C-O bond cleavage, decreasing the rate of dehydration. Steady-state reactive molecular beam scattering (RMBS) shows that dehydration is the dominant reaction pathway on clean Mo(1 1 0), while C-Mo(1 1 0) selectively promotes dehydrogenation. Kinetic analysis of RMBS data reveals that formic acid dehydrogenation on Mo(1 1 0) has an activation energy of 34.4 ± 3.3 kJ mol-1 while the C-Mo(1 1 0) surface promotes distinct pathways for dehydrogenation with an activation energy of only 12.8 ± 1.0 kJ mol-1. RAIRS spectra suggest the new pathways include the formation of monodentate formate, and at temperatures of 500 K and greater, direct activation of the C-H bond to form carboxyl, both of which decompose via a CO2δ - intermediate to evolve CO2 and H2.

Original languageEnglish (US)
Pages (from-to)33-43
Number of pages11
JournalJournal of Catalysis
Volume269
Issue number1
DOIs
StatePublished - Jan 1 2010
Externally publishedYes

Keywords

  • Carboxyl
  • Formate
  • Infrared spectroscopy
  • Selective dehydrogenation
  • Transition metal carbide

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

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