Theoretical study of solvent effects on the decomposition of formic acid over a Co(111) surface

Research output: Contribution to journalArticle

Abstract

Solvent effects on the decomposition of formic acid over a Co(111) surface were studied via density functional theory calculations combined with a continuum implicit solvation model. The solvents used here were water, methanol, and acetone. The adsorption energies of key intermediates, the activation barriers and the rate and equilibrium constants of various elementary reactions in vacuum and in the solvents were obtained. Solvent presences decrease the adsorption energies of species. Formic acid decomposition on the surface goes through HCOO rather than COOH both in vacuum and in the solvents. The most favorable decomposition pathways in vacuum and in acetone are HCOOH → HCOO → HCO → CO. The corresponding rate determining steps are HCOO deoxidation to HCO with activation barriers of 0.78 and 0.76 eV, respectively. In the presences of water and methanol, the preferred pathways are shifted to HCOOH → HCOO → HCOO-m → CO2 below 750–800 K. Above those temperatures, the path of HCOOH → HCOO → HCO → CO becomes dominant again.

Details

Authors
Organisations
External organisations
  • Ningbo University
Research areas and keywords

Subject classification (UKÄ) – MANDATORY

  • Energy Systems

Keywords

  • Bio-oil, Cobalt, Density functional theory, Formic acid, Hydrogen, Solvent
Original languageEnglish
Pages (from-to)24726-24736
Number of pages11
JournalInternational Journal of Hydrogen Energy
Volume42
Issue number39
Publication statusPublished - 2017 Sep 28
Publication categoryResearch
Peer-reviewedYes