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

Li, Xinbao LU ; Zhu, Yingying ; Chen, Geng ; Yang, Guohua ; Wu, Zan LU and Sunden, Bengt LU (2017) In International Journal of Hydrogen Energy 42(39). p.24726-24736
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... (More)

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.

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author
; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Bio-oil, Cobalt, Density functional theory, Formic acid, Hydrogen, Solvent
in
International Journal of Hydrogen Energy
volume
42
issue
39
pages
11 pages
publisher
Elsevier
external identifiers
  • wos:000413125900012
  • scopus:85028606894
ISSN
0360-3199
DOI
10.1016/j.ijhydene.2017.08.022
language
English
LU publication?
yes
id
cb52f0c6-0700-4b46-948b-c6b9df03eca7
date added to LUP
2017-09-28 07:05:01
date last changed
2025-01-07 21:25:07
@article{cb52f0c6-0700-4b46-948b-c6b9df03eca7,
  abstract     = {{<p>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 → CO<sub>2</sub> below 750–800 K. Above those temperatures, the path of HCOOH → HCOO → HCO → CO becomes dominant again.</p>}},
  author       = {{Li, Xinbao and Zhu, Yingying and Chen, Geng and Yang, Guohua and Wu, Zan and Sunden, Bengt}},
  issn         = {{0360-3199}},
  keywords     = {{Bio-oil; Cobalt; Density functional theory; Formic acid; Hydrogen; Solvent}},
  language     = {{eng}},
  month        = {{09}},
  number       = {{39}},
  pages        = {{24726--24736}},
  publisher    = {{Elsevier}},
  series       = {{International Journal of Hydrogen Energy}},
  title        = {{Theoretical study of solvent effects on the decomposition of formic acid over a Co(111) surface}},
  url          = {{http://dx.doi.org/10.1016/j.ijhydene.2017.08.022}},
  doi          = {{10.1016/j.ijhydene.2017.08.022}},
  volume       = {{42}},
  year         = {{2017}},
}