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

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Theoretical study of solvent effects on the decomposition of formic acid over a Co(111) surface. / Li, Xinbao; Zhu, Yingying; Chen, Geng; Yang, Guohua; Wu, Zan; Sunden, Bengt.

In: International Journal of Hydrogen Energy, Vol. 42, No. 39, 28.09.2017, p. 24726-24736.

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T1 - Theoretical study of solvent effects on the decomposition of formic acid over a Co(111) surface

AU - Li, Xinbao

AU - Zhu, Yingying

AU - Chen, Geng

AU - Yang, Guohua

AU - Wu, Zan

AU - Sunden, Bengt

PY - 2017/9/28

Y1 - 2017/9/28

N2 - 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.

AB - 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.

KW - Bio-oil

KW - Cobalt

KW - Density functional theory

KW - Formic acid

KW - Hydrogen

KW - Solvent

U2 - 10.1016/j.ijhydene.2017.08.022

DO - 10.1016/j.ijhydene.2017.08.022

M3 - Article

AN - SCOPUS:85028606894

VL - 42

SP - 24726

EP - 24736

JO - International Journal of Hydrogen Energy

JF - International Journal of Hydrogen Energy

SN - 1879-3487

IS - 39

ER -