CO₂ Hydrogenation to Formic Acid on Ni(111)

Journal Article · Mon Dec 26 00:00:00 EST 2011 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/jp210408x· OSTI ID:1053362

Peng, Guowen; Sibener, S. J.; Schatz, George C.; Ceyer, Sylvia T.; Mavrikakis, Manos

Periodic, self-consistent, density functional theory (DFT) calculations are employed to study CO₂ hydrogenation on Ni(111). CO₂ hydrogenation with H adsorbed on the surface and with H absorbed in the subsurface is investigated systematically, and the respective microscopic reaction mechanisms are elucidated. We show that on Ni(111) CO₂ hydrogenation to formate intermediate is more favorable than to carboxyl intermediate. The hydrogenation to formate goes through the unidentate structure that rapidly transforms into the bidentate structure. Further hydrogenation from formate to formic acid is energetically more difficult than formate formation. Formation of adsorbed formic acid from adsorbed CO₂ and surface hydrogen is an endothermic reaction. Because subsurface H in Ni(111) is substantially less stable compared to surface H, its reaction with adsorbed CO₂ to adsorbed formic acid is an exothermic one. Finally, our results may have significant implications for the synthesis of liquid fuels from CO₂ and for catalytic hydrogenation reactions in general.

• Research Organization: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
• Sponsoring Organization: USDOE Office of Science (SC)
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1053362
• Journal Information: Journal of Physical Chemistry. C, Vol. 116, Issue 4; ISSN 1932-7447
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

Related Subjects

Environmental Molecular Sciences Laboratory