Understanding the effect of adsorption sites of CO at cobalt surface on its reactivity with H2/H by DFT calculations.

Cobalt (Co) is widely used in Fischer-Tropsch synthesis (FTS), converting synthesis gas, carbon monoxide + hydrogen (CO + H₂), to long-chain hydrocarbons. The adsorption of CO on the Co surface is the key step in FTS. In this work, the effect of CO adsorption sites on the reactions between CO and H₂ was investigated by using density functional theory (DFT). The energetics and structures of the reactions between the adsorbed CO (CO*) and H₂/adsorbed H₂ (H₂*)/adsorbed H atom (H*) were calculated. The results show that the reaction between CO* and H₂ is initiated by the molecular adsorption of H₂ on the Co surface. The reactions between CO* and H₂*/H* are influenced by CO adsorption sites. For the reaction system of CO* + H₂*, it has the lowest reaction barrier when CO is adsorbed at the hcp site, while for CO* + H*, it has the lowest reaction barrier when CO is adsorbed on the top site. Kinetic analysis indicates that to improve the reactivity of CO + H₂ in FTS, the adsorption of CO should be controlled to favour the top and bridge sites. This article is part of the theme issue 'Celebrating the 15th anniversary of the Royal Society Newton International Fellowship'.