The increasing demand for clean fuels and sustainable products has attracted much interest in the development of active and selective catalysts for CO conversion to desirable products. This review maps the theoretical progress of the different facets of most commercial catalysts, including Co, Fe, Ni, Rh, and Ru. All relevant elementary steps involving CO dissociation and hydrogenation and their dependence on surface structure, surface coverage, temperature, and pressure are considered. The dominant Fischer-Tropsch synthesis mechanism is also explored, including the sensitivity to the structure of H-assisted CO dissociation and direct CO dissociation. Low-coordinated step sites are shown to enhance catalytic activity and suppress methane formation. The hydrogen adsorption and CO dissociation mechanisms are highly dependent on the surface coverage, in which hydrogen adsorption increases, and the CO insertion mechanism becomes more favorable at high coverages. It is revealed that the chain-growth probability and product selectivity are affected by the type of catalyst and its structure as well as the applied temperature and pressure.
Keywords: DFT; Fischer-Tropsch synthesis; carbon monoxide; cobalt; transition metals.