Numerical basis-set based density functional theory (DFT) calculations were performed to investigate the routes for CO2 reduction to methanol on extended CeO2(110) surface. Thermochemistry of elementary steps for the suggested routes of CO2 reduction to CH3OH was evaluated. Calculations were performed to determine the most favorable adsorption orientation and corresponding binding energy of reaction intermediates. Mechanistic routes considering the formation of the carboxyl (COOH) or the formate (HCOO) intermediate species were considered. Formate was observed to be stable with a binding energy of -222.9 kJ/mole on the surface of the stoichiometric ceria as compared to the carboxyl (E-binding = -36.0 kJ/mole). Formate species on subsequent hydrogenation produce H2COOH. In order to produce methanol, H2COOH is required to dissociate into H2CO and OH which is a significantly endothermic (Delta E-rxn = 64.0 kJ/mol) step. On the contrary, the overall route involving a carboxyl intermediate is exothermic, on both stoichiometric and reduced ceria surface, except for the dissociation of carboxyl (COOH) into CO and OH (COOH -> CO + OH) which is endothermic by 5.0 kJ/mole and 24.4 kJ/mole on stoichiometric and reduced ceria respectively. On the stoichiometric ceria, the activation barrier (E-a = 126.9 kJ/mole) for COOH dissociation was estimated to be significantly higher as compared to the expected rate limiting step of CO2 hydrogenation (E-a = 36.5 kJ/mole). A possible lateral route for the reduction of CO2 to methane via the fomation of adsorbed CO was considered. CO dissociation on the ceria surface was estimated to be highly endothermic (DErxn = 772.9 kJ/mole) and is unlikely to produce methane. (C) 2015 Elsevier Ltd. All rights reserved.