CO2 hydrogenation to methanol on tungsten-doped Cu/CeO2 catalysts

The catalytic hydrogenation of CO2 to methanol depends significantly on the structures of metal-oxide interfaces. We show that doping a high-valency metal, viz. tungsten, to CeO2 could render improved catalytic activity for the hydrogenation of CO2 on a Cu/CeW0.25Ox catalyst, whilst making it more selective towards methanol than the undoped Cu/CeO2. We experimentally investigated and elucidated the structural-functional relationship of the Cu/CeO2 interface for CO2 hydrogenation. The promotional effects are attributed to the irreversible reduction of Ce4+ to Ce3+ by W-doping, the suppression of the formation of redox-active oxygen vacancies on CeO2, and the activation of the formate pathway for CO2 hydrogenation. This catalyst design strategy differs fundamentally from those commonly used for CeO2-supported catalysts, in which oxygen vacancies with high redox activity are considered desirable. [Display omitted] •Cu/CeW0.25Ox shows a 10-fold boost in methanol space-time yield compared to Cu/CeO2.•Cu/CeW0.25Ox shows an improved methanol selectivity of 87% over the 51% of Cu/CeO2.•W-doping reduces CeO2 and produces large amount of stabile Ce3+ species.•W-doping activates the formate pathway on Cu/CeW0.25Ox.•Cu/CeW0.25Ox shows stable performance over 72 h time-on-stream.