Dynamic Features of Cu-Ceria Interface under CO₂Hydrogenation to Methanol

It is generally accepted that metal–support interaction is very important for the hydrogenation of CO₂ to methanol, but little has been revealed about the feature of interfacial active sites under real reaction conditions since there are only limited techniques that can be applied under high-pressure conditions. In this work, by combining multiple in situ and operando techniques on a model Cu/ceria catalyst, we have tracked Cu and ceria sites for methanol formation. Under the reaction condition, it is found that upon reaching the reaction temperature, oxidized Cu species in the as-synthesized catalyst immediately change into metallic Cu species. Following this, it is the gradual formation of methanol, the changing rate of which coincides with the formation of a unique Ce³⁺ species. The combined experimental results and density functional theory (DFT) calculations have determined that the formed Ce³⁺ sites driven by the reaction conditions are bound to hydrides, adsorbed carbonate species, and interfacial active Cu sites. The Cu-ceria interaction in this complex moiety is weak and can be easily disturbed with reaction environment variations, leading to dynamic changes at the interface upon the hydrogenation of active carbonate intermediates, which are precursors for the formation of methanol. The formation of this unique Cu–Ce³⁺ interface and its dynamicity lead to an increase of methanol selectivity from less than 20% to 60%. These results suggest that reactant-derived species (H^– and carbonate in this work) can be essential components of the active center with the functions of manipulating the metal−oxide interaction and directing reaction pathways.