CO2‐to‐Methanol Hydrogenation on Zirconia‐Supported Copper Nanoparticles: Reaction Intermediates and the Role of the Metal–Support Interface

Abstract Methanol synthesis by CO 2 hydrogenation is a key process in a methanol‐based economy. This reaction is catalyzed by supported copper nanoparticles and displays strong support or promoter effects. Zirconia is known to enhance both the methanol production rate and the selectivity. Nevertheless, the origin of this observation and the reaction mechanisms associated with the conversion of CO 2 to methanol still remain unknown. A mechanistic study of the hydrogenation of CO 2 on Cu/ZrO 2 is presented. Using kinetics, in situ IR and NMR spectroscopies, and isotopic labeling strategies, surface intermediates evolved during CO 2 hydrogenation were observed at different pressures. Combined with DFT calculations, it is shown that a formate species is the reaction intermediate and that the zirconia/copper interface is crucial for the conversion of this intermediate to methanol.