Enhanced Methanol Synthesis from CO 2 Hydrogenation Achieved by Tuning the Cu-ZnO Interaction in ZnO/Cu 2 O Nanocube Catalysts Supported on ZrO 2 and SiO 2 .

The nature of the Cu-Zn interaction and especially the role of Zn in Cu/ZnO catalysts used for methanol synthesis from CO ₂ hydrogenation are still debated. Migration of Zn onto the Cu surface during reaction results in a Cu-ZnO interface, which is crucial for the catalytic activity. However, whether a Cu-Zn alloy or a Cu-ZnO structure is formed and the transformation of this interface under working conditions demand further investigation. Here, ZnO/Cu ₂ O core-shell cubic nanoparticles with various ZnO shell thicknesses, supported on SiO ₂ or ZrO ₂ were prepared to create an intimate contact between Cu and ZnO. The evolution of the catalyst's structure and composition during and after the CO ₂ hydrogenation reaction were investigated by means of operando spectroscopy, diffraction, and ex situ microscopy methods. The Zn loading has a direct effect on the oxidation state of Zn, which, in turn, affects the catalytic performance. High Zn loadings, resulting in a stable ZnO catalyst shell, lead to increased methanol production when compared to Zn-free particles. Low Zn loadings, in contrast, leading to the presence of metallic Zn species during reaction, showed no significant improvement over the bare Cu particles. Therefore, our work highlights that there is a minimum content of Zn (or optimum ZnO shell thickness) needed to activate the Cu catalyst. Furthermore, in order to minimize catalyst deactivation, the Zn species must be present as ZnO _x and not metallic Zn or Cu-Zn alloy, which is undesirably formed during the reaction when the precatalyst ZnO overlayer is too thin.