Probing the Nature of Zinc in Copper-Zinc-Zirconium Catalysts by Operando Spectroscopies for CO 2 Hydrogenation to Methanol.

Active Zn species in Cu-based methanol synthesis catalysts have not been clearly identified yet due to their complex nature and dynamic structural changes during reactions. Herein, atomically dispersed Zn on ZrO 2 support is established in Cu-based catalysts by separating Zn and Zr components from Cu (Cu-ZnZr) via the double-nozzle flame spray pyrolysis (DFSP) method. It exhibits superiority in methanol selectivity and yield compared to those with Cu-ZnO interface and isolated ZnO nanoparticles. Operando X-ray absorption spectroscopy (XAS) reveals that the atomically dispersed Zn species are induced during the reaction due to the strengthened Zn-Zr interaction. They can suppress formate decomposition to CO and decrease the H 2 dissociation energy, shifting the reaction to methanol production. This work enlightens the rational design of unique Zn species by regulating coordination environments and offers a new perspective for exploring complex interactions in multi-component catalysts.