Recent progress in understanding the nature of active sites for methanol synthesis over Cu/ZnO catalysts

Copper-zinc-alumina (Cu/ZnO/Al₂O₃) has been utilized as the leading catalyst for industrial methanol synthesis via hydrogenation of CO and CO₂ for more than 50 years. Understanding the nature of active Zn sites at the atomic level is vital for gaining insight into the reaction mechanism and rational design of more efficient Cu/ZnO catalysts for methanol synthesis but remains greatly challenging and has been intensively debated for decades. In this mini-review, we first describe the fundamental insights obtained from well-defined model catalysts and then summarize the recent experimental evidence with respect to dynamic structural and electronic changes in the active Zn phase under realistic working conditions by in situ/operando microscopy/spectroscopy and surface site titration using probing molecules. In the following, we discuss the catalytic mechanism of diverse active structures by theoretical calculations and simulations. Therefore, the critical role of interfacial sites between metallic Cu and ZnO, especially those with oxygen defects, in methanol synthesis via CO₂ hydrogenation is emphasized. Finally, we discuss the technical challenges and perspectives in understanding the origins of this Cu-ZnO synergy and rational design of next-generation Cu-based methanol synthesis catalysts.