Exploring the phase transformation in ZnO/Cu(111) model catalysts in CO_(2) hydrogenation

Sustainable methanol production via CO_(2) hydrogenation leads to increased interest in the understanding of active phase of Cu/ZnO/Al_(2)O_(3)(CZA) catalyst. Model catalysts of ZnO/Cu(111) with structures varied from two-dimensional planar to three-dimensional nanoparticles were prepared by atomic layer deposition(ALD) method. By combing scanning tunneling microscopy(STM) and X-ray photoelectron spectroscopy(XPS) at near-ambient pressure of CO_(2) hydrogenation, we reveal that the submonolayer ZnO/Cu(111) transformed into Cu-Zn alloy under 10 mbar CO_(2)/H_(2) at 493 K, and underwent a partial reoxidation during evacuation. The dynamic phase transformation of ZnO/Cu(111) may partly explain the existence of differences and apparently contradictory theories to account for the origin of active phase in CZA catalysts.