Visualizing the gas-sensitive structure of the CuZn surface in methanol synthesis catalysis

Abstract

Methanol formation over Cu/ZnO catalysts is linked with a catalytically active phase created by contact between Cu nanoparticles and Zn species whose chemical and structural state depends on reaction conditions. Herein, we use variable-temperature scanning tunneling microscopy at elevated pressure conditions combined with X-ray photoelectron spectroscopy measurements to investigate the surface structures and chemical states that evolve when a CuZn/Cu(111) surface alloy is exposed to reaction gas mixtures. In CO2 hydrogenation conditions, Zn stays embedded in the CuZn surface, but once CO gas is added to the mixture, the Zn segregates onto the Cu surface. The Zn segregation is CO-induced, and establishes a new dynamic state of the catalyst surface where Zn is continually exchanged at the Cu surface. Candidates for the migrating few-atom Zn clusters are further identified in time-resolved imaging series. The findings point to a significant role of CO affecting the distribution of Zn in the multiphasic ZnO/CuZn/Cu catalysts.