Unravelling the Zn-Cu Interaction during Activation of a Zn-promoted Cu/MgO Model Methanol Catalyst

TLDR: In this article, an inverse model of the Cu/MgO methanol catalyst with 5% zinc oxide at the Cu surface was presented to probe the interplay of metallic copper and zinc oxide during reductive activation.

Abstract: We report on an inverse model Cu/MgO methanol catalyst modified with 5 % zinc oxide at the Cu surface to element‐specifically probe the interplay of metallic copper and zinc oxide during reductive activation. The structure of copper and zinc was unraveled by in situ X‐ray diffraction (XRD) and in situ X‐ray absorption spectroscopy (XAS) supported by theoretical modelling of the extended X‐ray absorption fine structure and X‐ray absorption near‐edge structure spectra. Temperature‐programmed reduction in H2 during in situ XAS showed that copper was reduced starting at 145 °C. With increasing reduction temperature, zinc underwent first a geometrical change in its structure, followed by reduction. The reduced zinc species were identified as surface alloy sites, which coexisted from 200 °C to 340 °C with ZnO species at the copper surface. At 400 °C Zn−Cu bulk‐alloyed particles were formed. According to in situ XRD and in situ XAS, about half of the ZnO was not fully reduced, which can be explained by a lack of contact with copper. Our experimental results were further substantiated by density functional theory calculations, which verified that ZnO with neighboring Cu atoms reduced more easily. By combining these results, the distribution, phase and oxidation state of Zn species on Cu were estimated for the activated state of this model catalyst. This insight into the interplay of Cu and Zn forms the basis for deeper understanding the active sites during methanol synthesis.