Dynamic Cu/Zn Interaction in SiO2Supported Methanol Synthesis Catalysts Unraveled by in Situ XAFS

Abstract

In situ X-ray absorption spectroscopy XAFS at the Cu and Zn K-edge has been used to unravel the Cu/Zn interaction and identify the possible active site of Cu-based methanol synthesis catalysts in the Cu/ZnO/SiO2 ternary system. These highly dispersed silica supported catalysts, whose activity increases sharply as a function of the reduction temperature, were studied calcined, reduced at 200, 300, and 400 °C, and for each reduction temperature under passivation/rereduction and methanol synthesis conditions. Results showed that the calcined form consists mainly of a mixed Cu/Zn hydrosilicate that is progressively transformed as the reduction temperature increases into (i) Cu metal particles, (ii) increasingly dispersed ZnO species on SiO2, and (iii) finally a Zn metallic phase forming segregated bimetallic Cu–Zn α-brass alloy particles. These different structures and Cu/Zn interfaces may correspond to different active phases and activities in methanol synthesis. After reduction at 200 and 300 °C, Cu0 is lik...