Microstructural characterization of Cu/ZnO/Al2O3 catalysts for methanol steam reforming—A comparative study

Abstract

Microstructural characteristics of various real Cu/ZnO/Al2O3 catalysts for methanol steam reforming (MSR) were investigated by in situ X-ray diffraction (XRD), in situ X-ray absorption spectroscopy (XAS), temperature programmed reduction (TPR) and electron microscopy (TEM). Structure–activity correlations of binary Cu/ZnO model catalysts were compared to microstructural properties of the ternary catalysts obtained from in situ experiments under MSR conditions. Similar to the binary system, in addition to a high specific copper surface area the catalytic activity of Cu/ZnO/Al2O3 catalysts is determined by defects in the bulk structure. The presence of lattice strain in the copper particles as the result of an advanced Cu–ZnO interface was detected only for the most active Cu/ZnO/Al2O3 catalyst in this study. Complementarily, a highly defect rich nature of both Cu and ZnO has been found in the short-range order structure (XAS). Conventional TPR and TEM investigations confirm a homogeneous microstructure of Cu and ZnO particles with a narrow particle size distribution. Conversely, a heterogeneous microstructure with large copper particles and a pronounced bimodal particle size distribution was identified for the less active catalysts. Apparently, lattice strain in the copper nanoparticles is an indicator for a homogeneous microstructure of superior Cu/ZnO/Al2O3 catalyst for methanol chemistry.