Boosting Hydrogen Production from Methanol and Water by in situ Activation of Bimetallic Cu−Zr Species

Abstract A bimetallic Cu/Cu 51 Zr 14 precatalyst, activated in situ, for hydrogen generation from methanol and water provides very high CO 2 selectivity (>99.9 %) and high H 2 yields. Referenced to the geometric surface area of our model surface, higher activity of at least one order of magnitude was observed in comparison to supported Cu/ZrO 2 and Cu/ZnO/ZrO 2 catalysts. Evolution of structural activation monitored by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), and electron microscopy indicates transformation of the bimetallic Cu/Cu 51 Zr 14 precatalyst into an active, selective, and self‐stabilizing state with coexistence of dispersed Cu and partially hydroxylated tetragonal ZrO 2 . The outstanding performance is assigned to the presence of a high interface‐site concentration following in situ decomposition of the intermetallic compound. These active sites result from the cooperation of Cu, responsible for methanol activation, and tetragonal ZrO 2 , which activates the water by surface hydroxylation.