Reactants‐Driven Surface‐Active Sites on a Cu/CeO2 Catalyst for Methanol Synthesis from Syngas

This study investigated the dynamic structure of a working Cu/CeO2 catalyst and its catalytic consequences for CH3OH synthesis via CO hydrogenation by kinetics, high‐precise chemical titration, and a series of in‐situ X‐ray spectroscopies. We have revealed that the apparent rate coefficients for CH3OH synthesis from CO hydrogenation are a single‐valued function of the CO2‐to‐CO ratio in the contacting gas phase. This ratio determines the extent of surface oxidation of Ce2O3 to CeO2, the relative abundance of surface Ce3+ and Ce4+ sites, and in turn the density of Cu0‐Ce3+ sites pair on the working Cu/CeO2 catalyst, although the chemical state of Cu and elemental distribution of both Cu and Ce were insensitive to the ratio. Both the reactivity of CH3OH formation and the Cu0‐Ce3+ sites decrease monotonously with an increase in the CO2‐to‐CO ratio. The direct connection of the reactivity and the oxidant‐to‐reductant ratio appears to be general for heterogeneous catalysis, for which the oxidant oxidizes metal atoms whereas the reductant scavenges surface oxygen atoms, thus dictating the density of surface sites and their thermodynamic activities.