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Isotopic and Kinetic Assessment of the Mechanism of CH3OH−H2O Catalysis on Supported Copper Clusters

This study provides kinetic and isotopic evidence for the identity and kinetic relevance of elementary steps in CH3OH−H2O reactions on monofunctional Cu-based catalysts. H2, CO2, and CO were the only products formed in these reactions, which proceed via kinetically relevant C−H bond activation in chemisorbed methoxides. All other elementary steps are in quasi-equilibrium, consistent with the effects of reactants and products on rates, with isotopic tracing and kinetic isotope evidence, and with the equilibrated nature of water gas shift reactions at all reaction conditions. Turnover rates increased with CH3OH pressure but did not depend on CO, CO2, or H2O concentrations. H2 inhibited CH3OH−H2O reactions by decreasing the concentration of surface methoxide intermediates via quasi-equilibrated CH3OH dissociation steps. Isotopic scrambling was complete among hydroxyl groups in methanol and water, but undetectable among hydroxyl and methyl groups in methanol, consistent with quasi-equilibrated O−H activation ...