Oxidative coupling of alcohols on gold: Insights from experiments and theory

Molecular level understanding of the mechanism of oxidative coupling of alcohols on metallic Au(111) activated by oxygen is achieved through a combination of experiments and theoretical calculations. The facility of the beta-H elimination of the alkoxys, which increases with the length of the alkyl chain, is identified to be critical in determining the product distributions. Dioxymethylene serves as a formaldehyde reservoir in the cross-coupling reaction between methanol and formaldehyde through its reversible formation and decomposition, contributing to the high selectivity for the coupling products.