Surface Coverage Tuning for Suppressing Over‐oxidation: A Case of Photoelectrochemical Alcohol‐to‐Aldehyde/Ketone Conversion

Suppressing over‐oxidation is a crucial challenge for various chemical intermediate synthesis in heterogeneous catalysis. The distribution of oxidative species and the substrate coverage, governed by the direction of electron transfer, are believed to influence the oxidation extent. In this study, we present an experimental realization of surface coverage modulation on a photoelectrode using a photo‐induced charge activation method. Through the surface coverage modulation, both pre‐oxidized alcohol substrates and surface coverage are increased, which not only improves the reaction kinetics but also suppresses the over‐oxidation of the generated aldehydes/ketones. As a demonstration, the Faradaic efficiency for the conversion of glycerol to dihydroxyacetone increased from 31.8% to 46.8% (with selectivity rising from 47.6% to 71.3%), from 73.4% to 87.8% for benzyl alcohol to benzyl aldehyde (selectivity increasing from 76.7% to 92.4%) and from 4.2% to 53.6% for ethylene glycol to glycolaldehyde (selectivity increasing from 6.2% to 62.7%). Our findings offer a promising strategy for the production of high‐value carbon products in heterogeneous catalysis.