Regulation of Catalyst Immediate Environment Enables Acidic Electrochemical Benzyl Alcohol Oxidation to Benzaldehyde

Electrocatalytic alcohol oxidation in acid offers a promising alternative to the kinetically sluggish water oxidation reaction toward low-energy H₂ generation. However, electrocatalysts driving active and selective acidic alcohol electrochemical transformation are still scarce. In this work, we demonstrate efficient alcohol-to-aldehyde conversion achieved by reticular chemistry-based modification of the catalyst’s immediate environment. Specifically, coating a Bi-based electrocatalyst with a thin layer of metal–organic framework (MOF) substantially improves its performance toward benzyl alcohol electro-oxidation to benzaldehyde in a 0.1 M H₂SO₄ electrolyte. Detailed analysis reveals that the MOF adlayer influences catalysis by increasing the reactivity of surface hydroxides as well as weakening the catalyst-benzaldehyde binding strength. In turn, low-potential (0.65 V) cathodic H₂ evolution was obtained through coupling it with anodic benzyl alcohol electro-oxidation. Consequently, the presented approach could be implemented in a wide range of electrocatalytic oxidation reactions for energy-conversion application.