Tailoring the oxidation of benzyl alcohol and its derivatives with (photo)electrocatalysis.

The electrochemical oxidation of alcohol molecules has gained significance as a key anode reaction, offering an alternative to the oxygen evolution reaction (OER) for hydrogen (H2) production and carbon dioxide (CO2) reduction. The (photo)electrochemical oxidation of benzyl alcohol and its derivatives serves as an important model system, not only because benzyl alcohol oxidation is a critical industrial process, but also because it offers valuable insights into electrocatalytic biomass conversion. Tailoring this reaction through electrochemical and photoelectrochemical methods using heterogeneous noble and transition metal electrocatalysts presents a green approach and the potential for uncovering new reaction mechanisms. This review article positions the electrochemical oxidation of benzyl alcohol as an alternative to the OER to produce H2, highlighting recent mechanistic studies involving noble and transition metal electrocatalysts. Furthermore, we discuss the electronic substituent effects on this reaction, which have been well-explored in organic oxidation pathways but remain underexplored in (photo)electrocatalytic contexts.