Thermochemical Aerobic Oxidation Catalysis in Water Proceeds via Coupled Electrochemical Half-Reactions

Heterogeneous aqueous-phase aerobic oxidations are an important emerging class of catalytic transformations, particularly for upgrading next generation bio-derived substrates. The mechanism of these reactions and the precise role of O₂ in particular remains unclear. Herein, we test the hypothesis that thermochemical aerobic oxidation proceeds via two coupled electrochemical half-reactions for oxygen reduction and substrate oxidation. We collect electrochemical and thermochemical data on common noble metal catalysts under identical reaction/transport environments, and find that the electrochemical polarization curves of the O₂ reduction and the substrate oxidation half-reaction closely predict the mixed potential of the catalyst measured in operando during thermochemical catalysis across 13 diverse variables spanning reaction conditions, catalyst composition, reactant identity, and pH. Additionally, we find that driving the oxidation half-reaction reaction electrochemically in the absence of O₂ at the mixed potential leads to very similar rates and selectivities as for the thermochemical reaction in all cases examined. These findings strongly indicate that the role of O₂ in thermochemical aerobic oxidation is solely as an electron scavenger that provides an incipient electrochemical driving force for substrate oxidation. These studies provide a quantitative and predictive link between thermochemical and electrochemical catalysis, thereby enabling the rational design of new thermochemical liquid-phase aerobic oxidation schemes by applying the principles of electrochemistry.