Crossing the Oxo‐Peroxo Wall for Selective Electrochemical Epoxidation

Abstract Electrochemical oxidation in water requires the formation of reactive oxygen species to be able to oxidize unsaturated hydrocarbons to epoxides, aldehydes, and ketones. These reactions, broadly classified as alternative oxidation reactions (AOR), directly compete with the prevalent oxygen evolution reaction (OER). In molecular catalysis, the Oxo‐Wall dictates a transition from a stable oxo intermediate (OER active) to a meta‐stable metal‐oxo (OER inactive) generally occurs. In this work on heterogeneous catalysis, the same Oxo‐Wall applies, however, a meta‐stable oxo preferentially coordinates with lattice oxygen to form a more stable surface peroxo intermediate. A universal free energy onset of this process is identified at 3.39 eV under electrochemical activation in water and show that it is completely decoupled from the OER oxo species. Such decoupling gives rise to a new region of oxygen reactivity relevant for AOR where a selective oxidation of the unsaturated C‐C bonds is predicted to occur instead of OER. A distinct AOR overpotential volcano is constructed and identify recently reported electrocatalysts, including palladium‐platinum for propylene epoxidation and silver‐nickel for ethylene epoxidation, along with others such as TiO ₂ and CuO. Broader implications and limitations of electrochemical AOR are discussed, highlighting their potential to enable electrochemically enhanced thermal catalysis.