The Implications of Coupling an Electron Transfer Mediated Oxidation with a Proton Coupled Electron Transfer Reduction in Hybrid Water Electrolysis

Electrolysis of water is a sustainable route to produce clean hydrogen. Full water-splitting requires a high applied potential, in part because of the pH-dependency of the H₂ and O₂ evolution reactions (HER and OER), which are proton-coupled electron transfer (PCET) reactions. Therefore, the minimum required potential will not change at different pHs. TEMPO [(2,2,6,6-tetramethyl-1-piperidin-1-yl)oxyl], a stable free-radical that undergoes fast electro-oxidation by a single-electron transfer (ET) process, is pH-independent. Here, we show that the combination of PCET and ET processes enables hydrogen production from water at low cell potentials below the theoretical value for full water-splitting by simple pH adjustment. As a case study, we combined the HER with the oxidation of benzylamine by anodically oxidized TEMPO. The pH-independent electrocatalytic oxidation of TEMPO permits the operation of a hybrid water-splitting cell that shows promise to perform at a low cell potential (≈1 V) and neutral pH conditions.