Mondal, BiswajitBiswajitMondalDinda, SoumitraSoumitraDindaKarjule, NeetaNeetaKarjuleMondal, SanjitSanjitMondalRaja Kottaichamy, AlagarAlagarRaja KottaichamyVolokh, MichaelMichaelVolokhShalom, MennyMennyShalom2025-08-312025-08-312023-05-1910.1002/cssc.2022022712-s2.0-85147097027https://d8.irins.org/handle/IITG2025/2679536576299Electrolysis 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 H<inf>2</inf> and O<inf>2</inf> 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.truebenzylamine oxidation | electrocatalysis | hydrogen evolution reaction | proton-coupled electron transfer | single-electron transferArticlehttps://doi.org/10.1002/cssc.2022022711864564X19 May 202311e202202271arJournal9