Electrode/Electrolyte Synergy for Concerted Promotion of Electron and Proton Transfers toward Efficient Neutral Water Oxidation

Abstract Neutral water oxidation is a crucial half‐reaction for various electrochemical applications requiring pH‐benign conditions. However, its sluggish kinetics with limited proton and electron transfer rates greatly impacts the overall energy efficiency. In this work, we created an electrode/electrolyte synergy strategy for simultaneously enhancing the proton and electron transfers at the interface toward highly efficient neutral water oxidation. The charge transfer was accelerated between the iridium oxide and in situ formed nickel oxyhydroxide on the electrode end. The proton transfer was expedited by the compact borate environment that originated from hierarchical fluoride/borate anions on the electrolyte end. These concerted promotions facilitated the proton‐coupled electron transfer (PCET) events. Due to the electrode/electrolyte synergy, Ir−O and Ir−OO − intermediates could be directly detected by in situ Raman spectroscopy, and the rate‐limiting step of Ir−O oxidation was determined. This synergy strategy can extend the scope of optimizing electrocatalytic activities toward more electrode/electrolyte combinations.