Field‐Regulated Dynamics at Electrode/Electrolyte Interface Toward Efficient H 2 O 2 Generation via Two‐Electron Water Oxidation

Abstract Two‐electron water oxidation reaction (2e − WOR) holds significant promise for efficient H 2 O 2 synthesis, but the activity of previous studies is not satisfactory. Most studies have focused on thermodynamic aspects, but neglected the critical role of interfacial dynamics in multistep 2e − WOR. In this work, the interfacial electric field is first adjusted at the electrolyte/solid interface to optimize the dynamic behaviors. As a result, the H 2 O 2 yield reaches 55.2 m m and 78.8 µmol min −1 cm −2 at 3.2 V versus RHE. These are much higher than most of state‐of‐the‐art anodes. The ab initio molecular dynamics (AIMD) simulations and in situ attenuated total reflectance Fourier transform infrared spectra (ATR‐FTIR) results certify that interfacial electric field control optimizes the dynamic behaviors of electrolyte/solid interface. The higher concentration of HCO 3 − anions, more abundant distribution of H‐bonds, and stabler formation of metal‐oxygen (M─O) bonds are realized at this interface. These result in better dynamics, thereby promoting the H 2 O 2 generation and suppressing the H 2 O 2 decomposition. This work exhibits a feasible approach to investigate and adjust the dynamic characteristics for highly efficient H 2 O 2 generation via 2e − WORs.