Super‐Oxidizing Covalent Triazine Framework Electrocatalyst for Two‐Electron Water Oxidation to H2O2

Abstract Electrochemical two‐electron water oxidation (2e WOR) is gaining surging research traction for sustainable hydrogen peroxide production. However, the strong oxidizing environment and thermodynamically competitive side‐reaction (4e WOR) posit as thresholds for the 2e WOR. We herein report a custom‐crafted covalent triazine network possessing strong oxidizing properties as a proof‐of‐concept metal‐free functional organic network electrocatalyst for catalyzing 2e WOR. As the first‐of‐its‐kind, the material shows a maximum of 89.9 % Faradaic Efficiency and 1428 μmol/h/cm 2 H 2 O 2 production rate at 3.0 V bias potential ( vs reversible hydrogen electrode, RHE), which are either better or comparable to the state‐of‐the‐art electrocatalysts. We have experimentally confirmed a stepwise 2e WOR mechanism which was further computationally endorsed by density functional theory studies.