Industrial‐Current H 2 O 2 from Water: P/O‐codoped Pentagon‐Rich Carbon in Neutral Electrolyte

ABSTRACT Achieving high‐purity, stable, and efficient hydrogen peroxide electrosynthesis at industrial current densities (>300 mA cm −2 ) in neutral media is a key pathway to replacing the pollution and energy‐intensive anthraquinone process. Therefore, developing of low‐cost, chemically robust, and high‐performance electrocatalysts has become one of the key tasks in the current research fields. In this work, a synergistic defect‐doping strategy using a fullerene precursor intrinsically rich in pentagonal defects was employed to introduce P and O into the carbon framework, yielding a P, O co‐doped pentagon‐rich carbon (PO‐PRC) catalyst. The PO‐PRC delivered nearly 100% H 2 O 2 selectivity in neutral electrolytes and enabled efficient electrosynthesis of H 2 O 2 at industrially relevant current densities up to 0.9 A cm −2 . Remarkably, a solid‐electrolyte electrochemical cell based on PO‐PRC produced concentrated H 2 O 2 solutions of up to 14 wt.% and can be driven by solar energy. DFT simulations coupled with in situ infrared radiation measurements reveal that pentagonal defects and P, O heteroatoms play a crucial role in modulating the adsorption and stabilization of the *OOH intermediate. This work provided new insights and an effective strategy for the rational design of high‐performance carbon‐based catalysts, which could accelerate the industrial implementation of sustainable H 2 O 2 electrosynthesis with large current density and high purity.