Enhanced Electron Delocalization Induced by Ferromagnetic Sulfur doped C 3 N 4 Triggers Selective H 2 O 2 Production

Abstract For the 2D metal‐free carbon catalysts, the atomic coplanar architecture enables a large number of p z orbitals to overlap laterally, thus forming π‐electron delocalization, and the delocalization degree of the central atom dominates the catalytic activity. Herein, designing sulfur‐doped defect‐rich graphitic carbon nitride (S‐Nv‐C 3 N 4 ) materials as a model, we propose a strategy to promote localized electron polarization by enhancing the ferromagnetism of ultra‐thin 2D carbon nitride nanosheets. The introduction of sulfur (S) further promotes localized ferromagnetic coupling, thereby inducing long‐range ferromagnetic ordering and accelerating the electron interface transport. Meanwhile, the hybridization of sulfur atoms breaks the symmetry and integrity of the unit structure, promotes electron enrichment and stimulating electron delocalization at the active site. This optimization enhances the *OOH desorption, providing a favorable kinetic pathway for the production of hydrogen peroxide (H 2 O 2 ). Consequently, S‐Nv‐C 3 N 4 exhibits high selectivity (>95 %) and achieves a superb H 2 O 2 production rate, approaching 4374.8 ppm during continuous electrolysis over 300 hour. According to theoretical calculation and in situ spectroscopy, the ortho‐S configuration can provide ferromagnetic perturbation in carbon active centers, leading to the electron delocalization, which optimizes the OOH* adsorption during the catalytic process.