Non‐Metal Silicon Single‐Atom Catalysts with Unsymmetrically Tetradentate O ₃ N ₁ Moiety Enabling Ampere‐Level H ₂ O ₂ Electrosynthesis

Abstract The development of efficient and stable catalysts for scalable and sustainable hydrogen peroxide (H ₂ O ₂ ) electrosynthesis via two‐electron oxygen reduction reaction (2e‐ORR) is of great significance to replace the high‐pollution anthraquinone oxidation process. Herein, O/N dual‐coordinated silicon (Si) single‐atom catalysts (SACs) uniformly immobilized on N‐doped graphene (SiO ₃ ‐NC) are successfully synthesized using silicate as Si dopant via controllable solvothermal and nitridation processes. In the synthesize reaction, Si centers convert from Si–O ₃ planar triangle to unsymmetrical Si–O ₃ N ₁ tetrahedron, which effectively modify the electronic distribution of the carbon matrix, providing high‐density active sites for electrocatalytic H ₂ O ₂ production. SiO ₃ ‐NC catalysts achieve industrial‐relevant current densities for H ₂ O ₂ production with a record‐high productivity of 63.69 mol h ⁻¹ g _cat. ⁻¹ , while maintaining exceptional Faradaic efficiencies and stability. In situ spectroscopic studies and theoretical calculations uncover that the unsymmetrically Si–O ₃ N ₁ configuration acts as an active center, which affords near‐optimal binding strength for OOH* adsorption and accelerates the kinetics of H ₂ O ₂ formation, thus promoting 2e‐ORR process.