Asymmetric Oxygen Activation Induced by Co─Pb Dual Atom Sites for Efficient pH‐Universal H ₂ O ₂ Electrosynthesis

ABSTRACT

The electrosynthesis of H ₂ O ₂ in acidic media represents a green and efficient strategy, but the local pH around the surface of the electrode may suffer significant changes from acid to neutral and even alkaline under high current density and long‐term operation, which raises issues linked to inadequate stability and activity for H ₂ O ₂ production. Therefore, an excellent catalyst for H ₂ O ₂ electrosynthesis demands expanded applicability in electrolytes with a full range of pH, but still poses a substantial challenge. Herein, we introduce p‐block metal (Pb) into the Co─N─C to construct a Co─Pb diatomic sites catalyst (CoPb/NC), which delivers a pH‐universal electrosynthesis of H ₂ O ₂ with excellent selectivity in acidic (91.2%), neutral (92.5%), and alkaline electrolyte (93.1%), respectively. In a solid‐state electrolyte cell, the CoPb/NC achieves a pure H ₂ O ₂ with the production rate of 11.26 mol g _cat ⁻¹ h ⁻¹ at 904.5 mA cm ⁻² . The introduction of O‐affinity Pb atoms effectively triggers preferent adsorption with hydroxyl, allowing asymmetric oxygen activation along the associative pathway and thus steering two‐electron ORR. Meanwhile, the d‐p hybridization interaction with Co redistributes the electronic structure, eventually optimizing the binding strength of *OOH intermediate and accelerating the kinetics of 2e ⁻ ORR. This work offers insights for designing excellent pH‐universal H ₂ O ₂ electrosynthesis catalysts.