Asymmetric Oxygen Activation Induced by Co-Pb Dual Atom Sites for Efficient pH-Universal H₂O₂ Electrosynthesis

The electrosynthesis of H₂O₂ in acidic media represents a green and efficient strategy, but the local pH around the surface of 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 H₂O₂ production. Therefore, an excellent catalyst for H₂O₂ electrosynthesis demands expanded applicability in electrolyte with 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 H₂O₂ 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 H₂O₂ with the production rate of 11.26 mol gcat -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 H₂O₂ electrosynthesis catalysts.