Plasmon-driven oxygenated chemisorption acceleration of oxygen electrocatalysis for high-current cycling zinc-air batteries

Abstract

Modulating heterointerfaces through spatially segregated active domains offers a rational strategy to decouple intermediate adsorption energetics, thereby circumventing the intrinsic scaling relationships that limit multi-step electrocatalysis. However, practical application remains challenging owing to free-energy disparities between adsorption-rich and -poor sites as well as interfacial barriers that hinder dynamic intermediate transfer. Here, we report a plasmon-driven generation of dual active sites in which localized surface plasmon resonance (LSPR) of exsolved Ag nanoparticles generates instantaneous chemisorption promoters. Operando X-ray absorption and in-situ Raman spectroscopy with density functional theory reveal that these transient spillover sites direct OH- migration to/from adjacent Co centers, reducing the Co 3d electron occupancy (from d6.43 to d6.30) and surpassing the theoretical overpotential limit (∼0.3 eV) of Ag. Under 530 nm light sources in Zinc-air battery application, the ICPH catalyst delivers outstanding durability over 150 h with no significant voltage loss, alongside a high energy efficiency (∼60%) at 50 mA cm−2. This design principle highlights an opportunity for utilizing plasmon-driven intermediate spillover to overcome universal scaling constraints in multi-step electrocatalysis. © 2026 Elsevier B.V.