Restricting Two‐Electron Oxygen Reduction via Secondary Coordinated Sulfur Enabling Ultralong‐Lifespan Zn‐Air Batteries

The direct four-electron oxygen reduction reaction (4e^- ORR) critically governs efficiency and lifespan in metal-air batteries and fuel cells, yet selectively suppressing competitive 2e^- and stepwise 2e^-pathways that generate corrosive hydrogen peroxide remains a major challenge. Herein, we demonstrate the strategic incorporation of secondary coordinated sulfur atoms into transition metal-N-C electrocatalysts to effectively promote direct 4e^- ORR and simultaneously suppress undesirable 2e^- pathways. Density functional theory (DFT) calculations and operando spectroscopy reveal that enhanced adsorption of key intermediate *OOH facilitates efficient O─O bond cleavage, underpinning altered catalytic selectivity. Importantly, this approach is universally applicable to various carbon-based catalysts, including Co─N@C, Ni─N@C, Mn─N@C, and N@C. Specifically, a sulfur-mediated Co─N/Co@C catalyst, comprising Co─N₄ sites and Co nanoparticles, dramatically lowers the 2e^- O₂-to-H₂O₂ rate constant to merely 0.05-fold of its original value at 0.78 V. Consequently, Zn-air batteries using Co─N/Co@C-S as cathode exhibits an outstanding peak power density of 220 mW cm^-2, remarkable lifespan over 2500 h, and outstanding rate performance from 5 to 50 mA cm^-2. This work paves a generalizable route for designing highly active and selective electrocatalysts suitable for advanced long-life energy storage devices.