Bimetal‐bridging Nitrogen Coordination in Carbon‐based Electrocatalysts for pH‐universal Oxygen Reduction

Electrocatalysts with atomically dispersed metal sites (e.g., metal-nitrogen-carbon) have been deemed as promising alternatives for noble-metal catalysts in couples of electrocatalytic reactions. However, the modulation of such atomic sites and the understanding of their interactions are still highly challenging. Herein, we propose a unique supermolecule assembly-profile coating strategy to prepare a series of diatomic electrocatalysts by profile coating of eight Prussian blue analogues (PBAs) on supramolecular supports respectively as bimetallic sources. The detailed microstructure analysis revealed that the metal-nitrogen-carbon sites with four- (Zn-N₄ ) and five-coordination (Fe-N₅ ) via the nitrogen coordination are similar to the cytochrome c oxidases. For promising electrocatalysis, such unique microstructure is able to activate oxygen molecules due to nitrogen-bonding coordination with bimetal sites, thus leading to efficient four-electron oxygen reduction in alkaline, neutral, and acid electrolytes. Especially, zinc group elements (e.g., Zn and Cd) with d¹⁰ electron configuration would significantly boost the nitrogen-bonding coordination with bimetal sites to enhance electrocatalytic activity. The proof-of-concept for the general synthesis of advanced electrocatalysts with controllable bimetal active sites and the mechanistic understanding will promote the promising electrocatalysis by applying the similar principles.