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

Abstract 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−N 4 ) and five‐coordination (Fe−N 5 ) 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 d 10 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.