Structural Sensitivity of Atomically Dispersed Catalysts in Electrocatalytic Reactions for Lithium‐Sulfur Batteries

Abstract Atomically dispersed catalysts have attracted significant attention for their high efficiency and excellent catalytic performance in electrocatalytic reactions. While numerous studies have demonstrated that altering the coordination environment of metal atoms can boost catalytic performance, the profound impact that even minor structural modifications at the catalytic active center can have on electrocatalytic activity remains largely unexplored. Here, two Pt‐Cu diatomic catalysts—Pt‐Cu/N enriched and Cu‐Pt/N enriched —featuring subtle differences are developed in metal coordination structures that are challenging to detect using conventional characterization methods. Operando X‐ray absorption spectroscopy and electrocatalytic tests on sulfur redox reaction revealed a significant gap between reactant adsorption–desorption process and catalytic activity. These differences are attributed to minor variations in the number of nitrogen atoms coordinating with the metal atom. This study highlights how small coordination changes in atomically dispersed metal catalysts can greatly impact electrocatalytic performance, offering insights into the rational design of atomically dispersed catalysts in electrochemical reactions.