Decoupled Catalysis in Lithium‐Oxygen Batteries: Directed Oxygen‐Species Spillover Between Dual Single‐Atoms to Circumvent Linear Scaling Limit

ABSTRACT Oxygen species spillover across sites in heterogeneous catalysis is a core strategy for reconfiguring reaction pathways and overcoming the theoretical limits of the Sabatier volcano plot. The key lies in achieving thermodynamic decoupling and kinetic synergy in multi‐step reactions. Based on Hard‐Soft Acid‐Base (HSAB) theory, this study constructs a series of Co‐based Ln (Sm, Eu, Gd, Tb, and Dy) dual single‐atom catalytic systems (CoLn‐DAC) through selective coordination design, serving as model platforms to decouple the fundamental electron‐transfer steps in electrochemical reactions. Directional oxygen species spillover is captured at the dual‐single‐atom scale: oxygen‐philic Ln sites activate O 2 and sequester LiO 2 , followed by dynamic lithiation and recombination within accessible migration channels engineered by energy gradients, ultimately localizing at sub‐central Co sites for further decomposition and desorption. Through oxygen‐shuttling‐mediated decoupling of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), a spatially tandem closed‐loop catalytic pathway is realized, fundamentally bypassing traditional scaling relationships. Theoretical calculations and experimental results confirm CoGd‐DAC as the optimal catalyst with exceptional overall catalytic performance. This work proposes a dynamic cascade catalytic design strategy that extends remote active‐site functionality and transcends traditional catalyst‐design dimensional constraints.