Ce Single‐Atoms Modulation of Cu Atomic Clusters for Enhanced Oxygen Reduction and Durable Zn‐Air Batteries

Abstract Atomically dispersed electrocatalysts represent promising alternatives to Pt‐based catalysts for the oxygen reduction reaction (ORR), yet their performance remains constrained by suboptimal electronic configurations and instability. A heteroatomic catalyst featuring Ce single atoms and Cu clusters anchored on nitrogen‐doped carbon (Ce‐N‐C/Cu _clu ) is presented and synthesized through a facile one‐step pyrolysis approach. The optimized Ce‐N‐C/Cu _clu exhibits exceptional ORR activity in alkaline media, along with remarkable stability (92% current retention after 30 000 s). When employed as an air cathode in Zn‐air batteries, it achieves both high specific capacity (729.9 mAh g _Zn ⁻¹ ) and unprecedented cycling stability (1600 h). Combined experimental and theoretical analyses reveal that Ce single‐atoms with distinctive 4 f electrons serve as electronic modulators, inducing charge redistribution and upshifting the d ‐band center of adjacent Cu clusters. This electronic synergy optimizes O ₂ adsorption energy and intermediate binding energy, thereby substantially enhancing ORR kinetics. This work establishes a universal strategy for rare‐earth‐mediated electronic modulation of transition metal catalysts toward the design of high‐performance electrocatalysts.