Rare‐Earth‐Cluster‐Mediated Long‐Range Electronic Modulation Activates Zn Atomic Sites for Oxygen Reduction Catalysis

ABSTRACT Activating the inert Zn ( d 10 ) centers via precise ligand‐field engineering to achieve superior oxygen reduction reaction (ORR) performance is highly appealing yet challenging. Herein, we report a general long‐range electronic structure regulation strategy to construct ultrafine rare‐earth oxide clusters anchored proximal to Zn single‐atom sites (LaO x ‐Zn‐SA/CNCl), aiming at boosting ORR activity. Benefiting from the tailored long‐range electronic modulation by LaO x clusters and the hierarchical porous carbon support that maximizes Zn atom utilization, the catalysts exhibit a high half‐wave potential of 0.90 V along with remarkable stability in alkaline media. This represents a non‐precious‐metal, rare‐earth‐based electrocatalyst among the best reported so far. A zinc–air battery (ZAB) integrating LaO x ‐Zn‐SA/CNCl as the cathode catalyst delivers a maximum power density of 177.3 mW cm −2 at 225 mA cm −2 . Theoretical calculations reveal that the proximal LaO x clusters remotely modulate the electronic structures of Zn sites, enhancing electron‐transfer efficiency by strengthening electronic interactions. With the optimized electronic state of Zn sites, the adsorption of key intermediates is balanced to alleviate the energy barriers of the rate‐determining step. This work provides insights into the long‐range electronic regulation of transition‐metal single‐atom sites within a hierarchical rare‐earth cluster‐coupled microenvironment for efficient electrocatalysis.