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

Activating the inert Zn (d¹⁰) 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.