Synergistic Ce-Ce dimerization regulates electronic hybridization for enhanced oxygen reduction.

Compared with 3d transition metals, rare-earth elements, particularly cerium, exhibit more markedly sluggish Fenton-like reaction kinetics, making them more stable under oxidative oxygen reduction reaction (ORR) conditions. Here, a dual-atom cerium catalyst is fabricated on nitrogen-doped graphene (Ce2-NG) through an ultrafast Joule-heating strategy. This rapid synthesis enables the construction of Ce-Ce dimers within milliseconds, effectively suppressing aggregation and ensuring the atomic-level stabilization. Ce2-NG demonstrates remarkable ORR performance, reaching a half-wave potential of 0.906 V, along with superior durability and strong resistance to methanol crossover. When employed as the cathode catalyst in a zinc-air battery (ZAB), the device exhibits an elevated open-circuit voltage and excellent long-term operational stability, clearly surpassing those of Pt/C + RuO2 counterparts. Operando spectroscopy combined with density functional theory supports the Ce2-N6 moiety as the active center, where dual-atom cerium cooperation drives charge redistribution, enhances *OH binding, and lowers the free energy change of the potential-determining step. This study introduces a controllable synthesis method for constructing rare-earth dual-atom catalysts, broadening the compositional landscape of atomically dispersed electrocatalysts for sustainable energy conversion.