Site-specific synergy by heteronuclear microenvironment atomic editing for oxygen reduction reaction.

Ji, Siqi; Wang, Yu-Hao; Liu, Hongxue; Lu, Xue; Wang, Yu; Tian, Xinlong; Zhao, Yasong; Horton, J Hugh et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

Although iron-nitrogen-carbon catalysts are appealing for use in the oxygen reduction reaction, achieving high activity and a long lifetime remains a persistent challenge. This necessitates the precise modulation of the active sites' microenvironment. Herein, we present a microenvironment atomic editing strategy for accessing heteronuclear triatomic Fe and Co sites of Fe<sub>1</sub>Co<sub>2</sub>N<sub>7</sub>O<sub>1</sub> supported on a nitrogen-doped carbon matrix (Fe<sub>1</sub>Co<sub>2</sub>/NC). Its performance is boosted by the orbital hybridization between Fe and Co atoms, which alters the d band centers to push the activity (half-wave potential of 0.94 V in alkaline and 0.88 V in acid conditions) and stability boundaries to a high level. The optimized metal-adsorbate interactions and strengthened metal - N bonding in Fe<sub>1</sub>Co<sub>2</sub>N<sub>7</sub>O<sub>1</sub> are responsible for the competitive activity and stability. Furthermore, rechargeable and flexible quasi-solid-state zinc-air batteries using this catalyst achieve high power density (282.7 mW cm<sup>-2</sup> and 95.8 mW cm<sup>-2</sup>) and high operational stability, and are therefore more energy-efficient than commercial catalysts. Our findings underscore the importance of atomic editing for designing low-nuclearity catalysts.