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Non‐planar Nest‐like [Fe <sub>2</sub> S <sub>2</sub> ] Cluster Sites for Efficient Oxygen Reduction Catalysis

Ming Wang, Zhong Zhang, Songlin Zhang, Wei Liu, Wenzhe Shang, Xiaofang Su, Liang Yan, Furi Wang, Xujiao Ma, Yadong Li, Yiwei Liu

2023Angewandte Chemie International Edition32 citationsDOIOpen Access PDF

Abstract

Abstract Metal‐nitrogen‐carbon catalysts, as promising alternative to platinum‐based catalysts for oxygen reduction reaction (ORR), are still highly expected to achieve better performance by modulating the composition and spatial structure of active site. Herein, we constructed the non‐planar nest‐like [Fe 2 S 2 ] cluster sites in N‐doped carbon plane. Adjacent double Fe atoms effectively weaken the O−O bond by forming a peroxide bridge‐like adsorption configuration, and the introduction of S atoms breaks the planar coordination of Fe resulting in greater structural deformation tension, lower spin state, and downward shifted Fe d‐band center, which together facilitate the release of OH* intermediate. Hence, the non‐planar [Fe 2 S 2 ] cluster catalyst, with a half‐wave potential of 0.92 V, displays superior ORR activity than that of planar [FeN 4 ] or [Fe 2 N 6 ]. This work provides insights into the co‐regulation of atomic composition and spatial configuration for efficient oxygen reduction catalysis.

Topics & Concepts

Cluster (spacecraft)Oxygen reductionPlanarReduction (mathematics)CatalysisOxygen reduction reactionOxygenNest (protein structural motif)Materials scienceComputer scienceChemistryPhysicsGeometryMathematicsNuclear magnetic resonancePhysical chemistryComputer graphics (images)Computer networkBiochemistryOrganic chemistryElectrodeElectrochemistryElectrocatalysts for Energy ConversionCatalytic Processes in Materials ScienceAdvanced Photocatalysis Techniques
Non‐planar Nest‐like [Fe <sub>2</sub> S <sub>2</sub> ] Cluster Sites for Efficient Oxygen Reduction Catalysis | Litcius