数字农科院2.0

Axial O-Bridge Bond Induced Electron High-Spin and Destroyed d-π Conjugation of Fe Single-Atom Sites for Enhanced CO2 Electroreduction

文献类型： 外文期刊

作者： Sun, Weiliang;Gao, Yixuan;Huang, Boyu;He, Zhenyu;Yin, Shimei;Li, Fan;Liu, Wen

作者机构：

关键词： axial O-bridge bond;d-pi conjugation;electrocatalytic CO2 reduction;electron low-spin;single-atoms catalyst

期刊名称： ADVANCED FUNCTIONAL MATERIALS

ISSN： 1616-301X

年卷期： 2026 年

页码：

收录情况： SCIE（2025版） ; ; EI（2025版） ; ; Nature Index（2023版）

摘要： Fine-tuning the electronic structure of single-atom sites (SAS) in catalysts is crucial yet challenging for improving electrocatalytic CO2 reduction (CO2RR). Herein, we construct axial O-bridge bond coordinated Fe single-atoms in a nitrogen-doped carbon-skeleton catalyst (O & horbar;Fe & horbar;N4 SACs) derived from ZIF-8, achieving Fe 3d-orbital spin regulation and destroyed d-pi conjugation. Experimental and theoretical results reveal that the axial O-bridge bond breaks the D4h symmetry of the Fe & horbar;N4 active center, resulting in the rearrangement of the spinning electron in the Fe 3d orbital to disrupt surface d-pi conjugation of the Fe & horbar;N & horbar;C structure. Meanwhile, the Jahn-Teller effect of the adjacent axial O-bridge bond can effectively induce the Fe spin-state transition from medium-spin (down arrow up arrow, down arrow up arrow, up arrow, up arrow, _) to high-spin (up arrow, up arrow, up arrow, up arrow, up arrow). Therefore, the decreased population of paired electrons on d orbitals is pivotal for activating *COOH intermediates, thus greatly enhancing the electrocatalytic CO2RR reaction activity. The optimized catalyst presents a superior faraday efficiency (FE, 98.67% at -0.7 V) during CO2RR process, which is 5.6-fold higher than that of non-axial coordinated Fe & horbar;N4 SACs. This work presents a new insight into electronic spin state regulation through the destroyed d-pi conjugation strategy of D4h symmetry SACs for enhancing electrocatalytic CO2RR performance.

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