Gd‐Mediated Spin‐State Modulation of Co Sites Enhances Oxygen Electrocatalysis in Zn‐Air Battery
- 1Jiangsu Key Laboratory of Long‐duration Energy Storage Battery Technology Jiangsu Key Laboratory of Micro Nano Sensing and Separation Science for Analytical Chemistry School of Chemistry and Materials Science Nanjing Normal University Nanjing China
- 2Advanced Institute for Materials Research (WPI‐AIMR) Tohoku University Sendai Japan
Abstract
Co‐based catalysts are promising alternatives to precious‐metal catalysts towards oxygen reduction reaction (ORR), yet the limited electronic flexibility of Co sites constrains the adsorption and conversion of oxygen‐containing intermediates. Herein, we propose a Gd‐mediated spin‐state modulation strategy to enhance electrocatalytic ORR performance of Co sites. The incorporation of Gd into Co sites is realized by zeolitic imidazolate framework‐8, forming a Gd‐modified Co─N─C catalyst (GdCo/NC). The resulting GdCo/NC exhibits a higher half‐wave potential of 0.861 V in alkaline media than that of Co/NC (0.824 V) and commercial Pt/C (0.843 V). The rechargeable Zn‐air battery assembled with GdCo/NC demonstrates great practical performance, delivering a high peak power density of 170.8 mW cm−2 and a large specific capacity of 733 mAh g−1, outperforming that of Pt/C + RuO2 benchmark. Theoretical calculations reveal that Gd incorporation modulates the local electronic structure of Co centers by inducing pronounced spin splitting and orbital‐selective spin polarization, which shifts the dominant spin polarization from dz2 orbital to dyz orbital and lifts the degeneracy of dxz and dyz orbitals. Such spin‐dependent electronic reconstruction optimizes the adsorption of oxygen‐containing intermediates and shifts the rate‐determining step from *O protonation to *OH desorption, thus leading to excellent ORR performance.
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BibTeX
@article{shen2026gdmediated,
title = {{Gd‐Mediated Spin‐State Modulation of Co Sites Enhances Oxygen Electrocatalysis in Zn‐Air Battery}},
author = {Yijie Shen and Yu Zhu and Tianrui Zhao and Yiwen An and Xuan Wang and Meng Li and Dongmei Sun and Linda Zhang and Hao Li and Yawen Tang and Gengtao Fu},
journal = {Advanced Science},
year = {2026},
month = nov,
doi = {10.1002/advs.78659},
url = {https://doi.org/10.1002/advs.78659},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Gd‐Mediated Spin‐State Modulation of Co Sites Enhances Oxygen Electrocatalysis in Zn‐Air Battery
AU - Yijie Shen
AU - Yu Zhu
AU - Tianrui Zhao
AU - Yiwen An
AU - Xuan Wang
AU - Meng Li
AU - Dongmei Sun
AU - Linda Zhang
AU - Hao Li
AU - Yawen Tang
AU - Gengtao Fu
PY - 2026
DA - 2026/11/05
JO - Advanced Science
DO - 10.1002/advs.78659
UR - https://doi.org/10.1002/advs.78659
AB - Co‐based catalysts are promising alternatives to precious‐metal catalysts towards oxygen reduction reaction (ORR), yet the limited electronic flexibility of Co sites constrains the adsorption and conversion of oxygen‐containing intermediates. Herein, we propose a Gd‐mediated spin‐state modulation strategy to enhance electrocatalytic ORR performance of Co sites. The incorporation of Gd into Co sites is realized by zeolitic imidazolate framework‐8, forming a Gd‐modified Co─N─C catalyst (GdCo/NC). The resulting GdCo/NC exhibits a higher half‐wave potential of 0.861 V in alkaline media than that of Co/NC (0.824 V) and commercial Pt/C (0.843 V). The rechargeable Zn‐air battery assembled with GdCo/NC demonstrates great practical performance, delivering a high peak power density of 170.8 mW cm−2 and a large specific capacity of 733 mAh g−1, outperforming that of Pt/C + RuO2 benchmark. Theoretical calculations reveal that Gd incorporation modulates the local electronic structure of Co centers by inducing pronounced spin splitting and orbital‐selective spin polarization, which shifts the dominant spin polarization from dz2 orbital to dyz orbital and lifts the degeneracy of dxz and dyz orbitals. Such spin‐dependent electronic reconstruction optimizes the adsorption of oxygen‐containing intermediates and shifts the rate‐determining step from *O protonation to *OH desorption, thus leading to excellent ORR performance.
SN - 2198-3844
ER -