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Nano Research 2023, 16(4): 4634-4642 https://doi.org/10.1007/s12274-022-5091-y
Research Article | Issue | Published: 05 November 2022

Individually-atomic governing d–π* orbital interactions via Cu-promoted optimization of Fe-d band centers for high-efficiency zinc-air battery

Show Author's Information Xinyan Zhou1,§,  Kexin Song1,§,  Yu Feng1,  Chao Jiang1,  Zhongjun Chen2,  Zizhun Wang1,  Nailin Yue1,  Xin Ge1,  Wei Zhang1( ),  Weitao Zheng1( )
Key Laboratory of Automobile Materials MOE, School of Materials Science & Engineering, Jilin Provincial International Cooperation Key Laboratory of High-Efficiency Clean Energy Materials, Electron Microscopy Center, and International Center of Future Science, Jilin University, Changchun 130012, China
Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China

§ Xinyan Zhou and Kexin Song contributed equally to this work.

Keywords:
oxygen reduction reaction (ORR), zinc-air battery, dual-atom catalysts (DACs), electronic configuration
Topics:
Oxygen reduction reaction
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Zhou X, Song K, Feng Y, et al. Individually-atomic governing d–π* orbital interactions via Cu-promoted optimization of Fe-d band centers for high-efficiency zinc-air battery. Nano Research, 2023, 16(4): 4634-4642. https://doi.org/10.1007/s12274-022-5091-y
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Abstract Full text Electronic supplementary material About this article

It is challenging for precise governing of electronic configuration of the individually-atomic catalysts toward optimal electrocatalysis, as d-band configuration of a metal center determines the adsorption behavior of reactive species to the center in oxygen reduction reaction (ORR). The addition of Cu atom modifies the d-band center position of Fe central atom, thus strengthening the d–π* orbital interactions. Herein, FeCu-NC catalyst in the nitrogen-doped carbon (NC) support containing individual dual-metal CuN4/FeN4 sites was prepared by the surface confinement strategy of zeolitic imidazolate framework (ZIF), treated as a model catalyst. Experimentally and theoretically co-verified dual-metal CuN4/FeN4 sites highly dispersed in the NC support, enable transferring more electrons from FeN4 sites to *OH intermediates, thereby accelerating the desorption process of *OH species. Superior to those commercial Pt/C, Our FeCu-NC catalyst exhibited extraordinary ORR activity (with a E1/2 as high as 0.87 V) and cycling stability in 0.1 M KOH electrolyte, and thereof demonstrated excellent discharge performance in zinc-air batteries. Our construction of dual-atom catalysts (DACs) provides a strategy for atom-by-atom designing high-efficiency catalysts via orbital regulation.


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About this article

Individually-atomic governing d–π* orbital interactions via Cu-promoted optimization of Fe-d band centers for high-efficiency zinc-air battery

Show Author's information Xinyan Zhou1,§, Kexin Song1,§, Yu Feng1, Chao Jiang1, Zhongjun Chen2, Zizhun Wang1, Nailin Yue1, Xin Ge1, Wei Zhang1( ), Weitao Zheng1( )
Key Laboratory of Automobile Materials MOE, School of Materials Science & Engineering, Jilin Provincial International Cooperation Key Laboratory of High-Efficiency Clean Energy Materials, Electron Microscopy Center, and International Center of Future Science, Jilin University, Changchun 130012, China
Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China

§ Xinyan Zhou and Kexin Song contributed equally to this work.

Abstract

It is challenging for precise governing of electronic configuration of the individually-atomic catalysts toward optimal electrocatalysis, as d-band configuration of a metal center determines the adsorption behavior of reactive species to the center in oxygen reduction reaction (ORR). The addition of Cu atom modifies the d-band center position of Fe central atom, thus strengthening the d–π* orbital interactions. Herein, FeCu-NC catalyst in the nitrogen-doped carbon (NC) support containing individual dual-metal CuN4/FeN4 sites was prepared by the surface confinement strategy of zeolitic imidazolate framework (ZIF), treated as a model catalyst. Experimentally and theoretically co-verified dual-metal CuN4/FeN4 sites highly dispersed in the NC support, enable transferring more electrons from FeN4 sites to *OH intermediates, thereby accelerating the desorption process of *OH species. Superior to those commercial Pt/C, Our FeCu-NC catalyst exhibited extraordinary ORR activity (with a E1/2 as high as 0.87 V) and cycling stability in 0.1 M KOH electrolyte, and thereof demonstrated excellent discharge performance in zinc-air batteries. Our construction of dual-atom catalysts (DACs) provides a strategy for atom-by-atom designing high-efficiency catalysts via orbital regulation.

Keywords: oxygen reduction reaction (ORR), zinc-air battery, dual-atom catalysts (DACs), electronic configuration

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Publication history
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Acknowledgements

Publication history

Received: 16 August 2022
Revised: 20 September 2022
Accepted: 22 September 2022
Published: 05 November 2022
Issue date: April 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This research was supported by the National Natural Science Foundation of China (Nos. 51872115 and 52272209) and 2020 International Cooperation Project of the Department of Science and Technology of Jilin Province (No. 20200801001GH).

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