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Nano Research 2023, 16(4): 4211-4218 https://doi.org/10.1007/s12274-022-5164-y
Flagship Article | Issue | Published: 29 November 2022

Regulating electronic structure of CoN4 with axial Co–S for promoting oxygen reduction and Zn-air battery performance

Show Author's Information Chang Chen1,§,  Zhiqiang Chen2,§,  Junxi Zhong3,§,  Xin Song4,  Dongfang Chen4,  Shoujie Liu5,  Weng-Chon Cheong6,  Jiazhan Li1,  Xin Tan1,  Chang He1,  Jiaqi Zhang1,  Di Liu1,  Qiuhua Yuan3( ),  Chen Chen1( ),  Qing Peng1( ),  Yadong Li1
Department of Chemistry, Tsinghua University, Beijing 100084, China
Beijing Key Laboratory of Research and Application for Aerospace Green Propellants, Beijing Institute of Aerospace Testing Technology, Beijing 100048, China
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, China
State Key Laboratory of Automtive Safety and Energy, Tsinghua University, Beijing 100084, China
Chemistry and Chemical Engineering Guangdong Laboratory, Shantou 515031, China
Department of Physics and Chemistry, Faculty of Science and Technology, University of Macau, Macau 999078, China

§ Chang Chen, Zhiqiang Chen, and Junxi Zhong contributed equally to this work.

Keywords:
oxygen reduction, Zn-air battery, single-atom Co, electronic structure regulation, axial Co–S coordination
Topics:
Graphene
Cite this article:
Chen C, Chen Z, Zhong J, et al. Regulating electronic structure of CoN4 with axial Co–S for promoting oxygen reduction and Zn-air battery performance. Nano Research, 2023, 16(4): 4211-4218. https://doi.org/10.1007/s12274-022-5164-y
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Abstract Full text Electronic supplementary material About this article

Regulating the coordination environment of transition-metal based materials in the axial direction with heteroatoms has shown great potential in boosting the oxygen reduction reaction (ORR). The coordination configuration and the regulation method are pivotal and elusive. Here, we report a combined strategy of matrix-activization and controlled-induction to modify the CoN4 site by axial coordination of Co–S (Co1N4-S1), which was validated by the aberration-corrected electron microscopy and X-ray absorption fine structure analysis. The optimal Co1N4-S1 exhibits an excellent alkaline ORR activity, according to the half-wave potential (0.897 V vs. reversible hydrogen electrode (RHE)), Tafel slope (24.67 mV/dec), and kinetic current density. Moreover, the Co1N4-S1 based Zn-air battery displays a high power density of 187.55 mW/cm2 and an outstanding charge–discharge cycling stability for 160 h, demonstrating the promising application potential. Theoretical calculations indicate that the better regulation of CoN4 on electronic structure and thus the highly efficient ORR performance can be achieved by axial Co–S.


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Electronic supplementary material
About this article

Regulating electronic structure of CoN4 with axial Co–S for promoting oxygen reduction and Zn-air battery performance

Show Author's information Chang Chen1,§, Zhiqiang Chen2,§, Junxi Zhong3,§, Xin Song4, Dongfang Chen4, Shoujie Liu5, Weng-Chon Cheong6, Jiazhan Li1, Xin Tan1, Chang He1, Jiaqi Zhang1, Di Liu1, Qiuhua Yuan3( ), Chen Chen1( ), Qing Peng1( ), Yadong Li1
Department of Chemistry, Tsinghua University, Beijing 100084, China
Beijing Key Laboratory of Research and Application for Aerospace Green Propellants, Beijing Institute of Aerospace Testing Technology, Beijing 100048, China
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, China
State Key Laboratory of Automtive Safety and Energy, Tsinghua University, Beijing 100084, China
Chemistry and Chemical Engineering Guangdong Laboratory, Shantou 515031, China
Department of Physics and Chemistry, Faculty of Science and Technology, University of Macau, Macau 999078, China

§ Chang Chen, Zhiqiang Chen, and Junxi Zhong contributed equally to this work.

Abstract

Regulating the coordination environment of transition-metal based materials in the axial direction with heteroatoms has shown great potential in boosting the oxygen reduction reaction (ORR). The coordination configuration and the regulation method are pivotal and elusive. Here, we report a combined strategy of matrix-activization and controlled-induction to modify the CoN4 site by axial coordination of Co–S (Co1N4-S1), which was validated by the aberration-corrected electron microscopy and X-ray absorption fine structure analysis. The optimal Co1N4-S1 exhibits an excellent alkaline ORR activity, according to the half-wave potential (0.897 V vs. reversible hydrogen electrode (RHE)), Tafel slope (24.67 mV/dec), and kinetic current density. Moreover, the Co1N4-S1 based Zn-air battery displays a high power density of 187.55 mW/cm2 and an outstanding charge–discharge cycling stability for 160 h, demonstrating the promising application potential. Theoretical calculations indicate that the better regulation of CoN4 on electronic structure and thus the highly efficient ORR performance can be achieved by axial Co–S.

Keywords: oxygen reduction, Zn-air battery, single-atom Co, electronic structure regulation, axial Co–S coordination

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Publication history
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Acknowledgements

Publication history

Received: 30 August 2022
Revised: 05 October 2022
Accepted: 07 October 2022
Published: 29 November 2022
Issue date: April 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was supported by the National Key Research and Development Program of China (No. 2021YFF0500503), the National Natural Science Foundation of China (Nos. 22275109, 21971135, 21925202, 21872076, and 21471102), the Beijing Municipal Natural Science Foundation (No. 2214060), the China Postdoctoral Science Foundation (No. 2020M680508), and Shenzhen Basic Research Foundation (No. JCYJ20190808110613626). We thank the BL14W1 in 1W1B station in Beijing Synchrotron Radiation Facility for XAS measurements. We acknowledge the support of Analysis Center of Tsinghua University for XPS measurements. We thank the Institute of Physics CAS for AC-STEM measurements.

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