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Flagship Article

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

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.

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Graphical Abstract

As shown in the illustration, Co1N4-S1 exhibits highly efficient oxygen reduction reaction (ORR) reactivity and remarkable ORR kinetics as well as good methanol tolerance and excellent stability in both alkaline and acid media, which outperforms the CoN4 sample, Co1N4-N1 sample, and the commercial Pt/C. Theoretical calculations show that, the axial S coordination benefits the adsorption and activation of O2 gas molecule because of better electronic structure regulation, which will reduce the magnitude of the potential-determining step.

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

electronic structure regulationaxial Co–S coordinationsingle-atom Cooxygen reductionZn-air battery

Electronic Supplementary Material

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Nano Research
Volume 16 Issue 4,
April 2023
Pages 4211-4218
DOI: 10.1007/s12274-022-5164-y
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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Received: 30 August 2022
Revised: 05 October 2022
Accepted: 07 October 2022
Published: 29 November 2022
© Tsinghua University Press 2022
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