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Nano Research 2022, 15(10): 8928-8935 https://doi.org/10.1007/s12274-022-4870-y
Research Article | Issue | Published: 22 August 2022

Intensifying uneven charge distribution via geometric distortion engineering in atomically dispersed M-Nx/S sites for efficient oxygen electroreduction

Show Author's Information Zhuting Zhang1,  Simin Yang1,  Rui Jiang1,  Tian Sheng2( ),  Chunfeng Shi3( ),  Yueguang Chen1( ),  Leyu Wang1( )
State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China
College of Chemistry and Materials Science, Anhui Normal University, Wuhu 214000, China
Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China
Keywords:
oxygen reduction reaction, charge distribution, single-atomic sites, geometric distortion engineering, seed encapsulation–decomposition strategy
Topics:
Oxygen reduction reaction Structural optimization
Cite this article:
Zhang Z, Yang S, Jiang R, et al. Intensifying uneven charge distribution via geometric distortion engineering in atomically dispersed M-Nx/S sites for efficient oxygen electroreduction. Nano Research, 2022, 15(10): 8928-8935. https://doi.org/10.1007/s12274-022-4870-y
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Abstract Full text Electronic supplementary material About this article

Fine regulation of geometric structures has great promise to acquire specific electronic structures and improve the catalytic performance of single-atom catalysts, yet it remains a challenge. Herein, a novel seed encapsulation–decomposition strategy is proposed for the geometric distortion engineering and thermal atomization of a series of Cu-Nx/S moieties anchored on carbon supports. During pyrolysis, seeds (Cu2+, CuO, or Cu7S4 nanoparticles) confined in metal organic framework can accommodate single Cu atoms with Cu–N or Cu–S coordination bonds and simultaneously induce C–S or C–N bond cleavage in the second coordination shell of Cu centers, which are identified to manipulate the distortion degree of Cu-Nx/S moieties. The severely distorted Cu-N3S molecular structure endows the resultant catalyst with excellent oxygen reduction reaction activity (E1/2 = 0.885 V) and zinc-air battery performance (peak power density of 210 mW·cm−2), outperforming the asymmetrical and symmetrical Cu-N4 structures. A combined experimental and theoretical study reveals that the geometric distortion of Cu-Nx/S moieties creates uneven charge distribution by a unique topological correlation effect, which increases the metal charge and shifts the d-band center toward the Fermi level, thereby optimizing the inter-mediate adsorption energy.


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Electronic supplementary material
About this article

Intensifying uneven charge distribution via geometric distortion engineering in atomically dispersed M-Nx/S sites for efficient oxygen electroreduction

Show Author's information Zhuting Zhang1, Simin Yang1, Rui Jiang1, Tian Sheng2( ), Chunfeng Shi3( ), Yueguang Chen1( ), Leyu Wang1( )
State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China
College of Chemistry and Materials Science, Anhui Normal University, Wuhu 214000, China
Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China

Abstract

Fine regulation of geometric structures has great promise to acquire specific electronic structures and improve the catalytic performance of single-atom catalysts, yet it remains a challenge. Herein, a novel seed encapsulation–decomposition strategy is proposed for the geometric distortion engineering and thermal atomization of a series of Cu-Nx/S moieties anchored on carbon supports. During pyrolysis, seeds (Cu2+, CuO, or Cu7S4 nanoparticles) confined in metal organic framework can accommodate single Cu atoms with Cu–N or Cu–S coordination bonds and simultaneously induce C–S or C–N bond cleavage in the second coordination shell of Cu centers, which are identified to manipulate the distortion degree of Cu-Nx/S moieties. The severely distorted Cu-N3S molecular structure endows the resultant catalyst with excellent oxygen reduction reaction activity (E1/2 = 0.885 V) and zinc-air battery performance (peak power density of 210 mW·cm−2), outperforming the asymmetrical and symmetrical Cu-N4 structures. A combined experimental and theoretical study reveals that the geometric distortion of Cu-Nx/S moieties creates uneven charge distribution by a unique topological correlation effect, which increases the metal charge and shifts the d-band center toward the Fermi level, thereby optimizing the inter-mediate adsorption energy.

Keywords: oxygen reduction reaction, charge distribution, single-atomic sites, geometric distortion engineering, seed encapsulation–decomposition strategy

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Publication history
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Acknowledgements

Publication history

Received: 16 July 2022
Revised: 03 August 2022
Accepted: 03 August 2022
Published: 22 August 2022
Issue date: October 2022

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This research was supported by the National Natural Science Foundation of China (Nos. 21701005 and 21903001), the Fundamental Research Funds for the Central Universities (No. XK2020-02), and China Petroleum & Chemical Corporation (SINOPEC) (No. 421028). We thank the 1W1B station and 4W1B station in the Beijing Synchrotron Radiation Facility (BSRF).

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