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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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Publication history

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

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© 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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Email: nanores@tup.tsinghua.edu.cn

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