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Research Article

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

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
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Graphical Abstract

A novel seed encapsulation–decomposition strategy was proposed for the geometric engineering and thermal atomization of a series of Cu-Nx/S sites by peripheral C–S or C–N bond cleavage. The increased distortion degree of the Cu-Nx/S molecular structure intensified charge redistribution, changed the rate-determining step and substantially decreased the overall ORR energy barriers for Zn-air batteries.

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

single-atomic sitesgeometric distortion engineeringseed encapsulation–decomposition strategycharge distributionoxygen reduction reaction

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Nano Research
Volume 15 Issue 10,
October 2022
Pages 8928-8935
DOI: 10.1007/s12274-022-4870-y
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
Topics:
Oxygen reduction reaction Structural optimization

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Received: 16 July 2022
Revised: 03 August 2022
Accepted: 03 August 2022
Published: 22 August 2022
© Tsinghua University Press 2022
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