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Nano Research 2022, 15(12): 10063-10069 https://doi.org/10.1007/s12274-022-4467-3
Research Article | Issue | Published: 21 June 2022

Axial coordination regulation of MOF-based single-atom Ni catalysts by halogen atoms for enhanced CO2 electroreduction

Show Author's Information Jia-Xin Peng1,  Weijie Yang2,  Zhenhe Jia2,  Long Jiao1( ),  Hai-Long Jiang1( )
Department of Chemistry, University of Science and Technology of China, Hefei 230026, China
Department of Power Engineering, School of Energy, Power and Mechanical Engineering, North China Electric Power University, Baoding 071003, China
Keywords:
CO2 electroreduction, metal–organic frameworks, single-atom catalysts, axial coordination environment
Topics:
Electrocatalysts
Cite this article:
Peng J-X, Yang W, Jia Z, et al. Axial coordination regulation of MOF-based single-atom Ni catalysts by halogen atoms for enhanced CO2 electroreduction. Nano Research, 2022, 15(12): 10063-10069. https://doi.org/10.1007/s12274-022-4467-3
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Abstract Full text Electronic supplementary material About this article

Single-atom catalysts (SACs), with the utmost atom utilization, have attracted extensive interests for various catalytic applications. The coordination environment of SACs has been recognized to play a vital role in catalysis while their precise regulation at atomic level remains an immense challenge. Herein, a post metal halide modification (PMHM) strategy has been developed to construct Ni-N4 sites with axially coordinated halogen atoms, named Ni1-N-C (X) (X = Cl, Br, and I), on pre-synthetic nitrogen-doped carbon derived from metal–organic frameworks. The axial halogen atoms with distinct electronegativity can break the symmetric charge distribution of planar Ni-N4 sites and regulate the electronic states of central Ni atoms in Ni1-N-C (X) (X = Cl, Br, and I). Significantly, the Ni1-N-C (Cl) catalyst, decorated with the most electronegative Cl atoms, exhibits Faradaic efficiency of CO up to 94.7% in electrocatalytic CO2 reduction, outperforming Ni1-N-C (Br) and Ni1-N-C (I) catalysts. Moreover, Ni1-N-C (Cl) also presents superb performance in Zn-CO2 battery with ultrahigh CO selectivity and great durability. Theoretical calculations reveal that the axially coordinated Cl atom remarkably facilitates *COOH intermediate formation on single-atom Ni sites, thereby boosting the CO2 reduction performance of Ni1-N-C (Cl). This work offers a facile strategy to tailor the axial coordination environments of SACs at atomic level and manifests the crucial role of axial coordination microenvironments in catalysis.


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About this article

Axial coordination regulation of MOF-based single-atom Ni catalysts by halogen atoms for enhanced CO2 electroreduction

Show Author's information Jia-Xin Peng1, Weijie Yang2, Zhenhe Jia2, Long Jiao1( ), Hai-Long Jiang1( )
Department of Chemistry, University of Science and Technology of China, Hefei 230026, China
Department of Power Engineering, School of Energy, Power and Mechanical Engineering, North China Electric Power University, Baoding 071003, China

Abstract

Single-atom catalysts (SACs), with the utmost atom utilization, have attracted extensive interests for various catalytic applications. The coordination environment of SACs has been recognized to play a vital role in catalysis while their precise regulation at atomic level remains an immense challenge. Herein, a post metal halide modification (PMHM) strategy has been developed to construct Ni-N4 sites with axially coordinated halogen atoms, named Ni1-N-C (X) (X = Cl, Br, and I), on pre-synthetic nitrogen-doped carbon derived from metal–organic frameworks. The axial halogen atoms with distinct electronegativity can break the symmetric charge distribution of planar Ni-N4 sites and regulate the electronic states of central Ni atoms in Ni1-N-C (X) (X = Cl, Br, and I). Significantly, the Ni1-N-C (Cl) catalyst, decorated with the most electronegative Cl atoms, exhibits Faradaic efficiency of CO up to 94.7% in electrocatalytic CO2 reduction, outperforming Ni1-N-C (Br) and Ni1-N-C (I) catalysts. Moreover, Ni1-N-C (Cl) also presents superb performance in Zn-CO2 battery with ultrahigh CO selectivity and great durability. Theoretical calculations reveal that the axially coordinated Cl atom remarkably facilitates *COOH intermediate formation on single-atom Ni sites, thereby boosting the CO2 reduction performance of Ni1-N-C (Cl). This work offers a facile strategy to tailor the axial coordination environments of SACs at atomic level and manifests the crucial role of axial coordination microenvironments in catalysis.

Keywords: CO2 electroreduction, metal–organic frameworks, single-atom catalysts, axial coordination environment

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Publication history
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Acknowledgements

Publication history

Received: 31 March 2022
Revised: 20 April 2022
Accepted: 21 April 2022
Published: 21 June 2022
Issue date: December 2022

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was supported by the National Key Research and Development Program of China (No. 2021YFA1500402), the National Natural Science Foundation of China (NSFC) (Nos. 21725101, 21871244, and 22001242), International Partnership Program of Chinese Academy of Sciences (CAS) (No. 211134KYSB20190109), Collaborative Innovation Program of Hefei Science Center, CAS (No. 2020HSC-CIP005), and the Fundamental Research Funds for the Central Universities (Nos. WK2060000038 and WK2060000040). We thank the XAFS measurements from 1W1B station at BSRF.

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