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Single-atom catalysts (SACs) have shown unexpected catalytic activity due to their unique electronic structure and coordination environment. Nonetheless, the synthesis of an atomically precise low-coordination single-atom catalyst remains a grand challenge. Herein, we report a coordinately unsaturated Ni-N3 single-atom electrocatalyst using a metal-organic framework (MOF) derived N-C support with abundant exposed N for excellent electrochemical CO2 reduction. The obtained Ni-N3/NC active site exhibited highly efficient CO2-to-CO conversion with a Faradaic efficiency of 94.6% at the current density of 100 mA/cm2. In situ X-ray absorption spectroscopy (XAS) measurement suggested that the Ni atomic center with unsaturated coordination had the lower initial chemical state and higher charge transfer ability. In situ Fourier transform infrared (FT-IR) and theoretical calculation results revealed that the unsaturated catalytically active center could facilitate activation of CO2 and thus heighten CO2 electroreduction activity. These findings provided insights into the rational design of definitive coordination structure of SACs for boosting activity and selectivity.


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Coordinately unsaturated nickel single atom electrocatalyst for efficient CO2 conversion

Show Author's information Wei Zhang1Dong Liu2( )Tong Liu2Chenglong Ding1Tao Chen3Yanming Li1Xiaokang Liu2Lan Wang1Changli Li1Jingfu He1( )Tao Ding2( )Tao Yao2
School of Materials, Sun Yat-Sen University, Guangzhou 510275, China
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China
School of National Defense Science and Technology, Southwest University of Science and Technology, Mianyang, 621010, China

Abstract

Single-atom catalysts (SACs) have shown unexpected catalytic activity due to their unique electronic structure and coordination environment. Nonetheless, the synthesis of an atomically precise low-coordination single-atom catalyst remains a grand challenge. Herein, we report a coordinately unsaturated Ni-N3 single-atom electrocatalyst using a metal-organic framework (MOF) derived N-C support with abundant exposed N for excellent electrochemical CO2 reduction. The obtained Ni-N3/NC active site exhibited highly efficient CO2-to-CO conversion with a Faradaic efficiency of 94.6% at the current density of 100 mA/cm2. In situ X-ray absorption spectroscopy (XAS) measurement suggested that the Ni atomic center with unsaturated coordination had the lower initial chemical state and higher charge transfer ability. In situ Fourier transform infrared (FT-IR) and theoretical calculation results revealed that the unsaturated catalytically active center could facilitate activation of CO2 and thus heighten CO2 electroreduction activity. These findings provided insights into the rational design of definitive coordination structure of SACs for boosting activity and selectivity.

Keywords: electrocatalyst, Ni single atom, in situ X-ray absorption spectroscopy, in situ Fourier transform infrared

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Publication history
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Acknowledgements

Publication history

Received: 04 April 2023
Revised: 07 June 2023
Accepted: 22 June 2023
Published: 06 July 2023
Issue date: August 2023

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© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was supported by Guangdong Basic and Applied Basic Research Foundation (No. 2022A1515011828), Natural Science Foundation of Guangdong Province (No. 2022A1515012661), the National Key R&D Program of China (Nos. 2021YFA1600800 and 2020YFA0710203), the National Natural Science Foundation of China (Nos. 12025505, 22179125, 22002147, 22106126, and 12205304), the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB0450200), the Youth Innovation Promotion Association CAS (Nos. 2015366 and 2022458), and the Collaborative Innovation Program of Hefei Science Center, CAS (No. 2021HSC-CIP006). We would thank NSRL, BSRF, SSRF, and NSRRC for the synchrotron beam time.

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