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Nano Research 2024, 17(4): 2400-2409 https://doi.org/10.1007/s12274-023-6079-y
Research Article | Issue | Published: 07 September 2023

Promoted surface charge density from interlayer Zn–N4 configuration in carbon nitride for enhanced CO2 photoreduction

Show Author's Information Xianjin Shi1,2,3,  Yu Huang1,2( ),  Gangqiang Zhu4,  Wei Peng1,2,  Meijuan Chen5
State Key Laboratory of Loess and Quaternary Geology (SKLLQG), Key Laboratory of Aerosol Chemistry and Physics, Institute of Earth Environment, Chinese Academy of Sciences, Xi’an 710061, China
Center of Excellence in Quaternary Science and Global Change, Chinese Academy of Sciences, Xi’an 710061, China
University of Chinese Academy of Sciences, Beijing 100049, China
School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710062, China
School of Human Settlements and Civil Engineering, Xi’an Jiaotong University, Xi’an 710049, China
Keywords:
photocatalytic CO2 reduction, surface charge density, single-atom catalysts, charge transfer dynamics, interlayer modification
Topics:
Photocatalysis
Cite this article:
Shi X, Huang Y, Zhu G, et al. Promoted surface charge density from interlayer Zn–N4 configuration in carbon nitride for enhanced CO2 photoreduction. Nano Research, 2024, 17(4): 2400-2409. https://doi.org/10.1007/s12274-023-6079-y
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Abstract Full text Electronic supplementary material About this article

The solar-driven reduction of CO2 into valuable products is a promising method to alleviate global environmental problems and energy crises. However, the low surface charge density limits the photocatalytic conversion performance of CO2. Herein, a polymeric carbon nitride (PCN) photocatalyst with Zn single atoms (Zn1/CN) was designed and synthesized for CO2 photoreduction. The results of the CO2 photoreduction studies show that the CO and CH4 yields of Zn1/CN increased fivefold, reaching 76.9 and 22.9 μmol/(g·h), respectively, in contrast to the unmodified PCN. Ar+ plasma-etched X-ray photoelectron spectroscopy and synchrotron radiation-based X-ray absorption fine structure results reveal that Zn single atom is mainly present in the interlayer space of PCN in the Zn–N4 configuration. Photoelectrochemical characterizations indicate that the interlayer Zn–N4 configuration can amplify light absorption and establish an interlayer charge transfer channel. Light-assisted Kelvin probe force microscopy confirms that more photogenerated electrons are delivered to the catalyst surface through interlayer Zn–N4 configuration, which increases its surface charge density. Further, in-situ infrared spectroscopy combined with density functional theory calculation reveals that promoted surface charge density accelerates key intermediates (*COOH) conversion, thus achieving efficient CO2 conversion. This work elucidates the role of internal single atoms in catalytic surface reactions, which provides important implications for the design of single-atom catalysts.


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Electronic supplementary material
About this article

Promoted surface charge density from interlayer Zn–N4 configuration in carbon nitride for enhanced CO2 photoreduction

Show Author's information Xianjin Shi1,2,3, Yu Huang1,2( ), Gangqiang Zhu4, Wei Peng1,2, Meijuan Chen5
State Key Laboratory of Loess and Quaternary Geology (SKLLQG), Key Laboratory of Aerosol Chemistry and Physics, Institute of Earth Environment, Chinese Academy of Sciences, Xi’an 710061, China
Center of Excellence in Quaternary Science and Global Change, Chinese Academy of Sciences, Xi’an 710061, China
University of Chinese Academy of Sciences, Beijing 100049, China
School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710062, China
School of Human Settlements and Civil Engineering, Xi’an Jiaotong University, Xi’an 710049, China

Abstract

The solar-driven reduction of CO2 into valuable products is a promising method to alleviate global environmental problems and energy crises. However, the low surface charge density limits the photocatalytic conversion performance of CO2. Herein, a polymeric carbon nitride (PCN) photocatalyst with Zn single atoms (Zn1/CN) was designed and synthesized for CO2 photoreduction. The results of the CO2 photoreduction studies show that the CO and CH4 yields of Zn1/CN increased fivefold, reaching 76.9 and 22.9 μmol/(g·h), respectively, in contrast to the unmodified PCN. Ar+ plasma-etched X-ray photoelectron spectroscopy and synchrotron radiation-based X-ray absorption fine structure results reveal that Zn single atom is mainly present in the interlayer space of PCN in the Zn–N4 configuration. Photoelectrochemical characterizations indicate that the interlayer Zn–N4 configuration can amplify light absorption and establish an interlayer charge transfer channel. Light-assisted Kelvin probe force microscopy confirms that more photogenerated electrons are delivered to the catalyst surface through interlayer Zn–N4 configuration, which increases its surface charge density. Further, in-situ infrared spectroscopy combined with density functional theory calculation reveals that promoted surface charge density accelerates key intermediates (*COOH) conversion, thus achieving efficient CO2 conversion. This work elucidates the role of internal single atoms in catalytic surface reactions, which provides important implications for the design of single-atom catalysts.

Keywords: photocatalytic CO2 reduction, surface charge density, single-atom catalysts, charge transfer dynamics, interlayer modification

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Publication history
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Acknowledgements

Publication history

Received: 26 June 2023
Revised: 28 July 2023
Accepted: 08 August 2023
Published: 07 September 2023
Issue date: April 2024

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was supported by the Strategic Priority Research Program of the Chinese Academy of Sciences, China (Nos. XDA23010300 and XDA23010000), the National Natural Science Foundation of China (Nos. 51878644 and 41573138), and the CAS Youth Interdisciplinary Team. The authors also thank professor Yujie Xiong (University of Science and Technology of China) for his helpful suggestions.

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