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Nano Research 2021, 14(8): 2790-2796 https://doi.org/10.1007/s12274-021-3287-1
Research Article | Issue | Published: 05 January 2021

Simultaneous diffusion of cation and anion to access N, S co-coordinated Bi-sites for enhanced CO2 electroreduction

Show Author's Information Zhiyuan Wang1,  Chun Wang2,  Yidong Hu1,  Shuai Yang4,  Jia Yang1,6,  Wenxing Chen5,  Huang Zhou1,  Fangyao Zhou1,  Lingxiao Wang1,  Junyi Du1,  Yafei Li2( ),  Yuen Wu1,3( )
School of Chemistry and Materials Science, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China
Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China
Dalian National Laboratory for Clean Energy, Dalian 116023, China
Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201210, China
Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
Institutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials, Ministry of Education, Anhui Graphene Engineering Laboratory, Anhui University, Hefei 230601, China
Keywords:
electronic structure modulation, electrochemical CO2 reduction, S, N-co-doped carbon nanotube, single bismuth sites
Topics:
Bismuth compoundsCarbonCarbon dioxideCatalystsDoping (additives)Electrocatalysis Electrolytic reduction Electronic structureLayered semiconductorsPositive ionsReaction intermediates
Cite this article:
Wang Z, Wang C, Hu Y, et al. Simultaneous diffusion of cation and anion to access N, S co-coordinated Bi-sites for enhanced CO2 electroreduction. Nano Research, 2021, 14(8): 2790-2796. https://doi.org/10.1007/s12274-021-3287-1
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Abstract Full text Electronic supplementary material About this article

Developing highly active single-atom sites catalysts for electrochemical reduction of CO2 is an effective and environmental-friendly strategy to promote carbon-neutral energy cycle and ameliorate global climate issues. Herein, we develop an atomically dispersed N, S co-coordinated bismuth atom sites catalyst (Bi-SAs-NS/C) via a cation and anion simultaneous diffusion strategy for electrocatalytic CO2 reduction. In this strategy, the bonded Bi cation and S anion are simultaneously diffused into the nitrogen-doped carbon layer in the form of Bi2S3. Then Bi is captured by the abundant N-rich vacancies and S is bonded with carbons support at high temperature, formed the N, S co-coordinated Bi sites. Benefiting from the simultaneous diffusion of Bi and S, different electronegative N and S can be effectively co-coordinated with Bi, forming the uniform Bi-N3S/C sites. The synthesized Bi-SAs-NS/C exhibits a high selectivity towards CO with over 88% Faradaic efficiency in a wide potential range, and achieves a maximum FECO of 98.3% at -0.8 V vs. RHE with a current density of 10.24 mA·cm-2, which can keep constant with negligible degradation in 24 h continuous electrolysis. Experimental results and theoretical calculations reveal that the significantly improved catalytic performance of Bi-SAs-NS/C than Bi-SAs-N/C is ascribed to the replacement of one coordinated-N with low electronegative S in Bi-N4C center, which can greatly reduce the energy barrier of the intermediate formation in rate-limiting step and increase the reaction kinetics. This work provides an effective strategy for rationally designing highly active single-atom sites catalysts for efficient electrocatalysis with optimized electronic structure.


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Electronic supplementary material
About this article

Simultaneous diffusion of cation and anion to access N, S co-coordinated Bi-sites for enhanced CO2 electroreduction

Show Author's information Zhiyuan Wang1, Chun Wang2, Yidong Hu1, Shuai Yang4, Jia Yang1,6, Wenxing Chen5, Huang Zhou1, Fangyao Zhou1, Lingxiao Wang1, Junyi Du1, Yafei Li2( ), Yuen Wu1,3( )
School of Chemistry and Materials Science, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China
Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China
Dalian National Laboratory for Clean Energy, Dalian 116023, China
Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201210, China
Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
Institutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials, Ministry of Education, Anhui Graphene Engineering Laboratory, Anhui University, Hefei 230601, China

Abstract

Developing highly active single-atom sites catalysts for electrochemical reduction of CO2 is an effective and environmental-friendly strategy to promote carbon-neutral energy cycle and ameliorate global climate issues. Herein, we develop an atomically dispersed N, S co-coordinated bismuth atom sites catalyst (Bi-SAs-NS/C) via a cation and anion simultaneous diffusion strategy for electrocatalytic CO2 reduction. In this strategy, the bonded Bi cation and S anion are simultaneously diffused into the nitrogen-doped carbon layer in the form of Bi2S3. Then Bi is captured by the abundant N-rich vacancies and S is bonded with carbons support at high temperature, formed the N, S co-coordinated Bi sites. Benefiting from the simultaneous diffusion of Bi and S, different electronegative N and S can be effectively co-coordinated with Bi, forming the uniform Bi-N3S/C sites. The synthesized Bi-SAs-NS/C exhibits a high selectivity towards CO with over 88% Faradaic efficiency in a wide potential range, and achieves a maximum FECO of 98.3% at -0.8 V vs. RHE with a current density of 10.24 mA·cm-2, which can keep constant with negligible degradation in 24 h continuous electrolysis. Experimental results and theoretical calculations reveal that the significantly improved catalytic performance of Bi-SAs-NS/C than Bi-SAs-N/C is ascribed to the replacement of one coordinated-N with low electronegative S in Bi-N4C center, which can greatly reduce the energy barrier of the intermediate formation in rate-limiting step and increase the reaction kinetics. This work provides an effective strategy for rationally designing highly active single-atom sites catalysts for efficient electrocatalysis with optimized electronic structure.

Keywords: electronic structure modulation, electrochemical CO2 reduction, S, N-co-doped carbon nanotube, single bismuth sites

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Publication history
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Acknowledgements

Publication history

Received: 15 November 2020
Revised: 06 December 2020
Accepted: 07 December 2020
Published: 05 January 2021
Issue date: August 2021

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021

Acknowledgements

This work was supported by the National Key R&D Program of China (Nos. 2017YFA0208300 and 2017YFA0700104), the National Natural Science Foundation of China (Nos. 21522107 and 21671180) and the DNL Cooperation Fund, CAS (No. NDL201918). We thank the photoemission endstations BL1W1B in Beijing Synchrotron Radiation Facility (BSRF), BL14W1 in Shanghai Synchrotron Radiation Facility (SSRF), BL10B and BL11U in National Synchrotron Radiation Laboratory (NSRL) for the help in characterizations.

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