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Nano Research 2022, 15(12): 10185-10193 https://doi.org/10.1007/s12274-022-4681-z
Research Article | Issue | Published: 22 July 2022

Porous copper cluster-based MOF with strong cuprophilic interactions for highly selective electrocatalytic reduction of CO2 to CH4

Show Author's Information Long-Zhang Dong1,2,§,  Yun-Feng Lu2,§,  Rui Wang2,  Jie Zhou1,  Yu Zhang2,  Lei Zhang1,  Jiang Liu1,2,  Shun-Li Li1,2,  Ya-Qian Lan1,2( )
National and Local Joint Engineering Research Center of MPTES in High Energy and Safety LIBs, Engineering Research Center of MTEES (Ministry of Education), Key Lab. of ETESPG (GHEI), School of Chemistry, South China Normal University, Guangzhou 510006, 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

§ Long-Zhang Dong and Yun-Feng Lu contributed equally to this work.

Keywords:
carbon dioxide, metal-organic framework, cuprophilic interactions, electroreduction
Topics:
Electrocatalysis Electrolytic reduction
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Dong L-Z, Lu Y-F, Wang R, et al. Porous copper cluster-based MOF with strong cuprophilic interactions for highly selective electrocatalytic reduction of CO2 to CH4. Nano Research, 2022, 15(12): 10185-10193. https://doi.org/10.1007/s12274-022-4681-z
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Abstract Full text Electronic supplementary material About this article

It is well known that the low-valent Cu species are important catalytically active centers in the reduction of CO2 to hydrocarbon products. However, the Cu(I)-based catalysts are easily reduced during the electroreduction of CO2, which causes phase transformation of catalysts and leads to a decrease of intrinsic catalytic activity. Therefore, it is of great significance to synthesize Cu(I)-based catalysts with specific interactions that can keep the catalytically active Cu sites stable in the electrocatalytic process. Based on the above considerations, a hexanuclear Cu cluster with strong cuprophilic interactions has been designed and utilized as a secondary building unit (SBU) to construct a stable metal-organic framework (MOF) electrocatalyst (NNU-50). As expected, the NNU-50 has served as an effective electrocatalyst for the CO2-to-CH4 conversion by exhibiting a high Faradaic efficiency for CH4 (FE CH4) of 66.40% and a large current density of ~ 400 mA·cm−2 at −1.0 V vs. reversible hydrogen electrode (RHE), which is one of the best catalytic performances among the stable MOF electrocatalysts until now. This work contributes more ideas for the design of stable and efficient MOF-based electrocatalysts for CO2 reduction reaction.


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Electronic supplementary material
About this article

Porous copper cluster-based MOF with strong cuprophilic interactions for highly selective electrocatalytic reduction of CO2 to CH4

Show Author's information Long-Zhang Dong1,2,§, Yun-Feng Lu2,§, Rui Wang2, Jie Zhou1, Yu Zhang2, Lei Zhang1, Jiang Liu1,2, Shun-Li Li1,2, Ya-Qian Lan1,2( )
National and Local Joint Engineering Research Center of MPTES in High Energy and Safety LIBs, Engineering Research Center of MTEES (Ministry of Education), Key Lab. of ETESPG (GHEI), School of Chemistry, South China Normal University, Guangzhou 510006, 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

§ Long-Zhang Dong and Yun-Feng Lu contributed equally to this work.

Abstract

It is well known that the low-valent Cu species are important catalytically active centers in the reduction of CO2 to hydrocarbon products. However, the Cu(I)-based catalysts are easily reduced during the electroreduction of CO2, which causes phase transformation of catalysts and leads to a decrease of intrinsic catalytic activity. Therefore, it is of great significance to synthesize Cu(I)-based catalysts with specific interactions that can keep the catalytically active Cu sites stable in the electrocatalytic process. Based on the above considerations, a hexanuclear Cu cluster with strong cuprophilic interactions has been designed and utilized as a secondary building unit (SBU) to construct a stable metal-organic framework (MOF) electrocatalyst (NNU-50). As expected, the NNU-50 has served as an effective electrocatalyst for the CO2-to-CH4 conversion by exhibiting a high Faradaic efficiency for CH4 (FE CH4) of 66.40% and a large current density of ~ 400 mA·cm−2 at −1.0 V vs. reversible hydrogen electrode (RHE), which is one of the best catalytic performances among the stable MOF electrocatalysts until now. This work contributes more ideas for the design of stable and efficient MOF-based electrocatalysts for CO2 reduction reaction.

Keywords: carbon dioxide, metal-organic framework, cuprophilic interactions, electroreduction

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Publication history
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Acknowledgements

Publication history

Received: 09 May 2022
Revised: 04 June 2022
Accepted: 20 June 2022
Published: 22 July 2022
Issue date: December 2022

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 21871141, 21871142, 22071109, 22105080, and 92061101), the Excellent Youth Foundation of Jiangsu Natural Science Foundation (No. BK20211593), Priority Academic Program Development of Jiangsu Higher Education Institutions, and the Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials.

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