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Research Article

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

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.

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Graphical Abstract

A copper cluster-based metal-organic framework (MOF) stabilized by cuprophilic interactions was constructed and utilized for highly efficient electrocatalytic CO2 reduction to CH4 in a gas diffusion flow cell. The high faradaic efficiencies can be attributed to the favorable combination of the pore channel and the enhanced cuprophilic interactions.

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

metal-organic frameworkcuprophilic interactionscarbon dioxideelectroreduction

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Nano Research
Volume 15 Issue 12,
December 2022
Pages 10185-10193
DOI: 10.1007/s12274-022-4681-z
Cite this article:
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
Topics:
Electrocatalysis Electrolytic reduction
Part of a topical collection:
NR45 Awards in Nanocatalysis, 2022

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Received: 09 May 2022
Revised: 04 June 2022
Accepted: 20 June 2022
Published: 22 July 2022
© Tsinghua University Press 2022
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