MOF Encapsulating N-Heterocyclic Carbene-Ligated Copper Single-Atom Site Catalyst towards Efficient Methane Electrosynthesis

Shenghua Chen; Wen-Hao Li; Wenjun Jiang; Jiarui Yang; Jiexin Zhu; Liqiang Wang; Honghui Ou; Zechao Zhuang; Mingzhao Chen; Xiaohui Sun; Dingsheng Wang; Yadong Li

doi:10.1002/anie.202114450

MOF Encapsulating N-Heterocyclic Carbene-Ligated Copper Single-Atom Site Catalyst towards Efficient Methane Electrosynthesis

Angew Chem Int Ed Engl. 2022 Jan 21;61(4):e202114450. doi: 10.1002/anie.202114450. Epub 2021 Dec 13.

Authors

Affiliations

¹ Department of Chemistry, Tsinghua University, Beijing, 100084, P. R. China.
² Qian Xuesen Laboratory of Space Technology, China Academy of Space Technology, Beijing, 100094, P. R. China.
³ State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, International School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, 430070, P. R. China.
⁴ Henan Province Industrial Technology Research Institute of Resources and Materials, School of Material Science and Engineering, Zhengzhou University, Zhengzhou, Henan, 450001, P. R. China.
⁵ Institute of Environmental Research at Greater Bay Area, Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education, Guangzhou Key Laboratory for Clean Energy and Materials, Guangzhou University, Guangzhou, 510006, P. R. China.

PMID: 34767294
DOI: 10.1002/anie.202114450

Abstract

The exploitation of highly efficient carbon dioxide reduction (CO₂ RR) electrocatalyst for methane (CH₄ ) electrosynthesis has attracted great attention for the intermittent renewable electricity storage but remains challenging. Here, N-heterocyclic carbene (NHC)-ligated copper single atom site (Cu SAS) embedded in metal-organic framework is reported (2Bn-Cu@UiO-67), which can achieve an outstanding Faradaic efficiency (FE) of 81 % for the CO₂ reduction to CH₄ at -1.5 V vs. RHE with a current density of 420 mA cm^-2 . The CH₄ FE of our catalyst remains above 70 % within a wide potential range and achieves an unprecedented turnover frequency (TOF) of 16.3 s^-1 . The σ donation of NHC enriches the surface electron density of Cu SAS and promotes the preferential adsorption of CHO* intermediates. The porosity of the catalyst facilitates the diffusion of CO₂ to 2Bn-Cu, significantly increasing the availability of each catalytic center.

Keywords: CH4 electrosynthesis; CO2RR; Cu single-atom site catalyst; n-heterocyclic carbene.

Abstract

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