Highly Ethylene-Selective Electrocatalytic CO2 Reduction Enabled by Isolated Cu-S Motifs in Metal-Organic Framework Based Precatalysts

Chun Fang Wen; Min Zhou; Peng Fei Liu; Yuanwei Liu; Xuefeng Wu; Fangxin Mao; Sheng Dai; Beibei Xu; Xue Lu Wang; Zheng Jiang; P Hu; Shuang Yang; Hai Feng Wang; Hua Gui Yang

doi:10.1002/anie.202111700

Highly Ethylene-Selective Electrocatalytic CO₂ Reduction Enabled by Isolated Cu-S Motifs in Metal-Organic Framework Based Precatalysts

Angew Chem Int Ed Engl. 2022 Jan 10;61(2):e202111700. doi: 10.1002/anie.202111700. Epub 2021 Dec 2.

Authors

Chun Fang Wen¹, Min Zhou², Peng Fei Liu¹, Yuanwei Liu¹, Xuefeng Wu¹, Fangxin Mao¹, Sheng Dai³, Beibei Xu⁴, Xue Lu Wang⁴, Zheng Jiang⁵, P Hu^{2

6}, Shuang Yang¹, Hai Feng Wang², Hua Gui Yang¹

Affiliations

¹ Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
² Key Laboratory for Advanced Materials, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
³ Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
⁴ Physics Department and Shanghai Key Laboratory of Magnetic Resonance, School of Physics and Materials Science, East China Normal University, 3663 North Zhongshan Road, Shanghai, 200062, China.
⁵ Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201204, China.
⁶ School of Chemistry and Chemical Engineering, The Queen's University of Belfast, Belfast, BT9 5AG, UK.

PMID: 34687123
DOI: 10.1002/anie.202111700

Abstract

Copper-based materials are efficient electrocatalysts for the conversion of CO₂ to C₂₊ products, and most these materials are reconstructed in situ to regenerate active species. It is a challenge to precisely design precatalysts to obtain active sites for the CO₂ reduction reaction (CO₂ RR). Herein, we develop a strategy based on local sulfur doping of a Cu-based metal-organic framework precatalyst, in which the stable Cu-S motif is dispersed in the framework of HKUST-1 (S-HKUST-1). The precatalyst exhibits a high ethylene selectivity in an H-type cell with a maximum faradaic efficiency (FE) of 60.0 %, and delivers a current density of 400 mA cm^-2 with an ethylene FE up to 57.2 % in a flow cell. Operando X-ray absorption results demonstrate that Cu^δ+ species stabilized by the Cu-S motif exist in S-HKUST-1 during CO₂ RR. Density functional theory calculations indicate the partially oxidized Cu^δ+ at the Cu/Cu_x S_y interface is favorable for coupling of the *CO intermediate due to the modest distance between coupling sites and optimized adsorption energy.

Keywords: CO2 reduction reaction; Cu−S species; electrocatalysis; metal-organic frameworks; operando XAFS.

Abstract

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