Stabilized Cu0 -Cu1+ dual sites in a cyanamide framework for selective CO2 electroreduction to ethylene

Kaihang Yue; Yanyang Qin; Honghao Huang; Zhuoran Lv; Mingzhi Cai; Yaqiong Su; Fuqiang Huang; Ya Yan

doi:10.1038/s41467-024-52022-0

Stabilized Cu⁰ -Cu¹⁺ dual sites in a cyanamide framework for selective CO₂ electroreduction to ethylene

Nat Commun. 2024 Sep 7;15(1):7820. doi: 10.1038/s41467-024-52022-0.

Authors

Kaihang Yue^#^{1

2}, Yanyang Qin^#³, Honghao Huang¹, Zhuoran Lv^{1

4}, Mingzhi Cai^{4

5}, Yaqiong Su⁶, Fuqiang Huang^{7

8}, Ya Yan^{9

10}

Affiliations

¹ State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China.
² Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China.
³ School of Chemistry, Xi'an Jiaotong University, Xi'an, 710049, China.
⁴ State Key Lab of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China.
⁵ State Key Laboratory of Rare Earth Materials Chemistry and Applications College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.
⁶ School of Chemistry, Xi'an Jiaotong University, Xi'an, 710049, China. yqsu1989@xjtu.edu.cn.
⁷ State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China. huangfq@sjtu.edu.cn.
⁸ State Key Lab of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China. huangfq@sjtu.edu.cn.
⁹ State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China. yanya@mail.sic.ac.cn.
¹⁰ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China. yanya@mail.sic.ac.cn.

^# Contributed equally.

Abstract

Electrochemical reduction of carbon dioxide to produce high-value ethylene is often limited by poor selectivity and yield of multi-carbon products. To address this, we propose a cyanamide-coordinated isolated copper framework with both metallic copper (Cu⁰) and charged copper (Cu¹⁺) sites as an efficient electrocatalyst for the reduction of carbon dioxide to ethylene. Our operando electrochemical characterizations and theoretical calculations reveal that copper atoms in the Cu^δ+NCN complex enhance carbon dioxide activation by improving surface carbon monoxide adsorption, while delocalized electrons around copper sites facilitate carbon-carbon coupling by reducing the Gibbs free energy for *CHC formation. This leads to high selectivity for ethylene production. The Cu^δ+NCN catalyst achieves 77.7% selectivity for carbon dioxide to ethylene conversion at a partial current density of 400 milliamperes per square centimeter and demonstrates long-term stability over 80 hours in membrane electrode assembly-based electrolysers. This study provides a strategic approach for designing catalysts for the electrosynthesis of value-added chemicals from carbon dioxide.

Abstract

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