Cascade Dual Sites Modulate Local CO Coverage and Hydrogen-Binding Strength to Boost CO2 Electroreduction to Ethylene

Junjun Li; Yu Chen; Bingqing Yao; Wenjuan Yang; Xiaoya Cui; Huiling Liu; Sheng Dai; Shibo Xi; Zhiyi Sun; Wenxing Chen; Yuchen Qin; Jinlan Wang; Qian He; Chongyi Ling; Dingsheng Wang; Zhicheng Zhang

doi:10.1021/jacs.4c00475

Cascade Dual Sites Modulate Local CO Coverage and Hydrogen-Binding Strength to Boost CO₂ Electroreduction to Ethylene

J Am Chem Soc. 2024 Feb 28;146(8):5693-5701. doi: 10.1021/jacs.4c00475. Epub 2024 Feb 9.

Authors

Junjun Li¹, Yu Chen², Bingqing Yao³, Wenjuan Yang⁴, Xiaoya Cui⁵, Huiling Liu⁶, Sheng Dai⁷, Shibo Xi⁸, Zhiyi Sun⁹, Wenxing Chen⁹, Yuchen Qin¹⁰, Jinlan Wang², Qian He³, Chongyi Ling², Dingsheng Wang¹¹, Zhicheng Zhang¹

Affiliations

¹ Department of Chemistry, School of Science; Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University, Tianjin 300072, China.
² Key Laboratory of Quantum Materials and Devices of Ministry of Education, School of Physics, Southeast University, Nanjing 211189, China.
³ Department of Material Science and Engineering, College of Design and Engineering, National University of Singapore, 9 Engineering Drive 1, EA #03-09, Singapore 117575, Singapore.
⁴ Julong College, Shenzhen Technology University, Shenzhen 518118, China.
⁵ Ministry of Education Key Laboratory of Protein Sciences, Beijing Advanced Innovation Center for Structural Biology, School of Life Sciences, Tsinghua University, Beijing 100084, China.
⁶ Institute for New Energy Materials and Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin Key Laboratory of Advanced Functional Porous Materials, Tianjin University of Technology, Tianjin 300384, China.
⁷ Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, School of Chemistry and Molecular Engineering, East China University of Science & Technology, Shanghai 200237, China.
⁸ Institute of Sustainability for Chemicals, Energy and Environment (ISCE2), Agency for Science, Technology and Research (A*STAR), 1 Pesek Road Jurong Island, Singapore 627833, Republic of Singapore.
⁹ Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China.
¹⁰ College of Sciences, Henan Agricultural University, Zhengzhou 450000, P. R. China.
¹¹ Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China.

PMID: 38335459
DOI: 10.1021/jacs.4c00475

Abstract

Rationally modulating the binding strength of reaction intermediates on surface sites of copper-based catalysts could facilitate C-C coupling to generate multicarbon products in an electrochemical CO₂ reduction reaction. Herein, theoretical calculations reveal that cascade Ag-Cu dual sites could synergistically increase local CO coverage and lower the kinetic barrier for CO protonation, leading to enhanced asymmetric C-C coupling to generate C₂H₄. As a proof of concept, the Cu₃N-Ag nanocubes (NCs) with Ag located in partial Cu sites and a Cu₃N unit center are successfully synthesized. The Faraday efficiency and partial current density of C₂H₄ over Cu₃N-Ag NCs are 7.8 and 9.0 times those of Cu₃N NCs, respectively. In situ spectroscopies combined with theoretical calculations confirm that Ag sites produce CO and Cu sites promote asymmetric C-C coupling to *COCHO, significantly enhancing the generation of C₂H₄. Our work provides new insights into the cascade catalysis strategy at the atomic scale for boosting CO₂ to multicarbon products.