Mechanistic insights into C-C coupling in electrochemical CO reduction using gold superlattices

Xiaoju Yang; Chao Rong; Li Zhang; Zhenkun Ye; Zhiming Wei; Chengdi Huang; Qiao Zhang; Qing Yuan; Yueming Zhai; Fu-Zhen Xuan; Bingjun Xu; Bowei Zhang; Xuan Yang

doi:10.1038/s41467-024-44923-x

Mechanistic insights into C-C coupling in electrochemical CO reduction using gold superlattices

Nat Commun. 2024 Jan 24;15(1):720. doi: 10.1038/s41467-024-44923-x.

Authors

Xiaoju Yang^#^{1

2}, Chao Rong^#³, Li Zhang^{1

2}, Zhenkun Ye^{1

2}, Zhiming Wei⁴, Chengdi Huang^{1

2}, Qiao Zhang⁴, Qing Yuan^{1

2}, Yueming Zhai⁴, Fu-Zhen Xuan³, Bingjun Xu⁵, Bowei Zhang⁶, Xuan Yang^{7

8}

Affiliations

¹ Key Laboratory of Material Chemistry for Energy Conversion and Storage, Huazhong University of Science and Technology, Wuhan, 430074, China.
² Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, 430074, China.
³ Shanghai Key Laboratory of Intelligent Sensing and Detection Technology, School of Mechanical and Power Engineering, East China University of Science and Technology, Shanghai, 200237, China.
⁴ The Institute for Advanced Studies, Wuhan University, Wuhan, 430072, China.
⁵ College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China. b_xu@pku.edu.cn.
⁶ Shanghai Key Laboratory of Intelligent Sensing and Detection Technology, School of Mechanical and Power Engineering, East China University of Science and Technology, Shanghai, 200237, China. boweiz@ecust.edu.cn.
⁷ Key Laboratory of Material Chemistry for Energy Conversion and Storage, Huazhong University of Science and Technology, Wuhan, 430074, China. xuanyang@hust.edu.cn.
⁸ Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, 430074, China. xuanyang@hust.edu.cn.

^# Contributed equally.

Abstract

Developing in situ/operando spectroscopic techniques with high sensitivity and reproducibility is of great importance for mechanistic investigations of surface-mediated electrochemical reactions. Herein, we report the fabrication of highly ordered rhombic gold nanocube superlattices (GNSs) as substrates for surface-enhanced infrared absorption spectroscopy (SEIRAS) with significantly enhanced SEIRA effect, which can be controlled by manipulating the randomness of GNSs. Finite difference time domain simulations reveal that the electromagnetic effect accounts for the significantly improved spectroscopic vibrations on the GNSs. In situ SEIRAS results show that the vibrations of CO on the Cu₂O surfaces have been enhanced by 2.4 ± 0.5 and 18.0 ± 1.3 times using GNSs as substrates compared to those on traditional chemically deposited gold films in acidic and neutral electrolytes, respectively. Combined with isotopic labeling experiments, the reaction mechanisms for C-C coupling of CO electroreduction on Cu-based catalysts are revealed using the GNSs substrates.

Grants and funding

22204054/National Natural Science Foundation of China (National Science Foundation of China)