Customizing CO2 Electroreduction by Pulse-Induced Anion Enrichment

Jianghao Wang; Yanyang Qin; Shoutong Jin; Yue Yang; Jie Zhu; Xiaotong Li; Xiangzhou Lv; Jie Fu; Zijian Hong; Yaqiong Su; Hao Bin Wu

doi:10.1021/jacs.3c08748

Customizing CO₂ Electroreduction by Pulse-Induced Anion Enrichment

J Am Chem Soc. 2023 Dec 6;145(48):26213-26221. doi: 10.1021/jacs.3c08748. Epub 2023 Nov 9.

Authors

Jianghao Wang^{1

2}, Yanyang Qin³, Shoutong Jin¹, Yue Yang¹, Jie Zhu², Xiaotong Li¹, Xiangzhou Lv¹, Jie Fu^{2

4}, Zijian Hong^{1

5}, Yaqiong Su³, Hao Bin Wu^{1

5}

Affiliations

¹ School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China.
² Institute of Zhejiang University-Quzhou, Quzhou 324000, China.
³ School of Chemistry, Xi'an Key Laboratory of Sustainable Energy Materials Chemistry, State Key Laboratory of Electrical Insulation and Power Equipment, Engineering Research Center of Energy Storage Materials and Devices of Ministry of Education, Xi'an Jiaotong University, Xi'an 710049, China.
⁴ Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. China.
⁵ State Key Laboratory of Silicon and Advanced Semiconductor Materials, Zhejiang University, Hangzhou Zhejiang 310027, China.

PMID: 37944031
DOI: 10.1021/jacs.3c08748

Abstract

Electrochemically converting CO₂ into specified high-value products is critical for carbon neutral economics. However, governing the product distribution of the CO₂ electroreduction on Cu-based catalysts remains challenging. Herein, we put forward an anion enrichment strategy to efficiently dictate the route of *CO reduction by a pulsed electrolysis strategy. Upon periodically applying a positive potential on the cathode, the anion concentration in the vicinity of the electrode increases apparently. By adopting KF, KCl, and KHCO₃ as electrolytes, the dominant CO₂ electroreduction product on commercial Cu foil can be tuned into CO (53% ± 2.5), C2+ (76.6 ± 2.1%), and CH₄ (42.6 ± 2.1%) under pulsed electrolysis. Notably, one can delicately tailor the ratios of CO/CH₄, CH₄/C2+, and C2+/CO by simply changing the composition of the electrolyte. Density functional theory calculations demonstrate that locally enriched anions can affect the key CO₂RR intermediates in different ways owing to their specific electronegativity and volume, which leads to the distinct selectivity. The present study highlights the importance of tuning ionic species at the electrode-electrolyte interface for customizing the CO₂ electroreduction products.