Guanosine-derived atomically dispersed Cu-N3-C sites for efficient electroreduction of carbon dioxide

Shuo Chen; Miao Xia; Xuefei Zhang; Lisun Pei; Zijia Li; Xin Ge; Mei-Jin Lin; Wei Zhang; Zailai Xie

doi:10.1016/j.jcis.2023.05.100

Guanosine-derived atomically dispersed Cu-N₃-C sites for efficient electroreduction of carbon dioxide

J Colloid Interface Sci. 2023 Sep 15:646:863-871. doi: 10.1016/j.jcis.2023.05.100. Epub 2023 May 19.

Authors

Shuo Chen¹, Miao Xia¹, Xuefei Zhang¹, Lisun Pei¹, Zijia Li¹, Xin Ge², Mei-Jin Lin³, Wei Zhang⁴, Zailai Xie⁵

Affiliations

¹ Fujian Provincial Key Laboratory of Electrochemical Energy Storage Materials and Fujian Provincial Key Laboratory of Advanced Inorganic Oxygenated Materials, College of Chemistry, Fuzhou University, Fuzhou 350016, China.
² Key Laboratory of Automobile Materials MOE, and School of Materials Science & Engineering, and Jilin Provincial International Cooperation Key Laboratory of High-Efficiency Clean Energy Materials, and Electron Microscopy Center, and International Center of Future Science, Jilin University, Changchun 130012, Jilin, China.
³ Fujian Provincial Key Laboratory of Electrochemical Energy Storage Materials and Fujian Provincial Key Laboratory of Advanced Inorganic Oxygenated Materials, College of Chemistry, Fuzhou University, Fuzhou 350016, China. Electronic address: meijin_lin@fzu.edu.cn.
⁴ Key Laboratory of Automobile Materials MOE, and School of Materials Science & Engineering, and Jilin Provincial International Cooperation Key Laboratory of High-Efficiency Clean Energy Materials, and Electron Microscopy Center, and International Center of Future Science, Jilin University, Changchun 130012, Jilin, China. Electronic address: weizhang@jlu.edu.cn.
⁵ Fujian Provincial Key Laboratory of Electrochemical Energy Storage Materials and Fujian Provincial Key Laboratory of Advanced Inorganic Oxygenated Materials, College of Chemistry, Fuzhou University, Fuzhou 350016, China. Electronic address: zlxie@fzu.edu.cn.

PMID: 37235932
DOI: 10.1016/j.jcis.2023.05.100

Abstract

Single-atom copper (Cu) embedded within carbon catalysts have demonstrated significant potential in the electrochemical reduction of carbon dioxide (CO₂) into valuable chemicals and fuels. Herein, we develop a straightforward and template-free strategy for synthesizing atomically dispersed CuNC catalysts (CuG) by annealing the self-assembled guanosine. The CuG catalysts display two-dimensional morphology, tunable pore size and large surface areas that can be adjusted by changing carbonization temperature. Spherical aberration-corrected transmission electron microscopy reveals that single-atom Cu are homogeneously dispersed on the surface of carbon nanosheets. The optimum CuG-1000 catalysts achieve a high CO Faradaic efficiency (FE_co) up to 99% and a high CO current density of 6.53 mA cm^-2 (-0.65 V vs. RHE). Besides, the flow cell test of CuG-1000 shows a high current density up to 25.2 mA cm^-2 and the FE_co still exceeded 91% after more than 20 h of testing. Specifically, the existence of Cu-N₃-C active sites was proved by extended X-ray absorption fine structure (EXAFS). Density functional theory evidences that tricoordinated copper with N can largely regulate the adsorption and desorption of key intermediates by transferring electrons to *COOH through Cu atoms, thereby improving selectivity toward CO. This work demonstrates the active origin of CuNC catalysts in CO₂ electroreduction and offers a blueprint to construct atomically dispersed transition site catalysts by supramolecular self-assembly strategy.

Keywords: CO(2)RR; Cu-N(3)-C; Guanosine; Self-assembly; Single atom.