1. Electron-withdrawing functional ligand promotes CO2 reduction catalysis in single atom catalyst
- Author
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Hongbin Yang, Tao Zhang, Huicong Li, Ling Li, Yanqiang Huang, Bin Liu, Linghui Liu, Song Liu, Xinyi Ren, Fu-Quan Bai, Jie Ding, and Zhichong Kuang
- Subjects
Materials science ,Ligand ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Electrocatalyst ,Photochemistry ,Electrochemistry ,01 natural sciences ,0104 chemical sciences ,Catalysis ,Electron transfer ,Transition metal ,Density functional theory ,0210 nano-technology ,Electrochemical reduction of carbon dioxide - Abstract
Electrochemical carbon dioxide reduction reaction (CO2RR) powered by renewable electricity offers an attractive approach to reduce carbon emission and at the same time produce valuable chemicals/fuels. To design efficient CO2 reduction electrocatalyst, it is important to understand the structure-activity relationship. Herein, we design a series of single Co atoms electrocatalysts with well-defined active sites electronic structures, which exhibit outstanding CO2RR activity with controllable selectivity to CO. Experimental and density functional theory (DFT) calculation studies show that introducing nitro (amino) ligand next to single Co atom catalytic center with electron-withdrawing (electron-donating) capability favors (hinders) CO2 reduction catalysis. This work provides an in-depth understanding of how functional ligand affects the splitting of transition metal 3d electron orbital, thereby changing the electron transfer from transition metal active site to CO2, which is closely related to the Gibbs free energy of the rate-determining step (CO2+e−+*→*CO2−).
- Published
- 2020