Theoretical exploration on the activity of copper single-atom catalysts for electrocatalytic reduction of CO 2

Enhancing the activity of the carbon dioxide reduction reaction (CO 2 RR) by controlling the structure of single-atom catalysts (SACs) has recently been shown to be a rather promising strategy. The effect of the structure and coordination environment on electrocatalytic CO 2 RR activity of single-at...

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Published in:Journal of materials chemistry. A, Materials for energy and sustainability Materials for energy and sustainability, 2023-04, Vol.11 (14), p.7735-7745
Main Authors: Min, Junyong, Liu, Lei, Chen, Fengjuan, Jin, Xuekun, Yuan, Tianjiao, Yao, Xiaoqian
Format: Article
Language:English
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Summary:Enhancing the activity of the carbon dioxide reduction reaction (CO 2 RR) by controlling the structure of single-atom catalysts (SACs) has recently been shown to be a rather promising strategy. The effect of the structure and coordination environment on electrocatalytic CO 2 RR activity of single-atom copper catalysts (Cu–N/C) was investigated by using density functional theory (DFT) calculations. The free energies of the adsorption of intermediates *CO and *COOH are linearly correlated, and among 11 kinds of Cu–N/C catalysts, CuN 3 V and CuN 2 V 2 have better CO 2 RR activity with Δ G *COOH as the descriptor. The free energy analysis of the CO 2 electrocatalytic reduction reaction shows that CuN 3 V and CuN 2 V 2 have the lowest limiting potentials in 11 Cu–N/C catalysts (−0.86 V and −0.93 V) too. For saturated structure catalysts, the production of *COOH is the decisive step, while the desorption of *CO is the decisive step for unsaturated ones. CuN 3 V and CuN 2 V 2 have a high CO 2 RR selectivity, and their activation energy barriers for the CO 2 RR (1.37 eV and 1.32 eV) are much lower than that for the hydrogen precipitation reaction (HER, 3.22 eV and 4.53 eV). The change in the catalyst structure can affect not only the adsorption properties, but also the potential-determining step of the CO 2 RR, and the unsaturated structure is more favorable for improvement of the catalyst activity. These results highlight the important influence of the structure and coordination environment on the activity and selectivity of single-atom copper catalysts for the CO 2 RR, and provide helpful information for design of other metal single-atom catalysts.
ISSN:2050-7488
2050-7496
DOI:10.1039/D2TA09599H