Kinetically matched C-N coupling toward efficient urea electrosynthesis enabled on copper single-atom alloy.

Autor: Xu M; College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, China., Wu F; College of Materials Science and Engineering, Zhejiang University of Technology, 310014, Hangzhou, Zhejiang, China., Zhang Y; College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, China., Yao Y; College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, China., Zhu G; College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, China., Li X; College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, China., Chen L; College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, China. liang_chen@hznu.edu.cn., Jia G; College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, China., Wu X; School of Chemistry and Chemical Engineering, Harbin Institute of Technology, 150001, Harbin, Heilongjiang, P. R. China. wuxiaohong@hit.edu.cn., Huang Y; College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, China., Gao P; College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, China. gaopeng@hrbeu.edu.cn., Ye W; College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, China. yewei@hznu.edu.cn.
Jazyk: angličtina
Zdroj: Nature communications [Nat Commun] 2023 Nov 01; Vol. 14 (1), pp. 6994. Date of Electronic Publication: 2023 Nov 01.
DOI: 10.1038/s41467-023-42794-2
Abstrakt: Chemical C-N coupling from CO 2 and NO 3 - , driven by renewable electricity, toward urea synthesis is an appealing alternative for Bosch-Meiser urea production. However, the unmatched kinetics in CO 2 and NO 3 - reduction reactions and the complexity of C- and N-species involved in the co-reduction render the challenge of C-N coupling, leading to the low urea yield rate and Faradaic efficiency. Here, we report a single-atom copper-alloyed Pd catalyst (Pd 4 Cu 1 ) that can achieve highly efficient C-N coupling toward urea electrosynthesis. The reduction kinetics of CO 2 and NO 3 - is regulated and matched by steering Cu doping level and Pd 4 Cu 1 /FeNi(OH) 2 interface. Charge-polarized Pd δ- -Cu δ+ dual-sites stabilize the key *CO and *NH 2 intermediates to promote C-N coupling. The synthesized Pd 4 Cu 1 -FeNi(OH) 2 composite catalyst achieves a urea yield rate of 436.9 mmol g cat. -1 h -1 and Faradaic efficiency of 66.4%, as well as a long cycling stability of 1000 h. In-situ spectroscopic results and theoretical calculation reveal that atomically dispersed Cu in Pd lattice promotes the deep reduction of NO 3 - to *NH 2 , and the Pd-Cu dual-sites lower the energy barrier of the pivotal C-N coupling between *NH 2 and *CO.
(© 2023. The Author(s).)
Databáze: MEDLINE
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