Efficient tandem electroreduction of nitrate into ammonia through coupling Cu single atoms with adjacent Co3O4

Yan Liu; Jie Wei; Zhengwu Yang; Lirong Zheng; Jiankang Zhao; Zhimin Song; Yuhan Zhou; Jiajie Cheng; Junyang Meng; Zhigang Geng; Jie Zeng

doi:10.1038/s41467-024-48035-4

Efficient tandem electroreduction of nitrate into ammonia through coupling Cu single atoms with adjacent Co₃O₄

Nat Commun. 2024 Apr 29;15(1):3619. doi: 10.1038/s41467-024-48035-4.

Authors

Yan Liu^#¹, Jie Wei^#¹, Zhengwu Yang^#¹, Lirong Zheng², Jiankang Zhao¹, Zhimin Song¹, Yuhan Zhou¹, Jiajie Cheng³, Junyang Meng¹, Zhigang Geng⁴, Jie Zeng^{5

6

7

8}

Affiliations

¹ Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, Anhui, PR China.
² Institute of High Energy Physics, Chinese Academy of Sciences, 100049, Beijing, PR China.
³ Department of Physics, University of Science and Technology of China, Hefei, 230026, Anhui, PR China.
⁴ Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, Anhui, PR China. gengzg@ustc.edu.cn.
⁵ Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, Anhui, PR China. zengj@ustc.edu.cn.
⁶ CAS Key Laboratory of Strongly-Coupled Quantum Matter Physics, University of Science and Technology of China, Hefei, 230026, Anhui, PR China. zengj@ustc.edu.cn.
⁷ Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, Department of Chemical Physics, University of Science and Technology of China, Hefei, 230026, Anhui, PR China. zengj@ustc.edu.cn.
⁸ School of Chemistry & Chemical Engineering, Anhui University of Technology, Ma'anshan, 243002, Anhui, PR China. zengj@ustc.edu.cn.

^# Contributed equally.

Abstract

The nitrate (NO₃^-) electroreduction into ammonia (NH₃) represents a promising approach for sustainable NH₃ synthesis. However, the variation of adsorption configurations renders great difficulties in the simultaneous optimization of binding energy for the intermediates. Though the extensively reported Cu-based electrocatalysts benefit NO₃^- adsorption, one of the key issues lies in the accumulation of nitrite (NO₂^-) due to its weak adsorption, resulting in the rapid deactivation of catalysts and sluggish kinetics of subsequent hydrogenation steps. Here we report a tandem electrocatalyst by combining Cu single atoms catalysts with adjacent Co₃O₄ nanosheets to boost the electroreduction of NO₃^- to NH₃. The obtained tandem catalyst exhibits a yield rate for NH₃ of 114.0 mg $_{{NH}_{3}}$ h^-1 cm^-2, which exceeds the previous values for the reported Cu-based catalysts. Mechanism investigations unveil that the combination of Co₃O₄ regulates the adsorption configuration of NO₂^- and strengthens the binding with NO₂^-, thus accelerating the electroreduction of NO₃^- to NH₃.