Isolated Copper Atoms Boost *NO<sub>3</sub> Adsorption and Active Hydrogen Retention over Zinc Oxide for Ammonia Electrosynthesis at Ampere-Level Current Densities
The use of renewable electricity to drive the electroreduction of nitrate to ammonia can simultaneously achieve the green synthesis of ammonia and alleviate the environmental pollution of nitrate. However, the industrial requirement for ammonia synthesis with ampere-level current densities remains a grand challenge. In addition, the electroreduction of nitrate to ammonia reaction requires multiple steps of deoxygenation and hydrogenation of *NO<sub>3</sub> intermediates. Therefore, it is urgent to clarify the relationship between the adsorption strength of *NO<sub>3</sub>/*H (active hydrogen) intermediates and the catalytic activity. Herein, we achieved highly selective ammonia electrosynthesis at ampere-level current densities by anchoring atomically dispersed copper atoms on zinc oxide (ZnO) nanospheres (Cu<sub>1</sub>/ZnO). The synthesized Cu<sub>1</sub>/ZnO delivers a high NH<sub>3</sub> yield rate of 184.7 mg h<sup>-1</sup> cm<sup>-2</sup> with an NH<sub>3</sub> Faradaic efficiency of 96.1% and an NH<sub>3</sub> partial current density of 2.23 A cm<sup>-2</sup> in a flow cell. Based on mechanistic studies, anchoring Cu single atoms over ZnO enhances the adsorption of the *NO<sub>3</sub> intermediate and the retention of *H generated by water dissociation, resulting in the decreased energy barrier of the rate-determining step of *NO-to-*NHO.
Authors
- Licheng Liu (ORCID: https://orcid.org/0000-0002-2874-1420)
- Yusi Zhao (ORCID: https://orcid.org/0009-0002-7634-5702)
- Dingsheng S. Wang (ORCID: https://orcid.org/0000-0003-0074-7633)
- Mingkai Liu (ORCID: https://orcid.org/0000-0001-9060-848X)
- Haoran Huang (ORCID: https://orcid.org/0000-0003-2176-1899)
- Hongna Zhang (ORCID: https://orcid.org/0000-0002-9410-928X)
- Jie Zeng (ORCID: https://orcid.org/0000-0002-8812-0298)
- Zhipeng Chen (ORCID: https://orcid.org/0000-0003-2631-4596)
- Yan Yan (ORCID: https://orcid.org/0000-0001-8786-903X)
- Hongliang Li (ORCID: https://orcid.org/0000-0003-0348-7910)
- Gen Liu (ORCID: https://orcid.org/0000-0002-7011-034X)
Institutions
- University of Science and Technology of China (CN)
- Chinese Academy of Sciences (CN)
- Hefei Institutes of Physical Science (CN)
- Physical Sciences (United States) (US)
- Ocean University of China (CN)
- Anhui University of Technology (CN)
- Tsinghua University (CN)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-05-22
- DOI
- https://doi.org/10.1021/jacs.5c01863
- Citations
- 77
- Primary Topic
- Ammonia Synthesis and Nitrogen Reduction
- Type
- article
- Field-Weighted Citation Impact
- 29.95
Funders
- Natural Science Foundation for Distinguished Young Scholars of Anhui Province
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- Yulin University
- Hefei Science Center, Chinese Academy of Sciences
- National Key Research and Development Program of China
- Fundamental Research Funds for the Central Universities
- National Science Fund for Distinguished Young Scholars
- Dalian National Laboratory for Clean Energy