Achieving Record-Breaking Urea Synthesis on Crystalline–Amorphous Hybrid via Electrochemical-Chemical Looping
Electrocatalytic C-N coupling of nitrate and CO<sub>2</sub> represents a paradigm shift in sustainable urea synthesis. We demonstrate that amorphous CuO<sub><i>x</i></sub>-coated crystalline Cu nanowires achieve a record-breaking urea yield rate of 0.89 mol h<sup>-1</sup> g<sup>-1</sup> via novel electrochemical-chemical looping. Mechanistic investigations reveal a three-step catalytic cycle: (i) electro-reductive generation of Cu<sup>0</sup> and oxygen vacancies (O<sub>v</sub>); (ii) O<sub>v</sub>-mediated nitrate activation via oxygen atom insertion, spontaneously yielding nitrogen-bonded nitrite (*NO<sub>2</sub>) while oxidizing Cu<sup>0</sup> to catalytically active Cu<sup>+</sup>; and (iii) Cu<sup>+</sup>-catalyzing C-N coupling between *NO<sub>2</sub> and CO<sub>2</sub> to form urea. This pathway circumvents conventional rate-limiting nitrate reduction step, reducing the electron transfer requirement from 16e<sup>-</sup> to 12e<sup>-</sup> for urea synthesis. Notably, direct nitrite utilization fails to generate Cu<sup>+</sup> or nitrogen-bonded intermediates, instead forming oxygen-bonded species with markedly reduced C-N coupling activity-a finding that overturns conventional understanding. Our work establishes new fundamental principles for efficient urea synthesis and provides insights into catalyst design and green chemistry.
Authors
- Kefan Zhang (ORCID: https://orcid.org/0000-0002-9942-6989)
- Peilian Hou
- Dafeng Yan (ORCID: https://orcid.org/0000-0003-0161-9780)
- Yangyang Zhou (ORCID: https://orcid.org/0000-0001-5297-4497)
- Xupeng Qin
- Yansong Zhou (ORCID: https://orcid.org/0000-0003-4633-7947)
- Shuangyin Wang (ORCID: https://orcid.org/0000-0001-7185-9857)
- Peng Jin (ORCID: https://orcid.org/0000-0001-6925-9094)
- Kaizhi Gu
- Xiaoxiao Wei
- Chade Lv (ORCID: https://orcid.org/0000-0002-0964-1037)
- Xiaodeng Wang
- Dawei Chen (ORCID: https://orcid.org/0000-0001-5269-4794)
- Yujie Wang (ORCID: https://orcid.org/0000-0002-3656-6773)
- Qinghua Liu (ORCID: https://orcid.org/0000-0003-4090-3311)
- Chen Chen (ORCID: https://orcid.org/0000-0002-1862-8627)
- Cheng Ming Zhong (ORCID: https://orcid.org/0000-0003-1852-5860)
- Chu Zhang (ORCID: https://orcid.org/0000-0002-2989-7486)
Institutions
- University of Science and Technology of China (CN)
- Ministry of Education of the People's Republic of China (CN)
- Central South University (CN)
- Hunan University (CN)
- Shenzhen University (CN)
- Harbin Institute of Technology (CN)
- Ministry of Education (SA)
- Chongqing University of Arts and Sciences (CN)
- Department of Physics, Mathematics and Informatics (BY)
- Division of Materials Science and Engineering (AU)
- Laboratoire de Synthèse Organique (FR)
- National Synchrotron Radiation Laboratory (CN)
- Chemical Synthesis Lab (SG)
- Hubei University (CN)
- Ministry of Industry and Information Technology (CN)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-10-18
- DOI
- https://doi.org/10.1021/jacs.5c13721
- Citations
- 5
- Primary Topic
- Ammonia Synthesis and Nitrogen Reduction
- Type
- article
- Field-Weighted Citation Impact
- 1.94