journal article·2025-06Open access

Tuning C─N Coupling Mode by Cu─In Dual Metal Sites in Covalent Organic Framework for Enhanced Urea Electrosynthesis

Nan Wang, Yuan Zhang, Chunfeng Shao, Lei Yuan, Mingming Sun, Huiyong Wang, Suojiang Zhang, Jianji Wang

Advanced Functional Materials· Volume 35· Issue 25

Abstract

Abstract Electrochemical conversion of CO 2 and NO 3 − to high value‐added urea is a win–win strategy for both resources and the environment. However, the yield rate and selectivity of urea are still low. In this work, Cu and In metals are grafted into the interlayers of an imine‐linked covalent organic framework (COF) to form stable Cu─In dual metal sites by strong coordination of hydroxyl O and imine N atoms in the framework. It is found that the optimal CuIn 1.07 ‐COF electrocatalyst exhibits an impressive urea yield rate of 2924.4 µg h −1 mg −1 and high Faradaic efficiency (FE) of 54.7% in H‐cell, which surpasses that of most previously reported catalysts for urea electrosynthesis. In situ spectroscopy and theoretical calculations reveal that due to the stronger electronic interaction between Cu and In, * NH 2 intermediate is generated on the In site from NO 3 − reduction, and then couples with * CO 2 on neighbor Cu site to produce * CO 2 NH 2 with a lower energy barrier, which effectively promotes the electrochemical co‐reduction of CO 2 and NO 3 − to urea. The work provides new clues for understanding the structure‐performance relationship in urea electrosynthesis.
Source: crossref · Quality: baseline

Research context

OpenAlex topics: Covalent Organic Framework Applications · Advanced Photocatalysis Techniques · Electrocatalysts for Energy Conversion

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Key Laboratory of Green Chemical Media and Reactions (Ministry of Education) Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals School of Chemistry and Chemical Engineering Henan Normal University Xinxiang Henan 453007 P. R. China

Luoyang R&D Center of Technology SINOPEC Engineering Group Luoyang Henan 471003 P. R. China

Anhui Province Key Laboratory of Pollutant Sensitive Materials and Environmental Remediation School of Physics and Electronic Information Huaibei Normal University Huaibei Anhui 235000 P. R. China

Beijing Key Laboratory of Ionic Liquids Clean Process State Key Laboratory of Multiphase Complex Systems Institute of Process Engineering Chinese Academy of Sciences Beijing 100190 P. R. China

College of Chemistry and Molecular Sciences Longzihu New Energy Laboratory Henan University Zhengzhou Henan 450000 P. R. China

Funding

National Natural Science Foundation of China · Higher Education Discipline Innovation Project · Natural Science Foundation of Henan Province

References (65)

Show source-provided references
1. 10.1039/D3GC04920E10.1039/D3GC04920E ↗
2. 10.1038/s41467-021-24400-510.1038/s41467-021-24400-5 ↗
3. 10.1039/D4EE00561A10.1039/D4EE00561A ↗
4. 10.1039/D1EE02485J10.1039/D1EE02485J ↗
5. 10.1002/cctc.20240156510.1002/cctc.202401565 ↗
6. 10.1016/j.joule.2024.02.02110.1016/j.joule.2024.02.021 ↗
7. 10.3866/PKU.WHXB20230704910.3866/PKU.WHXB202307049 ↗
8. 10.1002/adfm.20220088210.1002/adfm.202200882 ↗
9. 10.1039/D4TA02891K10.1039/D4TA02891K ↗
10. 10.1016/j.joule.2024.04.00410.1016/j.joule.2024.04.004 ↗
11. 10.1002/aenm.20230358810.1002/aenm.202303588 ↗
12. 10.1002/aenm.20220150010.1002/aenm.202201500 ↗
13. 10.1038/s41929-023-01020-410.1038/s41929-023-01020-4 ↗
14. 10.1002/anie.20240194310.1002/anie.202401943 ↗
15. 10.1021/jacs.3c0835910.1021/jacs.3c08359 ↗
16. 10.1038/s44160-024-00603-810.1038/s44160-024-00603-8 ↗
17. 10.1002/anie.20241062510.1002/anie.202410625 ↗
18. 10.1002/aenm.20240230910.1002/aenm.202402309 ↗
19. 10.1038/s42004-023-01001-510.1038/s42004-023-01001-5 ↗
20. 10.1002/adfm.20240089210.1002/adfm.202400892 ↗
21. 10.1002/anie.20240221510.1002/anie.202402215 ↗
22. 10.1021/acsnano.4c0182110.1021/acsnano.4c01821 ↗
23. 10.1038/s41893-024-01302-010.1038/s41893-024-01302-0 ↗
24. 10.1038/s41467-023-44131-z10.1038/s41467-023-44131-z ↗
25. 10.1038/s41467-024-52832-210.1038/s41467-024-52832-2 ↗
26. 10.1038/s41893-021-00741-310.1038/s41893-021-00741-3 ↗
27. 10.1038/s41467-022-33066-610.1038/s41467-022-33066-6 ↗
28. 10.1039/D3QM00433C10.1039/D3QM00433C ↗
29. 10.1002/adma.20231302810.1002/adma.202313028 ↗
30. 10.1016/j.cej.2024.15399310.1016/j.cej.2024.153993 ↗
31. 10.1039/D3SC05793C10.1039/D3SC05793C ↗
32. 10.1021/jacs.3c1328810.1021/jacs.3c13288 ↗
33. 10.1021/acsami.4c0581810.1021/acsami.4c05818 ↗
34. 10.1039/D3CC05821B10.1039/D3CC05821B ↗
35. 10.1016/j.apcatb.2023.12326510.1016/j.apcatb.2023.123265 ↗
36. 10.1002/ange.20241353410.1002/ange.202413534 ↗
37. 10.1039/D3TA01011B10.1039/D3TA01011B ↗
38. 10.1021/acsnano.2c0726010.1021/acsnano.2c07260 ↗
39. 10.1021/acsnano.2c0195610.1021/acsnano.2c01956 ↗
40. 10.1016/j.cclet.2023.10854010.1016/j.cclet.2023.108540 ↗
41. 10.1039/D0CS01569E10.1039/D0CS01569E ↗
42. 10.1038/s41557-024-01527-810.1038/s41557-024-01527-8 ↗
43. 10.1002/anie.20200479610.1002/anie.202004796 ↗
44. 10.1002/adma.20220313910.1002/adma.202203139 ↗
45. 10.1002/anie.20231947210.1002/anie.202319472 ↗
46. 10.1002/anie.20211464810.1002/anie.202114648 ↗
47. 10.1002/adfm.20231536810.1002/adfm.202315368 ↗
48. 10.1021/acsami.7b0587010.1021/acsami.7b05870 ↗
49. 10.1021/acsami.2c1822610.1021/acsami.2c18226 ↗
50. 10.1038/s41467-023-36779-410.1038/s41467-023-36779-4 ↗
51. 10.1002/anie.20240709010.1002/anie.202407090 ↗
52. 10.1007/s12274-024-6517-510.1007/s12274-024-6517-5 ↗
53. 10.1002/anie.20210339810.1002/anie.202103398 ↗
54. 10.1021/acs.nanolett.2c0491110.1021/acs.nanolett.2c04911 ↗
55. 10.1002/anie.20240398010.1002/anie.202403980 ↗
56. 10.1021/acsnano.4c0914110.1021/acsnano.4c09141 ↗
57. 10.1016/j.cej.2024.15141010.1016/j.cej.2024.151410 ↗
58. 10.1002/smll.20230612910.1002/smll.202306129 ↗
59. 10.1002/anie.20230195710.1002/anie.202301957 ↗
60. 10.1039/D2TA00661H10.1039/D2TA00661H ↗
61. 10.1002/anie.20240901910.1002/anie.202409019 ↗
62. 10.1002/smtd.20210121210.1002/smtd.202101212 ↗
63. 10.1002/adma.20240216010.1002/adma.202402160 ↗
64. 10.1038/s41467-023-40273-210.1038/s41467-023-40273-2 ↗
65. 10.1002/anie.20240268410.1002/anie.202402684 ↗