Constructing Cu/Cu₂O Heterogeneous Interface for Efficient Urea Electrosynthesis

Abstract

Electrocatalytic coupling of CO₂ and \text{N}{\text{O}}_3^{-} enables urea synthesis under mild conditions while simultaneously converting greenhouse gases/pollutants, yet suffers from sluggish C–N coupling kinetics and low efficiency. To address this, a novel Cu/Cu₂O catalyst with a high-density heterogeneous interface and 3D crosslinking network structure was constructed. The high-angle annular dark-field scanning transmission electron microscope reveals the Cu/Cu₂O heterogeneous interface at the atomic scale, showing a distinct contrast discontinuity that defines the metal/metal oxides phase boundary. This unique structure exposes a large number of dual active sites. In-situ attenuated total reflection-surface enhanced infrared absorption spectroscopy and density functional theory calculations revealed a space-separated activation mechanism induced by the dual active sites at the heterogeneous interfaces. The electron-deficient Cu site preferentially activates CO₂ to produce *CO, while the electron-rich Cu₂O site dominates \text{N}{\text{O}}_3^{-} reduction to form *NOH intermediates. The built-in electric field formed at the heterogeneous interface further promotes the efficient C–N coupling of *CO and *NOH, significantly reducing the reaction energy barrier. Electrochemical tests showed Cu/Cu₂O outperformed Cu and Cu₂O in electrocatalytic coupling of CO₂ and \text{N}{\text{O}}_3^{-} for urea synthesis, achieving a record urea yield rate of 1156.63 mmol g⁻¹ h⁻¹ with 29.67% Faradaic efficiency at −1.0 V (vs RHE).

Keywords

C–N coupling / Cu-based electrocatalysts / electrocatalysis / interfacial engineering / urea synthesis

References

[1] Y.-C. Hao, Y. Guo, L.-W. Chen, M. Shu, X.-Y. Wang, T.-A. Bu, W.-Y. Gao, N. Zhang, X. Su, X. Feng, J.-W. Zhou, B. Wang, C.-W. Hu, A.-X. Yin, R. Si, Y.-W. Zhang, C.-H. Yan, Nat. Catal. 2019, 2, 448.

[2] C. Smith, A. K. Hill, L. Torrente-Murciano, Energy Environ. Sci. 2020, 13, 331.

[3] G. Soloveichik, Nat. Catal. 2019, 2, 377.

[4] N. W. Krase, V. L. Gaddy, J. Ind. Eng. Chem. 1922, 14, 611.

[5] J. Li, Y. Zhang, K. Kuruvinashetti, N. Kornienko, Nat. Rev. Chem. 2022, 6, 303.

[6] C. Lv, L. Zhong, H. Liu, Z. Fang, C. Yan, M. Chen, Y. Kong, C. Lee, D. Liu, S. Li, J. Liu, L. Song, G. Chen, Q. Yan, G. Yu, Nat. Sustain. 2021, 4, 868.

[7] Z. Tao, C. L. Rooney, Y. Liang, H. Wang, J. Am. Chem. Soc. 2021, 143, 19630.

[8] C. Chen, N. He, S. Wang, Small Sci. 2021, 1, 2100070.

[9] X. Tu, X. Zhu, S. Bo, X. Zhang, R. Miao, G. Wen, C. Chen, J. Li, Y. Zhou, Q. Liu, D. Chen, H. Shao, D. Yan, Y. Li, J. Jia, S. Wang, Angew. Chem. Int. Ed. 2024, 63, e202317087.

[10] X. Peng, L. Zeng, D. Wang, Z. Liu, Y. Li, Z. Li, B. Yang, L. Lei, L. Dai, Y. Hou, Chem. Soc. Rev. 2023, 52, 2193.

[11] X. Wei, X. Wen, Y. Liu, C. Chen, C. Xie, D. Wang, M. Qiu, N. He, P. Zhou, W. Chen, J. Cheng, H. Lin, J. Jia, X.-Z. Fu, S. Wang, J. Am. Chem. Soc. 2022, 144, 11530.

[12] C. Yang, Z. Li, J. Xu, Y. Jiang, W. Zhu, Green Chem. 2024, 26, 4908.

[13] Y. Wang, D. Chen, C. Chen, S. Wang, Acc. Chem. Res. 2024, 57, 247.

[14] Y. Wan, M. Zheng, W. Yan, J. Zhang, R. Lv, Adv. Energy Mater. 2024, 14, 2303588.

[15] D. Chen, J. Liu, J. Shen, Y. Zhang, H. Shao, C. Chen, S. Wang, Adv. Energy Mater. 2024, 14, 2303820.

[16] Q. Li, J. Liu, Z. Wu, A. Deng, J. Liu, T. Chen, J. Wei, Y. Zhang, H. Liu, ChemSusChem 2025, 18, e202401865.

[17] C. Zhang, S. Chen, L. Guo, Z. Li, C. Yan, C. Lv, Chin. J. Chem. 2024, 42, 3441.

[18] C. Zhang, Q. Zhou, Z. Li, C. Yan, H. Liu, D. Liu, L. Song, Q. Yan, C. Lv, Angew. Chem. Int. Ed. 2025, 64, e202507869.

[19] H. Wang, Y. Jiang, S. Li, F. Gou, X. Liu, Y. Jiang, W. Luo, W. Shen, R. He, M. Li, Appl. Catal. B Environ. 2022, 318, 121819.

[20] J. Qin, N. Liu, L. Chen, K. Wu, Q. Zhao, B. Liu, Z. Ye, ACS Sustain. Chem. Eng. 2022, 10, 15869.

[21] H. Chen, L. Liu, X.-H. Ma, S.-J. Zheng, X.-Y. Dong, R.-W. Huang, Z.-Y. Wang, J. Cai, S.-Q. Zang, Natl. Sci. Rev. 2025, 12, nwae440.

[22] X. Zhang, H. Sun, Y.-R. Wang, Z. Shi, R.-L. Zhong, C.-Y. Sun, J.-Y. Liu, Z.-M. Su, Y.-Q. Lan, Adv. Mater. 2024, 36, 2408510.

[23] K. Chen, D. Ma, Y. Zhang, F. Wang, X. Yang, X. Wang, H. Zhang, X. Liu, R. Bao, K. Chu, Adv. Mater. 2024, 36, 2402160.

[24] J. Leverett, T. Tran-Phu, J. A. Yuwono, P. Kumar, C. Kim, Q. Zhai, C. Han, J. Qu, J. Cairney, A. N. Simonov, R. K. Hocking, L. Dai, R. Daiyan, R. Amal, Adv. Energy Mater. 2022, 12, 2201500.

[25] X. Ma, B. Mao, Z. Yu, D. Wang, J. Xia, J. Hou, X. Meng, H. Lin, C. Hu, Angew. Chem. Int. Ed. 2025, 64, e202423706.

[26] X.-F. Qiu, J.-R. Huang, C. Yu, X.-M. Chen, P.-Q. Liao, Angew. Chem. Int. Ed. 2024, 63, e202410625.

[27] S. Tian, R. Wu, H. Liu, C. Yan, Z. Qi, P. Song, W.-J. Chen, L. Song, Z. Wang, C. Lv, Angew. Chem. Int. Ed. 2025, 64, e202510665.

[28] Y. Li, Z. Lu, L. Zheng, X. Yan, J. Xie, Z. Yu, S. Zhang, F. Jiang, H. Chen, Energy Environ. Sci. 2024, 17, 4582.

[29] L. Bian, Y. Bai, J.-Y. Chen, H.-K. Guo, S. Liu, H. Tian, N. Tian, Z.-L. Wang, ACS Nano 2025, 19, 9304.

[30] H. Tian, J.-T. Yang, X. Wang, H. Jiao, Z.-F. Gao, K.-Y. Zhu, Q. He, Z.-L. Wang, Appl. Catal. B Environ. 2025, 375, 125411.

[31] Z. Li, M. Zheng, C. Yan, D. Yang, R. Yang, C. Zhang, H. Liu, P. Song, C. Yin, Z. Qi, D. Liu, X. Zhou, L. Song, C. Lv, G. Yu, Nat. Commun. 2025, 16, 8940.

[32] X. Wei, S.-Q. Liu, H. Liu, Y. Ding, P.-X. Lei, S. Wu, L. Song, X.-Z. Fu, J.-L. Luo, J. Am. Chem. Soc. 2025, 147, 6049.

[33] H.-Q. Yin, Z.-S. Sun, Q.-P. Zhao, L.-L. Yang, T.-B. Lu, Z.-M. Zhang, J. Energy Chem. 2023, 84, 385.

[34] X. Song, X. Ma, T. Chen, L. Xu, J. Feng, L. Wu, S. Jia, L. Zhang, X. Tan, R. Wang, C. Chen, J. Ma, Q. Zhu, X. Kang, X. Sun, B. Han, J. Am. Chem. Soc. 2024, 146, 25813.

[35] X. Zhang, X. Zhu, S. Bo, C. Chen, K. Cheng, J. Zheng, S. Li, X. Tu, W. Chen, C. Xie, X. Wei, D. Wang, Y. Liu, P. Chen, S. P. Jiang, Y. Li, Q. Liu, C. Li, S. Wang, Angew. Chem. Int. Ed. 2023, 62, e202305447.

[36] C. Kim, K. M. Cho, K. Park, J. Y. Kim, G.-T. Yun, F. M. Toma, I. Gereige, H.-T. Jung, Adv. Funct. Mater. 2021, 31, 2102142.

Rights & permissions

2026 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.