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Mechanism of C-N bonds formation in electrocatalytic urea production revealed by ab initio molecular dynamics simulation

Author

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  • Xin Liu

    (The University of Adelaide
    The University of Adelaide)

  • Yan Jiao

    (The University of Adelaide
    The University of Adelaide)

  • Yao Zheng

    (The University of Adelaide
    The University of Adelaide)

  • Mietek Jaroniec

    (Kent State University)

  • Shi-Zhang Qiao

    (The University of Adelaide
    The University of Adelaide)

Abstract

Electrosynthesis of urea from CO2 and NOX provides an exceptional opportunity for human society, given the increasingly available renewable energy. Urea electrosynthesis is challenging. In order to raise the overall electrosynthesis efficiency, the most critical reaction step for such electrosynthesis, C-N coupling, needs to be significantly improved. The C-N coupling can only happen at a narrow potential window, generally in the low overpotential region, and a fundamental understanding of the C-N coupling is needed for further development of this strategy. In this regard, we perform ab initio Molecular Dynamics simulations to reveal the origin of C-N coupling under a small electrode potential window with both the dynamic nature of water as a solvent, and the electrode potentials considered. We explore the key reaction networks for urea formation on Cu(100) surface in neutral electrolytes. Our work shows excellent agreement with experimentally observed selectivity under different potentials on the Cu electrode. We discover that the *NH and *CO are the key precursors for C-N bonds formation at low overpotential, while at high overpotential the C-N coupling occurs between adsorbed *NH and solvated CO. These insights provide vital information for future spectroscopic measurements and enable us to design new electrochemical systems for more value-added chemicals.

Suggested Citation

  • Xin Liu & Yan Jiao & Yao Zheng & Mietek Jaroniec & Shi-Zhang Qiao, 2022. "Mechanism of C-N bonds formation in electrocatalytic urea production revealed by ab initio molecular dynamics simulation," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
  • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-33258-0
    DOI: 10.1038/s41467-022-33258-0
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    References listed on IDEAS

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    1. Xinyan Liu & Jianping Xiao & Hongjie Peng & Xin Hong & Karen Chan & Jens K. Nørskov, 2017. "Understanding trends in electrochemical carbon dioxide reduction rates," Nature Communications, Nature, vol. 8(1), pages 1-7, August.
    2. Gao-Feng Chen & Yifei Yuan & Haifeng Jiang & Shi-Yu Ren & Liang-Xin Ding & Lu Ma & Tianpin Wu & Jun Lu & Haihui Wang, 2020. "Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper–molecular solid catalyst," Nature Energy, Nature, vol. 5(8), pages 605-613, August.
    3. Vijaya R. Pattabiraman & Jeffrey W. Bode, 2011. "Rethinking amide bond synthesis," Nature, Nature, vol. 480(7378), pages 471-479, December.
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    Cited by:

    1. Meng He & Yongmeng Wu & Rui Li & Yuting Wang & Cuibo Liu & Bin Zhang, 2023. "Aqueous pulsed electrochemistry promotes C−N bond formation via a one-pot cascade approach," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    2. Qian Wu & Chencheng Dai & Fanxu Meng & Yan Jiao & Zhichuan J. Xu, 2024. "Potential and electric double-layer effect in electrocatalytic urea synthesis," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    3. Yilong Zhao & Yunxuan Ding & Wenlong Li & Chang Liu & Yingzheng Li & Ziqi Zhao & Yu Shan & Fei Li & Licheng Sun & Fusheng Li, 2023. "Efficient urea electrosynthesis from carbon dioxide and nitrate via alternating Cu–W bimetallic C–N coupling sites," Nature Communications, Nature, vol. 14(1), pages 1-12, December.

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