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Multi-scale modeling guided electrochemical C–N coupling for urea production in metal-organic frameworks.

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Title: Multi-scale modeling guided electrochemical C–N coupling for urea production in metal-organic frameworks.
Authors: Xu, Yuting1 (AUTHOR), Foley, Gregory D.2 (AUTHOR), On, Lan2 (AUTHOR), Thoi, V. Sara1,2,3 (AUTHOR) sarathoi@jhu.edu, Che, Fanglin1 (AUTHOR) fche@wpi.edu
Source: Journal of Catalysis. Jan2026, Vol. 453, pN.PAG-N.PAG. 1p.
Subjects: Metal-organic frameworks, Urea, Electrochemical analysis, Electrolytic reduction, Carbon dioxide reduction, Catalysts, Reaction mechanisms (Chemistry)
Abstract: [Display omitted] • Closed-loop DFT–MKM–experiment framework reveals urea synthesis from CO 2 and NO 3 – co-reduction. • CO and NH 2 OH identified as key intermediates for selective electrochemical C–N coupling within Cu-based BIFs. • Urea favored at lower applied potentials and nitrite/ammonia dominate at higher bias within Cu-based BIFs. • Effective catalyst design should strengthen CO adsorption while moderating NH 2 OH formation. Electrochemical C–N coupling via the co-reduction of carbon dioxide (CO 2) and nitrate (NO 3 –) in metal–organic framework (MOF) materials, such as Cu-based boron imidazolate frameworks (BIF-29), presents a promising route for urea production, offering an alternative to energy-intensive industrial processes. However, the reaction mechanisms are not fully understood due to the complexity of competing pathways and the transient nature of key intermediates. To address this, we employed a close-loop framework combining density functional theory (DFT), microkinetic modeling (MKM), and experimental validation. DFT and MKM mapped a comprehensive reaction network, identifying CO* and NH 2 OH as key intermediates in the selective formation of urea over Cu BIF-29. Sensitivity analyses revealed that promoting CO* and NH 2 OH formation are critical to favoring C–N coupling while suppressing its further hydrogenation to ammonia. MKM models indicated that urea production is maximized at low overpotentials, whereas nitrite and ammonia dominate at more negative potentials. These predictions were experimentally validated and further reinforced through systematic reactant substitution studies. CO 2 and NO 3 – were identified as the optimal precursors, outperforming alternatives such as CO, NO 2 –, NH 2 OH, and NH 3 , due to their superior ability to generate and sustain reactive key intermediates. These findings highlight a key design strategy: catalysts should enhance CO 2 reduction to CO* while moderately activating NO 3 – to produce NH 2 OH without favoring competing byproduct pathways. Overall, this multi-scale, closed-loop framework provides mechanistic insights and quantitative guidelines for designing dual-functional MOF catalysts, enabling energy-efficient and selective electrochemical urea synthesis and advancing sustainable nitrogen-carbon utilization. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Catalysis is the property of Academic Press Inc. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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DbLabel: Engineering Source
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  Data: Multi-scale modeling guided electrochemical C–N coupling for urea production in metal-organic frameworks.
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  Data: <searchLink fieldCode="AR" term="%22Xu%2C+Yuting%22">Xu, Yuting</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Foley%2C+Gregory+D%2E%22">Foley, Gregory D.</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22On%2C+Lan%22">On, Lan</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Thoi%2C+V%2E+Sara%22">Thoi, V. Sara</searchLink><relatesTo>1,2,3</relatesTo> (AUTHOR)<i> sarathoi@jhu.edu</i><br /><searchLink fieldCode="AR" term="%22Che%2C+Fanglin%22">Che, Fanglin</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> fche@wpi.edu</i>
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  Data: <searchLink fieldCode="DE" term="%22Metal-organic+frameworks%22">Metal-organic frameworks</searchLink><br /><searchLink fieldCode="DE" term="%22Urea%22">Urea</searchLink><br /><searchLink fieldCode="DE" term="%22Electrochemical+analysis%22">Electrochemical analysis</searchLink><br /><searchLink fieldCode="DE" term="%22Electrolytic+reduction%22">Electrolytic reduction</searchLink><br /><searchLink fieldCode="DE" term="%22Carbon+dioxide+reduction%22">Carbon dioxide reduction</searchLink><br /><searchLink fieldCode="DE" term="%22Catalysts%22">Catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Reaction+mechanisms+%28Chemistry%29%22">Reaction mechanisms (Chemistry)</searchLink>
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  Data: [Display omitted] • Closed-loop DFT–MKM–experiment framework reveals urea synthesis from CO 2 and NO 3 – co-reduction. • CO and NH 2 OH identified as key intermediates for selective electrochemical C–N coupling within Cu-based BIFs. • Urea favored at lower applied potentials and nitrite/ammonia dominate at higher bias within Cu-based BIFs. • Effective catalyst design should strengthen CO adsorption while moderating NH 2 OH formation. Electrochemical C–N coupling via the co-reduction of carbon dioxide (CO 2) and nitrate (NO 3 –) in metal–organic framework (MOF) materials, such as Cu-based boron imidazolate frameworks (BIF-29), presents a promising route for urea production, offering an alternative to energy-intensive industrial processes. However, the reaction mechanisms are not fully understood due to the complexity of competing pathways and the transient nature of key intermediates. To address this, we employed a close-loop framework combining density functional theory (DFT), microkinetic modeling (MKM), and experimental validation. DFT and MKM mapped a comprehensive reaction network, identifying CO* and NH 2 OH as key intermediates in the selective formation of urea over Cu BIF-29. Sensitivity analyses revealed that promoting CO* and NH 2 OH formation are critical to favoring C–N coupling while suppressing its further hydrogenation to ammonia. MKM models indicated that urea production is maximized at low overpotentials, whereas nitrite and ammonia dominate at more negative potentials. These predictions were experimentally validated and further reinforced through systematic reactant substitution studies. CO 2 and NO 3 – were identified as the optimal precursors, outperforming alternatives such as CO, NO 2 –, NH 2 OH, and NH 3 , due to their superior ability to generate and sustain reactive key intermediates. These findings highlight a key design strategy: catalysts should enhance CO 2 reduction to CO* while moderately activating NO 3 – to produce NH 2 OH without favoring competing byproduct pathways. Overall, this multi-scale, closed-loop framework provides mechanistic insights and quantitative guidelines for designing dual-functional MOF catalysts, enabling energy-efficient and selective electrochemical urea synthesis and advancing sustainable nitrogen-carbon utilization. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of Catalysis is the property of Academic Press Inc. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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RecordInfo BibRecord:
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      – Type: doi
        Value: 10.1016/j.jcat.2025.116523
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 1
        StartPage: N.PAG
    Subjects:
      – SubjectFull: Metal-organic frameworks
        Type: general
      – SubjectFull: Urea
        Type: general
      – SubjectFull: Electrochemical analysis
        Type: general
      – SubjectFull: Electrolytic reduction
        Type: general
      – SubjectFull: Carbon dioxide reduction
        Type: general
      – SubjectFull: Catalysts
        Type: general
      – SubjectFull: Reaction mechanisms (Chemistry)
        Type: general
    Titles:
      – TitleFull: Multi-scale modeling guided electrochemical C–N coupling for urea production in metal-organic frameworks.
        Type: main
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          Name:
            NameFull: Xu, Yuting
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            NameFull: Foley, Gregory D.
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            NameFull: On, Lan
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            NameFull: Thoi, V. Sara
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            NameFull: Che, Fanglin
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          Dates:
            – D: 01
              M: 01
              Text: Jan2026
              Type: published
              Y: 2026
          Identifiers:
            – Type: issn-print
              Value: 00219517
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              Value: 453
          Titles:
            – TitleFull: Journal of Catalysis
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