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

Electrosynthesis of urea from CO(2) and NO(X) 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 electrosyn...

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Autores principales: Liu, Xin, Jiao, Yan, Zheng, Yao, Jaroniec, Mietek, Qiao, Shi-Zhang
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9482648/
https://www.ncbi.nlm.nih.gov/pubmed/36115872
http://dx.doi.org/10.1038/s41467-022-33258-0
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author Liu, Xin
Jiao, Yan
Zheng, Yao
Jaroniec, Mietek
Qiao, Shi-Zhang
author_facet Liu, Xin
Jiao, Yan
Zheng, Yao
Jaroniec, Mietek
Qiao, Shi-Zhang
author_sort Liu, Xin
collection PubMed
description Electrosynthesis of urea from CO(2) and NO(X) 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.
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spelling pubmed-94826482022-09-19 Mechanism of C-N bonds formation in electrocatalytic urea production revealed by ab initio molecular dynamics simulation Liu, Xin Jiao, Yan Zheng, Yao Jaroniec, Mietek Qiao, Shi-Zhang Nat Commun Article Electrosynthesis of urea from CO(2) and NO(X) 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. Nature Publishing Group UK 2022-09-17 /pmc/articles/PMC9482648/ /pubmed/36115872 http://dx.doi.org/10.1038/s41467-022-33258-0 Text en © The Author(s) 2022 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Liu, Xin
Jiao, Yan
Zheng, Yao
Jaroniec, Mietek
Qiao, Shi-Zhang
Mechanism of C-N bonds formation in electrocatalytic urea production revealed by ab initio molecular dynamics simulation
title Mechanism of C-N bonds formation in electrocatalytic urea production revealed by ab initio molecular dynamics simulation
title_full Mechanism of C-N bonds formation in electrocatalytic urea production revealed by ab initio molecular dynamics simulation
title_fullStr Mechanism of C-N bonds formation in electrocatalytic urea production revealed by ab initio molecular dynamics simulation
title_full_unstemmed Mechanism of C-N bonds formation in electrocatalytic urea production revealed by ab initio molecular dynamics simulation
title_short Mechanism of C-N bonds formation in electrocatalytic urea production revealed by ab initio molecular dynamics simulation
title_sort mechanism of c-n bonds formation in electrocatalytic urea production revealed by ab initio molecular dynamics simulation
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9482648/
https://www.ncbi.nlm.nih.gov/pubmed/36115872
http://dx.doi.org/10.1038/s41467-022-33258-0
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