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Engineering Spin States of Isolated Copper Species in a Metal–Organic Framework Improves Urea Electrosynthesis

The catalytic activities are generally believed to be relevant to the electronic states of their active center, but understanding this relationship is usually difficult. Here, we design two types of catalysts for electrocatalytic urea via a coordination strategy in a metal–organic frameworks: Cu(III...

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Autores principales: Gao, Yuhang, Wang, Jingnan, Yang, Yijun, Wang, Jian, Zhang, Chuang, Wang, Xi, Yao, Jiannian
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Springer Nature Singapore 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10284786/
https://www.ncbi.nlm.nih.gov/pubmed/37341868
http://dx.doi.org/10.1007/s40820-023-01127-0
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author Gao, Yuhang
Wang, Jingnan
Yang, Yijun
Wang, Jian
Zhang, Chuang
Wang, Xi
Yao, Jiannian
author_facet Gao, Yuhang
Wang, Jingnan
Yang, Yijun
Wang, Jian
Zhang, Chuang
Wang, Xi
Yao, Jiannian
author_sort Gao, Yuhang
collection PubMed
description The catalytic activities are generally believed to be relevant to the electronic states of their active center, but understanding this relationship is usually difficult. Here, we design two types of catalysts for electrocatalytic urea via a coordination strategy in a metal–organic frameworks: Cu(III)-HHTP and Cu(II)-HHTP. Cu(III)-HHTP exhibits an improved urea production rate of 7.78 mmol h(−1) g(−1) and an enhanced Faradaic efficiency of 23.09% at − 0.6 V vs. reversible hydrogen electrode, in sharp contrast to Cu(II)-HHTP. Isolated Cu(III) species with S = 0 spin ground state are demonstrated as the active center in Cu(III)-HHTP, different from Cu(II) with S = 1/2 in Cu(II)-HHTP. We further demonstrate that isolated Cu(III) with an empty [Formula: see text] orbital in Cu(III)-HHTP experiences a single-electron migration path with a lower energy barrier in the C–N coupling process, while Cu(II) with a single-spin state ([Formula: see text] ) in Cu(II)-HHTP undergoes a two-electron migration pathway. [Image: see text] SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40820-023-01127-0.
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spelling pubmed-102847862023-06-23 Engineering Spin States of Isolated Copper Species in a Metal–Organic Framework Improves Urea Electrosynthesis Gao, Yuhang Wang, Jingnan Yang, Yijun Wang, Jian Zhang, Chuang Wang, Xi Yao, Jiannian Nanomicro Lett Article The catalytic activities are generally believed to be relevant to the electronic states of their active center, but understanding this relationship is usually difficult. Here, we design two types of catalysts for electrocatalytic urea via a coordination strategy in a metal–organic frameworks: Cu(III)-HHTP and Cu(II)-HHTP. Cu(III)-HHTP exhibits an improved urea production rate of 7.78 mmol h(−1) g(−1) and an enhanced Faradaic efficiency of 23.09% at − 0.6 V vs. reversible hydrogen electrode, in sharp contrast to Cu(II)-HHTP. Isolated Cu(III) species with S = 0 spin ground state are demonstrated as the active center in Cu(III)-HHTP, different from Cu(II) with S = 1/2 in Cu(II)-HHTP. We further demonstrate that isolated Cu(III) with an empty [Formula: see text] orbital in Cu(III)-HHTP experiences a single-electron migration path with a lower energy barrier in the C–N coupling process, while Cu(II) with a single-spin state ([Formula: see text] ) in Cu(II)-HHTP undergoes a two-electron migration pathway. [Image: see text] SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40820-023-01127-0. Springer Nature Singapore 2023-06-21 /pmc/articles/PMC10284786/ /pubmed/37341868 http://dx.doi.org/10.1007/s40820-023-01127-0 Text en © The Author(s) 2023 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 licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence 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 licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Gao, Yuhang
Wang, Jingnan
Yang, Yijun
Wang, Jian
Zhang, Chuang
Wang, Xi
Yao, Jiannian
Engineering Spin States of Isolated Copper Species in a Metal–Organic Framework Improves Urea Electrosynthesis
title Engineering Spin States of Isolated Copper Species in a Metal–Organic Framework Improves Urea Electrosynthesis
title_full Engineering Spin States of Isolated Copper Species in a Metal–Organic Framework Improves Urea Electrosynthesis
title_fullStr Engineering Spin States of Isolated Copper Species in a Metal–Organic Framework Improves Urea Electrosynthesis
title_full_unstemmed Engineering Spin States of Isolated Copper Species in a Metal–Organic Framework Improves Urea Electrosynthesis
title_short Engineering Spin States of Isolated Copper Species in a Metal–Organic Framework Improves Urea Electrosynthesis
title_sort engineering spin states of isolated copper species in a metal–organic framework improves urea electrosynthesis
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10284786/
https://www.ncbi.nlm.nih.gov/pubmed/37341868
http://dx.doi.org/10.1007/s40820-023-01127-0
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