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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...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Springer Nature Singapore
2023
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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. |
format | Online Article Text |
id | pubmed-10284786 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | Springer Nature Singapore |
record_format | MEDLINE/PubMed |
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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