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Spatial intimacy of binary active-sites for selective sequential hydrogenation-condensation of nitriles into secondary imines
Precisely controlling the spatial intimacy of multiple active sites at sub-nanoscale in heterogeneous catalysts can improve their selectivity and activity. Herein, we realize a highly selective nitrile-to-secondary imine transformation through a cascaded hydrogenation and condensation process by Pt(...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8184996/ https://www.ncbi.nlm.nih.gov/pubmed/34099687 http://dx.doi.org/10.1038/s41467-021-23705-9 |
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author | Zhang, Sai Xia, Zhaoming Zou, Yong Zhang, Mingkai Qu, Yongquan |
author_facet | Zhang, Sai Xia, Zhaoming Zou, Yong Zhang, Mingkai Qu, Yongquan |
author_sort | Zhang, Sai |
collection | PubMed |
description | Precisely controlling the spatial intimacy of multiple active sites at sub-nanoscale in heterogeneous catalysts can improve their selectivity and activity. Herein, we realize a highly selective nitrile-to-secondary imine transformation through a cascaded hydrogenation and condensation process by Pt(1)/CoBO(x) comprising the binary active sites of the single-dispersed Pt and interfacial Lewis acidic B. Atomic Pt sites with large inter-distances (>nanometers) only activate hydrogen for nitrile hydrogenation, but inhibit condensation. Both adjacent B…B on CoBO(x) and neighbouring Pt…B pairs with close intimacy of ~0.45 nm can satisfy the spatial prerequisites for condensation. Mechanism investigations demonstrate the energetically favorable pathway occurred on adjacent Lewis acidic B sites through the nitrile adsorption (acid-base interaction), hydrogenation via hydrogen spillover from Pt to B sites and sequential condensation. Strong intermolecular tension and steric hindrance of secondary imines on active sites lead to their effective desorption and thereby a high chemoselectivity of secondary imines. |
format | Online Article Text |
id | pubmed-8184996 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-81849962021-06-11 Spatial intimacy of binary active-sites for selective sequential hydrogenation-condensation of nitriles into secondary imines Zhang, Sai Xia, Zhaoming Zou, Yong Zhang, Mingkai Qu, Yongquan Nat Commun Article Precisely controlling the spatial intimacy of multiple active sites at sub-nanoscale in heterogeneous catalysts can improve their selectivity and activity. Herein, we realize a highly selective nitrile-to-secondary imine transformation through a cascaded hydrogenation and condensation process by Pt(1)/CoBO(x) comprising the binary active sites of the single-dispersed Pt and interfacial Lewis acidic B. Atomic Pt sites with large inter-distances (>nanometers) only activate hydrogen for nitrile hydrogenation, but inhibit condensation. Both adjacent B…B on CoBO(x) and neighbouring Pt…B pairs with close intimacy of ~0.45 nm can satisfy the spatial prerequisites for condensation. Mechanism investigations demonstrate the energetically favorable pathway occurred on adjacent Lewis acidic B sites through the nitrile adsorption (acid-base interaction), hydrogenation via hydrogen spillover from Pt to B sites and sequential condensation. Strong intermolecular tension and steric hindrance of secondary imines on active sites lead to their effective desorption and thereby a high chemoselectivity of secondary imines. Nature Publishing Group UK 2021-06-07 /pmc/articles/PMC8184996/ /pubmed/34099687 http://dx.doi.org/10.1038/s41467-021-23705-9 Text en © The Author(s) 2021 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 Zhang, Sai Xia, Zhaoming Zou, Yong Zhang, Mingkai Qu, Yongquan Spatial intimacy of binary active-sites for selective sequential hydrogenation-condensation of nitriles into secondary imines |
title | Spatial intimacy of binary active-sites for selective sequential hydrogenation-condensation of nitriles into secondary imines |
title_full | Spatial intimacy of binary active-sites for selective sequential hydrogenation-condensation of nitriles into secondary imines |
title_fullStr | Spatial intimacy of binary active-sites for selective sequential hydrogenation-condensation of nitriles into secondary imines |
title_full_unstemmed | Spatial intimacy of binary active-sites for selective sequential hydrogenation-condensation of nitriles into secondary imines |
title_short | Spatial intimacy of binary active-sites for selective sequential hydrogenation-condensation of nitriles into secondary imines |
title_sort | spatial intimacy of binary active-sites for selective sequential hydrogenation-condensation of nitriles into secondary imines |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8184996/ https://www.ncbi.nlm.nih.gov/pubmed/34099687 http://dx.doi.org/10.1038/s41467-021-23705-9 |
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