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Controlled release of hydrogen isotope compounds and tunneling effect in the heterogeneously-catalyzed formic acid dehydrogenation
The hydrogen isotope deuterium is widely used in the synthesis of isotopically-labeled compounds and in the fabrication of semiconductors and optical fibers. However, the facile production of deuterium gas (D(2)) and hydrogen deuteride (HD) in a controlled manner is a challenging task, and rational...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6761165/ https://www.ncbi.nlm.nih.gov/pubmed/31554785 http://dx.doi.org/10.1038/s41467-019-12018-7 |
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author | Mori, Kohsuke Futamura, Yuya Masuda, Shinya Kobayashi, Hisayoshi Yamashita, Hiromi |
author_facet | Mori, Kohsuke Futamura, Yuya Masuda, Shinya Kobayashi, Hisayoshi Yamashita, Hiromi |
author_sort | Mori, Kohsuke |
collection | PubMed |
description | The hydrogen isotope deuterium is widely used in the synthesis of isotopically-labeled compounds and in the fabrication of semiconductors and optical fibers. However, the facile production of deuterium gas (D(2)) and hydrogen deuteride (HD) in a controlled manner is a challenging task, and rational heterogeneously-catalyzed protocols are still lacking. Herein, we demonstrate the selective production of hydrogen isotope compounds from a combination of formic acid and D(2)O, through cooperative action by a PdAg nanocatalyst on a silica substrate whose surface is modified with amine groups. In this process, D(2) is predominantly evolved by the assist of weakly basic amine moieties, while nanocatalyst particles in the vicinity of strongly basic amine groups promote the preferential formation of HD. Kinetic data and calculations based on semi-classically corrected transition state theory coupled with density functional theory suggest that quantum tunneling dominates the hydrogen/deuterium exchange reaction over the metallic PdAg surfaces. |
format | Online Article Text |
id | pubmed-6761165 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-67611652019-09-27 Controlled release of hydrogen isotope compounds and tunneling effect in the heterogeneously-catalyzed formic acid dehydrogenation Mori, Kohsuke Futamura, Yuya Masuda, Shinya Kobayashi, Hisayoshi Yamashita, Hiromi Nat Commun Article The hydrogen isotope deuterium is widely used in the synthesis of isotopically-labeled compounds and in the fabrication of semiconductors and optical fibers. However, the facile production of deuterium gas (D(2)) and hydrogen deuteride (HD) in a controlled manner is a challenging task, and rational heterogeneously-catalyzed protocols are still lacking. Herein, we demonstrate the selective production of hydrogen isotope compounds from a combination of formic acid and D(2)O, through cooperative action by a PdAg nanocatalyst on a silica substrate whose surface is modified with amine groups. In this process, D(2) is predominantly evolved by the assist of weakly basic amine moieties, while nanocatalyst particles in the vicinity of strongly basic amine groups promote the preferential formation of HD. Kinetic data and calculations based on semi-classically corrected transition state theory coupled with density functional theory suggest that quantum tunneling dominates the hydrogen/deuterium exchange reaction over the metallic PdAg surfaces. Nature Publishing Group UK 2019-09-25 /pmc/articles/PMC6761165/ /pubmed/31554785 http://dx.doi.org/10.1038/s41467-019-12018-7 Text en © The Author(s) 2019 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/. |
spellingShingle | Article Mori, Kohsuke Futamura, Yuya Masuda, Shinya Kobayashi, Hisayoshi Yamashita, Hiromi Controlled release of hydrogen isotope compounds and tunneling effect in the heterogeneously-catalyzed formic acid dehydrogenation |
title | Controlled release of hydrogen isotope compounds and tunneling effect in the heterogeneously-catalyzed formic acid dehydrogenation |
title_full | Controlled release of hydrogen isotope compounds and tunneling effect in the heterogeneously-catalyzed formic acid dehydrogenation |
title_fullStr | Controlled release of hydrogen isotope compounds and tunneling effect in the heterogeneously-catalyzed formic acid dehydrogenation |
title_full_unstemmed | Controlled release of hydrogen isotope compounds and tunneling effect in the heterogeneously-catalyzed formic acid dehydrogenation |
title_short | Controlled release of hydrogen isotope compounds and tunneling effect in the heterogeneously-catalyzed formic acid dehydrogenation |
title_sort | controlled release of hydrogen isotope compounds and tunneling effect in the heterogeneously-catalyzed formic acid dehydrogenation |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6761165/ https://www.ncbi.nlm.nih.gov/pubmed/31554785 http://dx.doi.org/10.1038/s41467-019-12018-7 |
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