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Formic Acid‐Assisted Selective Hydrogenolysis of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N‐Doped Mesoporous Carbon
Biomass‐derived 5‐hydroxymethylfurfural (HMF) is regarded as one of the most promising platform chemicals to produce 2,5‐dimethylfuran (DMF) as a potential liquid transportation fuel. Pd nanoparticles supported on N‐containing and N‐free mesoporous carbon materials were prepared, characterized, and...
Autores principales: | , , , , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7986868/ https://www.ncbi.nlm.nih.gov/pubmed/33284506 http://dx.doi.org/10.1002/anie.202012816 |
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author | Hu, Bin Warczinski, Lisa Li, Xiaoyu Lu, Mohong Bitzer, Johannes Heidelmann, Markus Eckhard, Till Fu, Qi Schulwitz, Jonas Merko, Mariia Li, Mingshi Kleist, Wolfgang Hättig, Christof Muhler, Martin Peng, Baoxiang |
author_facet | Hu, Bin Warczinski, Lisa Li, Xiaoyu Lu, Mohong Bitzer, Johannes Heidelmann, Markus Eckhard, Till Fu, Qi Schulwitz, Jonas Merko, Mariia Li, Mingshi Kleist, Wolfgang Hättig, Christof Muhler, Martin Peng, Baoxiang |
author_sort | Hu, Bin |
collection | PubMed |
description | Biomass‐derived 5‐hydroxymethylfurfural (HMF) is regarded as one of the most promising platform chemicals to produce 2,5‐dimethylfuran (DMF) as a potential liquid transportation fuel. Pd nanoparticles supported on N‐containing and N‐free mesoporous carbon materials were prepared, characterized, and applied in the hydrogenolysis of HMF to DMF under mild reaction conditions. Quantitative conversion of HMF to DMF was achieved in the presence of formic acid (FA) and H(2) over Pd/NMC within 2 h. The reaction mechanism, especially the multiple roles of FA, was explored through a detailed comparative study by varying hydrogen source, additive, and substrate as well as by applying in situ ATR‐IR spectroscopy. The major role of FA is to shift the dominant reaction pathway from the hydrogenation of the aldehyde group to the hydrogenolysis of the hydroxymethyl group via the protonation by FA at the C‐OH group, lowering the activation barrier of the C−O bond cleavage and thus significantly enhancing the reaction rate. XPS results and DFT calculations revealed that Pd(2+) species interacting with pyridine‐like N atoms significantly enhance the selective hydrogenolysis of the C−OH bond in the presence of FA due to their high ability for the activation of FA and the stabilization of H(−). |
format | Online Article Text |
id | pubmed-7986868 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-79868682021-03-25 Formic Acid‐Assisted Selective Hydrogenolysis of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N‐Doped Mesoporous Carbon Hu, Bin Warczinski, Lisa Li, Xiaoyu Lu, Mohong Bitzer, Johannes Heidelmann, Markus Eckhard, Till Fu, Qi Schulwitz, Jonas Merko, Mariia Li, Mingshi Kleist, Wolfgang Hättig, Christof Muhler, Martin Peng, Baoxiang Angew Chem Int Ed Engl Research Articles Biomass‐derived 5‐hydroxymethylfurfural (HMF) is regarded as one of the most promising platform chemicals to produce 2,5‐dimethylfuran (DMF) as a potential liquid transportation fuel. Pd nanoparticles supported on N‐containing and N‐free mesoporous carbon materials were prepared, characterized, and applied in the hydrogenolysis of HMF to DMF under mild reaction conditions. Quantitative conversion of HMF to DMF was achieved in the presence of formic acid (FA) and H(2) over Pd/NMC within 2 h. The reaction mechanism, especially the multiple roles of FA, was explored through a detailed comparative study by varying hydrogen source, additive, and substrate as well as by applying in situ ATR‐IR spectroscopy. The major role of FA is to shift the dominant reaction pathway from the hydrogenation of the aldehyde group to the hydrogenolysis of the hydroxymethyl group via the protonation by FA at the C‐OH group, lowering the activation barrier of the C−O bond cleavage and thus significantly enhancing the reaction rate. XPS results and DFT calculations revealed that Pd(2+) species interacting with pyridine‐like N atoms significantly enhance the selective hydrogenolysis of the C−OH bond in the presence of FA due to their high ability for the activation of FA and the stabilization of H(−). John Wiley and Sons Inc. 2021-01-22 2021-03-15 /pmc/articles/PMC7986868/ /pubmed/33284506 http://dx.doi.org/10.1002/anie.202012816 Text en © 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Research Articles Hu, Bin Warczinski, Lisa Li, Xiaoyu Lu, Mohong Bitzer, Johannes Heidelmann, Markus Eckhard, Till Fu, Qi Schulwitz, Jonas Merko, Mariia Li, Mingshi Kleist, Wolfgang Hättig, Christof Muhler, Martin Peng, Baoxiang Formic Acid‐Assisted Selective Hydrogenolysis of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N‐Doped Mesoporous Carbon |
title | Formic Acid‐Assisted Selective Hydrogenolysis of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N‐Doped Mesoporous Carbon |
title_full | Formic Acid‐Assisted Selective Hydrogenolysis of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N‐Doped Mesoporous Carbon |
title_fullStr | Formic Acid‐Assisted Selective Hydrogenolysis of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N‐Doped Mesoporous Carbon |
title_full_unstemmed | Formic Acid‐Assisted Selective Hydrogenolysis of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N‐Doped Mesoporous Carbon |
title_short | Formic Acid‐Assisted Selective Hydrogenolysis of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N‐Doped Mesoporous Carbon |
title_sort | formic acid‐assisted selective hydrogenolysis of 5‐hydroxymethylfurfural to 2,5‐dimethylfuran over bifunctional pd nanoparticles supported on n‐doped mesoporous carbon |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7986868/ https://www.ncbi.nlm.nih.gov/pubmed/33284506 http://dx.doi.org/10.1002/anie.202012816 |
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