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Recycling of CO(2) by Hydrogenation of Carbonate Derivatives to Methanol: Tuning Copper–Oxide Promotion Effects in Supported Catalysts
The selective hydrogenation of organic carbonates to methanol is a relevant transformation to realize flexible processes for the recycling of waste CO(2) with renewable H(2) mediated by condensed carbon dioxide surrogates. Oxide‐supported copper nanoparticles are promising solid catalysts for this s...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7216934/ https://www.ncbi.nlm.nih.gov/pubmed/32061179 http://dx.doi.org/10.1002/cssc.202000166 |
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author | Kim, Jonglack Pfänder, Norbert Prieto, Gonzalo |
author_facet | Kim, Jonglack Pfänder, Norbert Prieto, Gonzalo |
author_sort | Kim, Jonglack |
collection | PubMed |
description | The selective hydrogenation of organic carbonates to methanol is a relevant transformation to realize flexible processes for the recycling of waste CO(2) with renewable H(2) mediated by condensed carbon dioxide surrogates. Oxide‐supported copper nanoparticles are promising solid catalysts for this selective hydrogenation. However, essential for their optimization is to rationalize the prominent impact of the oxide support on performance. Herein, the role of Lewis acid centers, exposed on the oxide support at the periphery of the Cu nanoparticles, was systematically assessed. For the hydrogenation of propylene carbonate, as a model cyclic carbonate, the conversion rate, the apparent activation energy, and the selectivity to methanol correlate with the Lewis acidity of the coordinatively unsaturated cationic sites exposed on the oxide support. Lewis sites of markedly low and high electron‐withdrawing character promote unselective decarbonylation and decarboxylation reaction pathways, respectively. Supports exposing Lewis sites of intermediate acidity maximize the selectivity to methanol while inhibiting acid‐catalyzed secondary reactions of the propanediol product, and thus enable its recovery in cyclic processes of CO(2) hydrogenation mediated by condensed carbonate derivatives. These findings help rationalize metal–support promotion effects that determine the performance of supported metal nanoparticles in this and other selective hydrogenation reactions of significance in the context of sustainable chemistry. |
format | Online Article Text |
id | pubmed-7216934 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-72169342020-05-13 Recycling of CO(2) by Hydrogenation of Carbonate Derivatives to Methanol: Tuning Copper–Oxide Promotion Effects in Supported Catalysts Kim, Jonglack Pfänder, Norbert Prieto, Gonzalo ChemSusChem Full Papers The selective hydrogenation of organic carbonates to methanol is a relevant transformation to realize flexible processes for the recycling of waste CO(2) with renewable H(2) mediated by condensed carbon dioxide surrogates. Oxide‐supported copper nanoparticles are promising solid catalysts for this selective hydrogenation. However, essential for their optimization is to rationalize the prominent impact of the oxide support on performance. Herein, the role of Lewis acid centers, exposed on the oxide support at the periphery of the Cu nanoparticles, was systematically assessed. For the hydrogenation of propylene carbonate, as a model cyclic carbonate, the conversion rate, the apparent activation energy, and the selectivity to methanol correlate with the Lewis acidity of the coordinatively unsaturated cationic sites exposed on the oxide support. Lewis sites of markedly low and high electron‐withdrawing character promote unselective decarbonylation and decarboxylation reaction pathways, respectively. Supports exposing Lewis sites of intermediate acidity maximize the selectivity to methanol while inhibiting acid‐catalyzed secondary reactions of the propanediol product, and thus enable its recovery in cyclic processes of CO(2) hydrogenation mediated by condensed carbonate derivatives. These findings help rationalize metal–support promotion effects that determine the performance of supported metal nanoparticles in this and other selective hydrogenation reactions of significance in the context of sustainable chemistry. John Wiley and Sons Inc. 2020-03-13 2020-04-21 /pmc/articles/PMC7216934/ /pubmed/32061179 http://dx.doi.org/10.1002/cssc.202000166 Text en © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. 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 | Full Papers Kim, Jonglack Pfänder, Norbert Prieto, Gonzalo Recycling of CO(2) by Hydrogenation of Carbonate Derivatives to Methanol: Tuning Copper–Oxide Promotion Effects in Supported Catalysts |
title | Recycling of CO(2) by Hydrogenation of Carbonate Derivatives to Methanol: Tuning Copper–Oxide Promotion Effects in Supported Catalysts |
title_full | Recycling of CO(2) by Hydrogenation of Carbonate Derivatives to Methanol: Tuning Copper–Oxide Promotion Effects in Supported Catalysts |
title_fullStr | Recycling of CO(2) by Hydrogenation of Carbonate Derivatives to Methanol: Tuning Copper–Oxide Promotion Effects in Supported Catalysts |
title_full_unstemmed | Recycling of CO(2) by Hydrogenation of Carbonate Derivatives to Methanol: Tuning Copper–Oxide Promotion Effects in Supported Catalysts |
title_short | Recycling of CO(2) by Hydrogenation of Carbonate Derivatives to Methanol: Tuning Copper–Oxide Promotion Effects in Supported Catalysts |
title_sort | recycling of co(2) by hydrogenation of carbonate derivatives to methanol: tuning copper–oxide promotion effects in supported catalysts |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7216934/ https://www.ncbi.nlm.nih.gov/pubmed/32061179 http://dx.doi.org/10.1002/cssc.202000166 |
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