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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...

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Autores principales: Kim, Jonglack, Pfänder, Norbert, Prieto, Gonzalo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
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.
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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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