Decisive Role of Perimeter Sites in Silica-Supported Ag Nanoparticles in Selective Hydrogenation of CO2 to Methyl Formate in the Presence of Methanol ...
Methyl formate synthesis by hydrogenation of carbon dioxide in the presence of methanol offers a promising path to valorize carbon dioxide. In this work, silica-supported silver nanoparticles are shown to be a significantly more active catalyst for the continuous methyl formate synthesis than the kn...
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Online Access: | https://dx.doi.org/10.3929/ethz-b-000296267 http://hdl.handle.net/20.500.11850/296267 |
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ftdatacite:10.3929/ethz-b-000296267 2024-04-28T08:15:39+00:00 Decisive Role of Perimeter Sites in Silica-Supported Ag Nanoparticles in Selective Hydrogenation of CO2 to Methyl Formate in the Presence of Methanol ... Corral-Pérez, Juan José Bansode, Atul Praveen, C.S. Kokalj, Anton Reymond, Helena Comas Vives, Aleix VandeVondele, Joost Copéret, Christophe Rudolf von Rohr, Philipp Urakawa, Atsushi 2018 application/pdf https://dx.doi.org/10.3929/ethz-b-000296267 http://hdl.handle.net/20.500.11850/296267 en eng ETH Zurich info:eu-repo/semantics/openAccess http://rightsstatements.org/page/InC-NC/1.0/ article-journal Text ScholarlyArticle Journal Article 2018 ftdatacite https://doi.org/10.3929/ethz-b-000296267 2024-04-02T12:33:25Z Methyl formate synthesis by hydrogenation of carbon dioxide in the presence of methanol offers a promising path to valorize carbon dioxide. In this work, silica-supported silver nanoparticles are shown to be a significantly more active catalyst for the continuous methyl formate synthesis than the known gold and copper counterparts, and the origin of the unique reactivity of Ag is clarified. Transient in situ and operando vibrational spectroscopy and DFT calculations shed light on the reactive intermediates and reaction mechanisms: a key feature is the rapid formation of surface chemical species in equilibrium with adsorbed carbon dioxide. Such species is assigned to carbonic acid interacting with water/hydroxyls on silica and promoting the esterification of formic acid with adsorbed methanol at the perimeter sites of Ag on SiO2 to yield methyl formate. This study highlights the importance of employing combined methodologies to verify the location and nature of active sites and to uncover fundamental ... : Journal of the American Chemical Society, 140 (24) ... Article in Journal/Newspaper Carbonic acid DataCite Metadata Store (German National Library of Science and Technology) |
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DataCite Metadata Store (German National Library of Science and Technology) |
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ftdatacite |
language |
English |
description |
Methyl formate synthesis by hydrogenation of carbon dioxide in the presence of methanol offers a promising path to valorize carbon dioxide. In this work, silica-supported silver nanoparticles are shown to be a significantly more active catalyst for the continuous methyl formate synthesis than the known gold and copper counterparts, and the origin of the unique reactivity of Ag is clarified. Transient in situ and operando vibrational spectroscopy and DFT calculations shed light on the reactive intermediates and reaction mechanisms: a key feature is the rapid formation of surface chemical species in equilibrium with adsorbed carbon dioxide. Such species is assigned to carbonic acid interacting with water/hydroxyls on silica and promoting the esterification of formic acid with adsorbed methanol at the perimeter sites of Ag on SiO2 to yield methyl formate. This study highlights the importance of employing combined methodologies to verify the location and nature of active sites and to uncover fundamental ... : Journal of the American Chemical Society, 140 (24) ... |
format |
Article in Journal/Newspaper |
author |
Corral-Pérez, Juan José Bansode, Atul Praveen, C.S. Kokalj, Anton Reymond, Helena Comas Vives, Aleix VandeVondele, Joost Copéret, Christophe Rudolf von Rohr, Philipp Urakawa, Atsushi |
spellingShingle |
Corral-Pérez, Juan José Bansode, Atul Praveen, C.S. Kokalj, Anton Reymond, Helena Comas Vives, Aleix VandeVondele, Joost Copéret, Christophe Rudolf von Rohr, Philipp Urakawa, Atsushi Decisive Role of Perimeter Sites in Silica-Supported Ag Nanoparticles in Selective Hydrogenation of CO2 to Methyl Formate in the Presence of Methanol ... |
author_facet |
Corral-Pérez, Juan José Bansode, Atul Praveen, C.S. Kokalj, Anton Reymond, Helena Comas Vives, Aleix VandeVondele, Joost Copéret, Christophe Rudolf von Rohr, Philipp Urakawa, Atsushi |
author_sort |
Corral-Pérez, Juan José |
title |
Decisive Role of Perimeter Sites in Silica-Supported Ag Nanoparticles in Selective Hydrogenation of CO2 to Methyl Formate in the Presence of Methanol ... |
title_short |
Decisive Role of Perimeter Sites in Silica-Supported Ag Nanoparticles in Selective Hydrogenation of CO2 to Methyl Formate in the Presence of Methanol ... |
title_full |
Decisive Role of Perimeter Sites in Silica-Supported Ag Nanoparticles in Selective Hydrogenation of CO2 to Methyl Formate in the Presence of Methanol ... |
title_fullStr |
Decisive Role of Perimeter Sites in Silica-Supported Ag Nanoparticles in Selective Hydrogenation of CO2 to Methyl Formate in the Presence of Methanol ... |
title_full_unstemmed |
Decisive Role of Perimeter Sites in Silica-Supported Ag Nanoparticles in Selective Hydrogenation of CO2 to Methyl Formate in the Presence of Methanol ... |
title_sort |
decisive role of perimeter sites in silica-supported ag nanoparticles in selective hydrogenation of co2 to methyl formate in the presence of methanol ... |
publisher |
ETH Zurich |
publishDate |
2018 |
url |
https://dx.doi.org/10.3929/ethz-b-000296267 http://hdl.handle.net/20.500.11850/296267 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_rights |
info:eu-repo/semantics/openAccess http://rightsstatements.org/page/InC-NC/1.0/ |
op_doi |
https://doi.org/10.3929/ethz-b-000296267 |
_version_ |
1797581106638225408 |