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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ftethz:oai:www.research-collection.ethz.ch:20.500.11850/296267 2023-05-15T15:52:42+02:00 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 2018-10-24 application/application/pdf https://hdl.handle.net/20.500.11850/296267 https://doi.org/10.3929/ethz-b-000296267 en eng American Chemical Society (ACS) info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.8b08505 info:eu-repo/semantics/altIdentifier/wos/000448755200053 info:eu-repo/grantAgreement/SNF/Sinergia/154448 http://hdl.handle.net/20.500.11850/296267 doi:10.3929/ethz-b-000296267 info:eu-repo/semantics/openAccess http://rightsstatements.org/page/InC-NC/1.0/ In Copyright - Non-Commercial Use Permitted Journal of the American Chemical Society, 140 (24) info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion 2018 ftethz https://doi.org/20.500.11850/296267 https://doi.org/10.3929/ethz-b-000296267 https://doi.org/10.1021/jacs.8b08505 2022-04-25T13:38:39Z 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 catalytic reaction steps taking place at metal–support interfaces. ISSN:0002-7863 ISSN:1520-5126 Article in Journal/Newspaper Carbonic acid ETH Zürich Research Collection |
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ETH Zürich Research Collection |
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ftethz |
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 catalytic reaction steps taking place at metal–support interfaces. ISSN:0002-7863 ISSN:1520-5126 |
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 |
American Chemical Society (ACS) |
publishDate |
2018 |
url |
https://hdl.handle.net/20.500.11850/296267 https://doi.org/10.3929/ethz-b-000296267 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
Journal of the American Chemical Society, 140 (24) |
op_relation |
info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.8b08505 info:eu-repo/semantics/altIdentifier/wos/000448755200053 info:eu-repo/grantAgreement/SNF/Sinergia/154448 http://hdl.handle.net/20.500.11850/296267 doi:10.3929/ethz-b-000296267 |
op_rights |
info:eu-repo/semantics/openAccess http://rightsstatements.org/page/InC-NC/1.0/ In Copyright - Non-Commercial Use Permitted |
op_doi |
https://doi.org/20.500.11850/296267 https://doi.org/10.3929/ethz-b-000296267 https://doi.org/10.1021/jacs.8b08505 |
_version_ |
1766387807408881664 |