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Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts

Single-site gallium centers on the surface of silica are prepared via grafting of [Ga(OSi(OtBu)(3))(3)(THF)] on SiO(2–700) followed by a thermolysis step. The resulting surface species corresponds to well-defined tetra-coordinate gallium single-sites, [([triple bond, length as m-dash]SiO)(3)Ga(XOSi[...

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Autores principales: Searles, Keith, Siddiqi, Georges, Safonova, Olga V., Copéret, Christophe
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5433511/
https://www.ncbi.nlm.nih.gov/pubmed/28553501
http://dx.doi.org/10.1039/c6sc05178b
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author Searles, Keith
Siddiqi, Georges
Safonova, Olga V.
Copéret, Christophe
author_facet Searles, Keith
Siddiqi, Georges
Safonova, Olga V.
Copéret, Christophe
author_sort Searles, Keith
collection PubMed
description Single-site gallium centers on the surface of silica are prepared via grafting of [Ga(OSi(OtBu)(3))(3)(THF)] on SiO(2–700) followed by a thermolysis step. The resulting surface species corresponds to well-defined tetra-coordinate gallium single-sites, [([triple bond, length as m-dash]SiO)(3)Ga(XOSi[triple bond, length as m-dash])] (X = –H or [triple bond, length as m-dash]Si) according to IR, X-ray absorption near-edge structure and extended X-ray absorption fine structure analysis. These gallium sites show high activity, selectivity and stability for propane dehydrogenation with an initial turnover frequency of 20 per h per gallium center, propylene selectivity of ≥93% and remarkable stability over 20 h. The stability of the catalyst probably results from site-isolation of the active site on a non-reducible support such as silica, diminishing facile reduction typical of Ga(2)O(3)-based catalysts.
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spelling pubmed-54335112017-05-26 Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts Searles, Keith Siddiqi, Georges Safonova, Olga V. Copéret, Christophe Chem Sci Chemistry Single-site gallium centers on the surface of silica are prepared via grafting of [Ga(OSi(OtBu)(3))(3)(THF)] on SiO(2–700) followed by a thermolysis step. The resulting surface species corresponds to well-defined tetra-coordinate gallium single-sites, [([triple bond, length as m-dash]SiO)(3)Ga(XOSi[triple bond, length as m-dash])] (X = –H or [triple bond, length as m-dash]Si) according to IR, X-ray absorption near-edge structure and extended X-ray absorption fine structure analysis. These gallium sites show high activity, selectivity and stability for propane dehydrogenation with an initial turnover frequency of 20 per h per gallium center, propylene selectivity of ≥93% and remarkable stability over 20 h. The stability of the catalyst probably results from site-isolation of the active site on a non-reducible support such as silica, diminishing facile reduction typical of Ga(2)O(3)-based catalysts. Royal Society of Chemistry 2017-04-01 2017-01-03 /pmc/articles/PMC5433511/ /pubmed/28553501 http://dx.doi.org/10.1039/c6sc05178b Text en This journal is © The Royal Society of Chemistry 2017 https://creativecommons.org/licenses/by-nc/3.0/This is an Open Access article distributed under the terms of the Creative Commons Attribution-NonCommercial 3.0 Unported License (http://creativecommons.org/licenses/by-nc/3.0/ (https://creativecommons.org/licenses/by-nc/3.0/) ) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Chemistry
Searles, Keith
Siddiqi, Georges
Safonova, Olga V.
Copéret, Christophe
Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts
title Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts
title_full Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts
title_fullStr Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts
title_full_unstemmed Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts
title_short Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts
title_sort silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5433511/
https://www.ncbi.nlm.nih.gov/pubmed/28553501
http://dx.doi.org/10.1039/c6sc05178b
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