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Identification of Active and Spectator Sn Sites in Sn-β Following Solid-State Stannation, and Consequences for Lewis Acid Catalysis

Lewis acidic zeolites are rapidly emerging liquid-phase Lewis acid catalysts. Nevertheless, their inefficient synthesis procedure currently prohibits greater utilization and exploitation of these promising materials. Herein, we demonstrate that Sn(IV)-containing zeolite beta can readily be prepared...

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Autores principales: Hammond, Ceri, Padovan, Daniele, Al-Nayili, Abbas, Wells, Peter P, Gibson, Emma K, Dimitratos, Nikolaos
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Blackwell Publishing Ltd 2015
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4641460/
https://www.ncbi.nlm.nih.gov/pubmed/26583051
http://dx.doi.org/10.1002/cctc.201500545
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author Hammond, Ceri
Padovan, Daniele
Al-Nayili, Abbas
Wells, Peter P
Gibson, Emma K
Dimitratos, Nikolaos
author_facet Hammond, Ceri
Padovan, Daniele
Al-Nayili, Abbas
Wells, Peter P
Gibson, Emma K
Dimitratos, Nikolaos
author_sort Hammond, Ceri
collection PubMed
description Lewis acidic zeolites are rapidly emerging liquid-phase Lewis acid catalysts. Nevertheless, their inefficient synthesis procedure currently prohibits greater utilization and exploitation of these promising materials. Herein, we demonstrate that Sn(IV)-containing zeolite beta can readily be prepared both selectively and extremely rapidly by solid-state incorporation (SSI) method. Through a combination of spectroscopic (XRD, UV/Vis, X-ray absorption, magic-angle spinning NMR, and diffuse reflectance infrared Fourier transform spectroscopy) studies, we unambiguously demonstrate that site-isolated, isomorphously substituted Sn(IV) sites dominate the Sn population up to a loading of 5 wt % Sn. These sites are identical to those found in conventionally prepared Sn-beta, and result in our SSI material exhibiting identical levels of intrinsic activity (that is, turnover frequency) despite the threefold increase in Sn loading, and the extremely rapid and benign nature of our preparation methodology. We also identify the presence of spectator sites, in the form of Sn(IV) oligomers, at higher levels of Sn loading. The consequences of this mixed population with regards to catalysis (Meerwein–Pondorf–Verley reaction and glucose isomerization) are also identified.
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spelling pubmed-46414602015-11-16 Identification of Active and Spectator Sn Sites in Sn-β Following Solid-State Stannation, and Consequences for Lewis Acid Catalysis Hammond, Ceri Padovan, Daniele Al-Nayili, Abbas Wells, Peter P Gibson, Emma K Dimitratos, Nikolaos ChemCatChem Full Papers Lewis acidic zeolites are rapidly emerging liquid-phase Lewis acid catalysts. Nevertheless, their inefficient synthesis procedure currently prohibits greater utilization and exploitation of these promising materials. Herein, we demonstrate that Sn(IV)-containing zeolite beta can readily be prepared both selectively and extremely rapidly by solid-state incorporation (SSI) method. Through a combination of spectroscopic (XRD, UV/Vis, X-ray absorption, magic-angle spinning NMR, and diffuse reflectance infrared Fourier transform spectroscopy) studies, we unambiguously demonstrate that site-isolated, isomorphously substituted Sn(IV) sites dominate the Sn population up to a loading of 5 wt % Sn. These sites are identical to those found in conventionally prepared Sn-beta, and result in our SSI material exhibiting identical levels of intrinsic activity (that is, turnover frequency) despite the threefold increase in Sn loading, and the extremely rapid and benign nature of our preparation methodology. We also identify the presence of spectator sites, in the form of Sn(IV) oligomers, at higher levels of Sn loading. The consequences of this mixed population with regards to catalysis (Meerwein–Pondorf–Verley reaction and glucose isomerization) are also identified. Blackwell Publishing Ltd 2015-10 2015-09-01 /pmc/articles/PMC4641460/ /pubmed/26583051 http://dx.doi.org/10.1002/cctc.201500545 Text en © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. http://creativecommons.org/licenses/by/4.0/ This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Full Papers
Hammond, Ceri
Padovan, Daniele
Al-Nayili, Abbas
Wells, Peter P
Gibson, Emma K
Dimitratos, Nikolaos
Identification of Active and Spectator Sn Sites in Sn-β Following Solid-State Stannation, and Consequences for Lewis Acid Catalysis
title Identification of Active and Spectator Sn Sites in Sn-β Following Solid-State Stannation, and Consequences for Lewis Acid Catalysis
title_full Identification of Active and Spectator Sn Sites in Sn-β Following Solid-State Stannation, and Consequences for Lewis Acid Catalysis
title_fullStr Identification of Active and Spectator Sn Sites in Sn-β Following Solid-State Stannation, and Consequences for Lewis Acid Catalysis
title_full_unstemmed Identification of Active and Spectator Sn Sites in Sn-β Following Solid-State Stannation, and Consequences for Lewis Acid Catalysis
title_short Identification of Active and Spectator Sn Sites in Sn-β Following Solid-State Stannation, and Consequences for Lewis Acid Catalysis
title_sort identification of active and spectator sn sites in sn-β following solid-state stannation, and consequences for lewis acid catalysis
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4641460/
https://www.ncbi.nlm.nih.gov/pubmed/26583051
http://dx.doi.org/10.1002/cctc.201500545
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