Identifying Sn Site Heterogeneities Prevalent Among Sn-Beta Zeolites

Patrick Wolf; Wei Chih Liao; Ta Chung Ong; Maxence Valla; James W. Harris; Rajamani Gounder; William N.P. van der Graaff; Evgeny A. Pidko; Emiel J.M. Hensen; Paola Ferrini; Jan Dijkmans; Bert Sels; Ive Hermans; Christophe Copï¿½ret

doi:10.1002/hlca.201600234

Identifying Sn Site Heterogeneities Prevalent Among Sn-Beta Zeolites

Patrick Wolf, Wei Chih Liao, Ta Chung Ong, Maxence Valla, James W. Harris, Rajamani Gounder, William N.P. van der Graaff, Evgeny A. Pidko, Emiel J.M. Hensen, Paola Ferrini, Jan Dijkmans, Bert Sels, Ive Hermans, Christophe Copï¿½ret

Chemical Engineering and Materials Science

Research output: Contribution to journal › Article › peer-review

43 Scopus citations

Abstract

In recent years, various protocols on preparing Lewis acidic Sn-β zeolite hydrothermally and postsynthetically have been reported. However, very little is known about the effects of different synthesis protocols on the Sn(IV) speciation in the final material. Even the effects of individual synthesis parameters within a certain preparation method have not been studied systematically. Here, we demonstrate that hydrothermally synthesized Sn-β zeolites prepared via very similar recipes show significantly different¹¹⁹Sn-NMR spectra, suggesting different Sn site speciation. Among postsynthetically prepared Sn-β zeolites, less variation in the resulting¹¹⁹Sn-NMR spectra have been observed, indicating a more reproducible synthesis procedure compared to hydrothermal synthesis in fluoride media. This work highlights the importance of¹¹⁹Sn-NMR measurements to elucidate the precise local geometry of the Sn heteroatoms in Sn-β, and the need to quantify the number of reactive Sn sites on each sample that participate in a given catalytic reaction, in order to accurately compare materials prepared by different routes.

Original language	English (US)
Pages (from-to)	916-927
Number of pages	12
Journal	Helvetica Chimica Acta
Volume	99
Issue number	12
DOIs	https://doi.org/10.1002/hlca.201600234
State	Published - Dec 2016

Bibliographical note

Funding Information:
ETH acknowledges the SNF for the 600 MHz DNP spectrometer (206021_150710) and funding for W. C. L. (200020_149704), M. V. (200021_143600) and P. W. (200021_146661). We acknowledge Dr. David Gajan for the assistance on the measurements on the 400 MHz DNP spectrometer. Purdue University acknowledges Cindy Tavera (Universidad Nacional de Colombia) for assistance with sample preparation, and financial support provided by the Purdue Process Safety and Assurance Center (P2SAC). P. F. acknowledges FiSCH SBO ARBOREF. TU Eindhoven acknowledges Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), an NWO Gravitation programme funded by the Ministry of Education, Culture and Science of the Government of the Netherlands. The authors thank Prof. Lyndon Emsley and Dr. Anne Lesage for helpful discussions and for providing measurement time at their institution.

Publisher Copyright:
© 2016 Wiley-VHCA AG, Zurich, Switzerland

Keywords

DNP-NMR
Lewis acid
Sn-Beta
Sn-NMR
Zeolites

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10.1002/hlca.201600234

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title = "Identifying Sn Site Heterogeneities Prevalent Among Sn-Beta Zeolites",

abstract = "In recent years, various protocols on preparing Lewis acidic Sn-β zeolite hydrothermally and postsynthetically have been reported. However, very little is known about the effects of different synthesis protocols on the Sn(IV) speciation in the final material. Even the effects of individual synthesis parameters within a certain preparation method have not been studied systematically. Here, we demonstrate that hydrothermally synthesized Sn-β zeolites prepared via very similar recipes show significantly different119Sn-NMR spectra, suggesting different Sn site speciation. Among postsynthetically prepared Sn-β zeolites, less variation in the resulting119Sn-NMR spectra have been observed, indicating a more reproducible synthesis procedure compared to hydrothermal synthesis in fluoride media. This work highlights the importance of119Sn-NMR measurements to elucidate the precise local geometry of the Sn heteroatoms in Sn-β, and the need to quantify the number of reactive Sn sites on each sample that participate in a given catalytic reaction, in order to accurately compare materials prepared by different routes.",

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author = "Patrick Wolf and Liao, {Wei Chih} and Ong, {Ta Chung} and Maxence Valla and Harris, {James W.} and Rajamani Gounder and {van der Graaff}, {William N.P.} and Pidko, {Evgeny A.} and Hensen, {Emiel J.M.} and Paola Ferrini and Jan Dijkmans and Bert Sels and Ive Hermans and Christophe Cop{\"i}¿½ret",

note = "Funding Information: ETH acknowledges the SNF for the 600 MHz DNP spectrometer (206021_150710) and funding for W. C. L. (200020_149704), M. V. (200021_143600) and P. W. (200021_146661). We acknowledge Dr. David Gajan for the assistance on the measurements on the 400 MHz DNP spectrometer. Purdue University acknowledges Cindy Tavera (Universidad Nacional de Colombia) for assistance with sample preparation, and financial support provided by the Purdue Process Safety and Assurance Center (P2SAC). P. F. acknowledges FiSCH SBO ARBOREF. TU Eindhoven acknowledges Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), an NWO Gravitation programme funded by the Ministry of Education, Culture and Science of the Government of the Netherlands. The authors thank Prof. Lyndon Emsley and Dr. Anne Lesage for helpful discussions and for providing measurement time at their institution. Publisher Copyright: {\textcopyright} 2016 Wiley-VHCA AG, Zurich, Switzerland",

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doi = "10.1002/hlca.201600234",

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AU - Wolf, Patrick

AU - Liao, Wei Chih

AU - Ong, Ta Chung

AU - Valla, Maxence

AU - Harris, James W.

AU - Gounder, Rajamani

AU - van der Graaff, William N.P.

AU - Pidko, Evgeny A.

AU - Hensen, Emiel J.M.

AU - Ferrini, Paola

AU - Dijkmans, Jan

AU - Sels, Bert

AU - Hermans, Ive

AU - Copï¿½ret, Christophe

N1 - Funding Information: ETH acknowledges the SNF for the 600 MHz DNP spectrometer (206021_150710) and funding for W. C. L. (200020_149704), M. V. (200021_143600) and P. W. (200021_146661). We acknowledge Dr. David Gajan for the assistance on the measurements on the 400 MHz DNP spectrometer. Purdue University acknowledges Cindy Tavera (Universidad Nacional de Colombia) for assistance with sample preparation, and financial support provided by the Purdue Process Safety and Assurance Center (P2SAC). P. F. acknowledges FiSCH SBO ARBOREF. TU Eindhoven acknowledges Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), an NWO Gravitation programme funded by the Ministry of Education, Culture and Science of the Government of the Netherlands. The authors thank Prof. Lyndon Emsley and Dr. Anne Lesage for helpful discussions and for providing measurement time at their institution. Publisher Copyright: © 2016 Wiley-VHCA AG, Zurich, Switzerland

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N2 - In recent years, various protocols on preparing Lewis acidic Sn-β zeolite hydrothermally and postsynthetically have been reported. However, very little is known about the effects of different synthesis protocols on the Sn(IV) speciation in the final material. Even the effects of individual synthesis parameters within a certain preparation method have not been studied systematically. Here, we demonstrate that hydrothermally synthesized Sn-β zeolites prepared via very similar recipes show significantly different119Sn-NMR spectra, suggesting different Sn site speciation. Among postsynthetically prepared Sn-β zeolites, less variation in the resulting119Sn-NMR spectra have been observed, indicating a more reproducible synthesis procedure compared to hydrothermal synthesis in fluoride media. This work highlights the importance of119Sn-NMR measurements to elucidate the precise local geometry of the Sn heteroatoms in Sn-β, and the need to quantify the number of reactive Sn sites on each sample that participate in a given catalytic reaction, in order to accurately compare materials prepared by different routes.

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Identifying Sn Site Heterogeneities Prevalent Among Sn-Beta Zeolites

Abstract

Bibliographical note

Keywords

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