Elucidation of Anchoring and Restructuring Steps during Synthesis of Silica-Supported Vanadium Oxide Catalysts

Alyssa M. Love; Carlos A. Carrero; Alessandro Chieregato; Joseph T. Grant; Sabrina Conrad; René Verel; Ive Hermans

doi:10.1021/acs.chemmater.6b02118

Elucidation of Anchoring and Restructuring Steps during Synthesis of Silica-Supported Vanadium Oxide Catalysts

Alyssa M. Love, Carlos A. Carrero, Alessandro Chieregato, Joseph T. Grant, Sabrina Conrad, René Verel, Ive Hermans

Chemical Engineering and Materials Science

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

32 Scopus citations

Abstract

We investigate the chemical reactions involved during the synthesis of supported vanadium oxide catalysts using chemical grafting of vanadium oxytriisopropoxide (VO(OⁱPr)₃) to thermally pretreated silica under solvent-free conditions. VO(OⁱPr)₃ is found to react with both site-isolated silanol (Si-OH) groups and strained siloxane (≡Si-O-Si≡) bridges at the silica surface. Solid-state ⁵¹V and ¹³C MAS NMR confirms the formation of two slightly different vanadium species associated with the two anchoring mechanisms. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), in situ Raman spectroscopy, and thermogravimetric analysis-differential scanning calorimetry-mass spectrometry (TGA-DSC-MS) were used to study the subsequent calcination, revealing the formation of a transient V - OH intermediate upon the release of propene, followed by the formation of isolated VO₄ surface species upon elimination of water. X-ray absorption spectroscopy (XAS) and ⁵¹V MAS NMR of the calcined material confirm the conversion of the two original vanadium sites to a species with a single isotropic shift, confirming the formation of isolated, tetrahedral VO₄ sites.

Original language	English (US)
Pages (from-to)	5495-5504
Number of pages	10
Journal	Chemistry of Materials
Volume	28
Issue number	15
DOIs	https://doi.org/10.1021/acs.chemmater.6b02118
State	Published - Aug 9 2016

Bibliographical note

Funding Information:
The authors acknowledge financial support from the University of Wisconsin-Madison. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We specifically acknowledge support from Sam Burt and beamline engineer Dale Brewe, who assisted in the collection of XANES data reported in this publication.

Publisher Copyright:
© 2016 American Chemical Society.

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10.1021/acs.chemmater.6b02118

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title = "Elucidation of Anchoring and Restructuring Steps during Synthesis of Silica-Supported Vanadium Oxide Catalysts",

abstract = "We investigate the chemical reactions involved during the synthesis of supported vanadium oxide catalysts using chemical grafting of vanadium oxytriisopropoxide (VO(OiPr)3) to thermally pretreated silica under solvent-free conditions. VO(OiPr)3 is found to react with both site-isolated silanol (Si-OH) groups and strained siloxane (≡Si-O-Si≡) bridges at the silica surface. Solid-state 51V and 13C MAS NMR confirms the formation of two slightly different vanadium species associated with the two anchoring mechanisms. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), in situ Raman spectroscopy, and thermogravimetric analysis-differential scanning calorimetry-mass spectrometry (TGA-DSC-MS) were used to study the subsequent calcination, revealing the formation of a transient V - OH intermediate upon the release of propene, followed by the formation of isolated VO4 surface species upon elimination of water. X-ray absorption spectroscopy (XAS) and 51V MAS NMR of the calcined material confirm the conversion of the two original vanadium sites to a species with a single isotropic shift, confirming the formation of isolated, tetrahedral VO4 sites.",

author = "Love, {Alyssa M.} and Carrero, {Carlos A.} and Alessandro Chieregato and Grant, {Joseph T.} and Sabrina Conrad and Ren{\'e} Verel and Ive Hermans",

note = "Funding Information: The authors acknowledge financial support from the University of Wisconsin-Madison. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We specifically acknowledge support from Sam Burt and beamline engineer Dale Brewe, who assisted in the collection of XANES data reported in this publication. Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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AU - Grant, Joseph T.

AU - Conrad, Sabrina

AU - Verel, René

AU - Hermans, Ive

N1 - Funding Information: The authors acknowledge financial support from the University of Wisconsin-Madison. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We specifically acknowledge support from Sam Burt and beamline engineer Dale Brewe, who assisted in the collection of XANES data reported in this publication. Publisher Copyright: © 2016 American Chemical Society.

PY - 2016/8/9

Y1 - 2016/8/9

N2 - We investigate the chemical reactions involved during the synthesis of supported vanadium oxide catalysts using chemical grafting of vanadium oxytriisopropoxide (VO(OiPr)3) to thermally pretreated silica under solvent-free conditions. VO(OiPr)3 is found to react with both site-isolated silanol (Si-OH) groups and strained siloxane (≡Si-O-Si≡) bridges at the silica surface. Solid-state 51V and 13C MAS NMR confirms the formation of two slightly different vanadium species associated with the two anchoring mechanisms. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), in situ Raman spectroscopy, and thermogravimetric analysis-differential scanning calorimetry-mass spectrometry (TGA-DSC-MS) were used to study the subsequent calcination, revealing the formation of a transient V - OH intermediate upon the release of propene, followed by the formation of isolated VO4 surface species upon elimination of water. X-ray absorption spectroscopy (XAS) and 51V MAS NMR of the calcined material confirm the conversion of the two original vanadium sites to a species with a single isotropic shift, confirming the formation of isolated, tetrahedral VO4 sites.

AB - We investigate the chemical reactions involved during the synthesis of supported vanadium oxide catalysts using chemical grafting of vanadium oxytriisopropoxide (VO(OiPr)3) to thermally pretreated silica under solvent-free conditions. VO(OiPr)3 is found to react with both site-isolated silanol (Si-OH) groups and strained siloxane (≡Si-O-Si≡) bridges at the silica surface. Solid-state 51V and 13C MAS NMR confirms the formation of two slightly different vanadium species associated with the two anchoring mechanisms. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), in situ Raman spectroscopy, and thermogravimetric analysis-differential scanning calorimetry-mass spectrometry (TGA-DSC-MS) were used to study the subsequent calcination, revealing the formation of a transient V - OH intermediate upon the release of propene, followed by the formation of isolated VO4 surface species upon elimination of water. X-ray absorption spectroscopy (XAS) and 51V MAS NMR of the calcined material confirm the conversion of the two original vanadium sites to a species with a single isotropic shift, confirming the formation of isolated, tetrahedral VO4 sites.

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Elucidation of Anchoring and Restructuring Steps during Synthesis of Silica-Supported Vanadium Oxide Catalysts

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