Titanium-germoxy precursor route to germanium-modified epoxidation catalysts with enhanced activity

Paul J. Cordeiro; Pascal Guillo; Charles S. Spanjers; Ji Woong Chang; Mike I. Lipschutz; Meg E. Fasulo; Robert M. Rioux; T. Don Tilley

doi:10.1021/cs400529x

Titanium-germoxy precursor route to germanium-modified epoxidation catalysts with enhanced activity

Paul J. Cordeiro, Pascal Guillo, Charles S. Spanjers, Ji Woong Chang, Mike I. Lipschutz, Meg E. Fasulo, Robert M. Rioux, T. Don Tilley

Chemical Engineering and Materials Science

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

26 Scopus citations

Abstract

The complex Ti[OGeⁱPr₃]₄ (1), prepared via the reaction of Ti(OⁱPr)₄ with ⁱPr ₃GeOH, represents a useful structural and spectroscopic model for titanium-germanium species dispersed onto silica. This precursor was used to introduce site-isolated Ti(IV) centers onto the surface of a mesoporous SBA15 support via the thermolytic molecular precursor method. The local environments of the supported materials (TiGe₃SBA15 and calcined TiGe ₃SBA15-O₂) were studied by various spectroscopic methods, including X-ray absorption spectroscopy. These materials are active catalysts for the epoxidation of cyclic and terminal olefins with alkyl hydroperoxides under anhydrous conditions. Compared to catalysts synthesized from siloxide-only precursors, the new catalysts produce 2-3 times more product after 9 h under identical reaction conditions for the epoxidations of cyclohexene and 1-octene. The new materials did not significantly leach under reaction conditions.

Original language	English (US)
Pages (from-to)	2269-2279
Number of pages	11
Journal	ACS Catalysis
Volume	3
Issue number	10
DOIs	https://doi.org/10.1021/cs400529x
State	Published - Oct 4 2013

Keywords

SBA15
epoxidation
germanium
site-isolated catalysts
titanium

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10.1021/cs400529x

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title = "Titanium-germoxy precursor route to germanium-modified epoxidation catalysts with enhanced activity",

abstract = "The complex Ti[OGeiPr3]4 (1), prepared via the reaction of Ti(OiPr)4 with iPr 3GeOH, represents a useful structural and spectroscopic model for titanium-germanium species dispersed onto silica. This precursor was used to introduce site-isolated Ti(IV) centers onto the surface of a mesoporous SBA15 support via the thermolytic molecular precursor method. The local environments of the supported materials (TiGe3SBA15 and calcined TiGe 3SBA15-O2) were studied by various spectroscopic methods, including X-ray absorption spectroscopy. These materials are active catalysts for the epoxidation of cyclic and terminal olefins with alkyl hydroperoxides under anhydrous conditions. Compared to catalysts synthesized from siloxide-only precursors, the new catalysts produce 2-3 times more product after 9 h under identical reaction conditions for the epoxidations of cyclohexene and 1-octene. The new materials did not significantly leach under reaction conditions.",

keywords = "SBA15, epoxidation, germanium, site-isolated catalysts, titanium",

author = "Cordeiro, {Paul J.} and Pascal Guillo and Spanjers, {Charles S.} and Chang, {Ji Woong} and Lipschutz, {Mike I.} and Fasulo, {Meg E.} and Rioux, {Robert M.} and Tilley, {T. Don}",

year = "2013",

month = oct,

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doi = "10.1021/cs400529x",

language = "English (US)",

volume = "3",

pages = "2269--2279",

journal = "ACS Catalysis",

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T1 - Titanium-germoxy precursor route to germanium-modified epoxidation catalysts with enhanced activity

AU - Cordeiro, Paul J.

AU - Guillo, Pascal

AU - Spanjers, Charles S.

AU - Chang, Ji Woong

AU - Lipschutz, Mike I.

AU - Fasulo, Meg E.

AU - Rioux, Robert M.

AU - Tilley, T. Don

PY - 2013/10/4

Y1 - 2013/10/4

N2 - The complex Ti[OGeiPr3]4 (1), prepared via the reaction of Ti(OiPr)4 with iPr 3GeOH, represents a useful structural and spectroscopic model for titanium-germanium species dispersed onto silica. This precursor was used to introduce site-isolated Ti(IV) centers onto the surface of a mesoporous SBA15 support via the thermolytic molecular precursor method. The local environments of the supported materials (TiGe3SBA15 and calcined TiGe 3SBA15-O2) were studied by various spectroscopic methods, including X-ray absorption spectroscopy. These materials are active catalysts for the epoxidation of cyclic and terminal olefins with alkyl hydroperoxides under anhydrous conditions. Compared to catalysts synthesized from siloxide-only precursors, the new catalysts produce 2-3 times more product after 9 h under identical reaction conditions for the epoxidations of cyclohexene and 1-octene. The new materials did not significantly leach under reaction conditions.

AB - The complex Ti[OGeiPr3]4 (1), prepared via the reaction of Ti(OiPr)4 with iPr 3GeOH, represents a useful structural and spectroscopic model for titanium-germanium species dispersed onto silica. This precursor was used to introduce site-isolated Ti(IV) centers onto the surface of a mesoporous SBA15 support via the thermolytic molecular precursor method. The local environments of the supported materials (TiGe3SBA15 and calcined TiGe 3SBA15-O2) were studied by various spectroscopic methods, including X-ray absorption spectroscopy. These materials are active catalysts for the epoxidation of cyclic and terminal olefins with alkyl hydroperoxides under anhydrous conditions. Compared to catalysts synthesized from siloxide-only precursors, the new catalysts produce 2-3 times more product after 9 h under identical reaction conditions for the epoxidations of cyclohexene and 1-octene. The new materials did not significantly leach under reaction conditions.

KW - SBA15

KW - epoxidation

KW - germanium

KW - site-isolated catalysts

KW - titanium

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DO - 10.1021/cs400529x

M3 - Article

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JO - ACS Catalysis

JF - ACS Catalysis

IS - 10

ER -

Titanium-germoxy precursor route to germanium-modified epoxidation catalysts with enhanced activity

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