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

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

28 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

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry

Access to Document

10.1021/cs400529x

Cite this

@article{a12daca45a874e85980cd23753880505,

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.",

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,

day = "4",

doi = "10.1021/cs400529x",

language = "English (US)",

volume = "3",

pages = "2269--2279",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

number = "10",

}

TY - JOUR

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.

UR - https://www.scopus.com/pages/publications/84885351886

UR - https://www.scopus.com/inward/citedby.url?scp=84885351886&partnerID=8YFLogxK

U2 - 10.1021/cs400529x

DO - 10.1021/cs400529x

M3 - Article

AN - SCOPUS:84885351886

SN - 2155-5435

VL - 3

SP - 2269

EP - 2279

JO - ACS Catalysis

JF - ACS Catalysis

IS - 10

ER -

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

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this