Khouw, C. B. and Dartt, C. B. and Labinger, J. A. and Davis, M. E. (1994) Studies on the Catalytic-Oxidation of Alkanes and Alkenes by Titanium Silicates. Journal of Catalysis, 149 (1). pp. 195-205. ISSN 0021-9517. https://resolver.caltech.edu/CaltechAUTHORS:20170710-090722816
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Abstract
Titanium containing, aluminum-free ZSM-5 (TS-1) and amorphous TiO_2-SiO_2 coprecipitate are investigated as catalysts for the selective oxidation of alkanes and alkenes using a variety of oxidants at temperatures below 100°C. Comparisons between the activities of TS-1 and the TiO2-SiO2 coprecipitate for alkane oxidation and alkene epoxidation using nonaqueous H_2O_2 indicate that the absence of water is crucial for the catalytic activity of silica-supported titanium. Due to the hydrophobicity of TS-1, the concentration of water surrounding the titanium is maintained at a low value, and thus TS-1 can be used as an oxidation catalyst with aqueous H_2O_2 as oxidant. Alkyl hydroperoxides are active as oxidants for alkene epoxidation on the TiO_2-SiO_2 coprecipitate but not for alkane oxidation reactions on both TS-1 and the TiO_2-SiO_2 coprecipitate. A plausible explanation for the above results is provided. The presence of stereoscrambling without any "radical clock" rearrangement during alkane oxidation on TS-1 indicates that the radicals formed may have a very short life-time, or their movements are restricted such that no rearrangement can occur. A proposal for the mechanism of alkane oxidation on TS-1 is given and compared to a mechanism suggested for alkene epoxidation on TS-1 and the TiO_2-SiO_2 coprecipitate.
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| Additional Information: | © 1994 Academic Press. Support of this work was provided by the Shell Development Co. and the NSF Alan T. Waterman Award to M.E.D. | |||||||||
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| Issue or Number: | 1 | |||||||||
| Record Number: | CaltechAUTHORS:20170710-090722816 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20170710-090722816 | |||||||||
| Official Citation: | C.B. Khouw, C.B. Dartt, J.A. Labinger, M.E. Davis, Studies on the Catalytic-Oxidation of Alkanes and Alkenes by Titanium Silicates, Journal of Catalysis, Volume 149, Issue 1, September 1994, Pages 195-205, ISSN 0021-9517, https://doi.org/10.1006/jcat.1994.1285. (http://www.sciencedirect.com/science/article/pii/S0021951784712851) | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 78887 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Ruth Sustaita | |||||||||
| Deposited On: | 10 Jul 2017 16:30 | |||||||||
| Last Modified: | 09 Mar 2020 13:18 |
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