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Molecules 2010, 15(2), 747-765; doi:10.3390/molecules15020747
Article

Catalytic Performance of Ceria Nanorods in Liquid-Phase Oxidations of Hydrocarbons with tert-Butyl Hydroperoxide

1,2
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2, 2
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1, 1 and 2,*
1 Department of Physics, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal 2 Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal
* Author to whom correspondence should be addressed.
Received: 9 December 2009 / Revised: 28 January 2010 / Accepted: 29 January 2010 / Published: 2 February 2010
(This article belongs to the Special Issue Nano-catalysts and Nano-technologies for Green Organic Synthesis)
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Abstract

The CeO2 nanorods (CeNR) promote the oxidation of ethylbenzene (PhEt) and cyclohexene with t-BuOOH, at temperatures as low as 55 ºC. For both substrates the saturated C-H bonds are preferentially activated over the unsaturated ones. The catalyst seems fairly stable towards leaching phenomena. The liquid-phase oxidation catalysis may be associated with the Ce3+/Ce4+ inter-conversion in the one-electron redox processes mediating the formation of tert-butyl-(per)oxy radicals. CeNR is very effective in H2O2 disproportionation. Pre-treatment of CeNR with H2O2 or t-BuOOH prior to the catalytic reaction enhances the reaction rate of PhEt with t-BuOOH in comparison to CeNR. Textural characterization and spectroscopic studies suggest that catalytic activation is associated to defect sites.
Keywords: cerium oxide; nanorods; catalysis; oxidation; liquid phase; free radical mechanism cerium oxide; nanorods; catalysis; oxidation; liquid phase; free radical mechanism
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).
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Macedo, A.G.; Fernandes, S.E.M.; Valente, A.A.; Ferreira, R.A.S.; Carlos, L.D.; Rocha, J. Catalytic Performance of Ceria Nanorods in Liquid-Phase Oxidations of Hydrocarbons with tert-Butyl Hydroperoxide. Molecules 2010, 15, 747-765.

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