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Role of the Ti(IV)-Superoxide Species in the Selective Oxidation of Alkanes with Hydrogen Peroxide in the Gas Phase on Titanium Silicalite-1: An In Situ EPR Investigation

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Abstract

The interaction of TS-1 with gaseous hydrogen peroxide at temperatures above 373 K has been investigated by in situ EPR measurements. Treatment of TS-1 with hydrogen peroxide in the gas phase leads to a strong EPR signal, assigned to the Ti(IV)-superoxide species. In contrast to investigations with liquid hydrogen peroxide, here only one Ti(IV)-superoxide species could be detected in the EPR spectrum. The time constant of the reaction of the Ti(IV)-superoxide species detected by in situ EPR measurements was much larger than that observed for the rate of consumption of propane or propene via gas chromatographic analysis. Thus, we conclude that the superoxide species may take part in the oxidation reaction (via side reactions or the formation of unselective products), but is probably not the main responsible species in the oxidation of propane or propene.

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Acknowledgments

The authors are grateful to Prof. Rudolf Holze, Chemnitz University of Technology, for providing access to his EPR Spectrometer and to Prof. Angelika Brückner for fruitful discussions.

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Authors and Affiliations

  1. BAM Federal Institute for Materials Research and Testing, Chemical Safety Engineering, 12200, Berlin, Germany

    Sebastian Heinrich

  2. Department for Industrial Chemistry, Faculty of Natural Sciences, Chemnitz University of Technology, 09107, Chemnitz, Germany

    Martin Plettig

  3. University of Stuttgart, Institute for Technical Chemistry, Faculty of Chemistry, 70550, Stuttgart, Germany

    Elias Klemm

Authors
  1. Sebastian Heinrich
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  2. Martin Plettig
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  3. Elias Klemm
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Correspondence to Sebastian Heinrich.

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Heinrich, S., Plettig, M. & Klemm, E. Role of the Ti(IV)-Superoxide Species in the Selective Oxidation of Alkanes with Hydrogen Peroxide in the Gas Phase on Titanium Silicalite-1: An In Situ EPR Investigation. Catal Lett 141, 251–258 (2011). https://doi.org/10.1007/s10562-010-0534-6

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  • DOI: https://doi.org/10.1007/s10562-010-0534-6

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