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Oxidation of diphenylamine to diphenylnitroxide in faujasite zeolite studied by electron paramagnetic resonance

Authors
Journal
Solid State Ionics
0167-2738
Publisher
Elsevier
Publication Date
Volume
100
Identifiers
DOI: 10.1016/s0167-2738(97)00346-9
Keywords
  • Zeolite
  • Catalysis
  • Amine
  • Oxidation
  • Nitroxide

Abstract

Abstract Oxidation of diphenylamine to diphenylnitroxide in neutral, K-exchanged, X-type faujasite zeolite (K-X) has been observed. The oxidation, as assessed by the intensity of the diphenylnitroxide electron paramagnetic resonance (EPR) spectrum, is favored in K-X in comparison with diphenylamine doped into X-type faujasite zeolites exchanged with Li, Na, Rb or Cs. Similar experiments with analine gave no detectable free radical product. The weakly allowed Δm s = ± 2 half-field peak of a triplet state EPR spectrum with √ D 2 + 3 E 2/ g e β e = 1200 ± 150 G is observed. The triplet spectrum is attributed to molecular oxygen probably immobilized at a cation site in the zeolite. We proposed that O 2 also binds to Lewis acid sites in the zeolite and hydrogen bonds to diphenylamine. This diphenylamine-O 2 complex rearranges to form diphenylnitroxide and the OH . radical. The mechanism implies that the OH . is somewhat stabilized by the zeolite. The temperature dependence of the diphenylnitroxide EPR spectrum indicates a restricted degree of molecular motion in the zeolite cages.

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