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Research on Chemical Intermediates

, Volume 35, Issue 2, pp 145–154 | Cite as

An EPR investigation of acetonitrile reactivity with superoxide radicals on polycrystalline TiO2

  • Jason Green
  • Emma Carter
  • Damien M. MurphyEmail author
Article

Abstract

The interaction of acetonitrile with superoxide radicals over a polycrystalline TiO2 (Degussa P25) surface was investigated using continuous-wave electron paramagnetic resonance (cw-EPR) spectroscopy. For the first time, a thermally unstable radical intermediate has been observed following the low-temperature exposure of acetonitrile to surface-adsorbed O 2 radicals. The radical intermediate has been identified as an [O 2 ···CH3CN] type surface complex characterised by the g values of g 1 = 2.031, g 2 = 2.010 and g 3 = 2.003. This surface complex is thermally unstable and decomposes at temperatures of T > 240 K. A second oxygen-centred species was also observed following acetonitrile adsorption, characterised by the spin Hamiltonian parameters of g 1 = 2.028, g 2 = 2.010, g 3 = 2.004, A 1 = 1.2 mT, A 2 = 1.0 mT and A 3 = 1.0 mT, and was assigned to a hydroperoxy radical (HO 2 ).

Keywords

TiO2 Acetonitrile Surface oxygen radicals EPR 

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Copyright information

© Springer Science+Business Media B.V. 2009

Authors and Affiliations

  1. 1.School of ChemistryCardiff UniversityCardiffUK

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