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

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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 ).

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Authors and Affiliations

  1. School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, UK

    Jason Green, Emma Carter & Damien M. Murphy

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  1. Jason Green
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  2. Emma Carter
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  3. Damien M. Murphy
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Correspondence to Damien M. Murphy.

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Green, J., Carter, E. & Murphy, D.M. An EPR investigation of acetonitrile reactivity with superoxide radicals on polycrystalline TiO2 . Res Chem Intermed 35, 145–154 (2009). https://doi.org/10.1007/s11164-008-0022-4

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  • DOI: https://doi.org/10.1007/s11164-008-0022-4

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