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

Green, Jason, Carter, Emma and Murphy, Damien Martin 2009. An EPR investigation of acetonitrile reactivity with superoxide radicals on polycrystalline TiO2. Research on Chemical Intermediates 35 (2) , pp. 145-154. 10.1007/s11164-008-0022-4

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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 O2− radicals. The radical intermediate has been identified as an [O2−···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 (HO2•).

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Uncontrolled Keywords: TiO2 - Acetonitrile - Surface oxygen radicals - EPR
Publisher: Springer
ISSN: 0922-6168
Last Modified: 02 May 2019 05:06
URI: http://orca.cf.ac.uk/id/eprint/5960

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