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

Green, Jason, Carter, Emma ORCID: https://orcid.org/0000-0001-6691-2377 and Murphy, Damien Martin ORCID: https://orcid.org/0000-0002-5941-4879 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:	16 Oct 2024 10:19
URI:	https://orca.cardiff.ac.uk/id/eprint/5960

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