title: Electron spin resonance studies on the oxidation mechanism of sterically hindered cyclic amines in TiO2 photocatalytic systems.
abstract: A sterically hindered cyclic amine, 4-hydroxy-2,2,6,6-tetramethylpiperidine (HTMP), is converted to the corresponding aminoxyl radical (nitroxide radical), 4-hydroxy-2,2,6,6-tetramethyl piperidine 1-oxyl (TEMPOL radical) as a result of a photocatalytic reaction in TiO2 aqueous suspension. The time profile of the radical formation and the effect of additives, such as SCN-, I-, methanol, and H2O2, on the initial formation rate were measured in order to elucidate the reaction mechanism. The experimental observations indicated that the direct photocatalytic oxidation of HTMP followed by reaction with O2 is the dominant process in the formation of TEMPOL radicals. Electrochemical measurements showed that HTMP is oxidized at 0.7 V (vs NHE), which is consistent with the proposed mechanism. The possibility of other processes, involving reactions with singlet molecular oxygen, superoxide radical, and hydroxyl radical, were excluded from the reaction mechanism.
authors.affiliation: Department of Chemistry, Nagaoka University of Technology, Kamitomioka, Nagaoka 940-2188, Japan. nosaka@nagaokaut.ac.jp
authors.forename: Yoshio
authors.initials: Y
authors.lastname: Nosaka
authors.forename: Hayato
authors.initials: H
authors.lastname: Natsui
authors.forename: Mariko
authors.initials: M
authors.lastname: Sasagawa
authors.forename: Atsuko Y
authors.initials: AY
authors.lastname: Nosaka