Phenol transformation photosensitised by quinoid compounds

Abstract

The phototransformation of phenol in aqueous solution was studied with different quinoid compounds, which are usually detected on atmospheric particulate matter: 2-ethylanthraquinone (EtAQ), benzanthracene-7,12-dione (BAD), 5,12-naphthacenequinone (NQ), 9,10-anthraquinone (AQ), and 2,6-dihydroxyanthraquinone (DAQ). All the studied quinones were able to sensitise the phototransformation of phenol. Under blue-light irradiation the approximated, polychromatic quantum yields for phenol photodegradation were in the order AQ > BAD > EtAQ > NQ > DAQ. Quantum mechanical calculations showed that AQ and DAQ have a very different spin distribution in the triplet state (largely located on the carbonyl oxygen and delocalised over the aromatic ring, respectively) that could account for the difference in reactivity. The spin distribution of EtAQ is similar to that of AQ. Under simulated sunlight, EtAQ induced the highest rate of phenol degradation. Radiation-excited EtAQ would oxidise both ground-state EtAQ and phenol; a kinetic model that excludes the ˙OH radical and singlet oxygen as reactive species is supported by the experimental data. Quinones were also able to oxidise nitrite to nitrogen dioxide, thereby inducing phenol nitration. Such a process is a potential source of nitrogen dioxide and nitrophenols in the atmospheric aerosols.