Reaction pathways of dimethyl phthalate degradation in TiO2-UV-O2 and TiO2-UV-Fe(VI) systems

The photocatalytic degradation of dimethyl phthalate (DMP) in aqueous TiO₂ suspension under UV illumination has been investigated using oxygen (O₂) and ferrate (Fe(VI)) as electron acceptors. The experiments demonstrated that Fe(VI) was a more effective electron acceptor than O₂ for scavenging the conduction band electrons from the surface of the catalyst. Some major intermediate products from DMP degradation were identified by HPLC and GC/MS analyses. The analytical results identified dimethyl 3-hydroxyphthalate and dimethyl 2-hydroxyphthalate as the two main intermediate products from the DMP degradation in the TiO₂–UV–O₂ system, while in contrast phthalic acid was found to be the main intermediate product in the TiO₂–UV–Fe(VI) system. These findings indicate that DMP degradation in the TiO₂–UV–O₂ and TiO₂–UV–Fe(VI) systems followed different reaction pathways. An electron spin resonance analysis confirmed that hydroxyl radicals existed in the TiO₂–UV–O₂ reaction system and an unknown radical species (most likely an iron–oxo species) is suspected to exist in the TiO₂–UV–Fe(VI) reaction system. Two pathway schemes of DMP degradation in the TiO₂–UV–O₂ and TiO₂–UV–Fe(VI) reaction systems are proposed. It is believed that the radicals formed in the TiO₂–UV–O₂ reaction system preferably attack the aromatic ring of the DMP, while in contrast the radicals formed in the TiO₂–UV–Fe(VI) reaction systems attack the alkyl chain of DMP.