The mechanism and kinetics of synergetic effect in TiO 2 /O 3 /UV process on H-acid degradation were investigated. The experimental results showed that H-acid removal rate of TiO 2 /O 3 /UV process was the highest among TiO 2 /UV, O 3 /UV and TiO 2 /O 3 /UV processes. The investigation of reactions with suitable active species scavengers confirmed that H-acid was mainly oxidised by ozone and holes on TiO 2 in the TiO 2 /O 3 /UV process. The recombination between holes and electrons in TiO 2 reduced in the presence of ozone, as indicated by fluorescence emission spectra. Moreover, the intermediates generated during H-acid oxidation in various processes were analysed by LC/MSD trap. It is proposed that H-acid was oxidised to polyhydroxy aromatics, benzene carboxylic acids and quinoids in the first step. Then, saturated aliphatics carboxylic acids were formed and mineralised to inorganic compounds through the Photo-Kolbe reaction. Finally, a kinetic study on TiO 2 /UV, O 3 /UV and TiO 2 /O 3 /UV processes was conducted and it was confirmed that both ozonation and photocatalytic activity were improved in TiO 2 /O 3 /UV process because of the synergetic effect.
Alumina supported bimetallic cobalt-iron oxide (Co 3 O 4 -Fe 2 O 3 /Al 2 O 3 ) catalyst was prepared via co-impregnation of boehmite with the mixture solution of cobalt nitrate and iron nitrate followed by calcination in air. X-ray photoelectron spectroscopy and high-resolution transmission electron microscope analyses confirmed the existence of highly dispersed Co 3 O 4 and Fe 2 O 3 nanoparticles in the as-prepared catalysts. The catalytic activity of Co 3 O 4 -Fe 2 O 3 /Al 2 O 3 was evaluated for the degradation of H-acid in aqueous solution by heterogeneous activation of peroxymonosulfate. The results indicated that the Co 3 O 4 -Fe 2 O 3 /Al 2 O 3 catalyst exhibited an identical initial activity but much better recyclability than Co 3 O 4 /Al 2 O 3 due to its low amount of metal leaching and possible redox circle of Co(II)/Co(III). Electron paramagnetic resonance spectroscopy and radical quenching experiments suggested that singlet oxygen ( 1 O 2 ) contributed much more than ·OH and SO 4 • to H-acid degradation, and the degradation mainly followed a nonradical reaction mechanism.
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