Improved phenol degradation by catalytic wet air oxidation on the Co3O4 spinel catalysts supported on SBA-15 modified with TiO2

The removal of phenol from aqueous industrial effluents by catalytic wet-air oxidation (CWAO) is a challenging process that requires novel catalysts resistant to leaching of the active phases during residence time in a batch reactor. In this sense, this work demonstrated that this can be archived with the catalyst having the spinel phase Co3O4 supported on mesoporous silica SBA-15 doped with an optimized amount of TiO2 (3 wt.%). In the phenol CWAO reaction carried out at 160°C and 10 bar O2, this best Co3O4/TiO2/SBA-15 catalyst showed an increase of phenol conversion from 49.0% to 68.3% and of CO2 selectivity from 87% to 98%. The extensive catalyst characterization and overall activity results indicated that this was related to the strength and nature of the acid sites and the oxidation states of the cobalt oxide phases. Combined factors influenced the final behaviour of the catalyst, such as its intrinsic activity, dispersion of the active phase, inhibition of CoSiO4 phase formation, high Lewis acidity and the large amount of active Co3O4 spinel phase. The presence of TiO2 nanoparticles (NPs) decorating the support surface improved the stability of the catalyst by inhibiting the leaching of cobalt species during the reaction. After three reaction cycles, the most efficient Co/3Ti/S15 catalyst showed high CO2 selectivity (∼92.7%) and low selectivity towards carboxylic acid (∼5.3%) and polyphenolic compounds (∼2%). It is proposed that surface oxidation is the rate-determining step in the CWAO reaction over TiO2/SBA-15-supported Co3O4 spinel catalysts.