Influence of the solid titanium source on the activity of La1_xTixFeO3 photo-CWPO catalysts under UV-A light

In the search for more efficient low-temperature catalysts able to oxidise biorecalcitrant pollutants in water, the selective substitution of La3+ by Ti3+ cations was reported to boost the UV-A light driven activity of LaFeO3 orthoferrites as H2O2-mediated photo-CWPO catalysts. La1_xTixFeO3 catalysts with 0 < x < 0.11 were obtained by a modified Pechini sol-gel route via the addition of a solid source of titanium during the synthesis. By using a span of crystallized and amorphous TiO2, the influence of the titanium source on the substitution rate in the orthoferrite network and on the performances of the catalysts under UV-A light was demonstrated using the degradation of 4-chlorophenol as test reaction. The amorphous content of the TiO2 precursor is proposed to be the key factor driving the substitution of La3+, the largest substitution of 11 % being obtained using a dried sol-gel TiO2 precursor. We suggest that the substitution proceeds during the thermal treatment via a solid-solid diffusion between TiO2 and the amorphous LaFeO3 before it crystallises. The catalyst robustness was influ-enced by the TiO2 nature. Small size Ti-LaFeO3 crystallites strongly lowered or blocked the Fe release, while no improvement was observed for large size crystallites vs. the pristine material, what was associated to a poor homogenization of the titanium in the network. We showed that the mineralization activity was proportional to the substitution rate of La1_xTixFeO3 catalysts, while a similar relationship could be drawn for the degradation activity only in the case of highly robust catalysts with pure heterogeneous surface reactions.