Conversion of benzoic acid during TiO2-mediated photocatalytic degradation in water

The photocatalytic degradation of benzoic acid in water over Degussa P-25 TiO2 suspensions was studied. UVA irradiation at 365 nm was supplied by a medium pressure mercury lamp providing 25 mW cm−2 light intensity. Experiments were conducted at benzoic acid initial concentrations between 25 and 150 mg L−1, catalyst loadings between 0.2 and 1 g L−1 and initial solution pH values between 2 and 10.6. Conversion increased with increasing catalyst loading up to about 0.6 g L−1 and it was favored at alkaline or neutral conditions but impeded at extremely acidic conditions. Increasing initial substrate concentration led to decreased benzoic acid conversion, which was found to follow a Langmuir–Hinshelwood kinetic expression. High performance liquid chromatography (HPLC) was employed to follow benzoic acid concentration profiles as well as to identify reaction by-products, while chemical oxygen demand (COD) and total organic carbon (TOC) analyses were carried out to assess the extent of mineralization. Benzoic acid hydroxylation by-products, namely 2-, 3- and 4-hydroxybenzoic acids as well as phenol were identified as reaction intermediates, although these contributed only a small fraction of the residual organic content. Although benzoic acid at 50 mg L−1 was not ecotoxic to marine photobacteria Vibrio fischeri, its photodegraded solution exhibited substantial toxicity, which, however, proved not to be due to the identified intermediates.