Mechanistic implications of the effect of TiO2 accessibility in TiO2-SiO2 coatings upon chlorinated organics photocatalytic removal in water.

The photocatalytic removal rates r of dichloroacetic acid (DCAA), 4-chlorobenzoic acid (4-CBA) and 4-chlorophenol (4-CP) in water were compared for TiO2 samples used either as a powder or as a coating on a fiber glass tissue, SiO2 being the binder. From SEM-EDX measurements it was deduced that SiO2 prevails over TiO2 in the coating top layers and 18O2-Ti16O2 isotopic exchange showed that the accessibility of O2 to TiO2 was markedly reduced when TiO2 was thus coated. The unfavorable effect of the restricted TiO2 accessibility on r was drastic for DCAA, much less pronounced for 4-CBA, and still smaller for 4-CP. It is inferred that DCAA can be attacked only when it directly interacts with TiO2, whereas 4-CP can also react within the near-TiO2 surface water layers. The 4-CBA intermediate behavior is in line with the structural similarities of 4-CBA with DCAA and 4-CP.