EXPLOITING THE INTERPARTICLE ELECTRON-TRANSFER PROCESS IN THE PHOTOCATALYZED OXIDATION OF PHENOL, 2-CHLOROPHENOL AND PENTACHLOROPHENOL - CHEMICAL EVIDENCE FOR ELECTRON AND HOLE TRANSFER BETWEEN COUPLED SEMICONDUCTORS

The photocatalysed oxidation of phenol, 2-chlorophenol and pentachlorophenol was re-examined under conditions in which TiO2 anatase was sensitized by CdS in air-equilibrated aqueous media; this was to assess whether or not the interparticle electron transfer pathway, first discovered a decade ago (N. Serpone, E. Borgarello and M. Gratzel, J. Chem. Sec., Chem. Commun., (1984) 342) and subsequently applied to enhance reductive processes on titania, could also be applied to photooxidative processes. The results indicate that combinations such as CdS/TiO2 lead to an enhanced rate of disappearance of the initial substrate by a factor greater than two, consistent with the notion that (irradiated) CdS electrons are vectorially displaced onto the non-illuminated TiO2 particulates. Cadmium sulphide is a poorer photo-oxidation catalyst than titania. Other semiconductor materials have also been examined under a variety of conditions of pH and irradiation wavelength. The data also show that when both semiconductors in a coupled system are illuminated simultaneously and their valence and conduction bands are suitably disposed, both electron and hole transfer occur (as in the CdS/TiO2, ZnO/TiO2, TiO2/Fe2O3 and ZnO/Fe2O3 couples), which will influence the efficiency of photo-oxidation. N2O-saturated aqueous dispersions of TiO2 have no effect on the photo-oxidation of phenol, although it was expected that nitrous oxide would scavenge the photogenerated electrons in a manner similar to chemisorbed molecular oxygen, and enhance the efficiency. It is suggested that the role of oxygen in photo- oxidations may be more than just a simple electron scavenger.