Photo-oxidation of phenol and monochlorophenols in oxygen-saturated aqueous solutions by different photosensitizers

The photo-oxidation of phenol and 2-, 3- and 4-monochlorophenols by irradiation with visible light in aqueous alkaline solution in the presence of photosensitizers and oxygen is described. The reactions were carried out in the absence or presence of detergents. The photosensitizers used were Al(III), Zn(II) and Ga(III) complexes of 2,9,16,23-tetrasulphophthalocyanine (1a–1c), 5,10,15,20-tetrakis(4-carboxy-phenyl)porphyrin (2), a cationically charged perylene tetracarboxylic acid diimide (3), rose bengal (4) and methylene blue (5). The photosensitizers exhibit different activities and photo-oxidative stabilities which are strongly dependent on the pH, hydrolysis sensitivity and aggregation tendency. Singlet oxygen, obtained by photoinduced energy transfer from the excited photosensitizers, dominates the initial steps of photo-oxidation. A reaction sequence is proposed on the basis of the identification of carbon dioxide and maleic or fumaric acid as the products of photo-oxidation in the absence of detergent and the evaluated mass balances.