Effect of metal phthalocyanine complex aggregation on the catalytic and photocatalytic oxidation of sulfur containing compounds

• Published in: Journal of molecular catalysis. A, Chemical Chemical, 1999-01, Vol.137 (1), p.15-22
• Main Authors: Iliev, V., Alexiev, V., Bilyarska, L.
• Format: Article
• Language: English
• Subjects: Catalysis; Catalysts: preparations and properties; Catalytic reactions; Chemistry; Exact sciences and technology; General and physical chemistry; Mercaptans; Oxidation; Photocatalysis; Phthalocyanine complexes; Solvent effect; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Thiosulphates
• ISSN: 1381-1169; 1873-314X
• DOI: 10.1016/S1381-1169(98)00069-7

Water soluble zinc (II) 2,9,16,23-phthalocyanine tetrasulfonic acid [ZnPc(SO 3H) 4], zinc (II) 2,9,16,23-phthalocyanine tetracarboxylic acid [ZnPc(COOH) 4] and sterically hindered bulky zinc(II) 2,9,16,23-tetrakis(8-quinolineoxy-5-sulfonicacid)-phthalocyanine [ZnPc(QnSO 3H) 4] complexes have been studied as photocatalysts for oxidation of 2-mercaptoethanol and sodium thiosulfate. The ZnPc(QnSO 3H) 4 complex exhibited the highest photocatalytic activity due to its low aggregation degree in aqueous medium. In the presence of tetrabutylammonium chloride, quinoline and ethanol additives the monomerization degree of the ZnPc(SO 3H) 4 and ZnPc(COOH) 4 complexes is increased, their photocatalytic activity being close to that of ZnPc(QnSO 3H) 4. Because of high aggregation degree of ZnPc(SO 3H) 4 and ZnPc(COOH) 4 in viscous medium, the quantum yields of singlet dioxygen generation and the photocatalytic oxidation rates of the sulfur-containing compounds are decreased. The photocatalytic activity of ZnPc(QnSO 3H) 4 is slightly changed in viscous medium and in the presence of additives. The low aggregation degree of this complex allowed to establish enhanced and lowered rates of photocatalytic oxidation of 2-mercaptoethanol and sodium thiosulfate, respectively, on increasing medium viscosity. The effect of medium viscosity on ZnPc(QnSO 3H) 4 photocatalyzed oxidation of the two substrates is discussed.