Φωτοκαταλυτική αναγωγή του νερού με χρήση διθειολενικών συμπλόκων

Abstract

This work was conducted within the PhD thesis in the field of Inorganic Chemistry andInorganic Technology, at the Inorganic Laboratory of the Chemistry Department of UoA. Itcovers literature photocatalytic systems for hydrogen production with homogeneousphotocatalysis, whereas experimental deals with the synthesis and characterization of complexesthat show strong absorptions in the visible region and could act as chromophores orphotocatalysts for hydrogen production. During this thesis complexes [Cu(4,4΄-dcbpy)2]Cl,where dcbpy=2,2'-bypiridine-4,4'-dicarboxylate and [Cu(5,5΄-dcbpy)2]Cl, where dcbpy=2,2'-bypiridine-5,5'-dicarboxylate, which can be used as proton reductive catalysts, have beensynthesized. Also, rhenium complexes have been prepared following the literature procedures:[Rebpy(CO)3Br], [Rebpy(CO)3Cl], [Rebpy(CO)3(MeCN)](PF6), [Rebpy(CO)3(NCS)](PF6),which can be used as chromophores. All these complexes were characterized byphysicochemical methods, FT-IR, UV-Vis, 1H-NMR, cyclic voltammetry (CV), andspectroscopy methods, emission. During this thesis the photocatalytic systems have been testedfor hydrogen production where the complexes [Rebpy(CO)3Br], [Rebpy(CO)3Cl],[Rebpy(CO)3(MeCN)](PF6), [Rebpy(CO)3(NCS)](PF6), [Ru(bpy)3]Cl2, [Ru(dcbpy)2Cl2],[Ru(dcbpy)2qdt] were used as photosensitizers (PS), the complexes [Ni{S2C2(Ph)2}2],[Ni{S2C2(Ph)2}2](NEt4), [Ni{S2C2(Ph)(Ph-OCH3-4)}2], [Ni{S2C2(Ph)(Ph-OCH3-4)}2](NEt4),[Ni{S2C2(Ph-OCH3-4)2}2], [Ni{S2C2(Ph-OCH3-4)2}2](NEt4), [Ni{S2C2(Ph)2}2C3],[Ni{S2C2(Ph)(Ph-OCH3-4)}2C3], [Ni{S2C2(Ph-OCH3-4)2}2C3], [Ni(bdt)2](TBA), [Ni(bdt)2C3],[Ni(S4C3)Fe(CO)Cp*](BF4), [W{S2C2(C6H5)2}3], [W{S2C2(C6H5)2}3](TBA), [Cu(4,4΄-dcbpy)2]Cl, and [Cu(5,5΄-dcbpy)2]Cl as proton reductive catalysts, and the speciestriethanolamine TEOA and ascorbic acid/sodium ascorbate as sacrificial electron donors. Σhesolvents used were DMF, DMF/ H2O, CH3CN/H2O, acetone, CH2Cl2, H2O. For the detection ofH2 a gas chromatographer with a thermal conductivity detector (TCD) was used.