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Poly-alkoxides as Functional Polymer Photocatalyst

Metal alkoxides polymerize to form metal-oxygen polymers. In the present work polymers and co-polymers of metal alkoxides were prepared and their physical and chemical properties were investigated using tetra-hydrofuran (THF) as solvent. One of the properties is photocatalytic activity and another is visible light excited ESR absorption. Tetrabutyl orthotitanate, pentaethyl niobate, and other alkoxides which dissolve in THF were polymerized under fluorescent lamps. ESR spectra were recorded while the polymer was illuminated by a halogen lamp. Catalytic activity was measured using visible light and gas chromatograph. All polymers gave visible light excited ESR spectra. The analysis of ESR intensity change caused by the light-on and light-off procedure have elucidated that there are more than two excited states, the shorter lived one of which is the reaction intermediate of photocatalysis. Among the copolymers of (-TiO-O-NbO-O-) copolymers, Nb 10–20% copolymers gave the highest catalytic activity. It has also been found that the copolymer which has the largest number of Ti3O2 unit has the highest activity. These results seem to indicate that the catalyst polymer is a linear polymer. The merit of using alkoxide polymers and copolymers as photocatalyst lies in the facts that in these stable radical type molecules the absorption of visible light is made possible and that in these molecules the catalytic reaction sites are more accessible to the reaction substrate than 3-dimensional crystalline materials.