Studies on development and analysis of highly active polymer catalysts towards creation of new energy resource

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Electron transfer in a photoexcited state was investigated which is of importance for photochemical energy conversion. Ru(bpv)_3^<2+> and methylviologen (MV^<2+>) were adsorbed into a Nafion film and the electron transfer from the photoexcited Ru complex to MV^<2+> was studied. In order to elucidate the role of water, wet and dry films were compared with respect to the electron transfer. From the photoluminescence intensity of the Ru complex and its decay as a function of the MV^<2+> concentration, it was found that the electron transfer takes by a static mechanism for which the molecules do not move during the electron transfer. For the dry film the molecules do not move at all resulting in an entirely static mechanism. However, for the wet film, the molecules can move a little bit during the photoexcited state resulting in the partial involvement of a dynamic mechanism, and the reaction efficiency was much higher than that of the dry film. Electron transport in a ground state was studied electrochemically, and it was clarified that the mechanism, i.e., diffusion of molecules or charge hopping between molecules, are different depending on the system and the positive or negative charge.As water oxidation catalysts, the catalytic activity of Ru complexes with ammonia or bipyridine ligands has been analyzed. The effects of interaction between the catalyst molecules in the polymer film on the four-electron process and on the bimolecular decomposition have been investigated. It was found that porphines and phthalocyanines dispersed in a polymer film has a high activity for the electrocatalytic proton reduction, and their fundamental behavior was studied.