Electrode Processes Utilizing the Interlayer Space of Inorganic Molecular Aggregates a Reaction Zone

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(1) Redox dehaviors of Ru(bpy)^2+_(bpy=2,2 '-bipyridine) and Fe(CN)^3-_ ions at a clay-modified electrode were investigated as a function of acidity of solution, and it was foound that the electrode reaction of cationic species, Ru(bpy)^2+_, is suppressed but that of anionic species, Fe(CN)^3-_, is promoted with an increase in acidity. These results are explained from the viewpoints that the increase in acidity results in an increase in protonation of the clay surface, causing the enhancement of electrostatic interaction between the positively charged electrode surface and the reaction species. In the present study, it has firstly been shown that the charged state of electrode surface plays an important role in electrochemical reactions at clay-modified electrodes.(2) Aniline was incorporated in the interlayer space of clay and then polymerized electrochemically. The electropolymerization was found to proceed so slowly that it took more than ten hours to complete the reaction, giving the suggestion that the rate of electrolytic reactions in the interlayer space of clay is very slow.(3) Microcrystalline Tio_2 incorporated in the interlayer space of clay was used as a photocatalyst for photodecomposition of normal carboxylic acids with different molecular size. It was found that the carboxylic acids the size of which are smsller than the clearance space of the clay can be incorporated in the interlayer space of clay to undergo the reactions, while the larger carboxylic acids can not be incorporated in the interlayer space of clay exhibiting low reactivities.(4) Zeolite-modified electrodes were prepared by using zeolited with different pore size, and redox behaviors of Fe^<2+> ions at the electrodes were investigated. It was found that the redox reactions of the incorporated Fe^<2+> ions can thke place in strongly acidic solutions if the pore size of the zeolite used is larger than the ionic diameters of both hydrated Fe^<2+> ions and electrolyte cations used.