STRUCTURAL AND ELECTRONICAL CONTROL OF METAL IONS SUPPORTED ON OXIDES

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1. Interaction of cupric acetate with silica support in the preparation of a silica- supported copper oxide catalyst: Interaction of with cupric acetate, a precursor of cupric ions, with silica support was studied as well as cupric mono-, di- and tri-chloro acetate. An OH- group on silica was found to stabilize the complexes by coordinating it to the terminal position by an IR or ESR technique.2. Copper-pyridine complex fixed on silica or in zeolite, and its structural and catalytic properties: Copper-pyridine complex, Cu(Py)_n n = 3-4, was found to be fixed on silica or in zeolite modified with 2-[2-(tricnlotosilyl)-ethyl] pyridine. This complex showed to be reduced and oxidized easily, to form its oxygen adducts of Cu:O_2 = 2:1 on silica or 1:1 in zeolite, and to give specific catalytic activity and selectivity in dimerization or polimerization of phenol. Successive methylation of supercage of zeolite increased its catalytic activity by its hydrophobic property, indicating the similarity with an enzymic reaction.3. Role of silica support in a silica-supported molybdenum catalyst: Molybdenum species on silica was found to be photoreduced easily in its terahedral structure induced by that of silica under CO atmosphere. Exposure of it to water gave 12 molybdosilic acid on silica, which showed catalytic property of a solid acid.4. Cobalt ions or cobalt porphyrine complex fixed on inorganic matrix and their catalytic property to reduction of CO_2: Fixation of cobalt tetraphenyl porphyrine ( CoTPP ) was carried out on tin oxide or glassy carbon modified with 4-[2-(trichlorosilyl)ethyl] pyridine or pyridine derivative of thionyl chloride with studies of its structure and electro- catalytic properties to reduction of CO_2. Formation of CoTPP/Py was confirmed spectroscopically. High catalytic activity was found to electroreduction of CO_2.