STRUCTURAL AND ELECTRONICAL CONTROL OF METAL IONS SUPPORTED ON OXIDES

氧化物负载金属离子的结构和电子控制

• 批准号: 63550589
• 负责人: KAZUSAKA Akio
• 金额: $ 1.28万
• 依托单位: FACULTY OF VETERINARY MEDICINE, HOKKAIDO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-63550589/
• 关键词: Silica-supported catalyst; Cupric acetate; Fixed copper complex; Copper-oxygen adducts; Molybdenum catalyst; Molybdosilic acid; Fixed complex electrode; Reduction of carbon dioxide; シリカ担持コバルト触媒; 炭酸ガスのメタン化反応; 固定化コバルト・ポルフィリン錯体電極; 炭酸ガスの電解還元; 高温焼成

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.

1. 制备二氧化硅负载氧化铜催化剂时醋酸铜与二氧化硅载体的相互作用：研究了铜离子前驱体醋酸铜与二氧化硅载体的相互作用以及一氯、二氯和三氯乙酸铜的相互作用。通过IR或ESR技术发现二氧化硅上的OH-基团通过将配合物配位到末端位置来稳定配合物。铜吡啶配合物Cu(Py)_n n = 3-4，固定在二氧化硅或沸石上，并在2-[2-(tricnlotosilyl)-乙基]吡啶修饰的沸石上。该配合物易于还原氧化，在二氧化硅上形成Cu:O_2 = 2:1或在沸石上形成1:1的氧加合物，对苯酚的二聚或聚合具有一定的催化活性和选择性。沸石超笼的连续甲基化通过其疏水性提高了其催化活性，表明其与酶反应相似。二氧化硅载体在二氧化硅负载钼催化剂中的作用：二氧化硅上的钼在CO气氛下容易被二氧化硅诱导的四面体结构光还原。与水接触得到12钼硅酸，表现出固体酸的催化性能。将钴离子或钴卟啉络合物固定在无机基质上及其对CO_2的催化还原性能：将四苯基卟啉钴（CoTPP）固定在4-[2-（三氯硅基）乙基]吡啶或亚硫酰氯吡啶衍生物修饰的氧化锡或玻碳上，研究了其结构和对CO_2的电催化还原性能。CoTPP/Py的形成在光谱上得到证实。电还原CO_2具有较高的催化活性。

项目成果

A.Kazusaka: "Catalysis on a Mo(CO)_6 derived supported molybdenum catalysts." J.Catal.111. 50-58 (1988)

A. Kazusaka：“Mo(CO)_6 衍生的负载型钼催化剂的催化。”

A. Kazusaka: "Catalysis on a Mo(CO)_6 derived supported molybdenum catalysts." J. Catalysis, 111, 50-58, 1988.

A. Kazusaka：“Mo(CO)_6 衍生的负载型钼催化剂的催化。”

A. Ogata: "Catalytic evidence of formation of water-induced silicomolybdic acid on a MoO_3/SiO_2." Chem., Lett., 1989, 15-18, 1989.

A. Ogata：“在 MoO_3/SiO_2 上形成水诱导硅钼酸的催化证据。”

Y. Ukisu: "Spectroscopic studies of the interaction of cupric acetate or cupric mono-, di-, or tri-chloroacetate hydrate with silica." Z. Phys. Chem., N. F., 158, 189-199, 1988.

Y. Ukisu：“乙酸铜或一氯乙酸铜、二氯乙酸铜或三氯乙酸铜水合物与二氧化硅相互作用的光谱研究。”

A.Ogata: "Silicomolybdic acid induced with water on a MoO_3/SiO_2 catalyst.-Its acidic and oxidizing propre^+,ies-" "Acid-Base catalysis",ed.,K.Tanabe et al.,Kodansha-VHC. 249-254 (1989)

A.Ogata：“在 MoO_3/SiO_2 催化剂上用水诱导硅钼酸。-其酸性和氧化性质-”“酸碱催化”，ed.，K.Tanabe 等人，Kodansha-VHC。