| Project/Area Number |
09304063
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| Research Category |
Grant-in-Aid for Scientific Research (A).
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | TOKYO METROPOLITAN UNIVERSITY |
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Principal Investigator |
INOUE Haruo Tokyo Metropolitan University, Graduate Course of Engineering, Professor, 工学研究科, 教授 (90087304)
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| Co-Investigator(Kenkyū-buntansha) |
SHIMADA Tetsuya Tokyo Metropolitan University, Graduate Course of Engineering, Research Associate, 工学研究科, 助手 (50252317)
TACHIBANA Hiroshi Tokyo Metropolitan University, Graduate Course of Engineering, Assistant Professor, 工学研究科, 講師 (00163478)
SGIRAGAMI Tsutomu Miyazaki University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (60235744)
TAKAGI Shinsuke Tokyo Metropolitan University, Graduate Course of Engineering, Research Associate, 工学研究科, 助手 (40281240)
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| Project Period (FY) |
1997 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥35,800,000 (Direct Cost: ¥35,800,000)
Fiscal Year 2000: ¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 1999: ¥3,800,000 (Direct Cost: ¥3,800,000)
Fiscal Year 1998: ¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 1997: ¥22,300,000 (Direct Cost: ¥22,300,000)
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| Keywords | Photochemical splitting of water / Porphyrin / Epoxidation / Oxygenation / Metal complex / Artificial photosynthesis / Antimony / Ruthenium / アルケン / オレフィン / 銀錯体 |
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| Research Abstract |
Photo-redox reactions with water as an electron donor and oxygen atom donor sensitized by metalloporphyrin such as antimony (V) porphyrin and ruthenium (II) porphyrin have been found in this research project. The redox reaction could be one of the most promising approaches to an artificial photosynthesis. The following results have been obtained.
1) Investigation for getting highly efficeint photochemical oxygenation reaction sensitized by ruthenium (II) porphyrin.
For the photochemical oxygenation reactions of alkene with water as an electron and an oxygen atom donor, detailed study on photochemical reactivity, product distribution, specificity of substrate, and stability of the sensitizer during the photoreaction revealed that Ru (II) complex had high quantum yields of 0.5 and 0.4 with high selectivity of 95% and 99% for the epoxidations of cyclohexene and norbornene, respectively.
2) The reaction mechanism of the photochemical oxygenation of alkenes were investigated by laser flash photolysis method. A characterization of the triplet excited state of Ru (II) porphyrin, electron transfer through the triplet state, and ligation of hydroxide ion to the resultant cation radical of Ru (II) porphyrin were clearly observed, giving crucial information about factors controlling the reactivity and the selectivity against substrate.
3) Development of photochemical electron transfer reaction in novel anisotropic chemical reaction field such as layered metal oxide semiconductor as a non-sacrificial electron accepting system was attempted. Zinc porphyrin was successfully intercalated into niobate layered semiconductor for the first time in the ppresence of cationic surfactants. Detailed studies by time resolved fluorescence spectroscopy have revealed that a visible light irradiation to zinc porphyrim induced an efficient electron injection to the layered semiconductor to evolve hydrogen.
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