2001 Fiscal Year Final Research Report Summary
Photochemical Epoxidation with Water as Electron and Oxygen Source upon Visible Light Irradiation
| Project/Area Number |
11555231
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 展開研究 |
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| Research Field |
工業物理化学
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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, 大学院・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, 大学院・工学研究科, 助手 (50252317)
TACHIBANA Hiroshi Tokyo Metropolitan University, Graduate Course of Engineering, Assistant Professor, 大学院・工学研究科, 講師 (00163478)
SGIRAGAMI Tsutomu Miyazaki University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (60235744)
EHARA Shunji Dainippon Ink and Chemicals, Inc. Epoxy Compounds Technical Department, General Manager, エポキシ技術クリレープ部長, 部長
TAKAGI Shinsuke Tokyo Metropolitan University, Graduate Course of Engineering, Research Associate, 大学院・工学研究科, 助手 (40281240)
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| Project Period (FY) |
1999 – 2001
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| Keywords | Photochemical splitting of water / Porphyrin / Epoxidation / Oxygenation / Metal complex / Artificial photosynthesis / Antimony / Ruthenium |
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| Research Abstract |
Efficient epoxidation of alkenes with water as an electron donor and oxygen atom donor sensitized by metalloporphyrin such ruthenium (II) porphyrin has been revealed to proceed upon visible light irradiation without using strong oxidizing agents in this research project The epoxidation reaction could be one of the most promising approaches to get an useful reaction which can utilize visible light. The following results have been obtained through the term of the present research.
1) Development of novel composite reaction systems for a highly efficient photochemical epoxidation reaction sensitized by ruthenium (II) porphyrin : For establishing the efficient photochemical oxygenation reactions of alkene with water as an electron and an oxygen atom donor, detailed study on construction of two independent systems 1) having an efficient absorption of visible light and a high reactivity to form the active reactive intermediate, cation radical of porphyrins, through an electron transfer from t
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he excited porphyrins to electron acceptors, and 2) cation radical of the porphyrins. Novel composite systems combining the two independent systems by a hole transfer reaction was developed.
2) Extension of substrates employed in the photochemical epoxidation : Various alkenes such as cyclic alkenes (cyclohexene, norbornene, and cyclooctene), aromatic alkenes (styrene and stilbene) and acyclic alkenes (1-hexene) were examined for the photochemical epoxidation. Among them norbornene has been revealed to exhibit a high selectivity of epoxide formation in nearly to 100 % with a high reactivity of the quantum yield of ca.0.4.
3) Development of novel anisotropic reaction fields for the photochemical electron transfer reaction : Novel anisotropic reaction fields such as layered metal oxide semiconductors as non-sacrificial electron accepting systems was adopted for the photo-redox reactions. A multi-channel glass plate with well ordered strucute where straight channel penetrating and being allined in perpendicular to the plate was also used for the anisotropic reaction fields. Less
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