Development of Catalytic Process for Photooxidation with Fluorinecontaining Molecules and Their Assemblies
| Project/Area Number |
05650782
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
触媒・化学プロセス
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| Research Institution | Osaka University |
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Principal Investigator |
WADA Yuji Osaka University Faculty of Engineering, Associate Professor, 工学部, 助教授 (40182985)
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| Co-Investigator(Kenkyū-buntansha) |
MURAKOSHI Kei Osaka University Faculty of Engineering, Assistant Professor, 工学部, 助手 (40241301)
YANAGIDA Shozo Osaka University Faculty of Engineering, Professor, 工学部, 教授 (10029126)
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| Project Period (FY) |
1993 – 1994
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| Project Status |
Completed (Fiscal Year 1994)
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| Budget Amount *help |
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1994: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1993: ¥1,600,000 (Direct Cost: ¥1,600,000)
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| Keywords | photocatalyst / artificial photosynthesis / water / oxidation / fluorinated compound / Fenton reaction / phenol / aromatic compound / ペルフルオロパラフェニレン / 光酸化 / 水光分解 / 混晶 / 部分フッ素化 / フェントン反応 / 水酸化 |
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| Research Abstract |
1) We succeeded in photo-splitting of water molecule into dihydrogen and hydroxyl radical with Rh-supported perfluoropoly (rho-phenylene) under UV irradiation. Hydroxyl radical formed via one-electron oxidation of water molecule is captured by benzene molecule in the reaction system, resulting in formation of phenol. The amount of H_2 evolved in the system is half of that expected from the amount of phenol formed and the reaction stoicheometry. It is due to consumption of electrons in the decomposition of perfluoropoly (rho-phenylene) through its radical anion and reduction of benzene. Molecular orbital calculations show that a water molecule interacts with fluorinated phenylene ring, suggesting an important role of the attractive interaction in the photooxidation of water.
2) Laser flash photlysis was carried out in order to reveal the mechanism of photooxidation of water with perfluorooligo (rho-phenylene) as a photocatalyst. The excited state of perfluorooligo (rho-phenylene) is readily converted to triplet stated through intersystem crossing. It is proposed that the triplet state of perfluorooligo (rho-phenylene) is oxidatively quenched to be converted to its cation radical, which acts as an oxidizing species of water molecule.
3) The cyclic voltammetry measurements of partially fluorinated oligo (rho-phenylene) have shown that the reduction and oxidation potentials shifts to the positive side with increase in the degree of fluorination.
4) Octafluorophenazine was sythesized. This compound induces one-electron oxidation of water under visible light irradiation.
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Report
(3 results)
Research Products
(18 results)
