| Project/Area Number |
15360430
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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 | 一般 |
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| Research Field |
Catalyst/Resource chemical process
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| Research Institution | Osaka University |
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Principal Investigator |
HIRAI Takayuki Osaka University, Research Center for Solar Energy Chemistry, Professor, 太陽エネルギー化学研究センター, 教授 (80208800)
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| Co-Investigator(Kenkyū-buntansha) |
SHIRAISHI Yasuhiro Osaka University, Research Center for Solar Energy Chemistry, Associate Professor, 太陽エネルギー化学研究センター, 助教授 (70343259)
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| Project Period (FY) |
2003 – 2005
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| Project Status |
Completed (Fiscal Year 2005)
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| Budget Amount *help |
¥10,600,000 (Direct Cost: ¥10,600,000)
Fiscal Year 2005: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2004: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2003: ¥8,600,000 (Direct Cost: ¥8,600,000)
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| Keywords | Photocatalyst / Nanopores / Porous materials / Organic synthesis / Silica / Titanium dioxide / 高選択的有機合成 / オレフィン / エポキシド / ケトン / ゼオライト / 選択的物質変換 / チタノシリケート / 無害化・再資源化 |
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| Research Abstract |
This research work aims at the design and development of selective organic transformation processes using organized nanopores as the photocatalytic reactor.
We have found that Ti-containing porous silica (titanosilicate) catalysts promote a selective conversion of molecules having a size close to the catalyst pores. This catalytic property can be applied for selective transformation of molecules having a size close to the catalyst pores to molecules having a smaller size. We also found that mesoporous titanium dioxide catalyzes a selective conversion of molecules adsorbed well on the catalyst surface. This catalytic property can be applied for selective transformation of well-adsorbed molecule to less-adsorbed molecule : for example, a direct hydroxylation of benzene to phenol was successfully promoted with >80% selectivity. We also found that a zeolite containing an organic photosensitizer within the supercage, when activated by a visible light with molecular oxygen, promote a selectiv
… More
e transformation of olefins to carbonyl compounds with >99% selectivity.
We also aimed at the selective organic transformation through the precise designing of the photocatalytic active species. We found that Ti-containing mesoporous silica (meso-titanosilicate), when activated by UV irradiation with molecular oxygen, catalyzes selective photoepoxidation of olefins with very high selectivity. We also found that Cr-containing silica, when activated by visible light with molecular oxygen, catalyzes selective transformation of cyclohexane to cyclohexanone and partial oxidation of olefins. In addition, we synthesized new V-containing mesoporous silica, which contains V-oxide species "confined" within the silica layer. The V-oxide species are stable against water and show high photocatalytic activity.
We also aimed at the selective organic transformation with organic polymer catalysts. We synthesized an amphiphilic dendrimer photocatalyst containing a photosensitizing core within the hydrophobic environment surrounded by hydrophilic dendrons. The photocatalyst efficiently catalyzes a photooxygenation of sulfides to sulfoxides. We also synthesized a random polymer photocatalyst comprised of an organic photosensitizing molecule and poly-N-isopropylacrylamide. We found that the catalyst shows unprecedented temperature-dependent photocatalytic activity for oxygenation in water. Less
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