| Project/Area Number |
11450303
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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 |
触媒・化学プロセス
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| Research Institution | THE UNIVERSITY OF TOKYO |
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Principal Investigator |
MIZUNO Noritaka GRADUATE SCHOOL OF ENGINEERING, THE UNIVERSITY OF TOKYO, PROFESSOR, 大学院・工学系研究科, 教授 (50181904)
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| Co-Investigator(Kenkyū-buntansha) |
KOYANO Gaku GRADUATE SCHOOL OF ENGINEERING, THE UNIVERSITY OF TOKYO, ASSISTANT, 大学院・工学系研究科, 助手 (20292774)
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| Project Period (FY) |
1999 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥13,600,000 (Direct Cost: ¥13,600,000)
Fiscal Year 2001: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 2000: ¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 1999: ¥8,700,000 (Direct Cost: ¥8,700,000)
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| Keywords | Selective oxidation / Hydrocarbon / Liquid phase / Silicotungstate / Iron / メタン / 過酸化水素 / 水 / バナジウム / 反応機構 / ポリオキソメタレート / 合成 |
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| Research Abstract |
The Keggin-type di-iron-substituted silicotungstate, γ-SiW_10 {Fe(OH_2)}_2O_<38>^<6-> (I), was synthesized by the reaction of the lacunary [γ-SiW_<10>O_<36>]^<8-> with Fe(NO_3)_3 in an acidic aqueous solution and isolated as the tetra-n-butyl ammonium salt (TBA-I). It was characterized by various analyzes and the structure with the oxo-bridged di-iron site was clarified. TBA-I was stable and catalyzed selective oxidation of various alkenes and alkenes with hydrogen peroxide : Cyclohexane, adamantane, n-hexane, and n-pentane were catalytically oxidized. Even lower alkenes such as methane, ethane, propane, and n-butane were catalytically oxidized. It was remarkable that the efficiency of hydrogen peroxide utilization to oxygenated products reached up to ca. 100 % for the" oxidation of cyclopean and adamantine. Alkenes were mainly deoxidized with hydrogen peroxide. It was demonstrated that the TBA-I showed high turnover number of 135-147 for the oxidation of cyctohexane with 1 atm oxygen. The catalytic activity greatly depended on structures of iron centers and TBA-I showed the highest turnover number of 135-147 for the oxidation of cyclopean with 1 atm oxygen among iron and tri-transition-metal-substituted silicotungstates.
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