| Project/Area Number |
14078207
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | The University of Tokyo |
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Principal Investigator |
MIZUNO Noritaka The University of Tokyo, Graduate School of Engineering, Professor, 大学院工学系研究科, 教授 (50181904)
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| Co-Investigator(Kenkyū-buntansha) |
HIKICHI Shiro Kanagawa University, Faculty of engineering, Professor, 工学部, 教授 (10282857)
内田 さやか 東京大学, 大学院・工学系研究科, 助手 (10361510)
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| Project Period (FY) |
2002 – 2005
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥23,200,000 (Direct Cost: ¥23,200,000)
Fiscal Year 2005: ¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 2004: ¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 2003: ¥5,600,000 (Direct Cost: ¥5,600,000)
Fiscal Year 2002: ¥5,600,000 (Direct Cost: ¥5,600,000)
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| Keywords | nolyoxometalate / tungsten / titanium / hydrogen peroxide / olefin epoxidation / dinuclear peroxotungstate / heterogeneous catalyst / バナジウム / 酸化反応 / ラクトン / オレフィン / エポキシ化 / 機能性固体 / イオン性結晶 / 形状選択性 / オキソクラスター / 微空間 / 制御 |
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| Research Abstract |
The dinuclear peroxotungstate, K2[{W(=O)(O_2)_2(H_2O)}_2(μ-O)]・2H_2O (W2), could act as an effective epoxidation catalyst using H_2O_2 in water under mild reaction conditions. Further, we synthesized organic-inorganic hybrid support materials by covalently anchoring dihydroimidazorium based ionic liquid fragments onto the SiO_2 to heterogenize W2 for the development of recoverable and recyclable epoxidation catalysts.
The epoxidation with H_2O_2 catalyzed by lacunary silicodecatungstate ([γ-SiW_<10>O_<34>(H_2O)_2]^<4->) proceeded with 【greater than or equal】99% selectivity to epoxide, 【greater than or equal】99% efficiency of H_2O_2 utilization, high stereospecificity.
A novel S-shaped disilicoeicosatungustate, [(γ-SiW_<10>O_<32>(H_2O)_2)_2(μ-O)_2]^<4->, is obtained by dehydrative condensation of a partially protonated divacant lacunary Keggin-type polyoxometalate, [γ-SiW_<10>O^<34>(H_2O)_2]^<4->, in an anhydrous organic solvent with CF_3SO_3H. In contrast, the dimerization of ([γ-SiW_<10>O_<34>(H_2O)_2]^<4-> without CF_3SO_3H results in the formation of a closed-shape cluster, ([γ-SiW_<10>O_<32>_2(μ-O)_4]^<8->. While ([γ-SiW_<10>O_<34>(H_2O)_2]^<4-> and ([γ-SiW_<10>O_<32>_2(μ-O)_4]^<8-> with the common [SiW_<10>O^<32>] fragment are almost inactive, the S-shaped cluster ([γ-SiW_<10>O_<34>(H_2O)_2]^<4-> efficiently promotes the H_2O_2-based Baeyer-Villiger oxidations of cycloalkanones.
On the other hand, a novel titanium-substituted silicotungstate cluster of ([γ-SiTi_2W_<10>O_<36>(OH)_2}_]^<8-> is synthesized by the introduction of titanium(IV) ions into a divacant lacunary γ-Keggin-type silicotungstate of ([γ-SiW_<10>O_<36>]^<8->. This titanium-substituted polyoxometalate exhibits a dimeric structure The epoxidation with ([γ-SiTi_2W_<10>O_<36>(OH)_2]^<8-> is stereospecific.
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