Development of Catalytic Reaction Fiekl From Nano-to Subnano-Scale by Utilizing Properties of Large Oxide Cluster

利用大氧化物团簇的性质发展从纳米到亚纳米尺度的催化反应

• 批准号: 14078207
• 负责人: MIZUNO Noritaka
• 金额: $ 14.85万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14078207/
• 关键词: 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

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.

双核过氧钨酸盐K2[{W(=O)(O_2)_2(H_2O)}_2(μ-O)]·2H_2O(W_2)在温和的反应条件下可作为水中H_2O_2的环氧化催化剂。此外，我们还通过将二氢咪唑基离子液体碎片共价锚定在SiO_2上来制备有机-无机杂化载体材料，以开发可回收和可循环的环氧化催化剂。缺位十钨硅酸盐([γ-SiW_&lt；10&gt；O_&lt；34&gt；(H_2O)_2]^&lt；4-&gt；催化H_2O_2环氧化反应[(γ-SiW_&lt；10&gt；O_&lt；32&gt；(H_2O)_2)_2(μ-O)_2]^&lt；4-&gt；，是由部分质子化的双缺位空位Keggin型多金属氧酸盐[γ-Siw_&lt；10&gt；O^&lt；34&gt；34&gt；(H_2O)_2]^&lt；4-&gt；，在无水有机溶剂中。相反，在没有CF3SO3H的情况下，([γ-SiW_&lt；10&gt；O_&lt；34&gt；(H_2O)_2]^&lt；4-&gt；的二聚化形成了闭合的团簇([γ-SiW_&lt；10&gt；O_&lt；32&gt；_2(μ-O)_4]^&lt；8-&gt；.而具有共同[Siw_&lt；10&gt；O^&lt；32&gt；]片段的([γ-SiW_&lt；10&gt；O_&lt；34&gt；(H_2O)_2]^&lt；4-&gt；和([γ-SiW_&lt；10&gt；O_&lt；32&gt；_2(μ-O)_4]^&lt；8-&gt；几乎不活跃，而S形状的簇([γ-Siw_&lt；10&gt；O_&lt；34&gt；(H_2O)_2]&lt；4-&gt；有效地促进了基于H_2O_2的环烷酮的Baeyer-Villiger氧化反应。另一方面，通过在([([γ-SiTi_2W_&lt；10&gt；O_&lt；36&gt；(OH)_2}_]^&lt；8-&gt；-Siw_&lt；10&gt；O_&lt；[γ-Siw_&lt；10&gt；O_&lt；[γ-Siw_&lt；O_&lt；36&>；]^&lt；8-&gt；。这种钛取代的多金属氧酸盐具有二聚体结构，与([γ-SiTi_2W_&lt；10&gt；O_&lt；36&gt；(OH)_2]^&lt；8-&gt；的环氧化反应是立体专一性的。

项目成果

Preparation and characterization of Cs2.8H1.2PMo11Fe(H2O)O39•6H2O and investigation of effects of iron-substitution on heterogeneous oxidative dehydrogenation of 2-propanol

• DOI: 10.1021/cm0348996
• 发表时间: 2004-07-13
• 期刊: CHEMISTRY OF MATERIALS
• 影响因子: 8.6
• 作者: Mizuno, N;Min, JS;Taguchi, A
• 通讯作者: Taguchi, A

S.Uchida et al.: "Novel Channeled Compound Based on Cr(III) Trinuclear Complex and Polyoxometalate Aimed for Heterogeneous Catalysis : Synthesis and Structure"Res. Chem. Intemed.. 28・5. 389-396 (2002)

S. Uchida 等：“基于 Cr(III) 三核配合物和多金属氧酸盐的多相催化的新型通道化合物：合成和结构”Res. 28・5。

Heterogeneously catalyzed aerobic oxidative biaryl coupling of 2-naphthols and substituted phenols in water

• DOI: 10.1021/ja050436k
• 发表时间: 2005-05-11
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Matsushita, M;Kamata, K;Mizuno, N
• 通讯作者: Mizuno, N

Synthesis, Structural Characterization, and Catalytic Performance Dititanium-substituted γ-Keggin silicotungstate

合成、结构表征和催化性能

• 发表时间: 2006
• 期刊: Inorg. Chem. 45
• 作者: Y.Goto;K.Kamata;K.Yamaguchi;K.Uehara;S.Hikichi;N.Mizuno
• 通讯作者: N.Mizuno

Efficient Epoxidation of Olefms with >99% Selectivity and Use of Hydrogen Peroxide

效率%20环氧化%20of%20烯烃%20与%20>99%%20选择性%20和%20使用%20of%20氢气%20过氧化物

• 发表时间: 2003
• 期刊: Science 300
• 作者: Keigo Kamata;Koji Yonehara;Yasutaka Sumida;Kazuya Yamaguchi;Shiro Hikichi;Noritaka Mizuno
• 通讯作者: Noritaka Mizuno