ヘテロポリ酸触媒の擬液相挙動と超強酸性の総括的定式化

杂多酸催化剂的准液相行为和超酸性的综合公式

• 批准号: 10450299
• 负责人: MISONO Makoto
• 金额: $ 8.83万
• 依托单位: Kogakuin University (1999)The University of Tokyo (1998)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10450299/
• 关键词: Heteropolyacid; Solid acid catalyst; Pseudoliquid; Transient-response method; Solid-state NMR; Hydrogen bond; Acidic proton; Methyl t-butyl ether; メチルtーブチルエーテル; 超強酸性

The important chaeacteristics of heteropolyacid catalysts, ''pseudoliquid behavior'' (found by this research group), was elucidated by applying comprehensively transient-response method, NMR, IR, etc.(1) The very high catalytic activity of a Dawson-We heteropolyacid for the synthesis of methyl t-butyl ether was demonstrated to be due to the formation of an active pseudoliquid phase brought about by the eclipse shape of polyanion.(2) The states and dynamic behavior of acidic protons in the pseudoliquid phase of 12-tungstophosphoric acid were clarified by solid-state P, H, O-NMR and IR. High mobility of acidic proton was shown by the temperature dependency of P-NMR spectra.(3) The surface acidity of active acidic cesium salts was directly quantitized by IR observation of adsorbed CO, which exhibited a close correlation with their catalytic activity.

综合应用瞬态响应方法、核磁共振、红外等技术，阐明了杂多酸催化剂的重要特征“拟液体行为”（本课题组发现）。（1）Dawson-We具有极高的催化活性杂多酸用于合成甲基叔丁基醚被证明是由于杂多酸的蚀形形成了活性假液相。 (2)通过固态P、H、O-NMR和IR阐明了12-钨磷酸拟液相中酸性质子的状态和动态行为。 P-NMR谱图显示了酸性质子的高迁移率。(3)活性酸性铯盐的表面酸度通过吸附CO的红外观察直接定量，其与催化活性密切相关。

项目成果

Sawami SHIKATA and Makoto MISONO: "Strong Influence of the Polyanion Structure on the Secondary of Solid Heteropolyacids and their Catalytic Activity; Methyl tert Butyl Ether Synthesis in the Pseudo-liquid phase of Heteropolyacids"Chem. Commun.. 1293-1294

Sawami SHIKATA 和 Makoto MISONO：“聚阴离子结构对固体杂多酸的次级及其催化活性的强烈影响；杂多酸的伪液相中甲基叔丁基醚的合成”Chem。

K.Inumaru et.al.: "Inhomogeneity in the Interaction Between Methanol Molecules and Bronsted Acid Sites of H-ZSM-5 Directly Detected by 2D CPMAS ^<13>C NMR Spectroscopy" Chem.Commun.1489-1490 (1998)

K.Inumaru 等人：“通过 2D CPMAS ^ 13 C NMR 光谱直接检测到甲醇分子与 H-ZSM-5 布朗斯台德酸位点之间相互作用的不均匀性” Chem.Commun.1489-1490 (1998)

Moritaka MIZUNO and Makoto MISONO: "Heterogeneous Catalysis(Polyoxometalates)"Chem. Rev.,. 199-217 (1998)

Moritaka MIZUNO 和 Makoto MISONO：“多相催化（多金属氧酸盐）”Chem。

Makoto Misono and Yasukazu Saito: "Catalytic Chemistry"Maruzen. 172 (1999)

Makoto Misono 和 Yasukazu Saito：“催化化学”Maruzen。

Takaya SAITO, Gaku KOYANO, and Makoto MISONO: "Surface Acidity of Cesium Hydrogen Salts of 12-Tungstophosphoric Acid Characterized by Low-Temperature CO Adsorption"Chem.Lett.. 1075-1076 (1998)

Takaya SAITO、Gaku KOYANO 和 Makoto MISONO：“通过低温 CO 吸附表征的 12-钨磷酸铯氢盐的表面酸度”Chem.Lett.. 1075-1076 (1998)