Dynamics of Pseudoliquid Phase of Heteropolyacids and Design of New Catalytic Reactions

杂多酸拟液相动力学及新催化反应设计

• 批准号: 03453082
• 负责人: MISONO Makoto
• 金额: $ 4.16万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453082/
• 关键词: Pseudoliquid Phase; Heteropolyacids; Solid Acid Catalysts; Solid-state NMR; Alkylation; X-ray Structure Determination; Dehydration of Ethanol; Ethoxy Group; アルチル化反応; ピナコール転位反応; 部分酸性塩; アルコ-ル脱水反応; ^<13>C NMR; プロトン化アルコ-ル; フェノ-ルのアルキル化; 極性分子

The aims of this study are (i) to elucidate the pseudoliquid phase behavior in catalysis, (ii) to reveal the activated state of the molecules in pseudoliquid phase, and (iii) to construct the new catalytic reaction systems, utilizing the pseudoliquid phase of heteropoly compounds.The results are summarized as follows:(1) The pseudoliquid phase brought about the high catalytic activity for dehydration of alcohols, since nearly all protons in the bulk takes part in catalysis. In addition, unique selectivity for the reaction of polar molecules due to the pseudoliquid phase was obtained.(2) The reaction mechanism of dehydration of ethanol in the pseudoliquid phase of H_3PW_<12>O_<40> was elucidated by using IR and solid state NMR. Protonated ethanol dimer (intermediate for diethyl ether),protonated monomer, and ethoxy group (intermediate for ethylene) were directly detected by ^<13>C solid state NMR.(3) The crystal structure of the complex, [(C_5H_5N)_2H]_3PW_<12>O_<40> was determined by the single crystal X-ray diffraction method, where pyridine molecules are paired forming the (C_5H_5N)-H^+-(NC_5H_5) cation in the structure.(4) By the pseudoliquid phase, the activity of liquid-phase alkylation of phenol was greatly enhanced. H_3PW_<12>O_<40> was much more active than ordinary solid acids and H_2SO_4.

这项研究的目的是（i）阐明催化中的假液相行为，（ii）以揭示分子在伪液相中的激活状态，并（iii）构建新的催化反应系统，利用催化阶段的催化阶段，从而构成了pse的催化阶段。醇的脱水，因为大体中的几乎所有质子都参与催化。此外，通过使用IR和使用IR和固态NMR阐明了乙醇在H_3PW_ <12> O_ <40>的假醇阶段中乙醇脱水的反应机理的独特选择性。（2）乙醇脱水的反应机理。质子化的乙醇二聚体（二乙基醚的中间体），质子化的单体和乙氧基二聚体（乙烯中间体）通过 ^<13> c固态NMR直接检测。分子是成对的，形成（C_5H_5N）-H^+ - （NC_5H_5）结构中的阳离子。（4）通过伪液相，苯酚液相烷基化的活性得到了很大的增强。 H_3PW_ <12> O_ <40>比普通的固体酸和H_2SO_4更活跃。

项目成果

Hiroo MORI: "Factors Controlling the Selectivity of the Oxidation of Acetaldehyde over Heteropoly Compounds" Journal of Catalysis. 131. 133-142 (1991)

Hiroo MORI：“控制乙醛氧化相对杂多化合物选择性的因素”催化杂志。

M. Misono: "New Catalytic Aspects of Heteropolyacids and Related Compounds - To the Molecular Design of Practical Catalysis" Proceedings of 10th International Congress on Catalysis.

M. Misono：“杂多酸和相关化合物的新催化方面 - 实用催化的分子设计”第十届国际催化大会论文集。

Toru NISHIMURA: "High Catalytic Activity of an Insuluble Acidic Caecium Sult of Dodecatunystophosphoic Acid for Liguid Phase Alkylation" Applied Catalysis. 73. L7-L11 (1991)

Toru NISHIMURA：“十二磷酸磷酸铯产物对液相烷基化的高催化活性”应用催化。

Makoto MISONO: "Heterogeneous by Heteroply Compounds. An Altempt of Molecular Design of Practical Solid Acid Acid Catalysts" Catalysis Letters. 12. 63-72 (1992)

Makoto MISONO：“异质化合物的异质性。实用固体酸酸催化剂分子设计的尝试”催化快报。

H. Mori, N. Mizuno, and M. Misono: "Factors Controlling the Selectivity of the Oxidation of Acetaldehyde over Heteropoly Compounds" Journal of Catalysis. 131. 133-142 (1991)

H. Mori、N. Mizuno 和 M. Misono：“控制乙醛氧化相对杂多化合物选择性的因素”催化杂志。