A Study of Catalyst Design by Use of Molecular or Crystalline Mixed Oxides

利用分子或晶体混合氧化物设计催化剂的研究

• 批准号: 62470070
• 负责人: MISONO Makoto
• 金额: $ 4.93万
• 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: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-62470070/
• 关键词: Molecular or crystalline mixed oxides; Heteropoly acids; Solid-state NMR; Perovskite; V-P oxides; ブタン酸化; プロトン化エタノール; V-P系複合酸化物; 触媒構造; 擬液相; Molecular or crystalline mixed oxides; Heteropoly acids; Solid-state NMR; Perovskite; V-P oxides; ブタン酸化; プロトン化エタノール; V-P系複合酸化物; 触媒構造; 擬液相

Catalyst design based on molecular or crystalline mixed oxides was attempted. Heteropoly compounds, perovskite-type mixed oxides and V-P oxides were examined for this purpose by elucidating reaction mechanism and the interaction between reactants and the active sites under the working conditions. Furthermore, the effects of the formation of their thin films and ultrafine particles on the catalytic performance were studied.(1) In situ measurement of pseudoliquid phase Chemical shifts of molecules in the pseudoliquid phase was analyzed by FT-IR and solid state NMR. Protonated ethanol monomer, dimer, and ethoxy group, which are important intermediates for the dehydration, were directly detected by ^1H and ^<13>C NMR. In situ FT-IR measurement supports the presence of these species. Catalyst for selective oxidation of aldehyde was designed. Control of acidity by substitution of alkali for H^+ and increase of oxidation ability by partial substitution of V for Mo (polyatom) were found to be effective for the design of selective catalyst.(2) Catalytic properties of thin films of perovskites The surface structure of LaCoO_3/ZrO_2, which was highly active for catalytic combustion, was characterized by XPS, TEM, SEM, EDX, and NO adsorption. It was shown that monolayer thin film of LaCoO_3 or the like covered uniformly the surface of ZrO_2.(3) Control of morphology of V-P-oxides The effect of morphology of (VO)_2P_2O_7, which is efficient catalyst for the selective oxidation of butane to maleic anhydride, was studied. It was concluded that large crystallites grown in the direction of [020] was high selective and was stable under the working conditions.

尝试了基于分子或晶体混合氧化物的催化剂设计。为此目的检查了杂色化合物，钙钛矿型混合氧化物和V-P氧化物，通过阐明反应机理以及反应物与工作条件下的活性位点之间的相互作用。此外，还研究了其薄膜和超铁颗粒对催化性能的影响。（1）通过FT-IR和固态NMR分析了伪液相中分子分子的伪液相化学移位的原位测量。质子化的乙醇单体，二聚体和乙氧氧基群，它们是脱水的重要中间体，由 ^1H和 ^1H和 ^<13> C NMR直接检测到。原位FT-IR测量支持这些物种的存在。设计了用于选择性氧化醛的催化剂。 Control of acidity by substitution of alkali for H^+ and increase of oxidation ability by partial substitution of V for Mo (polyatom) were found to be effective for the design of selective catalyst.(2) Catalytic properties of thin films of perovskites The surface structure of LaCoO_3/ZrO_2, which was highly active for catalytic combustion, was characterized by XPS, TEM, SEM, EDX, and NO adsorption.结果表明，lacoo_3或类似类似的单层薄膜均匀地覆盖了Zro_2的表面。（3）控制V-P-氧化物的形态（vo）_2P_2O_7的形态的影响，这是对丁烷对马利甲烷的选择性氧化的有效催化剂，研究了对马利甲烷的选择性氧化。得出的结论是，朝着[020]方向生长的大型微晶具有很高的选择性，并且在工作条件下是稳定的。