Design of Metallic Catalysts with Molecular Recognizing Function and Their Catalytic Activity for Highly Selective Challenging Reduction Reaction

具有分子识别功能的金属催化剂的设计及其对高选择性挑战性还原反应的催化活性

• 批准号: 18560741
• 负责人: NISHIYAMA Satoru
• 金额: $ 2.42万
• 依托单位: Kobe University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2006
• 资助国家: 日本
• 起止时间: 2006 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18560741/
• 关键词: PtSn alloy; Silica-supported; Ester hydrogenation; rbuvrolactone; 1,4-butandiol; Catalyst surface design; Highly active and selective catalysts; Reduction of environmental imnacts

Hydrogenation of γ-butyrolactone as a model compound of esters has been studied over supported Pt-Sn bimetallic catalysts. Effect of Sn/Pt ratio was also investigated. The Pt-Sn/SiO_2, which Sn/Pt ratio was less than unity, indicated a low activity for the hydrogenation of γ-butyrolactone. The Sn/Pt ratio between 1 and 2 showed the marked enhancement of the activity by the addition of Sn to Pt/SiO_2. X-ray diffraction powder patterns of the catalysts suggested that co-existence of Pt metal and an alloy of Pt-Sn brought about the enhancement of the activity. The catalysts, which Sn/Pt ratio was less than unity, indicated only Pt crystals, whereas the catalysts which Sn/Pt ratio was higher than 2, showed only PtSn alloy phase. The higher activity was observed on the catalysts of which Sn/Pt ratio was in the range between 1 and 2. Other additives in the Pt/SiO_2 catalysts were also investigated for the hydrogenation of γ-butyrolactone. Aluminium, Ge, In, Pb and Ti were tested for the additives of Pt/SiO_2. The addition of Al, Ge, and In indicated no alloy formation with Pt on SiO_2 was observed. The addition of Pb brought about the formation of PtPb alloy on the SiO_2 support. Although Pb addition was expected to enhance the hydrogenation reaction of γ-butyrolactone, only decrease of activity was observed on Pt-Pb/SiO_2 catalysts. The addition of Al, Ge, In and Pb would only decrease the surface area of active Pt The titanium-added Pt catalysts, Pt-Ti/SiO_2 indicated enhancement of the activity. Titanium would modified the Pt surfaces and selectively activate carbonyl, group in γ-butyrolactone. The similar modification of Pt surfaces by Ti element was well known as SMSI of Pt/TiO_2

研究了作为酯模型化合物的γ-丁内酯在负载型Pt-Sn双金属催化剂上的加氢反应，并研究了Sn/Pt比小于1的Pt-Sn/SiO_2。 γ-丁内酯的氢化活性较低。Sn/Pt 比在 1 和 2 之间，表明添加 Sn 后活性显着增强。催化剂的Pt/SiO_2粉末衍射图表明Pt金属和Pt-Sn合金的共存导致了Sn/Pt比小于1的催化剂的活性增强。仅有Pt晶体，而Sn/Pt比高于2的催化剂仅显示出PtSn合金相，Sn/Pt比在1之间的范围内的催化剂观察到较高的活性。 2.还研究了Pt/SiO_2催化剂中其他添加剂对γ-丁内酯加氢反应的影响。表明没有观察到 Pt 在 SiO_2 上形成合金，尽管 Pb 的添加预计会增强 PtPb 合金在 SiO_2 载体上的形成。在γ-丁内酯的加氢反应中，在Pt-Pb/SiO_2催化剂上仅观察到活性下降，Al、Ge、In和Pb的添加只会降低活性Pt的表面积，而添加钛的Pt催化剂， Pt-Ti/SiO_2表明钛会修饰Pt表面并选择性地活化γ-丁内酯中的羰基，Ti元素对Pt表面的修饰类似。被称为 Pt/TiO_2 的 SMSI

项目成果

Zinc Powder as an Effective Reducing Reagent during Liquid-Phase Oxidation of Benzene to Phenol Using Molecular Oxygen over V-Substituted Heteropoly Acid Catalysts

锌粉作为有效还原剂，在 V 取代杂多酸催化剂上使用分子氧将苯液相氧化为苯酚

• 发表时间: 2006
• 作者: S. Sumimoto; C. Tanaka; S. Yamaguchi; Y. Ichihashi; S. Nishiyama; S. Tsuruya
• 通讯作者: S. Tsuruya

Selective Oxidation of Cyclohexane to g-Caprolactone with Hydrogen Peroxide over Solid Acid Catalysts

固体酸催化剂上过氧化氢选择性氧化环己烷生成己内酯

• 发表时间: 2006
• 作者: M. Ohshika

Liquid-Phase Oxidation of Benzene to Phenol by Molecular Oxygen over La Catalysts

La 催化剂上分子氧液相氧化苯生成苯酚

• 作者: Y. Ichihashi

吸着法で調製したSn/Pt/SiO_2触媒上でのγ-ブチロラクトンの水素化-Snの微量添加による活性向上-

吸附法制备的Sn/Pt/SiO_2催化剂上γ-丁内酯加氢-添加少量Sn提高活性-

• 发表时间: 2007
• 作者: 齋藤 悠太

Kinetic Study of Water-Gas Shift Reaction over Cu-Based Mixed Oxide Catalysts

铜基混合氧化物催化剂水煤气变换反应动力学研究

• 发表时间: 2007
• 作者: T. Ishikawa