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

本文研究了酯类模型化合物γ-丁内酯在负载型Pt-Sn双金属催化剂上的加氢反应。Sn/Pt比的影响也进行了研究。Sn/Pt比值小于1的Pt-Sn/SiO_2催化剂对γ-丁内酯的加氢活性较低。当Sn/Pt比在1 ~ 2之间时，Sn的加入使催化剂的活性明显提高。催化剂的X-射线粉末衍射图谱表明，Pt金属和Pt-Sn合金的共存带来了活性的提高。当Sn/Pt比小于1时，催化剂中只有Pt晶体，而当Sn/Pt比大于2时，催化剂中只有PtSn合金相。Sn/Pt比在1 ~ 2范围内的催化剂具有较高的活性。并考察了Pt/SiO_2催化剂中其它助剂对γ-丁内酯加氢反应的影响。对Al、Ge、In、Pb、Ti等金属元素作为Pt/SiO_2的添加剂进行了实验研究。Al、Ge和In的加入表明没有观察到Pt在SiO_2上形成合金。Pb的加入使PtPb合金在SiO_2载体上形成。虽然Pb的加入对γ-丁内酯的加氢反应有促进作用，但对Pt-Pb/SiO_2催化剂的活性影响不大。Al、Ge、In和Pb的加入只会降低活性Pt的表面积。添加钛的Pt催化剂Pt-Ti/SiO_2的活性有所提高。钛可以修饰Pt表面，选择性地活化γ-丁内酯中的羰基。Pt/TiO_2的SMSI是Ti元素对Pt表面的类似改性

项目成果

Hydrogenation of Esters under Milder Reaction Conditions as an Energy Saving Process

较温和反应条件下的酯加氢是一种节能工艺

• 发表时间: 2006
• 作者: T.Hirano;Y.Ozawa;T.Sekido;H.Ogino;T.Miyao and S.Naito;Y. Murakami
• 通讯作者: Y. Murakami

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: S.Kado;N.Mohammad;Y.Mukainakano;Y.Miyazawa;K.Nakao;K.Okumura;T.Miyao;S.Naito;K.Suzuki;K.Fujimoto;K.Kunimori;K.Tomishige;服部 忠;齋藤 悠太
• 通讯作者: 齋藤 悠太

Selective Oxidation of Cyclohexane to s-Cprolactone 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顺丙内酯

• 发表时间: 2006
• 期刊: Proceedings of 11th Asian Pacific Confederation of Chemical Engineering Congress (Kuala Lumpur) 564(CD-ROM)
• 作者: M. Ohshika;M. Kuwajima;Y. Ichihashi;S. Nishiyama;S. Tsuruya
• 通讯作者: S. Tsuruya

Axopadial Degradation in the Heliozoon Raphidiophrys Contractilis : A Novel Bioassay System for Detecting Heavy Metal Toxicity in the Aquatic Environment

Heliozoon Raphidiophrys Contractilis 中的轴轴降解：一种用于检测水生环境中重金属毒性的新型生物测定系统

• 发表时间: 2006
• 期刊: Environmental Sciences 13
• 作者: T. Hirano;Y. Ozawa;T. Sekido;T. Ogino;T. Miyao;S. Naito;T.Kugita;S.M.Mostafa
• 通讯作者: S.M.Mostafa

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
• 期刊: Proceedings of 11th Asian Pacific Confederation of Chemical Engineering Congress (Kuala Lumpur), (CD-ROM)
• 作者: 釘田強志;丸山浩二;飯島樹一;A.Fukuoka;M. Ohshika
• 通讯作者: M. Ohshika