Synthesis and Applications of Ultrafine Particles Derived From Organometallic Complexes

有机金属配合物超细颗粒的合成及应用

• 批准号: 09555245
• 负责人: KOMIYA Sanshiro
• 金额: $ 3.78万
• 依托单位: Tokyo University of Agriculture & Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09555245/
• 关键词: ultrafine particles; platinum; palladium; siloxo ligand; hydrogenolysis; catalyst; 有機金属錯体; 担持触媒; 白金シロキソ錯体

Group 10 metal complexes with a siloxo ligand, M(Me)(OSiPhィイD23ィエD2)(cod) [1:M = Pt, 2 : M = Pd, cod = 1,5-cyclooctadiene] are newly prepared by the metathetical reaction of M(Me)(Cl)(cod) with NaOSiPhィイD23ィエD2. These complexes are found to form nano-scale ultrafine Pt or Pd particles with concomitant formation of cyclooctane, methane and triphenylsilanol by exposure to molecular hydrogen (1 atm) under ambient conditions. Adsorption of complex 1 on the surface of silica followed by exposure to HィイD22ィエD2 results in the formation of ultrafine Pt particles on silica (mean diameter = 8.2 ± 6.2 nm). These silica-supported Pt particles act as catalyst for hydrogenation of olefins and for reduction of nitrogen oxides. On the other hand, hydrogenolysis of polymer films containing 1 also gives polymer containing highly dispersed Pt particles with mean diameters of 1-8 nm. The Pt metal particles size decreases with decrease of reduction temperature and concentration of 1 in the polymer. The polar polymer such as poly(methyl methacrylate) gives the smallest particles less than 1 nm diameters. These particles are characterized as pure Pt crystals by TEM, FE-TEM, and XPS analyses.

组10个带有硅氧配体的金属配合物，M（me）（osiphyy d23e d2）（cod）[1：m = pt，2：m = m = pd，cod = 1,5-cyclooctadiene]是由m（me）（col）（cod）的naosiphyy d23e d23e d23e d23e d2的m（me）（cod）的元反应新制备的。发现这些络合物通过在环境条件下暴露于分子氢（1 atm）中，形成纳米级超细PT或PD颗粒，并与环销，甲烷和三苯基硅烷醇形成。在二氧化硅表面上的复合物1的吸附，然后暴露于HII D2会导致在二氧化硅上形成超细PT颗粒（平均直径= 8.2±6.2 nm）。这些二氧化硅支持的PT颗粒是烯烃氢化和还原氮氧化物的催化剂。另一方面，包含1的聚合物膜的氢解会提供含有高度分散的Pt颗粒的聚合物，平均直径为1-8 nm。 PT金属颗粒的尺寸随着聚合物的降低温度和1的浓度而降低。极性聚合物（例如聚甲基丙烯酸甲酯）的最小颗粒小于1 nm的直径。这些颗粒通过TEM，FE-TEM和XPS分析将纯PT晶体表征为纯PT晶体。

项目成果

S. Komiya., et al.: "Regio-and Stereoselective Insertion Reactions of Thiiranes into Pt-Mn (or Re) Bond in Organo-platinum-manganese or -rhenium Heterodinuclear Complexes as Intermediate toward Desulfurization Reaction"J. Am. Chem. Soc.. 122. 170-171 (200

S. Komiya., et al.：“硫杂环丙烷的区域选择性和立体选择性插入反应作为脱硫反应中间体的有机铂锰或铼异双核配合物中的 Pt-Mn（或 Re）键”J。

R.Domeki, et al.: "Effect of Pt precursors on N _2/N_2O selectivity for selective reduction of NO by hydrocarbon on supported Pt catalysts"Chem. Lett.. 515-516 (1999)

R.Domeki等人：“Pt前体对N _2/N_2O选择性的影响，用于通过负载型Pt催化剂上的烃选择性还原NO”。

Komiya et al.: "Hydrogen Transfer in Pt-Mo Heterodinuclear Hydride Complexes Promoted by Alkynes" Chem.Lett.29-30 (1998)

Komiya 等人：“炔烃促进的 Pt-Mo 异双核氢化物配合物中的氢转移”Chem.Lett.29-30 (1998)

Sanshiro Komiya: "Synthesis of Organometallic Compounds" Wiley, 433 (1997)

小宫三四郎：“有机金属化合物的合成”Wiley，433 (1997)

R. Domeki, et al.: "effect of Pt precursors on N_2/N_2O selectivity for selective reduction of NO by hydrocarbon on supported Pt catalysts"Chem. Lett.. 515-516 (1999)

R. Domeki 等人：“Pt 前体对 N_2/N_2O 选择性的影响，用于通过负载型 Pt 催化剂上的烃选择性还原 NO”。