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.

通过 M(Me)(Cl)(cod) 与 NaOSiPhiiD23ィエD2 的复分解反应，新制备了带有硅氧烷配体的第 10 族金属配合物 M(Me)(OSiPhiiD23ィエD2)(cod) [1:M = Pt, 2 : M = Pd, cod = 1,5-环辛二烯]。人们发现这些配合物在环境条件下暴露于分子氢（1 atm）时会形成纳米级超细 Pt 或 Pd 颗粒，同时形成环辛烷、甲烷和三苯基硅烷醇。配合物 1 吸附在二氧化硅表面，然后暴露于 HィイD22ィエD2 中，导致在二氧化硅上形成超细 Pt 颗粒（平均直径 = 8.2 ± 6.2 nm）。这些二氧化硅负载的 Pt 颗粒充当烯烃加氢和氮氧化物还原的催化剂。另一方面，含1的聚合物膜的氢解也产生含有高度分散的平均直径为1-8 nm的Pt颗粒的聚合物。 Pt金属颗粒尺寸随着还原温度和聚合物中1浓度的降低而减小。极性聚合物如聚甲基丙烯酸甲酯产生直径小于1纳米的最小颗粒。通过 TEM、FE-TEM 和 XPS 分析，这些颗粒被表征为纯 Pt 晶体。

项目成果

S. Komiya et al.: "Synthesis of Hydridoplatinum-Molybdenum(or Tungsten) heterodinuclear Complexes by βHydrido Elimination of (dppe)EtPt-WCp(CO)_3. Selective Hydride Transfer from Pt to Mo"J. Mol. Catal. A. (in press).

S. Komiya 等人：“通过 (dppe)EtPt-WCp(CO)_3 的 β 氢消除合成氢化铂-钼（或钨）异源双核配合物。从 Pt 到 Mo 的选择性氢化物转移”J。 （在新闻）。

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”。

N.Nakahara et al.: "Synthesis and Structure of Thiolato Bridged Early-Late Heterobimetallic Complexes with Methyl Group"J. Organomet.Chem.. 572. 81-85 (1999)

N.Nakahara等：“含甲基硫醇桥联早-晚杂双金属配合物的合成与结构”J。

Komiya et al.: "Synthesis and Structure of Thiolato Bridged Pt-Ti Heterobimetallic Complexes with Methyl Group" J.Organomet.Chem.572. 81-85 (1999)

Komiya 等人：“带有甲基的硫醇桥接 Pt-Ti 异双金属配合物的合成和结构”J.Organomet.Chem.572。

A. Fukuoka et al.: "Synthesis of organo(siloxo)platinum and-palladium complexes and preparation of supported nanoclusters by facile ligand reduction"Inorg. Chim. Acta. 294. 266-274 (1999)

A. Fukuoka 等人：“有机（硅氧烷）铂和钯复合物的合成以及通过简易配体还原制备负载纳米簇”Inorg。