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Studies on Preparation and Catalytic Propeties of Amorphous Thin Film Alloys

非晶薄膜合金的制备及其催化性能研究

基本信息

批准号：
60470080
负责人：
IMANAKA Toshinobu
金额：
$ 3.14万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1985
资助国家：
日本
起止时间：
1985 至 1987
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-60470080/
关键词：
Thin film Sputtering Amorphous Orientation Columnar Structure 部分水素化反応高部分水素化選択性

项目摘要

Metal thin films (Ni,Pd,Pt,Ru) and their borides and phosphides were prepared by using the RF sputtering method. Amorphous alloy thin films with various compositions were easily prepared by changing the sputtering conditions. In the metal boride films, boron donated electrons to metal, resulting in the high electron density of metal. With the metal phosphide films, phosphorous accepted electrons from metal, resulting in the low electron density of metal. In the hydrogenation of diolefins (1,3-butadiene and cyclopentadiene) and acetylene over these alloy thin films, the selectivity for the partial hydrogenation was explained in terms of the ensemble and the ligand effects. The small ensemble size and the low electron density of metal brought about the high selectivity for the partial hydrogenation. Especially, amorphous Pd_<75>P_<25> film showed the high selectivity (>95%) and further Pd_<75>P_<25> film heated in a vacuum, which was crystallized, exhibited the higher selectivity (>99%). On the other hand, the structure dependence in the hydrogenation of diolefins and acetylene was investigated on the Ru and Pd films. The orientation of the crystal faces changed with the film growth, that is, the orientation altered from (002) orientation to (101) orientation in the Ru films while changed from (111) orientation to (220) orientation in the Pd film. It was found that the (002) oriented Ru film and the (220) oriented Pd film showed the high selectivity for the hydrogenation. These metal films had the columnar structure and therefore the surface area of the films increased with the film growh. The active and selective film catalysts were developed by using the RF sputtering method.

采用射频溅射方法制备了金属薄膜（Ni、Pd、Pt、Ru）及其硼化物和磷化物。通过改变溅射条件可以很容易地制备出各种成分的非晶合金薄膜。在金属硼化物薄膜中，硼向金属提供电子，导致金属具有高电子密度。在金属磷化物薄膜中，磷从金属中接受电子，导致金属的电子密度较低。在二烯烃（1,3-丁二烯和环戊二烯）和乙炔在这些合金薄膜上的氢化中，部分氢化的选择性用整体和配体效应来解释。金属的小整体尺寸和低电子密度带来了部分氢化的高选择性。特别是，非晶Pd_ 75 P_ 25 膜表现出高选择性(>95％)，并且进一步在真空中加热结晶的Pd_ 75 P_ 25 膜表现出更高的选择性(>99％)。另一方面，研究了 Ru 和 Pd 薄膜上二烯烃和乙炔氢化的结构依赖性。随着薄膜的生长，晶面的取向发生变化，即Ru薄膜中的取向从(002)取向转变为(101)取向，而Pd薄膜中的取向从(111)取向转变为(220)取向。结果发现(002)取向的Ru膜和(220)取向的Pd膜表现出高的氢化选择性。这些金属薄膜具有柱状结构，因此薄膜的表面积随着薄膜的生长而增加。采用射频溅射方法研制了活性选择性薄膜催化剂。