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Basic Research on Photochemical Fixation and Design of OrganometallicComplex Catalysts.

光化学固定和有机金属配合物催化剂设计的基础研究。

基本信息

批准号：
05453107
负责人：
MORIKAWA Akira
金额：
$ 4.54万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1994
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453107/
关键词：
Organometallic Complex Photochemical Fixation

项目摘要

Photochemical fixation of rhodium complex (RhCl (CO) (PMe_3) _2 and CpRh (CO) _2) onto Porous Vycol Glass (PVG) was studied in order to create the active state of rhodium complex for photocatalytic reactions.The Photochemical change in the structure of RhCl (CO) (PMe_3) _2 complex supported on PVG was investigated by means of FT-IR,UV-VIS and EXAFS spectroscopies. It was revealed that the several species are formed during the photo-irradiation, accompanied with the photodesorption of CO and PMe_3 ligands. The structure of the RhCl (CO) (PMe_3) _2 complex was controlled by selecting the wavelength of the irradiated light. Photocatalytic behavior of the supported RhCl (CO) (PMe_3) _2 complex was studied by the hydrogenation of propene and the dehydrogenation of 2-methylpropane. The photocatalytic behavior is closely related to the structure resulted from the change of the RhCl (CO) (PMe_3) _2 complex on PVG.The photochemical change in the structure of CpRh (CO) _2 complex supported on PVG into Cp_2Rh_2 (CO) _3, [CpRh (u-CO)] _2 and CpRh (H) -O-Si was also evidenced by the spectroscopic investigations. The structure of the CpRh (CO) _2 complex is also controlled by selecting the wavelength of the irradiated light. The Rh complex of the structure CpRh (H) -O-Si showed the photocatalytic activity for hydrogenation of propene.In the present work, possibilities of the photochemical fixation of rhodium complexes onto PVG surface with various structure and an example of the design of the photocatalyst were successfully demonstrated.

研究了多孔乙烯玻璃（PVG）对铑（RhCl（CO）（PMe 3）2和CpRh（CO）2）的光化学固定，利用FT-IR、UV-VIS和EXAFS等光谱技术研究了PVG负载的RhCl（CO）（PMe 3）2的光化学结构变化。结果表明，在光照射过程中，伴随着CO和PMe_3配体的光脱附，形成了多种物种。RhCl（CO）（PMe_3）_2配合物的结构可以通过选择照射光的波长来控制。研究了负载型RhCl（CO）（PMe_3）_2配合物对丙烯加氢和2-甲基丙烷脱氢的光催化性能。PVG负载的CpRh（CO）_2络合物的光催化性能与其结构变化密切相关，光谱研究还证实了PVG负载的CpRh（CO）_2络合物的光化学结构变化为Cp_2Rh_2（CO）_3、[CpRh（u-CO）] _2和CpRh（H）-O-Si。CpRh（CO）_2配合物的结构也可通过选择照射光的波长来控制。结构为CpRh（H）-O-Si的铑配合物对丙烯加氢反应具有光催化活性，本文成功地展示了铑配合物在不同结构PVG表面光催化固定的可能性，并给出了光催化剂设计的一个实例。