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Studies on development and analysis of highly active polymer catalysts towards creation of new energy resource

新能源高活性聚合物催化剂的开发与分析研究

基本信息

批准号：
10650862
负责人：
KANEKO Masao
金额：
$ 2.24万
依托单位：
IBARAKI UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

项目摘要

Electron transfer in a photoexcited state was investigated which is of importance for photochemical energy conversion. Ru(bpv)_3^<2+> and methylviologen (MV^<2+>) were adsorbed into a Nafion film and the electron transfer from the photoexcited Ru complex to MV^<2+> was studied. In order to elucidate the role of water, wet and dry films were compared with respect to the electron transfer. From the photoluminescence intensity of the Ru complex and its decay as a function of the MV^<2+> concentration, it was found that the electron transfer takes by a static mechanism for which the molecules do not move during the electron transfer. For the dry film the molecules do not move at all resulting in an entirely static mechanism. However, for the wet film, the molecules can move a little bit during the photoexcited state resulting in the partial involvement of a dynamic mechanism, and the reaction efficiency was much higher than that of the dry film. Electron transport in a ground state was studied electrochemically, and it was clarified that the mechanism, i.e., diffusion of molecules or charge hopping between molecules, are different depending on the system and the positive or negative charge.As water oxidation catalysts, the catalytic activity of Ru complexes with ammonia or bipyridine ligands has been analyzed. The effects of interaction between the catalyst molecules in the polymer film on the four-electron process and on the bimolecular decomposition have been investigated. It was found that porphines and phthalocyanines dispersed in a polymer film has a high activity for the electrocatalytic proton reduction, and their fundamental behavior was studied.

研究了光激发态下的电子转移，这对于光化学能量转换非常重要。将Ru(bpv)_3^<2+>和甲基紫精(MV^<2+>)吸附到Nafion膜上，研究从光激发的Ru配合物到MV^<2+>的电子转移。为了阐明水的作用，对湿膜和干膜在电子转移方面进行了比较。从Ru络合物的光致发光强度及其作为MV 2+ 浓度的函数的衰减，发现电子转移通过静态机制进行，其中分子在电子转移期间不移动。对于干膜来说，分子根本不移动，形成完全静态的机制。然而，对于湿膜来说，分子在光激发状态下可以稍微移动，导致部分参与动力学机制，反应效率远高于干膜。通过电化学方法研究了基态电子传输，明确了分子扩散或分子间电荷跳跃的机理因体系和正电荷或负电荷而异。作为水氧化催化剂，分析了Ru与氨或联吡啶配体的配合物的催化活性。研究了聚合物膜中催化剂分子之间的相互作用对四电子过程和双分子分解的影响。研究发现分散在聚合物膜中的卟啉和酞菁对电催化质子还原具有较高的活性，并研究了它们的基本行为。