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Macromolecular Synthesis by Air Oxidative Polymerization through Multi-electron Transfer

多电子转移空气氧化聚合高分子合成

基本信息

批准号：
12650870
负责人：
YAMAMOTO Kimihisa
金额：
$ 2.37万
依托单位：
Keio University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2001
项目状态：
已结题

项目摘要

Research of the four-electron reduction of oxygen to water is important in order not only to determine the life mechanism but also to make novel catalysts.As face-to-face Cobalt Dinuclear Porphyrins (CoP2) are known as excellent catalysts to promote the reaction. Polymer complexes of CoP2 with Polyaniline were prepared on the electrode as a catalyst. Electrochemical properties of Polyaniline-CoP2 complex was investigated and proved to catalyze 4-electron reduction by 80%, compared to 50% by CoP2 modified electrode. In order to establish essential factor to promote catalytic efficiency of CoP2, various conducting polymers including self-dope polyaniline, and proton transfer redox polymer were synthesized. It probed that the efficiency of 4-electron reduction is strongly dependent on the redox potential of the polymer-matrix, indicating that redox potential of polymer is an important factor in this catalytic system. As PCAn acts as an efficient electron mediator even in neutral conditions due to its stable redox activity over wide pH range, catalytic reduction of oxygen was carried out using PCAn-CoP2 complex in neutral conditions (pH=6.2). A catalytic efficiency up to 95% toward 4-electron reduction of oxygen was observed by RDV, and RRDV measurements. One-step 4-electron reduction was occurred, not two steps 2-electron transfer by RRDV. It is because PCAn has acidic domain in the polymer matrix, which is thought to keep acidity in the film to some extent, even in neutral conditions, that 4-electron reduction of oxygen occurs in the neutral conditions.

氧的四电子还原反应是一个非常重要的反应，研究其机理和制备新型催化剂都具有重要意义，而钴双核卟啉（CoP 2）是一种新型的催化剂。在电极上制备了CoP 2与聚苯胺的高分子配合物作为催化剂。研究了聚苯胺-CoP 2复合物的电化学性质，发现其对4-电子还原的催化率由CoP 2修饰电极的50%提高到80%。为了确定提高CoP 2催化效率的关键因素，合成了各种导电聚合物，包括自掺杂聚苯胺和质子转移氧化还原聚合物。研究发现，四电子还原效率与聚合物-基体的氧化还原电位密切相关，表明聚合物的氧化还原电位是影响该催化体系的重要因素。由于PCAn在宽pH范围内具有稳定的氧化还原活性，即使在中性条件下也可作为有效的电子介体，因此在中性条件下（pH=6.2）使用PCAn-CoP 2络合物进行氧的催化还原。通过RDV和RRDV测量观察到对氧的4电子还原的催化效率高达95%。RRDV的4-电子还原反应是一步进行的，而不是两步进行的2-电子转移。这是因为PCan在聚合物基体中具有酸性结构域，这被认为在一定程度上保持膜中的酸性，即使在中性条件下，氧的4-电子还原在中性条件下发生。