一种简易型顺磁波谱电化学池的设计和卟啉π-阳离子自由基的检测

Construction of A Simple in-situ Electron Spin Resonance-Spectroelectrochemical Cell and Detection of Electrogenerated π-Cation Radicals of 21,23-Dihydro-5,10,15,20-tetraphenylporphine

设计了一种简易型全玻璃ESR薄层现场波谱电化学池,以高7mm,直径0.5mm的铂柱工作电极安放在直径1mm的玻璃管中,形成体积为4.7μl的薄层池,2ml溶液就可以工作。在二氯乙烷中,进行了薄层电化学性能表征,并对(TPP)H_2的电极氧化过程进行了研究,发现电生的(TPP)H_2阳离子自由基有动力学后行反应。可能的机理是自由基岐化反应伴随着Cl^-引起的异卟啉的生成反应。

A simple pyrex glass electron spin resonance (ESR) spectroelectrochemical cell has been designed and constructed . A piece of platinum rod working electrode is mounted on the bottom of an 1 mm i. d. glass tube to form a cylinder type thin-layer chamber of 4. 7 μl volume. Only 2 ml solution is needed for an experiment. The cell is characterized and used for studies of oxidation reaction of (TPP)H2 in dichloroethane solution. It has been observed that the strength of the ESR signal of electrogenerated π-cation radicals of (TPP) H2 is decreased with increase of electrolysis time. A mechanism of isoporphyrin formation coupled with a proportional reaction is suggested.