铜胺配合物在甲醇中对氧的催化还原研究

Catalytic Reduction of Oxygen in CH-3OH Solution of Copper(Ⅱ)-amine Complexes

研究了CuCl2和CuCl2 乙醇胺(体积比为1∶1)配合物在CH3OH中的循环伏安行为。实验结果证明:CuCl2 乙醇胺(体积比为1∶1)配合物在CH3OH中比较容易形成。而且CuCl2 乙醇胺(体积比为1∶1)配合物的循环伏安曲线比CuCl2增加了一个阴极还原峰,发现通入不同时间的Ar和O2后此阴极还原峰并没有发生改变,由此判断该峰为与铜胺配合物键合的O2的催化还原峰。在328K下,向体系添加1,1′＿联＿2＿萘酚发现该阴极还原峰消失,进一步证明了CuCl2 乙醇胺(体积比为1∶1)配合物与O2能够配位,铜胺配合物具有载氧功能,并且对O2具有催化还原作用。

The electrochemical behaviors of copper(Ⅱ)-amine complexes were studied in this paper. The experimental results showed that CuCl-2/ethanolamine(1∶1) complex is easily synthesized. By comparing CV curves of CuCl-2/ethanolamine(1∶1) complex with that of CuCl-2, it is observed that a new cathodic peak at -125 mV in the CV curves of CuCl-2/ethanolamine(1∶1) complex in CH-3OH solution. When argon and O-2 were bubbled into the CH\-3OH solution for different time, it was found that the new cathodic peak had little change and it is proposed that the new cathodic peak corresponds to the catalytic reduction of O-2. However, the reductive peak of O-2 disappeared after the reactive substrate 1,1′-bi-2-naphthol was added into the solution. All experimental results showed that CuCl-2/ethanolamine(1∶1) complex has dioxygen affinity and can catalyze the reduction of O-2.