AN INSITU RAMAN-SPECTROSCOPY STUDY OF THE ANODIC-OXIDATION OF COPPER IN ALKALINE MEDIA

被引:112
作者
MAYER, ST
MULLER, RH
机构
[1] UNIV CALIF BERKELEY,LAWRENCE BERKELEY LAB,DIV MAT & CHEM SCI,BERKELEY,CA 94720
[2] UNIV CALIF BERKELEY,DEPT CHEM ENGN,BERKELEY,CA 94720
关键词
D O I
10.1149/1.2069234
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
In situ Raman spectroscopy measurements were made during the anodic oxidation of copper in 1M and 6M KOH solutions. The formation of Cu2O occurs at potentials corresponding to the first anodic voltammetric peak (A1), and a porous layer of Cu(OH)2 composed of fine needle-like crystals is formed at the second voltammetric peak (A2). The compact underlayer of cuprous oxide is transformed to another species (presumably CuO) at potentials above 0 mV vs. Hg/HgO. At potentials near oxygen evolution, an unidentified trivalent species appears. The reduction of the oxide is shown to be strongly influenced by illumination. Under irradiation, the underlayer is first reduced to Cu2O at around 0 mV vs. Hg/HgO, followed by Cu(OH)2 reduction to copper, and finally Cu2O reduction to copper metal. Without intense illumination, the p-type semiconductive properties of the underlying Cu2O layer make it act as a Schottky barrier, causing the large degree of irreversibility found in this system.
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页码:426 / 434
页数:9
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