Electrochemistry of Steel Electrodes: A Combined Study by Linear Reflectivity Measurements and Second Harmonic Generation

R. Kohring, M. Buck, F. Eisert, M. Grunze, J. Vogelsang
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Abstract

Steel electrodes were investigated under electrochemically controlled conditions at pH 13. The linear reflectivity at 1064 nm and the second harmonic signal (SHG) at 532 nm generated in reflection were measured for different polarizations and recorded simultaneously with cyclovoltammograms. The potential was varied between −1.4 V and 0.5 V vs. SCE and the optical signals were recorded after repetitive cycling. The reflectivity which probes the whole thickness of the electrochemically active layer and the non-linear optical signal which, in contrast, only probes the electrode surface and its immediately vicinity, exhibit very different behavior with respect to their potential dependence. In a cathodic scan the increase of the respective optical signals is associated with different peaks of the cyclovoltammogram. Furthermore, the SHG signal is strongly dependent on the polarization. The pronounced changes around −1.25/-1.1 V in the cathodic/anodic scan direction, which are observed for pp-polarization, are absent in sp- and ms-polarization. The sp-signal shows features which are paralleled by a decrease in the linear reflectivity. Contrary to the other polarizations, the ms-polarized signal does not show any particular features correlated with peaks of the cyclovoltammogram. The potential dependence of the surface charge expressed by a simple parabolic model describes the SHG signal over extended parts of the potential range. The differences between the potential dependence of the SHG signal and the change of the linear reflectivity fully agree with the two layer model of electrochemically formed iron oxides.

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钢电极的电化学:线性反射率测量和二次谐波产生的结合研究
在pH为13的电化学控制条件下对钢电极进行了研究。测量了在1064 nm处的线性反射率和在532 nm处反射产生的二次谐波信号(SHG),并用环伏安图同时记录。电位在- 1.4 V ~ 0.5 V / SCE之间变化,重复循环后记录光信号。反射率探测整个电化学活性层的厚度,而非线性光信号,相反,只探测电极表面及其附近,表现出非常不同的行为,就它们的电位依赖性而言。在阴极扫描中,各自光信号的增加与环伏安图的不同峰相关联。此外,SHG信号强烈依赖于极化。在- 1.25/-1.1 V左右,阴极/阳极扫描方向的明显变化,在pp极化中观察到,而在sp和ms极化中则不存在。sp信号表现出与线性反射率下降平行的特征。与其他极化相反,ms极化信号不显示与环伏安图峰相关的任何特定特征。表面电荷的电位依赖关系用一个简单的抛物线模型来描述在电位范围的延伸部分上的SHG信号。SHG信号的电位依赖性与线性反射率变化之间的差异完全符合电化学生成的氧化铁的两层模型。
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