为了量化电极反应过程中液相组分和预吸附组分对总的氧化还原电流的贡献,采用双电势跃计时电流法,在长光程薄层电化学池中,测试了染料木黄酮在石墨-石蜡电极上的第一步氧化还原行为,在该反应体系的特征吸收波长259nm和286nm下,记录双电势跃计时吸光度数据;采用自编计算机程序对数据进行解析,导出了液相中的染料木黄酮及其氧化产物的计时电流曲线,从而提出了一种由光吸收信号获得双电势跃计时电流曲线的新方法。这种重构的计时电流曲线,对应于相应组分在反应过程中的液相浓度的变化,为氧化还原体系的动力学分析提供了更详细的信息。
A novel method of obtaining double potential step chronoamperometric (DSAmp) plots from optical absorption signals was developed. For this purpose double potential step chronoamperometry was used to investigate the first redox processes of genistein (GE) on a graphite-wax electrode in a long optical-path thin-layer spectroelectrochemical cell. Double potential step chronoabsorptometric (DSAbs) data were recorded at the characteristic absorption wavelengths of this system, 259 nm and 286 nm, respectively. The DSAbs data were analysed for reconstruction of DSAmp plots of the species (GE and its oxidation product) appeared in the solution during electrolysis using self-developed computer programs. Accordingly we can estimate the contributions of both the species in solution and those pre-adsorbed on the electrode surface to the total redox currents. The reconstructed DSAmp Plots correspond to the variation of their concentrations in the thin-layer chamber provided more detailed information on the redox system under investigation.