快扫循环伏安曲线的单纯形优化-数值模拟拟合方法

Simplex Optimization-Numerical Simulation Method for Fast Cyclic Voltammetric Curve Fitting

采用Gl算法改进了快扫伏安曲线的数值模拟,提高了模拟计算的速度.使用单纯形优化-数值模拟方法,以电流、峰电位误差的加权值作为拟合参数的评价函数,对二茂铁在0,3mm直径铂盘电极上,不同扫速下的循环伏安图进行了拟合.在拟合过程中自动进行伏安图基线的校正,同时拟合出标准非均相速度常数k^0,未补偿溶液电阻R_u以及双电层电容C_(dl)等重要的参数值,所得k^0值与文献报道结果一致.

The numerical simulation method for fast cyclic voltammetry (FCV) was modified by Glalgorithm to raise its computation speed. Voltammograms of ferrocene on φ0.3 mm Pt disk electrode atdifferent potential scan rates were fitted by a simplex optimization numerical simulation method. An evaluation function, which was a weighted error of the current and the peak potentials, was employed in this method. The baselines of the voltammograms were corrected automatically in the fitting process. Such important parameters as ko, Ru and Cdl were obtained simultaneously. The ko obtained by this method agrees well with the literature results.