不可逆电极过程方波伏安法动力学研究——Ⅰ.平行催化体系

A Study on Irreversible Electrode Kinetics in Square Wave Voltammetry Ⅰ. Parallel Catalytic Process

本文报道了在不可逆电极过程的强催化体系中,当采用快速方波扫描时,正、逆向电流将出现峰形。依据实验结果,提出了“迁出-进入”的等浓度面理论模型,推导并讨论了电流方程式。结果表明,文中提出的理论能较好地说明实验结果。

The relationship of is generally used to derive the E V equation of irreversible electrode process. But in square wave voltammetry(SWV), it is not correct theoretically to explain the experimental results. For SWV.the concentrational gradient caused by the forward pulse still effect on the reversible pulse directly and this leads to the accumulation of concentration on the surface of electrode rather than current. Based on the real electrode process, we proposed reaction-layer concept to treat the catalytic irreversible electrode process, and discussed the E-V equation in detail with the additive SWV which has higher sensitivity to the studied system. As expected, the theoetical results were in excellent agreement with the Ti4+-H2SO4-KBrO3 experimental ones and gave a clear explanation for the perk phenomenon in fast scan form.