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揭示电极反应的内在动力学:受传质影响下的旋转圆盘电极体系的极限扩散电流合理解析

Identifying Diffusion Limiting Current to Unravel the Intrinsic Kinetics of Electrode Reactions Affected by Mass Transfer at Rotating Disk Electrode

  • 摘要: 旋转圆盘电极体系被广泛用于研究可能因反应物传质不足而受影响的电催化反应动力学. 在该体系中,通过Koutecky-Levich方程计算的特定超电势下的动力学电流密度通常用作评价电催化剂活性的指标. 然而,普遍发现在文献中没有合理辨析极限扩散电流密度. 相比于动力学电流密度,实验测量的电流密度对极限扩散电流密度进行归一化(电流密度与极限电流的比值j/jL)的方法,也经常出现其有效性不合理的情况. 本文通过以氧还原反应/氢气氧化反应/氢析出反应为例,证明了从实验数据中合理解析在不同特定的实验条件下同一反应的实际极限扩散电流密度对于准确推导动力学电流密度的方法. 分析揭示了归一化电流(j/jL)是一个粗略的活性指标,它只能用于定性比较在传质和电极粗糙度因子完全相同的条件下的活性趋势. 除此之外,如果用归一化电流此作为活性指标去比较内在的活性,则需要排除浓差超电势的影响.

     

    Abstract: Rotating disk electrode systems are widely used to study the kinetics of electrocatalytic reactions that may suffer from insufficient mass transfer of the reactants. Kinetic current density at certain overpotential calculated by the Koutecky-Levich equation is commonly used as the metrics to evaluate the activity of electrocatalysts. However, it is frequently found that the diffusion limiting current density is not correctly identified in the literatures. Instead of kinetic current density, the measured current density normalized by diffusion limiting current density (j/jL) has also been frequently under circumstance where its validity is not justified. By taking oxygen reduction reaction/hydrogen oxidation reaction/hydrogen evolution reaction as examples, we demonstrate that identifying the actual diffusion limiting current density for the same reaction under otherwise identical conditions from the experimental data is essential to accurately deduce kinetic current density. Our analysis reveals that j/jL is a rough activity metric which can only be used to qualitatively compare the activity trend under conditions that the mass transfer conditions and the roughness factor of the electrode are exactly the same. In addition, if one wants to use j/jL to compare the intrinsic activity, the concentration overpotential should be eliminated.

     

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