利用K-L方程估算旋转圆盘电极体系反应动力学电流的误差来源分析

doi:10.13208/j.electrochem.131167

电化学（中英文） ›› 2014, Vol. 20 ›› Issue (5): 444-451. doi: 10.13208/j.electrochem.131167

• 电化学近期研究专辑（厦门大学姜艳霞教授主编） • 上一篇下一篇

利用K-L方程估算旋转圆盘电极体系反应动力学电流的误差来源分析

陈微，廖玲文，何政达，陈艳霞^*

中国科技大学化学物理系，合肥微尺度物质科学国家实验室（筹），安徽合肥 230026

收稿日期:2014-01-15 修回日期:2014-05-27 出版日期:2014-10-28 发布日期:2014-06-03
通讯作者: 陈艳霞 E-mail:yachen@ustc.edu.cn
基金资助:
国家自然科学基金项目（No. 21073176）及科技部973计划项目（No. 2010CB923302）资助

On the Origin of the Errors of i_k as Estimated from K-L Equation in Rotating Disk Electrode System

CHEN Wei，LIAO Ling-wen，HE Zheng-da，CHEN Yan-xia^*

Department of Chemical Physics, Hefei National Laboratory for Physical Sciences at Microscale; University of Science and Technology of China, Hefei 230026, China

Received:2014-01-15 Revised:2014-05-27 Published:2014-10-28 Online:2014-06-03
Contact: CHEN Yan-xia E-mail:yachen@ustc.edu.cn

摘要/Abstract

摘要： 旋转圆盘电极（RDE）体系主要用于低溶解度反应物的电极过程动力学研究. 在利用RDE技术研究不可逆电极反应动力学时，人们常利用Koutecky-Levich方程排除传质的影响，从总电流估算反应的动力学电流. 由于K-L方程是建立在系统满足稳态扩散模型的基础上，实际运用时如果体系偏离稳态扩散，就有可能对估算的动力学参数造成很大误差. 本文以氧气在多晶铂电极上的还原反应为例系统地估算了不同氧气浓度与电极转速下的误差，结果表明低氧气浓度与低圆盘转速的情况不满足稳态扩散条件，若此时仍根据K-L方程利用外推法进行分析，误差可达30%. 因此作者建议，在RDE体系中利用K-L方程估算动力学参数时，最好忽略低浓度与低转速下的数据，直接使用较高浓度与较高转速下的数据进行计算与分析.

关键词: 气体电极反应, 旋转圆盘电极方法, K-L方程, 扩散传质, 氧还原反应

Abstract: Rotating disk electrode system is mainly used to study the kinetics of reactions whose reactants have very low solubility in the electrolyte. For an irreversible reaction, Koutecky-Levich equation (K-L Eq.) is frequently used to deduce the kinetic current i_k). Since K-L Eq. is derived based on the assumption that a system should conform the steady-state diffusion conditions, the data recoded from the actual system which deviates from such a condition, great error may be induced for the i_k estimated. In this work, polarization curves for oxygen reduction reaction at polycrystalline Pt electrode recorded in solutions with various O₂ concentrations and under various electrode rotation speeds have been analyzed systematically. Our analysis reveals that an error of 30% may be introduced by extrapolation to infinite rotation speed in solution with low O₂ concentration or by including the data recorded under very slow electrode rotation speeds. The origins of the error and the ways to avoid such error are discussed.

Key words: gas electrode reaction, rotating disk electrode, Koutecky-Levich equation, diffusion, mmass transport, oxygen reduction reaction

中图分类号:

O646

陈微，廖玲文，何政达，陈艳霞*. 利用K-L方程估算旋转圆盘电极体系反应动力学电流的误差来源分析[J]. 电化学（中英文）, 2014, 20(5): 444-451.

CHEN Wei，LIAO Ling-wen，HE Zheng-da，CHEN Yan-xia*. On the Origin of the Errors of i_k as Estimated from K-L Equation in Rotating Disk Electrode System[J]. Journal of Electrochemistry, 2014, 20(5): 444-451.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.131167

https://electrochem.xmu.edu.cn/CN/Y2014/V20/I5/444

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利用K-L方程估算旋转圆盘电极体系反应动力学电流的误差来源分析

On the Origin of the Errors of i_k as Estimated from K-L Equation in Rotating Disk Electrode System

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利用K-L方程估算旋转圆盘电极体系反应动力学电流的误差来源分析

On the Origin of the Errors of ik as Estimated from K-L Equation in Rotating Disk Electrode System

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On the Origin of the Errors of i_k as Estimated from K-L Equation in Rotating Disk Electrode System