电极过程动力学反应速率常数测量的若干方法

doi:10.13208/j.electrochem.2303241

电化学（中英文） ›› 2024, Vol. 30 ›› Issue (2): 2303241. doi: 10.13208/j.electrochem.2303241

电极过程动力学反应速率常数测量的若干方法

韩联欢^a^,^*(), 郭佳瑶^b, 崔苗苗^b

^a厦门大学萨本栋微米纳米科学技术研究院，机电工程系，福建厦门 361005
^b厦门大学化学化工学院，福建厦门 361005

收稿日期:2023-04-10 修回日期:2023-06-27 接受日期:2023-09-25 出版日期:2024-02-28 发布日期:2023-06-14
通讯作者: * 韩联欢，Tel: (86-592)18638012492, E-mail: hanlianhuan@xmu.edu.cn
基金资助:
国家自然科学基金(22202166);国家自然科学基金(21827802);国家自然科学基金(22132003);国家自然科学基金(22021001);中央高校基本科研业务费专项资金(20720230076)

Measurements of Rate Constant for Electrode Reactions

Lian-Huan Han^a^,^*(), Jia-Yao Guo^b, Miao-Miao Cui^b

^aDepartment of Mechanical and Electrical Engineering, Pen-Tung Sah Institute of Micro-Nano Science and Technology, Xiamen University, Xiamen 361005, Fujian, China
^bCollege of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China

Received:2023-04-10 Revised:2023-06-27 Accepted:2023-09-25 Published:2024-02-28 Online:2023-06-14

摘要/Abstract

摘要：

电子转移反应的标准反应速率常数是电化学反应的“本征”动力学性质，也是电极过程动力学研究的重要内容之一，对于电极反应的机理和路径的理解以及电催化剂和电池材料等的筛选和理性设计均具有重要意义。本文将主要介绍电化学反应速率常数测定的实验方法，包括极化曲线、旋转圆盘、超微电极、扫描电化学显微镜、电化学阻抗谱、电流阶跃、电势阶跃以及循环伏安等方法，以期对开展电极过程动力学研究的相关研究人员和学生有所裨益。

关键词: 反应速率常数, 传质速率, 稳态方法, 暂态方法

Abstract:

Standard electron-transfer rate constant is one of the intrinsic properties for an electrochemical reaction, which is significant in the study of electrode kinetics. It is a key criterion for one to clarify the mechanism and pathway of a specific electrochemical reaction, and to screening and design the electrocatalysts and battery materials. Herein, we will introduce the measuring methods of rate constant for electrode reactions, including polarization curve, rotating disk electrode, ultramicroelectrode, scanning electrochemical microscopy, electrochemical impedance spectroscopy, current step, potential step and cyclic voltammetry, etc., to provide a guide to investigate electrode kinetics for graduate students and researchers in the related fields.

Key words: Rate constant, Mass-transfer coefficient, Stationary techniques, Transient techniques

韩联欢, 郭佳瑶, 崔苗苗. 电极过程动力学反应速率常数测量的若干方法[J]. 电化学（中英文）, 2024, 30(2): 2303241.

Lian-Huan Han, Jia-Yao Guo, Miao-Miao Cui. Measurements of Rate Constant for Electrode Reactions[J]. Journal of Electrochemistry, 2024, 30(2): 2303241.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.2303241

https://electrochem.xmu.edu.cn/CN/Y2024/V30/I2/2303241

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参考文献 12

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Electrode process condition		Mass-transfer coefficient（m_T）
Steady state of disk electrode (radius: 1 mm)		~10⁻³ cm·s⁻¹
Cyclic voltammetry on planar electrode		$\sim \sqrt{\frac{{{D}_{\text{O}}}}{RT/Fv}}$¹
Rotating disk electrode		$0.62D_{\text{O}}^{2/3}{{\omega }^{1/2}}{{v}^{-1/6}}$²
Ultramicroelectrode	Sphere/Hemisphere	$\frac{{{D}_{\text{O}}}}{{{r}_{0}}}$³
	Disk	$\frac{4{{D}_{\text{O}}}}{\pi {{r}_{0}}}$
	Cylinder	$\frac{2{{D}_{\text{O}}}}{{{r}_{0}}\ln \tau }$⁴
	Band	$\frac{2\pi {{D}_{\text{O}}}}{w\ln (64{{D}_{\text{O}}}t/{{w}^{2}})}$⁵

$\begin{matrix} & \text{ }n\Delta {{E}_{1/4}},\text{mV} \\ & n\Delta {{E}_{3/4}},\text{mV} \\ \end{matrix}$	Parameter	30.0	30.5	31.0	31.5	32.0	32.5	33.0	33.5
31.0	$\begin{matrix} & \lambda \\ & \alpha \\ & n\Delta {{E}^{0'}} \\ \end{matrix}$	4.17 0.78 9.0	0.84 0.94 27.0
31.5	$\begin{matrix} & \lambda \\ & \alpha \\ & n\Delta {{E}^{0'}} \\ \end{matrix}$		3.49 0.77 10.5	1.49 0.87 19.3
32.0	$\begin{matrix} & \lambda \\ & \alpha \\ & n\Delta {{E}^{0'}} \\ \end{matrix}$		6.12 0.61 6.8	1.45 0.86 19.6	0.40 0.92 41.4
32.5	$\begin{matrix} & \lambda \\ & \alpha \\ & n\Delta {{E}^{0'}} \\ \end{matrix}$		5.21 0.63 7.7	3.89 0.68 9.9	0.81 0.88 28.6	0.20 0.92 56.9
33.0	$\begin{matrix} & \lambda \\ & \alpha \\ & n\Delta {{E}^{0'}} \\ \end{matrix}$			5.34 0.58 7.8	2.50 0.74 13.8	0.43 0.89 40.6	0.08 0.91 81.5
33.5	$\begin{matrix} & \lambda \\ & \alpha \\ & n\Delta {{E}^{0'}} \\ \end{matrix}$			6.45 0.49 6.7	3.74 0.64 10.4	1.55 0.79 19.4	0.12 0.90 71.9
34.0	$\begin{matrix} & \lambda \\ & \alpha \\ & n\Delta {{E}^{0'}} \\ \end{matrix}$			7.36 0.41 6.1	4.67 0.55 8.8	2.70 0.68 13.3	0.77 0.83 30.4	0.17 0.88 64.0
34.5	$\begin{matrix} & \lambda \\ & \alpha \\ & n\Delta {{E}^{0'}} \\ \end{matrix}$				5.43 0.48 7.9	3.49 0.60 11.1	1.97 0.71 16.8	0.33 0.86 47.8	0.15 0.87 67.5

v/(V s⁻¹)	⁻lg(k⁰/m·s⁻¹)	ΔE_p/mV	Ψ
0.5	6.5	662.6	0.00128
0.02	7.0	617.6	0.00202
0.1	6.5	581.3	0.00286
0.5	6.0	543.8	0.00404
2	5.5	496.7	0.00639
0.01	6.5	461.5	0.00904
0.005	6.5	424.7	0.0128
2	5.0	382.4	0.0202
0.1	5.5	342.0	0.0286
0.5	5.0	305.3	0.0404
0.002	6.0	259.8	0.0639
1	4.5	225.7	0.0904
0.5	4.5	194.9	0.128
2	4.0	155.6	0.202
0.1	4.5	131.9	0.286
5	3.5	112.7	0.404
2	3.5	93.7	0.639
0.1	4.0	84.8	0.904
0.5	3.5	76.7	1.28
0.2	3.5	69.6	2.02
0.001	4.5	66.8	2.86
0.5	3.0	61.5	4.04
0.02	3.5	58.7	6.39
0.1	3.0	57.5	9.04
0.02	3.0	56.3	20.2

电极过程动力学反应速率常数测量的若干方法

Measurements of Rate Constant for Electrode Reactions

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