电催化动力学简介

doi:10.3866/PKU.WHXB202210025

摘要/Abstract

摘要：

电催化过程是实现社会向可再生能源与化学品转型的主要驱动力之一。电催化动力学分析是探索反应机理和建立电催化剂构效关系行之有效的方法。本文将通过三个广泛研究的电催化反应：电化学CO₂、CO还原反应和氧还原反应，探讨Tafel分析的普遍过程、隐含假设以及需要注意的问题。此外，本文将介绍电化学反应活化参数的基本概念和关键热力学、动力学变量之间的关系。

关键词: 电催化, 反应动力学, 电化学活化参数

Abstract:

Electrocatalytic reactions and processes are expected to be major drivers in society's shift toward renewable energy and chemicals. Electrocatalytic kinetic analysis is an accessible and informative technique to interrogate reaction mechanisms and establish structure–activity relationships. In this tutorial, we discuss general procedures, implicit assumptions, and potential pitfalls when conducting the Tafel analysis in the context of three widely investigated electrocatalytic reactions, i.e., the electrochemical CO₂, CO, and O₂ reduction reactions. Basic concepts and relations among key thermodynamic and kinetic variables are also covered to help interpret the activation parameters of electrochemical reactions.

Key words: Electrocatalysis, Reaction kinetics, Electrochemical activation parameter

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许义飞, 杨瀚文, 常晓侠, 徐冰君. 电催化动力学简介[J]. 物理化学学报, 2023, 39(4), 2210025. doi: 10.3866/PKU.WHXB202210025

Yifei Xu, Hanwen Yang, Xiaoxia Chang, Bingjun Xu. Introduction to Electrocatalytic Kinetics[J]. Acta Phys. -Chim. Sin. 2023, 39(4), 2210025. doi: 10.3866/PKU.WHXB202210025

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202210025

https://www.whxb.pku.edu.cn/CN/Y2023/V39/I4/2210025

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Reaction scheme ^a	n_i	n_rβ	a^b	b/(mV∙dec⁻¹) ^c
CE	0	0	0	∞
EC	0	0.5	0.5	120
EE	0	0.5	0.5	120
CE	0	0.5	0.5	120
EC	1	0	1	60
EE	1	0.5	1.5	40
ECE	1	0.5	1.5	40
EEC	2	0	2	30
EEE	2	0.5	2.5	24
ECEE	2	0.5	2.5	24
ECEC	2	0	2	30
ECECE	2	0.5	2.5	24

	Reaction scheme	b/(mV∙dec⁻¹)	pH dependent
M.1	$^* \mathrm{CO}+^* \mathrm{CO} / \mathrm{CO}_{\mathrm{b}}+\mathrm{e}^{-} \stackrel{\mathrm{RDS}}{\longrightarrow} {^*} \mathrm{OCCO}^{-} $	120	No
M.2	$\begin{aligned}& ^* \mathrm{CO}+\mathrm{H}_2 \mathrm{O}+\mathrm{e}^{-} \stackrel{\mathrm{RDS}}{\longrightarrow} {^} \mathrm{CO}(\mathrm{H})+\mathrm{OH}^{-} \\& ^ \mathrm{CO}(\mathrm{H})+^* \mathrm{CO}+\mathrm{e}^{-} \rightarrow{ }^* \mathrm{C}_2 \mathrm{O}_2(\mathrm{H})^{-} \\& \text {or } ^* \mathrm{CO}(\mathrm{H})+^* \mathrm{CO}(\mathrm{H})+\mathrm{e}^{-} \rightarrow ^* \mathrm{C}_2 \mathrm{O}_2(\mathrm{H})_2^{-}\end{aligned} $	120	No
M.3	$\begin{aligned}& ^* \mathrm{CO}+^* \mathrm{CO} / \mathrm{CO}_{\mathrm{b}}+\mathrm{e}^{-} \rightarrow ^* \mathrm{OCCO}^{-} \\& ^* \mathrm{OCCO}^{-}+\mathrm{H}_2 \mathrm{O}+\mathrm{e}^{-} \stackrel{\mathrm{RDS}}{\longrightarrow} {^*} \mathrm{C}_2 \mathrm{O}_2(\mathrm{H})^{-}+\mathrm{OH}^{-}\end{aligned} $	40	No
M.4	$\begin{aligned}& \mathrm{H}_2 \mathrm{O}+\mathrm{e}^{-} \rightarrow ^* \mathrm{H}+\mathrm{OH}^{-} \\& ^* \mathrm{CO}+^+\mathrm{H} \stackrel{\mathrm{RDS}}{\longrightarrow} {^} \mathrm{CO}(\mathrm{H})\end{aligned} $	60	Yes
M.5	$\begin{aligned}& ^* \mathrm{CO}+\mathrm{H}_2 \mathrm{O}+\mathrm{e}^{-} \rightarrow ^* \mathrm{CO}(\mathrm{H})+\mathrm{OH}^{-} \\& ^* \mathrm{CO}(\mathrm{H})+^* \mathrm{CO} / \mathrm{CO}_{\mathrm{b}}+\mathrm{e}^{-} \stackrel{\mathrm{RDS}}{\longrightarrow} {^*} \mathrm{C}_2 \mathrm{O}_2(\mathrm{H})^{-}\end{aligned} $	40	Yes

	Elementary step	b^a/(mV∙dec⁻¹)
M. i	CO₂ + H₂O + e⁻ + * ↔ *COOH + OH⁻	120
	COOH + H₂O ↔ COOHH ⁺+ OH⁻	60
	COOHH ⁺ + e⁻ ↔ CO + H₂O	40
	CO ↔ CO +	30
M. ii	CO₂ + e⁻ + * ↔ *CO₂⁻	120
	CO₂⁻ + H₂O ↔ COOH + OH⁻	60
	COOH + H₂O + e⁻ ↔ CO + OH⁻	40
	CO ↔ CO +	30

Elementary step	α if RDS	b/(mV·dec⁻¹) (θ_* = 1)
O₂ + H ⁺ + e⁻ + * ↔ *OOH	β₁ + θ_OH + 2θ_O + 3θ_OOH	120
OOH + ↔ O + OH	1 + 2θ_OH + 4θ_O − 2θ_OOH	60
O + H ⁺ + e⁻ ↔ OH	β₃ + 2 + θ_OH − 2θ_O − θ_OOH	24
2(OH + e⁻ ↔ H₂O + )	β₄ + 1 − θ_OH − θ_OOH	40

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