电催化动力学简介

doi:10.3866/PKU.WHXB202210025

Abstract

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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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

Figures/Tables 9

References 42

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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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Introduction to Electrocatalytic Kinetics

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