Jump to main content
Jump to site search

Issue 2, 2020
Previous Article Next Article

Interpreting Tafel behavior of consecutive electrochemical reactions through combined thermodynamic and steady state microkinetic approaches

Author affiliations

Abstract

Assessing the reaction pathway of multi-electron-transfer reactions is an essential yet difficult task for the rational design of electrocatalysts. In this work, we develop a heuristic approach that combines thermodynamic adsorption energetics calculated through density functional theory with microkinetic modeling using the steady state approximation to interpret the potential-dependent Tafel behavior of consecutive electrochemical reactions. In doing so, we introduce a kinetic framework for ab initio calculations that ensures self-consistent adsorption energetics based on kinetically limited adsorbate coverages. The approach is applied to experimental results on CoOx(OH)2−x single crystal electrocatalyst particles yielding coverage dependent mechanistic information and identification of the rate-limiting step with standard rate constants for the oxygen evolution reaction on the (11[2 with combining macron]0) surfaces of the β-Co(OH)2, β-CoOOH, and CoO2 bulk phases. This generalizable method enables catalyst benchmarking based on determining the active species involved and associated intrinsic reaction rate constants in consecutive multi-electron-transfer reactions.

Graphical abstract: Interpreting Tafel behavior of consecutive electrochemical reactions through combined thermodynamic and steady state microkinetic approaches

Back to tab navigation

Supplementary files

Article information


Submitted
23 Aug 2019
Accepted
17 Jan 2020
First published
17 Jan 2020

Energy Environ. Sci., 2020,13, 622-634
Article type
Paper

Interpreting Tafel behavior of consecutive electrochemical reactions through combined thermodynamic and steady state microkinetic approaches

J. T. Mefford, Z. Zhao, M. Bajdich and W. C. Chueh, Energy Environ. Sci., 2020, 13, 622
DOI: 10.1039/C9EE02697E

Social activity

Search articles by author

Spotlight

Advertisements