Interpreting Tafel behavior of consecutive electrochemical reactions through combined thermodynamic and steady state microkinetic approaches
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 ($$11\bar{2}0$$) surfaces of the β-Co(OH)2, β-CoOOH, and CoO2 bulk phases. Finally, 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.
- Authors:
-
[1];
[3];
[1]
- Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. of Notre Dame, IN (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1608944
- Alternate Identifier(s):
- OSTI ID: 1595496
- Grant/Contract Number:
- AC02-05CH11231; AC02-76SF00515; SC0008685
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy & Environmental Science
- Additional Journal Information:
- Journal Volume: 13; Journal Issue: 2; Journal ID: ISSN 1754-5692
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Mefford, J. Tyler, Zhao, Zhenghang, Bajdich, Michal, and Chueh, William C. Interpreting Tafel behavior of consecutive electrochemical reactions through combined thermodynamic and steady state microkinetic approaches. United States: N. p., 2020.
Web. doi:10.1039/c9ee02697e.
Mefford, J. Tyler, Zhao, Zhenghang, Bajdich, Michal, & Chueh, William C. Interpreting Tafel behavior of consecutive electrochemical reactions through combined thermodynamic and steady state microkinetic approaches. United States. https://doi.org/10.1039/c9ee02697e
Mefford, J. Tyler, Zhao, Zhenghang, Bajdich, Michal, and Chueh, William C. Fri .
"Interpreting Tafel behavior of consecutive electrochemical reactions through combined thermodynamic and steady state microkinetic approaches". United States. https://doi.org/10.1039/c9ee02697e. https://www.osti.gov/servlets/purl/1608944.
@article{osti_1608944,
title = {Interpreting Tafel behavior of consecutive electrochemical reactions through combined thermodynamic and steady state microkinetic approaches},
author = {Mefford, J. Tyler and Zhao, Zhenghang and Bajdich, Michal and Chueh, William C.},
abstractNote = {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 ($11\bar{2}0$) surfaces of the β-Co(OH)2, β-CoOOH, and CoO2 bulk phases. Finally, 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.},
doi = {10.1039/c9ee02697e},
journal = {Energy & Environmental Science},
number = 2,
volume = 13,
place = {United States},
year = {2020},
month = {1}
}
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