Mechanism of Electrochemical Oxidation of Nitroxide Radicals in Ethaline Deep Eutectic Solvent
Abstract
Deep eutectic solvents (DESs) are emerging as promising electrolytes for electrochemical energy storage applications. Electroactive nitroxide-radical-containing organics can be dissolved in DESs to facilitate redox reactions; however, mechanistic know-how of their charge transfer kinetics at the electrode surface is rather limited. In this work, we investigate the mechanism underlying the electrochemical oxidation of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-hydroxy-TEMPO). Using polarization measurements on a platinum rotating disk electrode and micro-electrode, we show that the anodic charge transfer coefficient ($$\alpha $$) for one-electron transfer oxidations of TEMPO and 4-hydroxy-TEMPO approaches 0.9 in DES as well as in aqueous electrolytes, i.e., a significant deviation from α ≈ 0.5 expected for symmetric redox behavior. To explain this observation, a two-step oxidation mechanism is proposed wherein the nitroxide-containing species undergo fast charge transfer at an electrode surface followed by slow rate-limiting desorption of the adsorbed oxidized species. Numerical simulations are reported to characterize how the proposed two-step mechanism manifests in transient cyclic voltammetry behavior of the 4-hydroxy-TEMPO oxidation reaction, and good agreement with experiments is noted.
- Authors:
-
[2];
[1]
- Case Western Reserve Univ., Cleveland, OH (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Case Western Reserve Univ., Cleveland, OH (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1808445
- Alternate Identifier(s):
- OSTI ID: 1716752
- Report Number(s):
- BNL-220597-2020-JAAM
Journal ID: ISSN 0013-4651
- Grant/Contract Number:
- SC0019409; SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Volume: 167; Journal Issue: 14; Journal ID: ISSN 0013-4651
- Publisher:
- IOP Publishing - The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Shaheen, Nora A., Ijjada, Mahesh, Vukmirovic, Miomir B., and Akolkar, Rohan. Mechanism of Electrochemical Oxidation of Nitroxide Radicals in Ethaline Deep Eutectic Solvent. United States: N. p., 2020.
Web. doi:10.1149/1945-7111/abc439.
Shaheen, Nora A., Ijjada, Mahesh, Vukmirovic, Miomir B., & Akolkar, Rohan. Mechanism of Electrochemical Oxidation of Nitroxide Radicals in Ethaline Deep Eutectic Solvent. United States. https://doi.org/10.1149/1945-7111/abc439
Shaheen, Nora A., Ijjada, Mahesh, Vukmirovic, Miomir B., and Akolkar, Rohan. Thu .
"Mechanism of Electrochemical Oxidation of Nitroxide Radicals in Ethaline Deep Eutectic Solvent". United States. https://doi.org/10.1149/1945-7111/abc439. https://www.osti.gov/servlets/purl/1808445.
@article{osti_1808445,
title = {Mechanism of Electrochemical Oxidation of Nitroxide Radicals in Ethaline Deep Eutectic Solvent},
author = {Shaheen, Nora A. and Ijjada, Mahesh and Vukmirovic, Miomir B. and Akolkar, Rohan},
abstractNote = {Deep eutectic solvents (DESs) are emerging as promising electrolytes for electrochemical energy storage applications. Electroactive nitroxide-radical-containing organics can be dissolved in DESs to facilitate redox reactions; however, mechanistic know-how of their charge transfer kinetics at the electrode surface is rather limited. In this work, we investigate the mechanism underlying the electrochemical oxidation of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-hydroxy-TEMPO). Using polarization measurements on a platinum rotating disk electrode and micro-electrode, we show that the anodic charge transfer coefficient ($\alpha $) for one-electron transfer oxidations of TEMPO and 4-hydroxy-TEMPO approaches 0.9 in DES as well as in aqueous electrolytes, i.e., a significant deviation from α ≈ 0.5 expected for symmetric redox behavior. To explain this observation, a two-step oxidation mechanism is proposed wherein the nitroxide-containing species undergo fast charge transfer at an electrode surface followed by slow rate-limiting desorption of the adsorbed oxidized species. Numerical simulations are reported to characterize how the proposed two-step mechanism manifests in transient cyclic voltammetry behavior of the 4-hydroxy-TEMPO oxidation reaction, and good agreement with experiments is noted.},
doi = {10.1149/1945-7111/abc439},
journal = {Journal of the Electrochemical Society},
number = 14,
volume = 167,
place = {United States},
year = {Thu Nov 05 00:00:00 EST 2020},
month = {Thu Nov 05 00:00:00 EST 2020}
}
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