Mechanism of Electrochemical Oxidation of Nitroxide Radicals in Ethaline Deep Eutectic Solvent

Shaheen, Nora A.; Vukmirovic, Miomir B.; Mahesh, Ijjada; Akolkar, Rohan

doi:10.1149/1945-7111/abc439

Mechanism of Electrochemical Oxidation of Nitroxide Radicals in Ethaline Deep Eutectic Solvent

Journal Article · Wed Nov 04 23:00:00 EST 2020 · Journal of the Electrochemical Society (Online)

DOI:https://doi.org/10.1149/1945-7111/abc439· OSTI ID:1716752

Shaheen, Nora A. ^[1]; ^[2]; Mahesh, Ijjada ^[1]; Akolkar, Rohan ^[1]

Case Western Reserve Univ., Cleveland, OH (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; SC0019409

OSTI ID:: 1716752

Alternate ID(s):: OSTI ID: 1808445

Report Number(s):: BNL--220597-2020-JAAM

Journal Information:: Journal of the Electrochemical Society (Online), Journal Name: Journal of the Electrochemical Society (Online) Journal Issue: 14 Vol. 167; ISSN 1945-7111

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

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