A1 Journal article (refereed)
Exploration of Vitamin B6‐Based Redox‐Active Pyridinium Salts towards the Application in Aqueous Organic Flow Batteries (2024)

Nechaev, A. A., Gonzalez, G., Verma, P., Peshkov, V. A., Bannykh, A., Hashemi, A., Hannonen, J., Hamza, A., Papai, I., Laasonen, K., Peljo, P., & Pihko, P. M. (2024). Exploration of Vitamin B6‐Based Redox‐Active Pyridinium Salts towards the Application in Aqueous Organic Flow Batteries. Chemistry: A European Journal, 30(36), Article e202400828. https://doi.org/10.1002/chem.202400828

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Publication details

All authors or editors: Nechaev, Anton A.; Gonzalez, Gabriel; Verma, Prachi; Peshkov, Vsevolod A.; Bannykh, Anton; Hashemi, Arsalan; Hannonen, Jenna; Hamza, Andrea; Papai, Imre; Laasonen, Kari; et al.

Journal or series: Chemistry: A European Journal

ISSN: 0947-6539

eISSN: 1521-3765

Publication year: 2024

Publication date: 19/04/2024

Volume: 30

Issue number: 36

Article number: e202400828

Publisher: Wiley-VCH Verlag

Publication country: Germany

Publication language: English

DOI: https://doi.org/10.1002/chem.202400828

Publication open access: Openly available

Publication channel open access: Partially open access channel

Web address of parallel published publication (pre-print): https://chemrxiv.org/engage/chemrxiv/article-details/65d34e5b66c1381729faf63b

Abstract

Pyridoxal hydrochloride, a vitamin B6 vitamer, was synthetically converted to a series of diverse redox-active benzoyl pyridinium salts. Cyclic voltammetry studies demonstrated redox reversibility under basic conditions, and two of the most promising salts were subjected to laboratory-scale redox flow battery tests involving galvanostatic cycling at 10 mM in 0.1 M NaOH. In these tests, the battery was charged completely, corresponding to the transfer of two electrons to the electrolyte, but no discharge was observed. Both CV analysis and electrochemical simulations confirmed that the redox wave observed in the experimental voltammograms corresponds to a two-electron process. To explain the irreversibility in the battery tests, we conducted bulk electrolysis with the benzoyl pyridinium salts, affording the corresponding benzylic secondary alcohols. Computational studies suggest that the reduction proceeds in three consecutive steps: first electron transfer (ET), then proton-coupled electron transfer (PCET) and finally proton transfer (PT) to give the secondary alcohol. 1H NMR deuterium exchange studies indicated that the last PT step is not reversible in 0.1 M NaOH, rendering the entire redox process irreversible. The apparent reversibility observed in CV at the basic media likely arises from the slow rate of the PT step at the timescale of the measurement.

Keywords: oxidation-reduction reaction; electrolytes; heterocyclic compounds; vitamin B6; accumulators; electrochemistry

Free keywords: pyridinium ions; pyridoxal; vitamin B6; electrochemistry; redox flow batteries

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Ministry reporting: Yes

VIRTA submission year: 2024

Preliminary JUFO rating: 2