TEMPO and RTILs for the sustainable development of TEMPO - mediated alcohol electrooxidation

Delorme, Astrid (2020) TEMPO and RTILs for the sustainable development of TEMPO - mediated alcohol electrooxidation. PhD thesis, University of Nottingham.

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Abstract

In this thesis, TEMPO-mediated alcohol electrooxidation in room-temperature ionic liquids (RTILs) is described and it is shown that the reactivity and selectivity of the electrocatalytic oxidations can be manipulated by design of the solvent medium. Moreover, higher reaction kinetics and selectivity are obtained in bis(trifluoromethanesulfonyl)imide ([NTf2]–)-based RTILs than in acetonitrile, often the solvent-of-choice in indirect alcohol electrooxidations.

Electrolytic TEMPO-mediated alcohol oxidations are performed using RTILs in a flow-electrolysis system. Excellent yields and reaction selectivity are achieved, demonstrating the opportunities of replacing volatile molecular solvents and extraneous electrolytes in efficient electrolyses of alcohol oxidations.

Furthermore, by increasing the functionality of the RTIL medium the chemical input as well as the waste formation can be reduced in TEMPO-mediated alcohol oxidations. The use of a stoichiometric base is avoided in the paired electrosynthesis where the base is generated in situ, through the electroreduction of a protic RTIL at the counter electrode in parallel with the alcohol oxidation at the working electrode.

Item Type: Thesis (University of Nottingham only) (PhD)
Supervisors: Licence, Peter
Walsh, Darren
Sans, Victor
Keywords: TEMPO, Alcohol oxidation, Ionic liquids, Electrosynthesis, Electrochemistry, Paired electrosynthesis
Subjects: Q Science > QD Chemistry
Faculties/Schools: UK Campuses > Faculty of Science > School of Chemistry
Item ID: 59635
Depositing User: Delorme, Astrid
Date Deposited: 03 Jun 2020 12:49
Last Modified: 03 Jun 2020 13:00
URI: http://eprints.nottingham.ac.uk/id/eprint/59635

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