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

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...

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Main Author: Delorme, Astrid
Format: Thesis (University of Nottingham only)
Language:English
Published: 2020
Subjects:
Online Access:https://eprints.nottingham.ac.uk/59635/
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author Delorme, Astrid
author_facet Delorme, Astrid
author_sort Delorme, Astrid
building Nottingham Research Data Repository
collection Online Access
description 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.
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format Thesis (University of Nottingham only)
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institution University of Nottingham Malaysia Campus
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language English
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publishDate 2020
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spelling nottingham-596352025-02-28T14:44:41Z https://eprints.nottingham.ac.uk/59635/ TEMPO and RTILs for the sustainable development of TEMPO - mediated alcohol electrooxidation Delorme, Astrid 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. 2020-03-15 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en arr https://eprints.nottingham.ac.uk/59635/1/Thesis_Final_after%20viva.pdf Delorme, Astrid (2020) TEMPO and RTILs for the sustainable development of TEMPO - mediated alcohol electrooxidation. PhD thesis, University of Nottingham. TEMPO Alcohol oxidation Ionic liquids Electrosynthesis Electrochemistry Paired electrosynthesis
spellingShingle TEMPO
Alcohol oxidation
Ionic liquids
Electrosynthesis
Electrochemistry
Paired electrosynthesis
Delorme, Astrid
TEMPO and RTILs for the sustainable development of TEMPO - mediated alcohol electrooxidation
title TEMPO and RTILs for the sustainable development of TEMPO - mediated alcohol electrooxidation
title_full TEMPO and RTILs for the sustainable development of TEMPO - mediated alcohol electrooxidation
title_fullStr TEMPO and RTILs for the sustainable development of TEMPO - mediated alcohol electrooxidation
title_full_unstemmed TEMPO and RTILs for the sustainable development of TEMPO - mediated alcohol electrooxidation
title_short TEMPO and RTILs for the sustainable development of TEMPO - mediated alcohol electrooxidation
title_sort tempo and rtils for the sustainable development of tempo - mediated alcohol electrooxidation
topic TEMPO
Alcohol oxidation
Ionic liquids
Electrosynthesis
Electrochemistry
Paired electrosynthesis
url https://eprints.nottingham.ac.uk/59635/