TEMPO and RTILs for the sustainable development of TEMPO - mediated alcohol electrooxidation
Publication Date
March 15, 2020
Creator
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
ethesis
Thesis Type
PhD
Supervisors
Subjects (LC)
Associated Schools / Departments
School of Chemistry
eprints ID
59635
UoN Repository URI
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Thesis_Final_after viva.pdf
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Full-text
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