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Insights into the reversible oxygen reduction reaction in a series of phosphonium-based ionic liquids

journal contribution
posted on 22.10.2014, 00:00 authored by Cristina Pozo-GonzaloCristina Pozo-Gonzalo, Patrick HowlettPatrick Howlett, J L Hodgson, L A Madsen, D R MacFarlane, Maria ForsythMaria Forsyth
New findings supporting the stability of the superoxide ion, O2˙(-), in the presence of the phosphonium cation, [P6,6,6,14](+), are presented. Extended electrochemical investigations of a series of neat phosphonium-based ILs with different anions, including chloride, bis(trifluoromethylsulfonyl)imide and dicyanamide, demonstrate the chemical reversibility of the oxygen reduction process. Quantum chemistry calculations show a short intermolecular distance (r = 3.128 Å) between the superoxide ion and the phosphonium cation. NMR experiments have been performed to assess the degree of long term degradation of [P6,6,6,14](+), in the presence of superoxide and peroxide species, showing no chemically distinct degradation products of importance in reversible air cathodes.

History

Journal

Physical chemistry chemical physics

Volume

16

Issue

45

Pagination

25062 - 25070

Publisher

Royal Society of Chemistry

Location

Cambridge, England

eISSN

1463-9084

Language

eng

Publication classification

C Journal article; C1 Refereed article in a scholarly journal

Copyright notice

2014, Royal Society of Chemistry