Issue 45, 2014

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

Abstract

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.

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

Supplementary files

Article information

Article type
Paper
Submitted
12 Sep 2014
Accepted
14 Oct 2014
First published
15 Oct 2014

Phys. Chem. Chem. Phys., 2014,16, 25062-25070

Author version available

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

C. Pozo-Gonzalo, P. C. Howlett, J. L. Hodgson, L. A. Madsen, D. R. MacFarlane and M. Forsyth, Phys. Chem. Chem. Phys., 2014, 16, 25062 DOI: 10.1039/C4CP04101A

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