Insights into the reversible oxygen reduction reaction in a series of phosphonium-based ionic liquids
Literature Information
Cristina Pozo-Gonzalo, Patrick C. Howlett, Jennifer L. Hodgson, Louis A. Madsen, Douglas R. MacFarlane, Maria 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.
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