Issue 20, 2013

Kinetics and mechanism of oxygen reduction in a protic ionic liquid

Abstract

The oxygen reduction reaction (ORR) has been studied at Pt surfaces in the protic ionic liquid diethylmethylammonium trifluoromethanesulfonate. Water content measurements suggested that the ORR proceeded in the ionic liquid predominantly via a 4-electron reduction to water. A mechanistic analysis using rotating ring-disk electrode (RRDE) voltammetry confirmed that negligible amounts of hydrogen peroxide were formed during the ORR. A kinetic analysis of the ORR was performed using rotating disk electrode (RDE) voltammetry and the importance of correcting for ohmic (iR) drop prior to performing kinetic measurements in the ionic liquid is demonstrated. A Tafel analysis of the RDE voltammetry data revealed a change in the ORR Tafel slope from 70 mV per decade at low ORR overpotentials to 117 mV per decade at high overpotentials, and the reason for this change is discussed. The change in the Tafel slope for the ORR with increasing overpotential meant that the exchange current density for the ORR varied from 0.007 nA cm−2 to 10 nA cm−2, depending on the applied potential. Finally, the implications of these results for the development of protic ionic liquid fuel cells are discussed.

Graphical abstract: Kinetics and mechanism of oxygen reduction in a protic ionic liquid

Supplementary files

Article information

Article type
Paper
Submitted
24 Dec 2012
Accepted
03 Apr 2013
First published
05 Apr 2013

Phys. Chem. Chem. Phys., 2013,15, 7548-7554

Kinetics and mechanism of oxygen reduction in a protic ionic liquid

D. A. Walsh, A. Ejigu, J. Smith and P. Licence, Phys. Chem. Chem. Phys., 2013, 15, 7548 DOI: 10.1039/C3CP44669G

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