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Transient study of the oxygen reduction reaction on reduced Pt and Pt alloys microelectrodes: evidence for the reduction of pre-adsorbed oxygen species linked to dissolved oxygen

Transient study of the oxygen reduction reaction on reduced Pt and Pt alloys microelectrodes: evidence for the reduction of pre-adsorbed oxygen species linked to dissolved oxygen
Transient study of the oxygen reduction reaction on reduced Pt and Pt alloys microelectrodes: evidence for the reduction of pre-adsorbed oxygen species linked to dissolved oxygen
Using chronoamperometry at preconditioned oxide-free Pt microdisc electrodes in aqueous media, we investigated the oxygen reduction reaction (ORR) on the millisecond timescale and obtained results consistent with the reduction of oxygen species which adsorb on the electrode before the ORR is electrochemically driven. Furthermore these adsorbed species are clearly linked to oxygen in solution. At long times, the amperometric response is solely controlled by the diffusion of dissolved oxygen towards the microelectrode. However, at short times, typically below 50 ms, the reduction of pre-adsorbed oxygen produces a large extra current whose magnitude depends on the oxygen concentration in solution, deliberate electrode poisoning and the rest time before the potential step. Using sampled current voltammetry we show that this extra current affects the entire potential range of the ORR. Using microdisc electrodes made with Pt alloys we find that the amperometric response is sufficiently sensitive to distinguish oxygen coverage differences between Pt, Pt0.9Rh0.1 and Pt0.9Ir0.1 microdiscs. These unexpected and, to our knowledge, never previously reported results provide new insight into the oxygen reduction reaction on Pt. The existence over a wide potential range of irreversibly adsorbed oxygen species arising from dissolved oxygen and different from Pt oxide is particularly relevant to the development of oxygen reduction catalysts for low temperature fuel cells.
1463-9076
30005-30012
Perry, Samuel
8e204d86-4a9c-4a5d-9932-cf470174648e
Denuault, Guy
5c76e69f-e04e-4be5-83c5-e729887ffd4e
Perry, Samuel
8e204d86-4a9c-4a5d-9932-cf470174648e
Denuault, Guy
5c76e69f-e04e-4be5-83c5-e729887ffd4e

Perry, Samuel and Denuault, Guy (2015) Transient study of the oxygen reduction reaction on reduced Pt and Pt alloys microelectrodes: evidence for the reduction of pre-adsorbed oxygen species linked to dissolved oxygen. Physical Chemistry Chemical Physics, 30005-30012. (doi:10.1039/C5CP04667J).

Record type: Article

Abstract

Using chronoamperometry at preconditioned oxide-free Pt microdisc electrodes in aqueous media, we investigated the oxygen reduction reaction (ORR) on the millisecond timescale and obtained results consistent with the reduction of oxygen species which adsorb on the electrode before the ORR is electrochemically driven. Furthermore these adsorbed species are clearly linked to oxygen in solution. At long times, the amperometric response is solely controlled by the diffusion of dissolved oxygen towards the microelectrode. However, at short times, typically below 50 ms, the reduction of pre-adsorbed oxygen produces a large extra current whose magnitude depends on the oxygen concentration in solution, deliberate electrode poisoning and the rest time before the potential step. Using sampled current voltammetry we show that this extra current affects the entire potential range of the ORR. Using microdisc electrodes made with Pt alloys we find that the amperometric response is sufficiently sensitive to distinguish oxygen coverage differences between Pt, Pt0.9Rh0.1 and Pt0.9Ir0.1 microdiscs. These unexpected and, to our knowledge, never previously reported results provide new insight into the oxygen reduction reaction on Pt. The existence over a wide potential range of irreversibly adsorbed oxygen species arising from dissolved oxygen and different from Pt oxide is particularly relevant to the development of oxygen reduction catalysts for low temperature fuel cells.

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20151019_C5CP04667J_article as accepted.pdf - Accepted Manuscript
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Submitted date: 6 August 2015
Accepted/In Press date: 19 October 2015
Published date: 19 October 2015
Organisations: Electrochemistry

Identifiers

Local EPrints ID: 383054
URI: http://eprints.soton.ac.uk/id/eprint/383054
ISSN: 1463-9076
PURE UUID: 07d3acc2-cea4-452d-b2d4-342686a3c91b
ORCID for Samuel Perry: ORCID iD orcid.org/0000-0002-6263-6114
ORCID for Guy Denuault: ORCID iD orcid.org/0000-0002-8630-9492

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Date deposited: 21 Oct 2015 09:26
Last modified: 11 Jun 2024 01:55

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Contributors

Author: Samuel Perry ORCID iD
Author: Guy Denuault ORCID iD

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