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The voltammetry of decamethylferrocene and coboltacene in supercritical difluoromethane (R32)

The voltammetry of decamethylferrocene and coboltacene in supercritical difluoromethane (R32)
The voltammetry of decamethylferrocene and coboltacene in supercritical difluoromethane (R32)
The voltammetry of decamethylferrocene, cobaltocene and decamethylcobaltocene at micro and macro disc electrodes in supercritical difluoromethane at 360 K and 17.6 MPa has been studied. In all cases the voltammetry is distorted to some degree by the effects of random convection but these can be supressed by adding a baffle around the electrode. The voltammetry of decamethylferrocene is well behaved with fast electrode kinetics at Pt microdisc electrodes. The limiting currents, corrected for random convection, obey the normal microdisc equation and are linear in electrode radius for decamethylferrocene up to the highest concentration (11 mM) used in this study. Based on the microelectrode studies, we find that the diffusion coefficient of decamethylferrocene in supercritical difluoromethane containing 20 mM [NBun4][BF4] at 360 K and 17.6 MPa is 8.3 x 10-5 cm2 s-1. Finally we have briefly investigated the voltammetry of cobaltocene and decamethylcobaltocene in supercritical difluoromethane under the same conditions. We find that reduction of the cobaltocenium cation leads to fouling of the Pt microdisc electrode which limits its use as a model redox system and that reduction of the decamethylcobaltocenium cation was not observed before electrolyte reduction at around -1.6 V vs. Pt.
1572-6657
282-289
Bartlett, Philip
d99446db-a59d-4f89-96eb-f64b5d8bb075
Branch, Jack
42ac8ec4-09f2-4cb7-b2c4-f81a73529e6d
Bartlett, Philip
d99446db-a59d-4f89-96eb-f64b5d8bb075
Branch, Jack
42ac8ec4-09f2-4cb7-b2c4-f81a73529e6d

Bartlett, Philip and Branch, Jack (2016) The voltammetry of decamethylferrocene and coboltacene in supercritical difluoromethane (R32). Journal of Electroanalytical Chemistry, 780, 282-289. (doi:10.1016/j.jelechem.2016.09.043).

Record type: Article

Abstract

The voltammetry of decamethylferrocene, cobaltocene and decamethylcobaltocene at micro and macro disc electrodes in supercritical difluoromethane at 360 K and 17.6 MPa has been studied. In all cases the voltammetry is distorted to some degree by the effects of random convection but these can be supressed by adding a baffle around the electrode. The voltammetry of decamethylferrocene is well behaved with fast electrode kinetics at Pt microdisc electrodes. The limiting currents, corrected for random convection, obey the normal microdisc equation and are linear in electrode radius for decamethylferrocene up to the highest concentration (11 mM) used in this study. Based on the microelectrode studies, we find that the diffusion coefficient of decamethylferrocene in supercritical difluoromethane containing 20 mM [NBun4][BF4] at 360 K and 17.6 MPa is 8.3 x 10-5 cm2 s-1. Finally we have briefly investigated the voltammetry of cobaltocene and decamethylcobaltocene in supercritical difluoromethane under the same conditions. We find that reduction of the cobaltocenium cation leads to fouling of the Pt microdisc electrode which limits its use as a model redox system and that reduction of the decamethylcobaltocenium cation was not observed before electrolyte reduction at around -1.6 V vs. Pt.

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More information

Accepted/In Press date: 26 September 2016
e-pub ahead of print date: 28 September 2016
Published date: 1 November 2016
Organisations: Electrochemistry

Identifiers

Local EPrints ID: 401569
URI: http://eprints.soton.ac.uk/id/eprint/401569
ISSN: 1572-6657
PURE UUID: 2fab2500-0b87-4bc3-b3db-27386bda9d44
ORCID for Philip Bartlett: ORCID iD orcid.org/0000-0002-7300-6900

Catalogue record

Date deposited: 18 Oct 2016 13:30
Last modified: 19 Nov 2019 06:34

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