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Use of Electrochemical Microscopy to Examine Counterion Ejection from Nafion Coatings on Electrodes

Lee, Chongmok and Anson, Fred C. (1992) Use of Electrochemical Microscopy to Examine Counterion Ejection from Nafion Coatings on Electrodes. Analytical Chemistry, 64 (5). pp. 528-533. ISSN 0003-2700. doi:10.1021/ac00029a015.

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The ideal cation permselectivity exhibited by electrode coatings prepared from the polyelectrolyte Nafion leads to ejection of countercatlons from the coatings during electrochemical oxidation of Os(bpy)_3^(2+) counterions incorporated in the coatings. If the coatings are saturated with Os(bpy)_3^(2+) so that these are the only counterions present, one-third of the incorporated cations are ejected during the oxidation of Os(bpy)_3^(2+) to Os(bpy)_3^(3+). The cyclic voltammetry of the incorporated Os(bpy)_3^(3+/2+) couple is altered substantially in the absence of additional counterions. The changes are attributed to contributions to the voltammetric potentials from the free energy of transfer of these strongly bound counterions. Microtip electrodes positioned just above Nafion-coated electrodes were used to monitor the ejection of both Os(bpy)_3^(3+) and Os(bpy)_3^(2+) from Nafion coatings. Much more of the former complex lo ejected from saturated coatings which is believed to be the result of electric field-assisted ejection.

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Additional Information:© 1992 American Chemical Soclety. Received for review September 19,1991. Accepted November 26, 1991. Published in print 1 March 1992. This work was supported by the National Science Foundation and the U.S. Army Research Office. This paper is contribution no. 8510 from the Division of Chemistry and Chemical Engineering.
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Army Research Office (ARO)UNSPECIFIED
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Caltech Division of Chemistry and Chemical Engineering8510
Issue or Number:5
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Official Citation:Use of electrochemical microscopy to examine counterion ejection from Nafion coatings on electrodes Chongmok. Lee and Fred C. Anson Analytical Chemistry 1992 64 (5), 528-533 DOI: 10.1021/ac00029a015
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:84571
Deposited By: Ruth Sustaita
Deposited On:31 Jan 2018 18:30
Last Modified:15 Nov 2021 20:21

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