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High Sensitivity of Electron Transfer Rates within Nafion Coatings Saturated with Os(bpy)^(2+)_3 to the Extent of Hydration of the Coating

Shi, Minglian and Anson, Fred C. (1995) High Sensitivity of Electron Transfer Rates within Nafion Coatings Saturated with Os(bpy)^(2+)_3 to the Extent of Hydration of the Coating. Journal of the Electrochemical Society, 142 (12). pp. 4205-4214. ISSN 0013-4651. http://resolver.caltech.edu/CaltechAUTHORS:20120702-110414259

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Abstract

The sensitivity of the electrochemical responses obtained from electroactive counterions incorporated in Nafion coatings to the extent of hydration of the coatings^(27-38) is shown to be enhanced significantly when the electroactive ion is the only counterion present in the coating. Nafion coatings fully saturated with Os(bpy)^(2+)_3 exhibit unusually narrow and sharply peaked anodic currents in first-scan oxidative voltammograms. This voltammetric feature is accompanied by the expulsion of one-third of the Os complex from the coating. The counterion actually ejected is primarily Os(bpy)^(3+)_3. As the Os(bpy)^(3+)_3 counterions are ejected, H_2O molecules enter the coatings. The quantity of H_2O molecules incorporated is so large that the mass of the coating (monitored with a quartz crystal microbalance) increases despite the ejection of the heavy Os(bpy)^(3+)_3 cations. After several voltammetric cycles, normally shaped voltammograms are obtained that are relatively insensitive to the initial state of hydration of the coatings. The contrasting behaviors of hydrated and unhydrated coatings are compared, and possible explanations are offered for the differences observed.


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Additional Information:© 1995 The Electrochemical Society, Inc. Submitted May 22, 1995; revised July 18, 1995. This work was supported by the National Science Foundation. We appreciated receiving a copy of Ref. 15 from Dr. I.-C. Jeon prior to publication. Manuscript submitted May 22, 1995:, revised manuscript received July 18, 1995. California Institute of Technology assisted in meeting the publication costs of this article.
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Record Number:CaltechAUTHORS:20120702-110414259
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20120702-110414259
Official Citation:High Sensitivity of Electron Transfer Rates within Nafion Coatings Saturated with Os(bpy)[sub 3][sup 2+] to the Extent of Hydration of the Coating Minglian Shi and Fred C. Anson, J. Electrochem. Soc. 142, 4205 (1995), DOI:10.1149/1.2048485
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ID Code:32234
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Deposited By: Aucoeur Ngo
Deposited On:03 Jul 2012 16:30
Last Modified:26 Dec 2012 15:27

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