Potential oscillations and S-shaped polarization curve in the continuous electro-oxidation of CO on platinum single-crystal electrodes

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The occurrence of an S-shaped polarization curve in a simple model for the continuous electrochemical oxidation of CO on a platinum electrode is discussed. In the model, the S-shaped polarization curve is caused by the competitive Langmuir-Hinshelwood mechanism between surface-bonded CO and OH. The reaction is studied experimentally on single-crystal platinum rotating disk electrodes in perchloric and sulfuric acid solution, and it is shown that the voltammetry is in good agreement with the model predictions. When studied under current-controlled conditions, a fast galvanodynamic scan indeed suggests the existence of the S-shaped polarization curve. At lower scan rates, however, irregularities and ... continued below

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15 pages

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Koper, Marc T.M.; Schmidt, Thomas J.; Markovic, Nenad M. & Ross, Philip N. March 1, 2001.

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The occurrence of an S-shaped polarization curve in a simple model for the continuous electrochemical oxidation of CO on a platinum electrode is discussed. In the model, the S-shaped polarization curve is caused by the competitive Langmuir-Hinshelwood mechanism between surface-bonded CO and OH. The reaction is studied experimentally on single-crystal platinum rotating disk electrodes in perchloric and sulfuric acid solution, and it is shown that the voltammetry is in good agreement with the model predictions. When studied under current-controlled conditions, a fast galvanodynamic scan indeed suggests the existence of the S-shaped polarization curve. At lower scan rates, however, irregularities and small-amplitude irregular fluctuations or oscillations in potential are observed. Very regular potential oscillations under current-controlled conditions are observed only on Pt(111) in sulfuric acid. The possible origin of these irregularities and oscillations is discussed in relation to the existing theories of electrochemical instabilities.

Physical Description

15 pages

Notes

OSTI as DE00836369

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  • Journal Name: Journal of Physical Chemistry; Journal Volume: 105; Journal Issue: 35; Other Information: Submitted to Journal of Physical Chemistry: Volume 105, No.35; Journal Publication Date: 09/06/2001

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  • Report No.: LBNL--48484
  • Grant Number: AC03-76SF00098
  • Office of Scientific & Technical Information Report Number: 836369
  • Archival Resource Key: ark:/67531/metadc779991

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Office of Scientific & Technical Information Technical Reports

Reports, articles and other documents harvested from the Office of Scientific and Technical Information.

Office of Scientific and Technical Information (OSTI) is the Department of Energy (DOE) office that collects, preserves, and disseminates DOE-sponsored research and development (R&D) results that are the outcomes of R&D projects or other funded activities at DOE labs and facilities nationwide and grantees at universities and other institutions.

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  • March 1, 2001

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  • Dec. 3, 2015, 9:30 a.m.

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  • April 4, 2016, 4:27 p.m.

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Koper, Marc T.M.; Schmidt, Thomas J.; Markovic, Nenad M. & Ross, Philip N. Potential oscillations and S-shaped polarization curve in the continuous electro-oxidation of CO on platinum single-crystal electrodes, article, March 1, 2001; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc779991/: accessed December 15, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.