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Absence of diffuse double layer effect on the vibrational properties and oxidation of chemisorbed carbon monoxide on a Pt(111) electrode

Published

Author(s)

Marta C. Figueiredo, Dennis Hiltrop, Ravishankar Sundararaman, Kathleen Schwarz, Marc Koper

Abstract

In this work we investigate the effects of the diffuse double layer thickness on the electrochemical Stark tuning and oxidation of carbon monoxide at Pt(111) surfaces in perchloric acid solution. The diffuse double layer thickness was modified by changing the concentration (ionic strength) of the supporting electrolyte. The Stark tuning slope of the adsorbed CO was evaluated with Fourier Transformed Infrared Spectroscopy, and the CO oxidation was monitored with cyclic voltammetry. The results show that both electrochemical Stark tuning and oxidation are independent of the HClO4 concentration of the supporting electrolyte, revealing the absence of diffuse layer effects on the aqueous Pt(111)/CO system. By comparison to previously reported theoretical calculations, we attribute this insensitivity to the special double layer structure of Pt(111)/CO, in which the potential drop occurs primarily between the terminating oxygen of the adsorbed CO adlayer and first water layer of the electrolyte, making the properties of adsorbed CO nearly independent of the ionic strength of the electrolyte.
Citation
Electrochimica ACTA

Citation

figueiredo, M. , Hiltrop, D. , Sundararaman, R. , Schwarz, K. and Koper, M. (2018), Absence of diffuse double layer effect on the vibrational properties and oxidation of chemisorbed carbon monoxide on a Pt(111) electrode, Electrochimica ACTA, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=924693 (Accessed June 22, 2024)

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Created May 22, 2018, Updated October 12, 2021