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

Marta C. Figueiredo, Dennis Hiltrop, Ravishankar Sundararaman, Kathleen A. Schwarz, Marc T.M. Koper (Corresponding author)

Research output: Contribution to journalArticleAcademicpeer-review

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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.

Original languageEnglish
Pages (from-to)127-132
Number of pages6
JournalElectrochimica Acta
Volume281
DOIs
Publication statusPublished - 10 Aug 2018
Externally publishedYes

Fingerprint

Carbon Monoxide
Carbon monoxide
Electrolytes
Oxidation
Electrodes
Tuning
Ionic strength
Cyclic voltammetry
Infrared spectroscopy
Oxygen
Acids
Water

Keywords

  • Carbon monoxide
  • Double layer effect
  • Electrocatalysis
  • Pt(111)
  • Stark tuning

Cite this

Figueiredo, Marta C. ; Hiltrop, Dennis ; Sundararaman, Ravishankar ; Schwarz, Kathleen A. ; Koper, Marc T.M. / Absence of diffuse double layer effect on the vibrational properties and oxidation of chemisorbed carbon monoxide on a Pt(111) electrode. In: Electrochimica Acta. 2018 ; Vol. 281. pp. 127-132.
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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. / Figueiredo, Marta C.; Hiltrop, Dennis; Sundararaman, Ravishankar; Schwarz, Kathleen A.; Koper, Marc T.M. (Corresponding author).

In: Electrochimica Acta, Vol. 281, 10.08.2018, p. 127-132.

Research output: Contribution to journalArticleAcademicpeer-review

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AU - Figueiredo, Marta C.

AU - Hiltrop, Dennis

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AU - Schwarz, Kathleen A.

AU - Koper, Marc T.M.

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AB - 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.

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