Proton transfer voltammetry at electrodes modified with acid thiol monolayers

Antonio M. Luque, Willem H. Mulder, Juan Jose Calvente, Angel Cuesta, Rafael Andreu

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

By combining a description of the potential profile at electrodes coated with acid thiol monolayers with a quadratic relationship between activation energy and electrode potential, a rather simple expression for proton transfer voltammograms is derived. Our electrostatic analysis shows that proton transfer can only produce narrow voltammetric peaks when the immobilized acid groups lie close to the metal substrate. Quantitative fits of experimental voltammograms obtained with an Au(111) electrode modified with a 11-mercaptoundecanoic monolayer at pH 8.5 reveal that less than 1% of the carboxylic groups in the monolayer participate in the potential induced proton transfer process and that these groups lay close to the metal surface. A preliminary analysis of the kinetic parameters suggests that the interfacial electric field facilitates an intrinsically slow proton exchange between a proton donor and acceptor pair that are not in close contact with each other at the interface.
Original languageEnglish
Pages (from-to)5778-5786
Number of pages9
JournalAnalytical Chemistry
Volume84
Issue number13
Early online date5 Jun 2012
DOIs
Publication statusPublished - 3 Jul 2012

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Proton transfer
Voltammetry
Sulfhydryl Compounds
Monolayers
Electrodes
Acids
Protons
Metals
Kinetic parameters
Electrostatics
Activation energy
Electric fields
Substrates

Cite this

Proton transfer voltammetry at electrodes modified with acid thiol monolayers. / Luque, Antonio M.; Mulder, Willem H.; Calvente, Juan Jose; Cuesta, Angel; Andreu, Rafael.

In: Analytical Chemistry, Vol. 84, No. 13, 03.07.2012, p. 5778-5786.

Research output: Contribution to journalArticle

Luque, Antonio M. ; Mulder, Willem H. ; Calvente, Juan Jose ; Cuesta, Angel ; Andreu, Rafael. / Proton transfer voltammetry at electrodes modified with acid thiol monolayers. In: Analytical Chemistry. 2012 ; Vol. 84, No. 13. pp. 5778-5786.
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