Evaluation of various strategies to formation of pH responsive hydroquinone-terminated films on carbon electrodes

Allan Hjarbæk Holm, Karina Højrup Vase, Bjorn Winther Jensen, Steen Uttrup Pedersen, Kim Daasbjerg

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

The hydroquinone/quinone (H2Q/Q) redox system was tethered to glassy carbon surfaces using first an electrochemical pre-oxidation treatment to afford carboxylic acid functionalities followed by immobilizing the H2Q precursor, n-(2,5-dimethoxyphenyl)alkan-1-amine (general structure: H2N-(CH2)n-C6H3(OCH3)2, n = 1, 2, 4, 8, and 12), by carbodiimide chemistry and a final demethylation reaction. The resultant surfaces exhibited the expected chemical reversibility in aqueous solution with a pH-sensitive position of the formal potential (∼55 mV/pH unit), and an increase in the peak potential separation going from 0.02 V for n = 1 to 0.21 V for n = 12. The films were very robust and could withstand prolonged sonication and relatively large potential excursions. While the films followed the expected kinetic distance dependence for up to 4 methylene units the electrode kinetics was faster than expected for longer alkyl spacers. We suggest that film disorder, electrode-mediating effects, and a roughened electrode material could account for these apparent inconsistencies. To further understand such effects, two complementary electrode modification strategies leading to better film ordering on carbon were adapted; immobilizing a thin layer of benzoic acid by oxidative deposition of 4-aminobenzoic acid or employing a plasma deposition process to tether an acid analogue. Analysis of the various electrodes was accomplished by electrochemical methods, atomic force microscopy, and X-ray photoelectron spectroscopy.

Original languageEnglish
Pages (from-to)1680-1688
Number of pages9
JournalElectrochimica Acta
Volume53
Issue number4
DOIs
Publication statusPublished - 2007 Dec 31
Externally publishedYes

Fingerprint

Carbon
Electrodes
4-Aminobenzoic Acid
Carbodiimides
Plasma deposition
Kinetics
Benzoic Acid
Sonication
Acids
Benzoic acid
Glassy carbon
Carboxylic Acids
Carboxylic acids
Amines
Atomic force microscopy
X ray photoelectron spectroscopy
hydroquinone
Oxidation

Keywords

  • Distance-dependent electrochemical properties
  • Hydroquinone
  • Modified electrodes
  • pH sensor

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Analytical Chemistry
  • Electrochemistry

Cite this

Evaluation of various strategies to formation of pH responsive hydroquinone-terminated films on carbon electrodes. / Holm, Allan Hjarbæk; Vase, Karina Højrup; Winther Jensen, Bjorn; Pedersen, Steen Uttrup; Daasbjerg, Kim.

In: Electrochimica Acta, Vol. 53, No. 4, 31.12.2007, p. 1680-1688.

Research output: Contribution to journalArticle

Holm, Allan Hjarbæk ; Vase, Karina Højrup ; Winther Jensen, Bjorn ; Pedersen, Steen Uttrup ; Daasbjerg, Kim. / Evaluation of various strategies to formation of pH responsive hydroquinone-terminated films on carbon electrodes. In: Electrochimica Acta. 2007 ; Vol. 53, No. 4. pp. 1680-1688.
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AB - The hydroquinone/quinone (H2Q/Q) redox system was tethered to glassy carbon surfaces using first an electrochemical pre-oxidation treatment to afford carboxylic acid functionalities followed by immobilizing the H2Q precursor, n-(2,5-dimethoxyphenyl)alkan-1-amine (general structure: H2N-(CH2)n-C6H3(OCH3)2, n = 1, 2, 4, 8, and 12), by carbodiimide chemistry and a final demethylation reaction. The resultant surfaces exhibited the expected chemical reversibility in aqueous solution with a pH-sensitive position of the formal potential (∼55 mV/pH unit), and an increase in the peak potential separation going from 0.02 V for n = 1 to 0.21 V for n = 12. The films were very robust and could withstand prolonged sonication and relatively large potential excursions. While the films followed the expected kinetic distance dependence for up to 4 methylene units the electrode kinetics was faster than expected for longer alkyl spacers. We suggest that film disorder, electrode-mediating effects, and a roughened electrode material could account for these apparent inconsistencies. To further understand such effects, two complementary electrode modification strategies leading to better film ordering on carbon were adapted; immobilizing a thin layer of benzoic acid by oxidative deposition of 4-aminobenzoic acid or employing a plasma deposition process to tether an acid analogue. Analysis of the various electrodes was accomplished by electrochemical methods, atomic force microscopy, and X-ray photoelectron spectroscopy.

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