Do alkanethiols adsorb onto the surfaces of TI-Ba-Ca-Cu-O-based high-temperature superconductors? The critical role of H2O content on the adsorption process

Kaimin Chen, Feng Xu, Chad A. Mirkin, Rung Kuang Lo, K. S. Nanjundaswamy, Ji Ping Zhou, John McDevitt

Research output: Contribution to journalArticle

Abstract

The reactivity of Tl1.4Ba2CaCu2O7.0, a high-temperature superconductor (HTSC), toward a redox-active adsorbate molecule with thiol functionality has been investigated as a function of solvent type and H2O content. Previously it had been reported that alkanethiols do not stably chemisorb onto the surface of Tl2Ba2CaCu2O8/Tl2Ba 2Ca2Cu3O10 phases, bringing into question the generality of alkanethiol adsorption onto cuprate-based HTSCs. Herein, we show that under rigorously dry conditions, 11-mercaptounde-canoylferrocene (1) adsorbs cleanly onto the surface of Tl1.4Ba2CaCu2O7.0 to form moderately stable, redox-active monolayer films. The redox activity of 1 was used to estimate adsorbate surface coverage, and it is shown that the addition of H2O to the modifying solutions of 1 adversely affects the monolayer adsorption process. No redox activity associated with 1 could be detected for electrodes soaked in 0.1 M solutions of 1 with 5% H2O in ethanol, which was attributed to the formation of a BaCO3 corrosion layer that prohibited the adsorption of 1 onto the HTSC surface. The importance of sample stoichiometry on the adsorption process also is discussed.

Original languageEnglish (US)
Pages (from-to)2622-2624
Number of pages3
JournalLangmuir
Volume12
Issue number11
StatePublished - May 29 1996

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High temperature superconductors
high temperature superconductors
Adsorption
adsorption
Adsorbates
Monolayers
Sulfhydryl Compounds
thiols
Stoichiometry
cuprates
stoichiometry
corrosion
Ethanol
ethyl alcohol
reactivity
Corrosion
Electrodes
Molecules
electrodes
Oxidation-Reduction

ASJC Scopus subject areas

  • Colloid and Surface Chemistry
  • Physical and Theoretical Chemistry

Cite this

Do alkanethiols adsorb onto the surfaces of TI-Ba-Ca-Cu-O-based high-temperature superconductors? The critical role of H2O content on the adsorption process. / Chen, Kaimin; Xu, Feng; Mirkin, Chad A.; Lo, Rung Kuang; Nanjundaswamy, K. S.; Zhou, Ji Ping; McDevitt, John.

In: Langmuir, Vol. 12, No. 11, 29.05.1996, p. 2622-2624.

Research output: Contribution to journalArticle

Chen, Kaimin ; Xu, Feng ; Mirkin, Chad A. ; Lo, Rung Kuang ; Nanjundaswamy, K. S. ; Zhou, Ji Ping ; McDevitt, John. / Do alkanethiols adsorb onto the surfaces of TI-Ba-Ca-Cu-O-based high-temperature superconductors? The critical role of H2O content on the adsorption process. In: Langmuir. 1996 ; Vol. 12, No. 11. pp. 2622-2624.
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abstract = "The reactivity of Tl1.4Ba2CaCu2O7.0, a high-temperature superconductor (HTSC), toward a redox-active adsorbate molecule with thiol functionality has been investigated as a function of solvent type and H2O content. Previously it had been reported that alkanethiols do not stably chemisorb onto the surface of Tl2Ba2CaCu2O8/Tl2Ba 2Ca2Cu3O10 phases, bringing into question the generality of alkanethiol adsorption onto cuprate-based HTSCs. Herein, we show that under rigorously dry conditions, 11-mercaptounde-canoylferrocene (1) adsorbs cleanly onto the surface of Tl1.4Ba2CaCu2O7.0 to form moderately stable, redox-active monolayer films. The redox activity of 1 was used to estimate adsorbate surface coverage, and it is shown that the addition of H2O to the modifying solutions of 1 adversely affects the monolayer adsorption process. No redox activity associated with 1 could be detected for electrodes soaked in 0.1 M solutions of 1 with 5{\%} H2O in ethanol, which was attributed to the formation of a BaCO3 corrosion layer that prohibited the adsorption of 1 onto the HTSC surface. The importance of sample stoichiometry on the adsorption process also is discussed.",
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