Electrode modification from the electrolysis of [M(Bipyridine)3](ClO4) 2 (M = CoII, FeII, and RuII) in media of low dielectric constant. Electrocatalytic behavior and an amperometric C60 sensor

Krzysztof Winkler, David A. Costa, Akari Hayashi, Alan L. Balch

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12 Citations (Scopus)

Abstract

The voltammetric behavior of transition metal complexes of 2,2′-bipyridine, [MII(bpy)3](ClO4)2 (MII = CoII, FeII, or RuII, in toluene/acetonitrile mixtures has been studied by cyclic voltammetry. In solutions with a low acetonitrile-to-toluene ratio and tetra(n-butyl)ammonium perchlorate as supporting electrolyte, oxidation of [MII(bpy)3](ClO4)2 leads to the precipitation of a solid, electrochemically inactive phase of [MIII(bpy)3](ClO4)3 (M = Co or Fe) on the electrode. Electrodes modified by this solid phase are shown to display catalytic waves that result from chemical reduction of the film by soluble species: [M(bpy)3]+ when no other electroactive species is present or [C60]- when C60 is also present in the solution. The redox behavior of C60 on an electrode covered by a [CoIII(bpy)3](ClO4)3 layer was extensively investigated. The catalytic current associated with the reduction of C60 at a [CoIII(bpy)3](ClO4)3 modified electrode can be used for the quantitative determination of fullerene concentration in solution. The reduction current associated with square wave voltammetric experiments increased linearly with the concentration of C60 in the range of 0.25-20 μM. The detection limit is 0.1 μM. This method of fullerene quantitative determination exhibits good reproducibility, simplicity, and is relatively fast. Electrochemical oxidation of [RuII(bpy)3](ClO4)2 does not produce an analogous redox inactive layer of [RuIII(bpy)3](ClO4)3.

Original languageEnglish
Pages (from-to)9640-9646
Number of pages7
JournalJournal of Physical Chemistry B
Volume102
Issue number48
Publication statusPublished - Nov 26 1998
Externally publishedYes

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Amperometric sensors
Electrolysis
electrolysis
Electrodes
Permittivity
permittivity
electrodes
sensors
Fullerenes
Acetonitrile
fullerenes
acetonitrile
Toluene
toluene
ammonium perchlorates
electrochemical oxidation
Electrochemical oxidation
square waves
Oxidation-Reduction
Metal complexes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

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title = "Electrode modification from the electrolysis of [M(Bipyridine)3](ClO4) 2 (M = CoII, FeII, and RuII) in media of low dielectric constant. Electrocatalytic behavior and an amperometric C60 sensor",
abstract = "The voltammetric behavior of transition metal complexes of 2,2′-bipyridine, [MII(bpy)3](ClO4)2 (MII = CoII, FeII, or RuII, in toluene/acetonitrile mixtures has been studied by cyclic voltammetry. In solutions with a low acetonitrile-to-toluene ratio and tetra(n-butyl)ammonium perchlorate as supporting electrolyte, oxidation of [MII(bpy)3](ClO4)2 leads to the precipitation of a solid, electrochemically inactive phase of [MIII(bpy)3](ClO4)3 (M = Co or Fe) on the electrode. Electrodes modified by this solid phase are shown to display catalytic waves that result from chemical reduction of the film by soluble species: [M(bpy)3]+ when no other electroactive species is present or [C60]- when C60 is also present in the solution. The redox behavior of C60 on an electrode covered by a [CoIII(bpy)3](ClO4)3 layer was extensively investigated. The catalytic current associated with the reduction of C60 at a [CoIII(bpy)3](ClO4)3 modified electrode can be used for the quantitative determination of fullerene concentration in solution. The reduction current associated with square wave voltammetric experiments increased linearly with the concentration of C60 in the range of 0.25-20 μM. The detection limit is 0.1 μM. This method of fullerene quantitative determination exhibits good reproducibility, simplicity, and is relatively fast. Electrochemical oxidation of [RuII(bpy)3](ClO4)2 does not produce an analogous redox inactive layer of [RuIII(bpy)3](ClO4)3.",
author = "Krzysztof Winkler and Costa, {David A.} and Akari Hayashi and Balch, {Alan L.}",
year = "1998",
month = "11",
day = "26",
language = "English",
volume = "102",
pages = "9640--9646",
journal = "Journal of Physical Chemistry B Materials",
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T1 - Electrode modification from the electrolysis of [M(Bipyridine)3](ClO4) 2 (M = CoII, FeII, and RuII) in media of low dielectric constant. Electrocatalytic behavior and an amperometric C60 sensor

AU - Winkler, Krzysztof

AU - Costa, David A.

AU - Hayashi, Akari

AU - Balch, Alan L.

PY - 1998/11/26

Y1 - 1998/11/26

N2 - The voltammetric behavior of transition metal complexes of 2,2′-bipyridine, [MII(bpy)3](ClO4)2 (MII = CoII, FeII, or RuII, in toluene/acetonitrile mixtures has been studied by cyclic voltammetry. In solutions with a low acetonitrile-to-toluene ratio and tetra(n-butyl)ammonium perchlorate as supporting electrolyte, oxidation of [MII(bpy)3](ClO4)2 leads to the precipitation of a solid, electrochemically inactive phase of [MIII(bpy)3](ClO4)3 (M = Co or Fe) on the electrode. Electrodes modified by this solid phase are shown to display catalytic waves that result from chemical reduction of the film by soluble species: [M(bpy)3]+ when no other electroactive species is present or [C60]- when C60 is also present in the solution. The redox behavior of C60 on an electrode covered by a [CoIII(bpy)3](ClO4)3 layer was extensively investigated. The catalytic current associated with the reduction of C60 at a [CoIII(bpy)3](ClO4)3 modified electrode can be used for the quantitative determination of fullerene concentration in solution. The reduction current associated with square wave voltammetric experiments increased linearly with the concentration of C60 in the range of 0.25-20 μM. The detection limit is 0.1 μM. This method of fullerene quantitative determination exhibits good reproducibility, simplicity, and is relatively fast. Electrochemical oxidation of [RuII(bpy)3](ClO4)2 does not produce an analogous redox inactive layer of [RuIII(bpy)3](ClO4)3.

AB - The voltammetric behavior of transition metal complexes of 2,2′-bipyridine, [MII(bpy)3](ClO4)2 (MII = CoII, FeII, or RuII, in toluene/acetonitrile mixtures has been studied by cyclic voltammetry. In solutions with a low acetonitrile-to-toluene ratio and tetra(n-butyl)ammonium perchlorate as supporting electrolyte, oxidation of [MII(bpy)3](ClO4)2 leads to the precipitation of a solid, electrochemically inactive phase of [MIII(bpy)3](ClO4)3 (M = Co or Fe) on the electrode. Electrodes modified by this solid phase are shown to display catalytic waves that result from chemical reduction of the film by soluble species: [M(bpy)3]+ when no other electroactive species is present or [C60]- when C60 is also present in the solution. The redox behavior of C60 on an electrode covered by a [CoIII(bpy)3](ClO4)3 layer was extensively investigated. The catalytic current associated with the reduction of C60 at a [CoIII(bpy)3](ClO4)3 modified electrode can be used for the quantitative determination of fullerene concentration in solution. The reduction current associated with square wave voltammetric experiments increased linearly with the concentration of C60 in the range of 0.25-20 μM. The detection limit is 0.1 μM. This method of fullerene quantitative determination exhibits good reproducibility, simplicity, and is relatively fast. Electrochemical oxidation of [RuII(bpy)3](ClO4)2 does not produce an analogous redox inactive layer of [RuIII(bpy)3](ClO4)3.

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