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

doi:10.1021/jp9814707

Electrode modification from the electrolysis of [M(Bipyridine)₃](ClO₄) ₂ (M = Co^II, Fe^II, and Ru^II) in media of low dielectric constant. Electrocatalytic behavior and an amperometric C₆₀ sensor

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

Research output: Contribution to journal › Article › peer-review

12 Citations (Scopus)

Abstract

The voltammetric behavior of transition metal complexes of 2,2′-bipyridine, [M^II(bpy)₃](ClO₄)₂ (M^II = Co^II, Fe^II, or Ru^II, 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 [M^II(bpy)₃](ClO₄)₂ leads to the precipitation of a solid, electrochemically inactive phase of [M^III(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 [Co^III(bpy)₃](ClO₄)₃ layer was extensively investigated. The catalytic current associated with the reduction of C₆₀ at a [Co^III(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 [Ru^II(bpy)₃](ClO₄)₂ does not produce an analogous redox inactive layer of [Ru^III(bpy)₃](ClO₄)₃.

Original language	English
Pages (from-to)	9640-9646
Number of pages	7
Journal	Journal of Physical Chemistry B
Volume	102
Issue number	48
DOIs	https://doi.org/10.1021/jp9814707
Publication status	Published - Nov 26 1998
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Surfaces, Coatings and Films
Materials Chemistry

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Electrode modification from the electrolysis of [M(Bipyridine)₃](ClO₄) ₂ (M = Co^II, Fe^II, and Ru^II) in media of low dielectric constant. Electrocatalytic behavior and an amperometric C₆₀ sensor. / Winkler, Krzysztof; Costa, David A.; Hayashi, Akari; Balch, Alan L.

In: Journal of Physical Chemistry B, Vol. 102, No. 48, 26.11.1998, p. 9640-9646.

Research output: Contribution to journal › Article › peer-review

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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.",

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AU - Winkler, Krzysztof

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AU - Balch, Alan L.

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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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