Electrochemical quartz crystal microbalance study on the redox transformations of ruthenium(III) trichloride microcrystals attached to a gold electrode

G. Inzelt, Z. Puskás

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13 Citations (Scopus)

Abstract

Ruthenium(III) trichloride solid crystals have been mechanically attached to gold surfaces and studied by cyclic electrochemical quartz crystal microbalance measurements in the presence of aqueous solutions containing 0.1 moldm-3 HCl+x moldm-3 M+Cl-, where M+=H+, Li+, Na+, K+, Rb+, Cs+. The first cycle differed from the subsequent ones not only for the virgin layer, but also when the electrode was used again after storing it in dry state. The RuCl3 and the complexes formed during the electrochemical transformations show two reduction and two reoxidation waves, in some cases (during the first break-in and in the presence of potassium ions) two peaks appear in the course of the second oxidation process. The peak potentials are shifted into the direction of more positive potentials with increasing electrolyte concentrations and in the series of H+, Li+, Na+, Rb+, K+, Cs+. The mass change was reversible, during reduction mass decrease, while during oxidation mass increase occurred in two distinct steps. It was concluded that during reduction the incorporation of M+ ions takes place, while simultaneously H2O molecules leave the surface layer. The opposite transport of ions and solvent molecules occurs during oxidation. A reaction scheme is proposed in which H+Ru3 IIICl10(H2O)8·xH 2O type complexes are formed from RuCl3·xH 2O during the break-in cycle. The two reduction/reoxidation waves are related to the redox transformations of two Ru(III) to Ru(II) sites while the composition of the polynuclear complexes and the structure of microcrystals change.

Original languageEnglish
Pages (from-to)805-811
Number of pages7
JournalElectrochemistry Communications
Volume6
Issue number8
DOIs
Publication statusPublished - Aug 2004

Fingerprint

Microcrystals
Ruthenium
Quartz crystal microbalances
Gold
Electrodes
Ions
Oxidation
Molecules
Electrolytes
Potassium
Crystals
Oxidation-Reduction
Chemical analysis

Keywords

  • Complex formation
  • Electrochemical quartz crystal microbalance
  • Microcrystals
  • Ruthenium(III) chloride
  • Solid state voltammetry

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Analytical Chemistry
  • Electrochemistry

Cite this

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title = "Electrochemical quartz crystal microbalance study on the redox transformations of ruthenium(III) trichloride microcrystals attached to a gold electrode",
abstract = "Ruthenium(III) trichloride solid crystals have been mechanically attached to gold surfaces and studied by cyclic electrochemical quartz crystal microbalance measurements in the presence of aqueous solutions containing 0.1 moldm-3 HCl+x moldm-3 M+Cl-, where M+=H+, Li+, Na+, K+, Rb+, Cs+. The first cycle differed from the subsequent ones not only for the virgin layer, but also when the electrode was used again after storing it in dry state. The RuCl3 and the complexes formed during the electrochemical transformations show two reduction and two reoxidation waves, in some cases (during the first break-in and in the presence of potassium ions) two peaks appear in the course of the second oxidation process. The peak potentials are shifted into the direction of more positive potentials with increasing electrolyte concentrations and in the series of H+, Li+, Na+, Rb+, K+, Cs+. The mass change was reversible, during reduction mass decrease, while during oxidation mass increase occurred in two distinct steps. It was concluded that during reduction the incorporation of M+ ions takes place, while simultaneously H2O molecules leave the surface layer. The opposite transport of ions and solvent molecules occurs during oxidation. A reaction scheme is proposed in which H+Ru3 IIICl10(H2O)8·xH 2O type complexes are formed from RuCl3·xH 2O during the break-in cycle. The two reduction/reoxidation waves are related to the redox transformations of two Ru(III) to Ru(II) sites while the composition of the polynuclear complexes and the structure of microcrystals change.",
keywords = "Complex formation, Electrochemical quartz crystal microbalance, Microcrystals, Ruthenium(III) chloride, Solid state voltammetry",
author = "G. Inzelt and Z. Pusk{\'a}s",
year = "2004",
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doi = "10.1016/j.elecom.2004.05.019",
language = "English",
volume = "6",
pages = "805--811",
journal = "Electrochemistry Communications",
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T1 - Electrochemical quartz crystal microbalance study on the redox transformations of ruthenium(III) trichloride microcrystals attached to a gold electrode

AU - Inzelt, G.

AU - Puskás, Z.

PY - 2004/8

Y1 - 2004/8

N2 - Ruthenium(III) trichloride solid crystals have been mechanically attached to gold surfaces and studied by cyclic electrochemical quartz crystal microbalance measurements in the presence of aqueous solutions containing 0.1 moldm-3 HCl+x moldm-3 M+Cl-, where M+=H+, Li+, Na+, K+, Rb+, Cs+. The first cycle differed from the subsequent ones not only for the virgin layer, but also when the electrode was used again after storing it in dry state. The RuCl3 and the complexes formed during the electrochemical transformations show two reduction and two reoxidation waves, in some cases (during the first break-in and in the presence of potassium ions) two peaks appear in the course of the second oxidation process. The peak potentials are shifted into the direction of more positive potentials with increasing electrolyte concentrations and in the series of H+, Li+, Na+, Rb+, K+, Cs+. The mass change was reversible, during reduction mass decrease, while during oxidation mass increase occurred in two distinct steps. It was concluded that during reduction the incorporation of M+ ions takes place, while simultaneously H2O molecules leave the surface layer. The opposite transport of ions and solvent molecules occurs during oxidation. A reaction scheme is proposed in which H+Ru3 IIICl10(H2O)8·xH 2O type complexes are formed from RuCl3·xH 2O during the break-in cycle. The two reduction/reoxidation waves are related to the redox transformations of two Ru(III) to Ru(II) sites while the composition of the polynuclear complexes and the structure of microcrystals change.

AB - Ruthenium(III) trichloride solid crystals have been mechanically attached to gold surfaces and studied by cyclic electrochemical quartz crystal microbalance measurements in the presence of aqueous solutions containing 0.1 moldm-3 HCl+x moldm-3 M+Cl-, where M+=H+, Li+, Na+, K+, Rb+, Cs+. The first cycle differed from the subsequent ones not only for the virgin layer, but also when the electrode was used again after storing it in dry state. The RuCl3 and the complexes formed during the electrochemical transformations show two reduction and two reoxidation waves, in some cases (during the first break-in and in the presence of potassium ions) two peaks appear in the course of the second oxidation process. The peak potentials are shifted into the direction of more positive potentials with increasing electrolyte concentrations and in the series of H+, Li+, Na+, Rb+, K+, Cs+. The mass change was reversible, during reduction mass decrease, while during oxidation mass increase occurred in two distinct steps. It was concluded that during reduction the incorporation of M+ ions takes place, while simultaneously H2O molecules leave the surface layer. The opposite transport of ions and solvent molecules occurs during oxidation. A reaction scheme is proposed in which H+Ru3 IIICl10(H2O)8·xH 2O type complexes are formed from RuCl3·xH 2O during the break-in cycle. The two reduction/reoxidation waves are related to the redox transformations of two Ru(III) to Ru(II) sites while the composition of the polynuclear complexes and the structure of microcrystals change.

KW - Complex formation

KW - Electrochemical quartz crystal microbalance

KW - Microcrystals

KW - Ruthenium(III) chloride

KW - Solid state voltammetry

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