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Journal of Solid State Electrochemistry

, Volume 11, Issue 6, pp 841–846 | Cite as

Mechanism of the catalyzed by cysteine electroreduction of the insoluble in water cobalt(II) salt as a component of carbon paste electrode

  • Jan Hrbac
  • Tomas Zeleny
  • Yakov I. Tur’yan
Original Paper

Abstract

The mechanism of the Co(II) catalytic electroreduction of water insoluble CoR2 salt in the presence of cysteine \({\left( {{\text{H}}_{{\text{2}}} {\text{L}}^{ \pm } } \right)}\) was developed. CoR2 = cobalt(II) cyclohexylbutyrate is the component of a carbon paste electrode. Electrode surface consecutive reactions are: (a) fast (equilibrium) reaction of the \({ {{\text{CoR}}_{{\text{2}}} {\left( {{\text{H}}_{{\text{2}}} {\text{L}}^{ \pm } } \right)}} }_{\text{ads}}\) complex formation, (b) rate-determining reversible reaction of the promoting process of CoR(Ac+) complex formation, (c) rate-determining irreversible reaction of the electroactive \({\left\{ {{\text{CoR}}{\left( {{\text{Ac}}} \right)}{\left( {{\text{H}}_{{\text{2}}} {\text{L}}^{{\text{ $ \pm $ }}} } \right)}} \right\}}{\text{ads}}\) complex formation with ligand-induced adsorption, and (d) fast irreversible reaction of the \({\text{CoR}}{\left( {{\text{Ac}}} \right)}{\left( {{\text{H}}_{{\text{2}}} {\text{L}}^{{\text{ $ \pm $ }}} } \right)}_{{{\text{ads}}}} \) electroreduction. Reactions (a,b) connected with CoR2 dissolution and reactions (c,d) connected with CoR2 electroreduction are catalyzed by \({\left( {{\text{H}}_{{\text{2}}} {\text{L}}^{{\text{ $ \pm $ }}} } \right)}_{{{\text{ads}}}} \). Regeneration of \({\left( {{\text{H}}_{{\text{2}}} {\text{L}}^{{\text{ $ \pm $ }}} } \right)}_{{{\text{ads}}}} \) (reactions “b,d”) and accumulation of atomic Co(0) (reaction “d”) take place. Experimental data [Sugawara et al., Bioelectrochem Bioenergetics 26:469, 1991]: i a vs E (i a is anodic peak, E is cathodic accumulation potential), i a vs \({\text{c}}_{{{\text{H}}_{{\text{2}}} {\text{L}}}} \), and i a vs pH have been quantitatively explained.

Keywords

Modified carbon paste electrode Co(II) catalytic electroreduction Cysteine as catalyst Catalysis mechanism Kinetic equations 

Notes

Acknowledgement

This work was supported by MSM6198959218 grant from the Ministry of Education, Youth and Sports of the Czech Republic.

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Copyright information

© Springer-Verlag 2007

Authors and Affiliations

  1. 1.Department of Physical Chemistry, Faculty of SciencePalacky UniversityOlomoucCzech Republic
  2. 2.NewtonUSA

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