Catalytic electrooxidation of hydrazine at the nickel ferricyanide modified electrode: can an array of surface bound one-electron redox centers act in concert?

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Abstract

The [NiFe(CN)6]2-/- derivatized nickel electrode represents an electrocatalytic surface for the mediated oxidation of hydrazine. The four-electron oxidation of hydrazine is employed as a probe of multiple electron charge transfer processes at the Ni[Fe(CN)6]2-/- interface since the observed product distribution is sensitive to the detailed mechanism and stoichiometry of electron transfer giving rise to production of NH3 if only one-electron transfer processes occur, while yielding N2H2 or N2 if multi-electron processes are present. A correlation between surface overlayer structure and charge transfer pathway is observed. A rather facile, pseudo-first order heterogeneous charge transfer rate (~3 × 10-2 cm s-1) was found for N2 production. The kinetics of the processes involved in this electrocatalysis were analyzed according to the Savéant-Andrieux theory. The electrocatalytic behavior of this system can be varied from R type behavior to R + S or (SR) and then to S + E behavior by varying the amount of the surface attached catalyst.

Original languageEnglish (US)
Pages (from-to)325-345
Number of pages21
JournalJournal of Electroanalytical Chemistry
Volume300
Issue number1-2
DOIs
StatePublished - Feb 11 1991

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry
  • Chemical Engineering(all)
  • Electrochemistry

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