Reaction of Nickel Electrode Surfaces with Anionic Metal-Cyanide Complexes

Formation of Precipitated Surfaces

Sujit Sinha, Brian Humphrey, Andrew B. Bocarsly

Research output: Contribution to journalArticleResearchpeer-review

178 Citations (Scopus)

Abstract

Anionic metallocyanide complexes (Fe(CN)63-, Ru(CN)63-, Mn(CN)63-, [Fe(CN)6-xLx]n-) (L = H2O, NO, histidine, 1, 2-cyclohexyldiamine) capable of precipitating aqueous Ni2+ are immobilized on Ni electrodes by potentiostating the electrode in aqueous solutions of the anions. The surface coverage obtained is shown to be a function of composition of derivatizing solution, nickel surface pretreatment, electrode potential, and the reaction time. Diffuse-reflectance FT IR spectra of derivatized Ni surfaces show a cyano-bridged bimetallic structure. The cyclic voltammograms of surface-immobilized Fe(CN)63- and Ru(CN)63- show zero peak to peak separation and 110-mV peak width at half-height, close to the ideal case for surface-attached species. These surfaces are very stable with ~10% loss on >18000 potential cycles between the FeII and FeIII states. The E1/2value and the shape of the surface cyclic voltammetric wave are shown to depend strongly on the supporting electrolyte cation. These surfaces also show a cation selectivity, indicating an ordered structure. Such surfaces are shown to stabilize the Ni electrode surface against oxide formation while allowing various solution redox couples to react at the electrode. Thus, reaction specificity can be induced by this type of derivatization.

Original languageEnglish
Pages (from-to)203-212
Number of pages10
JournalInorganic Chemistry
Volume23
Issue number2
DOIs
StatePublished - 1 Jan 1984

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Cyanides
cyanides
Nickel
Metals
nickel
Electrodes
electrodes
metals
Cations
cations
histidine
Histidine
reaction time
pretreatment
Oxides
Electrolytes
Anions
selectivity
electrolytes
anions

Cite this

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title = "Reaction of Nickel Electrode Surfaces with Anionic Metal-Cyanide Complexes: Formation of Precipitated Surfaces",
abstract = "Anionic metallocyanide complexes (Fe(CN)63-, Ru(CN)63-, Mn(CN)63-, [Fe(CN)6-xLx]n-) (L = H2O, NO, histidine, 1, 2-cyclohexyldiamine) capable of precipitating aqueous Ni2+ are immobilized on Ni electrodes by potentiostating the electrode in aqueous solutions of the anions. The surface coverage obtained is shown to be a function of composition of derivatizing solution, nickel surface pretreatment, electrode potential, and the reaction time. Diffuse-reflectance FT IR spectra of derivatized Ni surfaces show a cyano-bridged bimetallic structure. The cyclic voltammograms of surface-immobilized Fe(CN)63- and Ru(CN)63- show zero peak to peak separation and 110-mV peak width at half-height, close to the ideal case for surface-attached species. These surfaces are very stable with ~10{\%} loss on >18000 potential cycles between the FeII and FeIII states. The E1/2value and the shape of the surface cyclic voltammetric wave are shown to depend strongly on the supporting electrolyte cation. These surfaces also show a cation selectivity, indicating an ordered structure. Such surfaces are shown to stabilize the Ni electrode surface against oxide formation while allowing various solution redox couples to react at the electrode. Thus, reaction specificity can be induced by this type of derivatization.",
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Reaction of Nickel Electrode Surfaces with Anionic Metal-Cyanide Complexes : Formation of Precipitated Surfaces. / Sinha, Sujit; Humphrey, Brian; Bocarsly, Andrew B.

In: Inorganic Chemistry, Vol. 23, No. 2, 01.01.1984, p. 203-212.

Research output: Contribution to journalArticleResearchpeer-review

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T1 - Reaction of Nickel Electrode Surfaces with Anionic Metal-Cyanide Complexes

T2 - Formation of Precipitated Surfaces

AU - Sinha, Sujit

AU - Humphrey, Brian

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AB - Anionic metallocyanide complexes (Fe(CN)63-, Ru(CN)63-, Mn(CN)63-, [Fe(CN)6-xLx]n-) (L = H2O, NO, histidine, 1, 2-cyclohexyldiamine) capable of precipitating aqueous Ni2+ are immobilized on Ni electrodes by potentiostating the electrode in aqueous solutions of the anions. The surface coverage obtained is shown to be a function of composition of derivatizing solution, nickel surface pretreatment, electrode potential, and the reaction time. Diffuse-reflectance FT IR spectra of derivatized Ni surfaces show a cyano-bridged bimetallic structure. The cyclic voltammograms of surface-immobilized Fe(CN)63- and Ru(CN)63- show zero peak to peak separation and 110-mV peak width at half-height, close to the ideal case for surface-attached species. These surfaces are very stable with ~10% loss on >18000 potential cycles between the FeII and FeIII states. The E1/2value and the shape of the surface cyclic voltammetric wave are shown to depend strongly on the supporting electrolyte cation. These surfaces also show a cation selectivity, indicating an ordered structure. Such surfaces are shown to stabilize the Ni electrode surface against oxide formation while allowing various solution redox couples to react at the electrode. Thus, reaction specificity can be induced by this type of derivatization.

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