The electrochemistry of ferrocene in non-aqueous solvents

Zara, A. J.; Machado, Sérgio S.; Bulhões, L.O.S.; Benedetti, Assis Vicente; Rabockai, T.

doi:10.1016/0022-0728(87)80254-1

Cited by 41 publications

(25 citation statements)

References 17 publications

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“…[32][33][34] All voltammograms (except for those in Figure 4) have been adjusted so that the zero potential correlates to the oxidation of ferrocene.…”

Section: Resultsmentioning

confidence: 99%

Extended Electrochemical Windows Made Accessible by Room Temperature Ionic Liquid/Organic Solvent Electrolyte Systems

2006

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The electrochemical windows of acetonitrile solutions doped with 0.1 M concentrations of several ionic liquids were examined by cyclic voltammetry at gold and platinum microelectrodes. These results were compared with those observed in the commonly used 0.1 M tetrabutylammonium perchlorate/acetonitrile system as well as with neat ionic liquids. The use of a trifluorotris(pentafluoroethyl)phosphate-based ionic liquid, specifically, as supporting electrolyte in acetonitrile solutions affords a wider anodic window, which is attributed to the high stability of the anionic component of these intrinsically conductive and thermally robust compounds.

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“…[32][33][34] All voltammograms (except for those in Figure 4) have been adjusted so that the zero potential correlates to the oxidation of ferrocene.…”

Section: Resultsmentioning

confidence: 99%

Extended Electrochemical Windows Made Accessible by Room Temperature Ionic Liquid/Organic Solvent Electrolyte Systems

2006

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“…The aim of this work is to assess whether FeCp 2 can be used as a voltammetric standard in ACN/ACE solvent mixtures. An exploration of the literature indicated that, with an exception the articles which concern studies on the oxidation of FeCp 2 in aqueous solutions of ethanol [17], N,N-dimethylformamide [18], and propylene carbonate [18], electrochemical studies on the FeCp 2 ?/0 couple in binary solvent systems are still very rare, and therefore demand further investigation. Consequently, the present article constitutes the first systematic evaluation of the electrochemical properties of the FeCp 2…”

Section: Introductionmentioning

confidence: 99%

Electrochemical impedance spectroscopy and cyclic voltammetry of ferrocene in acetonitrile/acetone system

Tsierkezos

Ritter

2009

J Appl Electrochem

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The oxidation of ferrocene (FeCp 2 ) to ferrocenium cation (FeCp 2 ? ) (where Cp: cyclopentadienyl anion, C 5 H 5 -) was investigated by means of electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) on either platinum (Pt) or glassy carbon (G-C) electrodes in acetonitrile (ACN), acetone (ACE), and acetonitrile (ACN)/ acetone (ACE) binary mixtures with n-tetrabutylammonium hexafluorophosphate (TBAPF 6 ) as background electrolyte at T = 294.15 K. The half-wave potentials (E 1/2 ), the diffusion coefficients (D), and the heterogeneous electrontransfer rate constants (k s ) were derived. The activation free energies for electron transfer (DG exp = ) were experimentally determined and compared with the theoretical values (DG cal = ). The electron-transfer process was reversible and diffusion-controlled in all investigated solvent mixtures. The changes on the metal-ligand bond lengths upon electron transfer were almost insignificant. The E 1/2 values were shifted to less positive potentials with the increase of the ACN content. The k s values obtained on Pt electrode were slightly larger compared to k s measured on G-C electrode, while in both cases the k s values were diminished with the enrichment of the mixtures in ACN. The EIS spectra confirmed that the rate-determining step in the whole process is the diffusion of the FeCp 2 species and thus the process can be properly characterized as diffusion-controlled.

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“…10b, bottom). The irreversible electrochemical oxidation of Fc and its derivatives is well-known, but this effect is highly dependent on the experimental conditions such as electrode dimensions, the nature of the support electrolyte, the concentration of Fc functionalities together with the degree of ferrocene modification [29][30][31][32][33][34][35][36]. In a previous study [6], ethynyl Fc, Lip Fc and Fc-PVC in membranes that were plasticized by the ionic liquid, 1- exerts a similar influence on the reaction product formed from an aqueous electrolyte of 10 mM NaCl, which is due partially to severe suppression of the permeation of NaCl with water nanodroplets/ion exchange of Cl -from the aqueous electrolyte into these membranes containing very high concentrations of organic cations and anions in the IL plasticized membranes.…”

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confidence: 99%

Electrochemical Mechanism of Ferrocene-Based Redox Molecules in Thin Film Membrane Electrodes

Cuartero

Acres

Bradley

et al. 2017

Electrochimica Acta

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2 GRAPHICAL ABSTRACTCartoon illustrating NaCl permeation through water nanodroplets and Cl -exchange at the membrane/sample interface, both of which create an environment to enable the formation of FeCln 3-n complexes, leading to a non-reversibility in the redox chemistry of the membrane. RESEARCH HIGHLIGHTS electrochemistry of ferrocene derivatives in polymeric membranes  role of chloride on the irreversible oxidation of ferrocene in thin film membranes  synchrotron radiation study of chloride on the ferrocene reactivity in membranes  elimination of chloride induced irreversibility of the ferrocene reaction chemistry ABSTRACTCyclic voltammetry (CV) in chloride-based aqueous electrolytes of ferrocene molecule doped thin membranes (~200 nm in thickness) on glassy carbon (GC) substrate electrodes, both plasticized poly(vinyl chloride) (PVC) and unplasticized poly(methyl methacrylate)/poly(decyl methacrylate) (PMMA-PDMA) membranes, has shown that the electrochemical oxidation behavior is irreversible due most likely to 3 degradation of ferrocene at the buried interface (GC|membrane). Furthermore, CV of the ferrocene molecules at GC electrodes in organic solvents employing chloride-based and chloride-free organic electrolytes has demonstrated that the chloride anion is inextricably linked to this irreversible ferrocene oxidation electrochemistry. Accordingly, we have explored the electrochemical oxidation mechanism of ferrocenebased redox molecules in thin film plasticized and unplasticized polymeric membrane electrodes by coupling synchrotron radiation-X-ray photoelectron spectroscopy (SR-XPS) and near edge X-ray absorption fine structure (NEXAFS) with argon ion sputtering to depth profile the electrochemically oxidized thin membrane systems. With the PVC depth profiling studies, it was not possible to precisely study the influence of chloride on the ferrocene reactivity due to the high atomic ratio of chloride in the PVC membrane; however, the depth profiling results obtained with a chlorine-free polymer (PMMA-PDMA) provided irrefutable evidence for the formation of a chloride-based iron product at the GC|PMMA-PDMA interface. Finally, we have identified conditions that prevent the irreversible conversion of ferrocene by utilizing a high loading of redox active reagent and/or an ionic liquid (IL) membrane plasticizer with high ionicity that suppresses the mass transfer of chloride.

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The electrochemistry of ferrocene in non-aqueous solvents

Cited by 41 publications

References 17 publications

Extended Electrochemical Windows Made Accessible by Room Temperature Ionic Liquid/Organic Solvent Electrolyte Systems

Extended Electrochemical Windows Made Accessible by Room Temperature Ionic Liquid/Organic Solvent Electrolyte Systems

Electrochemical impedance spectroscopy and cyclic voltammetry of ferrocene in acetonitrile/acetone system

Electrochemical Mechanism of Ferrocene-Based Redox Molecules in Thin Film Membrane Electrodes

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