Spontaneous adsorption of ferrocenes on highly ordered pyrolytic graphite edges

Britton, Wayne E.; Assubaie, Fahad N.

doi:10.1016/s0022-0728(84)80030-3

Cited by 6 publications

(4 citation statements)

References 27 publications

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“…The redox charge for ferrocene oxidation Q Fc is in any case relatively low since it corresponds to 0.5−1.5 × 10 -10 mol cm -2 , depending on the substituent (i.e., it is significantly lower than that expected for a monolayer coverage (4 × 10 -10 mol cm -2 13 ) and is in marked contrast with the high (multilayer) coverages (ca. 2 × 10 -8 mol cm -2 ) obtained on pyrolytic graphite) . This fact might be due either to the unfavorable properties of the solvent for the adsorption process or to the activation treatment of the electrode surface.…”

Section: Resultsmentioning

confidence: 99%

“…2 × 10 -8 mol cm -2 ) obtained on pyrolytic graphite). 10 This fact might be due either to the unfavorable properties of the solvent for the adsorption process or to the activation treatment of the electrode surface. We have therefore selected other solvents and electrode-cleaning procedures to this purpose.…”

Section: Adsorption Of Ferrocene Compoundsmentioning

confidence: 99%

“…The adsorption of ferrocenes on another electrode substrate, namely pyrolytic graphite, has been previously reported. 10 Recently, the adsorption of a series of variously substituted ferrocenes over high-T c cuprate superconductors has been described. 11…”

Section: Introductionmentioning

confidence: 99%

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Adsorption of Ferrocene Compounds on Indium−Tin−Oxide Electrodes. Enhancement of Adsorption by Decomposition of Ferrocenium Molecules by Oxygen

Zotti¹,

Schiavon²,

Zecchin³

et al. 1998

Langmuir

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The adsorption of some substituted ferrocene molecules (Fc-R) on indium−tin-oxide electrodes has been investigated by cyclic voltammetry in acetonitrile. Adsorption occurs with carboxyl-substituted (R = −COOH and −(CH2)6COOH) and to a lesser extent with amino-substituted (R = −CH2N(CH3)2) ferrocenes. Adsorption from the neutral (ferrocene) carboxyl-substituted molecule produces layers with a coverage of 1 × 10-10 mol cm-2 which increases to 4 × 10-10 mol cm-2 from the oxidized (ferrocenium) molecule in air-saturated solution. In the latter case, adsorption occurs on a thin layer of amorphous iron oxide produced by oxidative decomposition of the ferrocenium. Electrodes modified by amorphous iron oxide layers are able to give stable monolayers from the carboxyl-terminated molecules, particularly with R = −(CH2)6COOH due to self-assembly. The layer structures are discussed on the basis of the adsorbate structure and the electrochemical parameters.

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Section: Resultsmentioning

confidence: 99%

Section: Adsorption Of Ferrocene Compoundsmentioning

confidence: 99%

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Adsorption of Ferrocene Compounds on Indium−Tin−Oxide Electrodes. Enhancement of Adsorption by Decomposition of Ferrocenium Molecules by Oxygen

Zotti¹,

Schiavon²,

Zecchin³

et al. 1998

Langmuir

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“…Herein, we report the power of CV as a quantitative method for determination of the adsorption isotherm by studying three ferrocene derivatives (Figure ) at the basal plane of highly oriented pyrolytic graphite (HOPG). Originally, covalent and noncovalent attachment of ferrocene derivatives was studied using the edge plane of HOPG. , Recently, reversible and specific adsorption of ferrocene derivatives on the basal plane of HOPG was investigated by CV and SECM-based CV to diagnostically demonstrate adsorption of only reduced forms, FcXY, i.e., The lack of adsorption of oxidized forms, Fc + XY, proves that the ferrocene derivatives undergo outer-sphere electron transfer, , i.e., because adsorption of the oxidized forms is required for inner-sphere electron-transfer and heterogeneous self-exchange , reactions. Adsorption of ferrocene derivatives on HOPG, however, has not been understood quantitatively.…”

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confidence: 99%

Voltammetric Measurement of Adsorption Isotherm for Ferrocene Derivatives on Highly Oriented Pyrolytic Graphite

et al. 2018

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Reversible and specific adsorption of redox-active molecules from the electrolyte solution to the electrode surface is an important process and is often diagnosed by cyclic voltammetry (CV). The entire voltammogram, however, is rarely analyzed quantitatively, thereby completely missing or incorrectly extracting inherent information about the adsorption isotherm. Herein, we report CV measurements of the adsorption isotherm for ferrocene derivatives on the basal plane of highly oriented pyrolytic graphite (HOPG) to quantitatively understand the thermodynamics of ferrocene−HOPG and ferrocene− ferrocene interactions at HOPG/water interfaces. Specifically, reversible CV of (ferrocenylmethyl)trimethylammonium, ferrocenemethanol, and 1,1′-ferrocenedimethanol is obtained at 0.05−10 V/s to confirm that only reduced forms of ferrocene derivatives are adsorbed on HOPG. Finite element analysis of the entire voltammogram yields the Frumkin isotherm to separately parametrize ferrocene−HOPG and ferrocene−ferrocene interactions. Adsorption of all ferrocene derivatives is driven by similarly weak ferrocene−HOPG interactions with free energy changes of approximately −20 kJ/mol. Adsorption of ferrocenemethanol is strengthened by intermolecular hydrogen bonding, which is quantitatively represented by a free energy change of −8 kJ/mol for surface saturation and is qualitatively characterized by a pair of sharp adsorption and desorption peaks following a pair of diffusional peaks. By contrast, adsorption of (ferrocenylmethyl)trimethylammonium and 1,1′-ferrocenedimethanol remains weak because of electrostatic repulsion and weak hydrogen bonding, respectively, which correspond to the respective free energy changes of +0.7 and −3 kJ/mol for surface saturation. The unfavorable or weakly favorable intermolecular interactions broaden or narrow a diffusional peak during the forward scan, respectively, without yielding a post peak.

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Modification of adsorption components of the processes for reduction of selenium(IV) and oxidation of ferrocene at gold electrodes in frozen aqueous pe

Bond

Zongpeng

1989

Journal of Electroanalytical Chemistry and Interfacial Electroc

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Spontaneous adsorption of ferrocenes on highly ordered pyrolytic graphite edges

Cited by 6 publications

References 27 publications

Adsorption of Ferrocene Compounds on Indium−Tin−Oxide Electrodes. Enhancement of Adsorption by Decomposition of Ferrocenium Molecules by Oxygen

Adsorption of Ferrocene Compounds on Indium−Tin−Oxide Electrodes. Enhancement of Adsorption by Decomposition of Ferrocenium Molecules by Oxygen

Voltammetric Measurement of Adsorption Isotherm for Ferrocene Derivatives on Highly Oriented Pyrolytic Graphite

Modification of adsorption components of the processes for reduction of selenium(IV) and oxidation of ferrocene at gold electrodes in frozen aqueous pe

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