Dynamic electrochemistry at the interface between two immiscible electrolytes

Samec, Zdeněk

doi:10.1016/j.electacta.2012.03.118

Cited by 82 publications

(84 citation statements)

References 136 publications

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“…These results were checked using a second glassy carbon electrode and found to be consistent. Our results for glassy carbon are similar to those reported by Kim et al [36]for glassy carbon in propylene carbonate containing 0.5 M [NBu n 4 ][BF 4 ]. For carbon electrodes, including glassy carbon, the density of states near the Fermi level is significantly lower than that for Au or Pt [37] and this affects the double layer capacitance.…”

Section: Double Layer Capacitance At Glassy Carbonsupporting

confidence: 82%

“…We will therefore discuss the two separately starting with the results for Au and Pt. 4 ] show little dependence on the electrode potential (figures 4 and 6) and no clear trends with the concentration (figure 6). Our capacitance values are very similar to those reported by Fawcett's group for tetraalkylammonium perchlorates in propylene carbonate at mercury [31] and for tetraethylammonium perchlorate in acetonitrile at platinum [32], and by Gambert and Baumgärtel for tetraalkylammonium perchlorates at mercury in acetonitrile [33] both in terms of the magnitude of the capacitance and the potential dependence.…”

Section: A)mentioning

confidence: 99%

“…These models are supported by extensive experimental studies and modelling for aqueous solutions and for high dielectric organic solvents such as acetonitrile. Similar models have been used to describe the semiconductor/electrolyte and liquid/liquid junctions [3,4]. Most recently intensive attention has turned to studies of the metal/ionic liquid interface where simple Gouy-Chapman models are clearly inappropriate because of the high ion density [5,6].…”

Section: Introductionmentioning

confidence: 99%

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Measurements of the double layer capacitance for electrodes in supercritical CO2/acetonitrile electrolytes

Bartlett

Cook

2015

Journal of Electroanalytical Chemistry

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Electrochemical impedance measurements were made in the single supercritical phase of CO 2 with 11 wt % acetonitrile as the co-solvent at temperatures and pressures between 306 and 316 K and 15.5 and 20.2 MPa over the potential range from -0.45 to +0.75 V vs. Pt. Gold, platinum and glassy carbon electrodes were studied together with the effects of electrolyte concentration for [ ], were also studied. We find that the impedance data can be described by a simple RC equivalent circuit where the uncompensated solution resistance is independent of the electrode potential and is consistent with earlier measurements for the electrolyte conductivity. The results for the double layer capacitance can be described by a simple Helmholtz layer model and are very similar to those found for similar electrolytes in non-aqueous solvents such as propylene carbonate. For glassy carbon the double layer capacitances show a parabolic like potential dependence which we attribute to the lower density of states near the Fermi level.

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Section: Double Layer Capacitance At Glassy Carbonsupporting

confidence: 82%

Section: A)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Measurements of the double layer capacitance for electrodes in supercritical CO2/acetonitrile electrolytes

Bartlett

Cook

2015

Journal of Electroanalytical Chemistry

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“…In a number of cases, operationally unstable potentiometric sensors can be made much more reproducible by controlling ion fluxes by instrumental means [22]. This class of ion sensors has its roots in the field of ion-transfer voltammetry between two immiscible electrolyte solutions (ITIES) [23,24]. Most experiments at the ITIES used non-permselective membranes (so-called ideally polarizable interfaces).…”

Section: Introductionmentioning

confidence: 99%

All solid state chronopotentiometric ion-selective electrodes based on ferrocene functionalized PVC

Jarolímová

Crespo

Afshar

et al. 2013

Journal of Electroanalytical Chemistry

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a b s t r a c tAn all solid contact ion-selective electrode based on poly(vinyl chloride) covalently modified with ferrocene moieties allows one to operate the membrane in a chronopotentiometric sensing mode. The membrane is considered as initially non-perm-selective towards anions, and an applied anodic current provokes a defined anion flux in direction of the membrane. With this protocol, a variety of anions can be depleted at the membrane surface. Since this model system does not yet contain an ionophore, their order of preference follows the expected Hofmeister selectivity sequence. The all solid-state configuration tolerates an imposed current density of 1.4 lA mm À2 , which translates into an upper detection limit of ca. 1.2 mM. Higher current densities of up to 31.2 lA mm À2 are possible with addition of freely dissolved alkyl ferrocene derivative for an expected upper detection limit of 17.0 mM. Numerical simulations are performed in order to establish the fundamental basis of the mechanism that takes place in this all solid-state membrane electrode. The oxidation of bound Fc and the ion-transfer process are considered in the simulation. In view of developing an analytical sensor, different anions are tested. A linear range of two orders of magnitude from 0.01 to 1 mM is found. The membranes are evaluated over several days, displaying practically the same slopes and intercepts, with a RSD of less than 2%. Electrochemical limitations of free Fc and bound Fc are critical evaluated. This approach should allow one to develop a new family of solid-state chronopotentiometric ion sensors that require relatively high current densities.

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“…Understanding electron transfer (ET) at the interface between two immiscible electrolyte solutions (IES) is of fundamental importance in electrochemistry, [1][2][3][4][5][6][7] solar energy conversion and "artificial photosynthesis," [8][9] and phase transfer catalysis, [10][11][12] and may also be relevant to understanding biological processes at membrane interfaces and in DNA environments. 13 The experimental study of ET at IES has a long history, 2 but up until recently, measurements of electron transfer rates have mainly utilized conventional electrochemical methods, where the interface was under potentiostatic control.…”

Section: Introductionmentioning

confidence: 99%

Photoinduced Excited State Electron Transfer at Liquid/Liquid Interfaces

Cooper

Benjamin

2014

J. Phys. Chem. B

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Abstract:Several aspects of the photoinduced electron transfer (ET) reaction between coumarin 314 (C314) and N,N-dimethylaniline (DMA) at the water/DMA interface are investigated by molecular dynamics simulations. New DMA and water/DMA potential energy surfaces are developed and used to characterize the neat water/DMA interface.The adsorption free energy, the rotational dynamics and the solvation dynamics of C314 at the liquid/liquid interface are investigated and are generally in reasonable agreement with available experimental data. The solvent free energy curves for the ET reaction between excited C314 and DMA molecules are calculated and compared with those calculated for a simple point charge model of the solute. It is found that the reorganization free energy is very small when the full molecular description of the solute is taken into account. An estimate of the ET rate constant is in reasonable agreement with experiment. Our calculations suggest that the polarity of the surface "reported" by the solute, as reflected by solvation dynamics and the reorganization free energy, is strongly solute-dependent.

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Dynamic electrochemistry at the interface between two immiscible electrolytes

Cited by 82 publications

References 136 publications

Measurements of the double layer capacitance for electrodes in supercritical CO2/acetonitrile electrolytes

Measurements of the double layer capacitance for electrodes in supercritical CO2/acetonitrile electrolytes

All solid state chronopotentiometric ion-selective electrodes based on ferrocene functionalized PVC

Photoinduced Excited State Electron Transfer at Liquid/Liquid Interfaces

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