The influence of crystallographic inhomogeneity of a polycrystalline electrode surface on the behavior of the electric double-layer

Bagotskaya, I. A.; Дамаскин, Б. Б.; Levi, M. D.

doi:10.1016/s0022-0728(80)80325-1

Cited by 65 publications

(23 citation statements)

References 6 publications

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“…19,20,24,25 Thus, the slope of Parsons-Zobel plot characterizes the increase of the surface roughness in the order of the electrodes Bi(111) EP Ͻ Bi(111) CN Ͻ Bi(111) C Ͻ Bi(001) C1 Ͻ Bi(111) C1 Ͻ Bi(001) C2 . 5,10,11,17,[28][29][30] However, as shown in Fig. 7, the shape of (C exp ) Ϫ1 , (C D ) Ϫ1 plot depends on the apparent surface-charge density and, thus, the inverse slope values of (C exp ) Ϫ1 , (C D ) Ϫ1 plots ͑i.e., the so-called experimental surface roughness factor values, f P-Z ) depend on the apparent value and, for that reason, f P-Z obtained from the inverse slope of ParsonsZobel plot is not a real physical quantity as the real surface areas have to be independent of .…”

Section: Results and Discussion Of Electrochemical Datamentioning

confidence: 99%

Influence of Surface Charge Density on the Electrochemically Derived Surface Roughness of Bi Electrodes

Lust

Kallip

Möller

et al. 2003

J. Electrochem. Soc.

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Electrical double-layer properties of variously treated Bi͑001͒ and Bi͑111͒ electrodes were studied in terms of the Debye length dependent roughness theory ͑i.e., nonlinear Poisson-Boltzmann theory͒, recently developed by Daikhin et al. The geometrical roughness factor, root mean square ͑rms͒ departure of the surface from flatness, the medium lateral correlation length values have been obtained. According to the experimental data and results of theoretical calculations, the surface roughness increases in the order of Bi electrodes: electrochemically polished single-crystal Bi͑111͒ plane Ͻ cut at the temperature of liquid nitrogen Bi͑111͒ plane Ͻ electrochemically etched Bi͑111͒ plane Ͻ chemically etched Bi͑111͒ plane Ͻ chemically etched Bi͑001͒ plane. This order of the electrode surface roughness is in agreement with the ex situ AFM data, i.e., with the rms roughness R ms values. At small electrolyte concentrations (c el р 0.01 M), the deviation of experimental roughness function vs. inverse Debye length curves from the theoretically calculated ones has been observed, which is explained by the influence of energetic inhomogeneity of the polycrystalline surfaces, i.e., the nonequal surface charge density values at the various homogeneous regions exposed at the macropolycrystalline electrode surface, on the interfacial capacitance values.The phase-boundary structure and adsorption properties, as well as the kinetics of various interfacial reactions at the solid surfaces depend significantly, not only on the chemical composition, but also on the morphology of the surface studied. 1-4 Thus, the surface roughness is an important property in electrochemistry of solid electrodes as the most of electric double-layer and adsorption characteristics, as well as kinetic parameters are extensive quantities and are referred to the unit apparent area ͑flat cross-sectional area͒ of the electrode surface. The examination of the working area of solid electrodes is a difficult matter owing to the irregularities at a submicroscopic level. For the determination of the real surface area of the solid electrodes different in situ and ex situ methods have been proposed and used. The in situ methods more commonly used in electrochemistry to obtain the surface roughness R ϭ S real /S geom ͓where S real and S geom are the real ͑working͒ surface and geometrical, so-called flat gross section surface area, respectively͔ are: ͑i͒ differential capacitance measurements in the region of ideal polarizability, 1-5 Parsons-Zobel plot method, 9 Valette-Hamelin approach, 7 and other similar methods; 1-5 ͑ii͒ mass transport under diffusion control with assumption of homogeneous current distribution; 12 ͑iii͒ adsorption of ratio-active organic compounds, hydrogen, oxygen as well as metal monolayers; 5,12 (iv) microscopy ͑optical, electron, scanning tunneling microscopy ͑STM͒, and atomic force microscopy ͑AFM͒; [2][3][4][5][14][15][16]24,25 (v) quartz microbalance, 16 as well as a number of ex situ methods. 1-5 It is to be noted that depending on the irr...

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Section: Results and Discussion Of Electrochemical Datamentioning

confidence: 99%

Influence of Surface Charge Density on the Electrochemically Derived Surface Roughness of Bi Electrodes

Lust

Kallip

Möller

et al. 2003

J. Electrochem. Soc.

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“…Far from the pzc the effects of nonlinear screening are found, which lead, for instance, to the charge dependence of the Parsons-Zobel plot, which has been observed experimentally. [3][4][5][6] Surface roughness is not the only possible reason for the deviations of the slope of the Parson-Zobel plot from unity. Another reason for this could be the effect of crystallographic inhomogeneity of the surface.…”

Section: Introductionmentioning

confidence: 99%

“…Another reason for this could be the effect of crystallographic inhomogeneity of the surface. 3,4,7,8 The latter was studied in detail for polished single crystals. 3,4,7 Generally, different crystal faces have different pzcs.…”

Section: Introductionmentioning

confidence: 99%

“…3,4,7,8 The latter was studied in detail for polished single crystals. 3,4,7 Generally, different crystal faces have different pzcs. This affects the charge distribution along the equipotential surface, and thereby the dependence of capacitance on electrolyte concentration, until the characteristic inhomogeneity range is greater than the Debye length.…”

Section: Introductionmentioning

confidence: 99%

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Nonlinear Poisson–Boltzmann theory of a double layer at a rough metal/electrolyte interface: A new look at the capacitance data on solid electrodes

Daikhin

Kornyshev

Urbakh

1998

The Journal of Chemical Physics

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Nonlinear Poisson-Boltzmann theory is developed to extend our previous work ͓Phys. Rev. E 53, 6192 ͑1996͔͒ on the case when the potential drop across the double layer is not small compared to the thermal energy. Close to the potentials of zero charge ͑pzc͒ the effect of surface roughness on the double-layer capacitance is mainly determined by an interplay between the lateral correlation length of roughness and the Debye length. However, far from the pzc dramatic effects of electrode potential are found which are not reduced to the potential-induced shortening of the diffuse layer thickness.

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“…These plots are used to test the validity of the GC theory, where a straight line with unit slope approves the GC theory for the diffuse layer with the corresponding intercept yielding the inverse capacitance of the compact layer [11]. Slopes lower than one are usually related to the geometrical roughness factor R [13], while any deviations from linear behavior are considered as indications of specific adsorption of ions, incomplete dissociation of electrolyte [8], crystallographic inhomogeneity [8,[13][14][15][16], and electrode roughness within the nonlinear PB theory [11].…”

Section: Introductionmentioning

confidence: 99%

Influence of self-affine roughness on Parsons-Zobel plots for electrical double layers

Palasantzas

Backx

2004

Phys. Rev. E

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In this paper we investigate the dependence of Parsons-Zobel plots on characteristic self-affine roughness parameters of the metal electrode in electrical double layers. Among the roughness amplitude w, the correlation length , and roughness exponent H, the latter appears to have the most prominent effect especially for values in the range H Ͻ 0.5. In addition, with decreasing compact layer thickness the influence of roughness leads to stronger nonlinear behavior of the plots for relatively large electrode potentials. Finally, it is shown that dynamic changes of the electrode roughness (for example by growth on metal films) should be carefully quantified with respect to their influence on the Parson-Zobel plots and related double-layer systems.

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The influence of crystallographic inhomogeneity of a polycrystalline electrode surface on the behavior of the electric double-layer

Cited by 65 publications

References 6 publications

Influence of Surface Charge Density on the Electrochemically Derived Surface Roughness of Bi Electrodes

Influence of Surface Charge Density on the Electrochemically Derived Surface Roughness of Bi Electrodes

Nonlinear Poisson–Boltzmann theory of a double layer at a rough metal/electrolyte interface: A new look at the capacitance data on solid electrodes

Influence of self-affine roughness on Parsons-Zobel plots for electrical double layers

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