Effect of surface roughness on interfacial reaction–diffusion admittance

Kant, Rama; Rangarajan, S.K.

doi:10.1016/s0022-0728(03)00039-1

Cited by 54 publications

(60 citation statements)

References 58 publications

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“…The solution of the Helmholtz equation or Debye-Hückel equation for arbitrary geometries and boundary conditions (Dirichlet, Neumann or Robin) are known in the form of "multiple scattering expansions" [42,43,44,45,46]. Also " multiple scattering expansion in curvature" results accounting for the arbitrary geometry of the surface is analysed for the diffusion problems [46,47,48,49,50,51]. Adapting a similar methodology to solve the electrostatic potential of electric double layer, we will obtain the capacitance of EDL near surfaces of arbitrary shapes in Debye-Hückel or linearized Gouy-Chapman regime.…”

Section: Model Of Diffuse Layer Near Curved Surfacesmentioning

confidence: 99%

Generalization of the Gouy-Chapman-Stern model of an electric double layer for a morphologically complex electrode: Deterministic and stochastic morphologies

Kant

Singh

2013

Phys. Rev. E

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We generalize linearized Gouy-Chapman-Stern theory of electric double layer for nanostructured and morphologically disordered electrodes. Equation for capacitance is obtained using linear Gouy-Chapman (GC) or Debye-Hückel equation for potential near complex electrode/electrolyte interface. The effect of surface morphology of an electrode on electric double layer (EDL) is obtained using "multiple scattering formalism" in surface curvature. The result for capacitance is expressed in terms of the ratio of Gouy screening length and the local principal radii of curvature of surface. We also include a contribution of compact layer, which is significant in overall prediction of capacitance. Our general results are analyzed in details for two special morphologies of electrodes, i.e. "nanoporous membrane" and "forest of nanopillars". Variations of local shapes and global size variations due to residual randomness in morphology are accounted as curvature fluctuations over a reference shape element. Particularly, the theory shows that the presence of geometrical fluctuations in porous systems causes enhanced dependence of capacitance on mean pore sizes and suppresses the magnitude of capacitance. Theory emphasizes a strong influence of overall morphology and its disorder on capacitance. Finally, our predictions are in reasonable agreement with recent experimental measurements on supercapacitive mesoporous systems.

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Section: Model Of Diffuse Layer Near Curved Surfacesmentioning

confidence: 99%

Generalization of the Gouy-Chapman-Stern model of an electric double layer for a morphologically complex electrode: Deterministic and stochastic morphologies

Kant

Singh

2013

Phys. Rev. E

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“…1), driven by a sinusoidal interfacial potential dV = V o exp(Àjxt) (V o = EÀE eq : E the working electrode potential and E eq the equilibrium potential) is obtained by solving the diffusion equations for the local concentration profile [37] …”

Section: Admittance Theory For Rough Electrodesmentioning

confidence: 99%

“…The total admittance is given by the Laplace transform of the interfacial surface current I(t) or [37] ( 1 which corresponds to the low frequency regime) [37] hY ðxÞi ¼Ŷ p 1 þ…”

Section: Admittance Theory For Rough Electrodesmentioning

confidence: 99%

“…Recently a theory was developed for the electrical admittance of a rough interface under partial diffusion-limited charge transfer conditions [37]. In this development, the large and small-frequency expansion gave the relationships between the average admittance and various morphological features of the rough electrode i.e.…”

Section: Introductionmentioning

confidence: 99%

“…In this development, the large and small-frequency expansion gave the relationships between the average admittance and various morphological features of the rough electrode i.e. area, curvature, and interface width [37]. So far the diffusion-limited reaction admittance was determined on an approximately self-affine surface without, however, analytic results for all lateral roughness wavelengths [37] spanning the range from qn ( 1 to qn ) 1 where n is the characteristic lateral roughness correlation length and q the lateral roughness wave vector.…”

Section: Introductionmentioning

confidence: 99%

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Self-affine roughness influence on redox reaction charge admittance

Palasantzas

2005

Surface Science

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In this work we investigate the influence of self-affine electrode roughness on the admittance of redox reactions during facile charge transfer kinetics. The self-affine roughness is characterized by the rms roughness amplitude w, the correlation length n, and the roughness exponent H (0 < H < 1). Our calculations allow analytic expressions to be derived for the admittance as a function of the characteristic self-affine roughness parameters. Furthermore, it is shown that the magnitude of the reaction admittance is strongly influenced by the local roughness exponent H or the fine roughness details at short roughness wavelengths, while the influence of the lateral correlation length n or the long wavelength roughness ratio w/n is of secondary importance. In addition, the dynamic roughness evolution can strongly influence the reaction admittance and it should taken carefully into consideration.

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Thionicotinamide SAM on Gold: Adsorption Studies and Electroactivity

et al. 2009

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STM and impedance results of the self-assembled monolayer (SAM) formed with thionicotinamide (TNA) on gold indicate the presence of defects that increase with the immersion time of the electrode in the TNA solution affecting the SAM electroactivity toward the electron transfer reaction of the cytochrome c metalloprotein and [Fe(CN) 6 ] 4À and [Ru(NH 3 ) 6 ] 3þ complexes. It was observed that this electroactivity was also affected by the pH of the electrolyte solution. SERS and STM data indicate sulfur coordination to the surface with contribution of the NH 2 group. From the dependence of the TNA surface coverage on the temperature and concentration in solution, thermodynamic parameters of adsorption were determined.

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Effect of surface roughness on interfacial reaction–diffusion admittance

Cited by 54 publications

References 58 publications

Generalization of the Gouy-Chapman-Stern model of an electric double layer for a morphologically complex electrode: Deterministic and stochastic morphologies

Generalization of the Gouy-Chapman-Stern model of an electric double layer for a morphologically complex electrode: Deterministic and stochastic morphologies

Self-affine roughness influence on redox reaction charge admittance

Thionicotinamide SAM on Gold: Adsorption Studies and Electroactivity

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