Theory of linear sweep voltammetry with finite diffusion space Part II. Totally irreversible and quasi-reversible cases

Transport Phenomena: Challenges and Opportunities for Molecular Catalysis in Metal–Organic Frameworks

“…Alternatively, Butler–Volmer kinetics can describe the electron transfer reaction occurring at the electrode surface if the reaction is slow relative to the CV time scale. Transition between these complementary behaviors and the overall current–potential response are captured by two dimensionless parameters, originally defined by Matsuda and co-workers 55 , 56 and Savéant and co-workers: 27 the finite diffusion parameter, λ e , and the kinetic parameter, Λ s , given below, where d f is the film thickness, ν is the scan rate, D e app is the electron-hopping diffusion coefficient, F is the Faraday constant, and k s is the standard rate constant for heterogeneous electron transfer. The competition between diffusion and interfacial electron transfer is expressed by Λ s , and λ e is the ratio of the film thickness to the diffusion layer thickness.…”

Numerical simulations of cyclic voltammetry for lithium-ion intercalation in nanosized systems: finiteness of diffusion versus electrode kinetics

“…The purpose of this work is to use numerical simulations to obtain theoretical voltammograms for LiMn 2 O 4 single particles and thin films of nanometric size in connection with the experimental works of Tao et al [15] and Mürter et al [16], and analyze the relevance of the nanometric size of the particles for the voltammetric response of the system. The results will be also discussed in the framework of the theoretical predictions of Aoki et al [27].…”

“…Before starting with the description of the present numerical simulations, we will briefly analyze particle size and sweep rate effects in the light of the work of Aoki et al [27]. These authors implemented a theoretical model to study voltammetry for finite diffusion space films.…”

“…Concerning the theory of voltammetry under different regimes, it is also worth mentioning the contributions of Aoki et al [26,27], which provide a theoretical framework for analyzing the voltammetric profiles for finite diffusion space films. This model describes kinetic and finite diffusion effects in terms of two dimensionless parameters, namely Λ and w. Calculated voltammograms were used to build different domains in a log(Λ) vs log (w) representation, where different regions were identified in terms of the reversibility, Λ, and the extent of the diffusion phenomena, w. This representation allows a straightforward prediction of the behavior of different systems in terms of experimentally measurable parameters.…”

Electrochemical Characterization of Glucose Bioanodes Based on Tetramethylferrocene-Modified Linear Poly(ethylenimine)

“…A plot of cD 1/2 e versus degree of cross-linking is shown in Fig. 4 [26][27][28]. The relative electron diffusion coefficient increases from 2.1 × 10 −9 ± 0.5 × 10 −9 mol/cm 2 sec 1/2 for films with 4 mol% EGDGE to 8.8 × 10 −9 ± 0.6 × 10 −9 mol/cm 2 sec 1/2 in films with 32 mol% EGDGE, however cD 1/2 e decreases to 6.9 × 10 −9 ± 0.7 × 10 −9 mol/cm 2 sec 1/2 for films with 43 mol% EGDGE.…”