Analysis for Voltammetric Responses of Molecular-Solid Tetrathionaphthalene Confined on an Electrode

Abstract

The cyclic voltammetry (CV) of solid-state tetrathionaphthalene (TTN; particles with diameters from a few tens to hundreds of nanometers) confined on electrodes was analyzed quantitatively by considering the inert-zone potential, the thermodynamic and kinetic interactions, and the kinetics of the electrode reaction. Theoretical treatments are applied for clarifying the experimentally accessible corresponding parameters. From the potential of full peak width at half-height current (ΔE(p1/2)) and the peak current (i(p)) for the reversible CV voltammogram obtained at the slowest potential scan rate, the thermodynamic attraction forces in their active materials are evaluated as W = 3.67 ± 0.30 kJ mol(-1) for the (TTN)(0/1+) redox couple. From the shift of peak potential (ΔE(p)) and the changes in ΔE(p1/2) and/or the magnitude of i(p) for the irreversible CV obtained against the moderate potential scan rate, the value of the formal rate constant (k°') regarding surface electrode reaction of the (TTN)(0/1+) couple was evaluated as 0.59 ± 0.10 s(-1). The interaction parameters of W and ΔW[symbol: see text] being related to the thermodynamic and the kinetic interactions of the electrode reaction for the (TTN)(0/1+) couple were also evaluated as 3.39 ± 0.41 kJ mol(-1) and -1.39 ± 0.31 kJ mol(-1), respectively, from analysis for the irreversible CV.

Ionophore-Based Voltammetric Ion Activity Sensing with Thin Layer Membranes

“…All solid-state ion-selective electrodes constructed with faradaic ion-to-electron transducing materials, such as poly­(3-octylthiophene) (POT), − poly­(3,4-ethylenedioxythiophene) (PEDOT), − polypyrrole, 7,7,8,8-tetracyanoquinodimethane (TCQN), tetrathialfulvane (TFN), tetrathionaphtalene, or ferrocene (Fc), ,, have offered the possibility of controlling electrochemical reactions (i.e., oxidation of POT to POT + ) at the inner interface of the electrode, thereby triggering an ion transfer reaction across the membrane/sample interface.…”

Evaluation of Thermodynamic and Kinetic Parameters from Voltammetric Responses for Molecular-Solid Li(Li1/3Ti5/3)O4Particles Confined on Electrode

“…The corresponding potential, which has been called unusual quasi-reversibility (UQR) or apparent non-kinetic hysteresis in CV, is defined as a "N-shaped" free energy which is needed in the process being akin to a slow molecular relaxation, 13 or a phase-transition energy of a reactant layer during the charge neutralization process. 14 In the previous paper, 11 this potential is defined as the inert-zone potential, contribution of which is reduced as a constant potential value from the E p shift observed for the irreversible wave in calculation of the related kinetic parameters. Figure 2B exhibits the response for the charge-discharge curves for a laminated cell using LTO electrode.…”

“…In our recent paper, 11 we have reported that the value of W can be evaluated from theoretical equations, which have been published by Laviron [15][16][17] in 1970 and later by Matsuda 12 in 1987, about the CV for the electro-active molecular confined on an electrode. Matsuda proposed the general equation (the eqn.…”

“…For further details of the analysis our recent paper should be referred to. 11 When the CV observed at the slow scan rate is reversible case, the values of W can be calculated from i p or E p1/2 at scan rate v for reversible CV response of LTO. Values of W obtained are summarized in Table I.…”

“…In the last three decades, although a large number of papers about evaluation of the chemical diffusion process 9 has been published, only a few papers have appeared on the kinetic study of the heterogeneous electron-transport process. [1][2][3] In recent reports we described the kinetic study for LTO 10 and an organic sulfur, 11 being electrode activematerials for LIB. In these cases, analysis 12 of the cyclic voltammogram (CV) observed for solid-state thin layers of the corresponding species have mainly been used for evaluating the related parameters.…”