Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Tokyo, Japan.
Anal Chem. 2011 Nov 15;83(22):8429-38. doi: 10.1021/ac201408w. Epub 2011 Oct 19.
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.
固态四硫代萘（TTN；直径从几十到几百纳米的颗粒）在电极上的循环伏安法（CV）通过考虑惰性区电势、热力学和动力学相互作用以及电极反应动力学进行了定量分析。理论处理应用于阐明实验上可获得的相应参数。从半峰宽全电流的电势（ΔE(p1/2))和在最慢的电位扫描速率下获得的可逆 CV 伏安图的峰电流（i(p))，评估了活性材料中热力学吸引力为 W = 3.67 ± 0.30 kJ mol(-1)，对于 (TTN)(0/1+) 氧化还原对。从不可逆 CV 中获得的峰电位（ΔE(p))的偏移以及 ΔE(p1/2)和/或 i(p)的变化，评估了 (TTN)(0/1+) 偶对表面电极反应的形式速率常数（k°')为 0.59 ± 0.10 s(-1)。对于 (TTN)(0/1+) 偶对的电极反应的热力学和动力学相互作用，W 和 ΔW[symbol: see text]的相互作用参数也通过不可逆 CV 的分析分别评估为 3.39 ± 0.41 kJ mol(-1)和-1.39 ± 0.31 kJ mol(-1)。
