电化学（中英文）2025，Vol.31Issue(6)：51-63,13.DOI:10.61558/2993-074X.3530
后酰胺化和直接酯化法制备铟锡氧化物基氧化还原活性单层膜及其光谱电化学特性分析
Redox-Active Monolayers on ITO Prepared by Post-Amidation and Direct Esterification and Their Spectroelectrochemical Characterization
摘要
Abstract
A redox-active monolayer on an optically transparent electrode constitutes a typical platform for spectroelectrochemical sensing.The necessity for its sophistication arises from the availability of multi-dimensional sensing signals.Simultaneous monitoring of the redox current and color change synchronized with the oxidation state change significantly enhances sen-sitivity and selectivity.This study aimed to elucidate the modification of an indium tin oxide(ITO)electrode with a viologen monolayer with an ordered orientation.Novel methods were developed to immobilize a viologen molecule bearing a car-boxyl group to form assembled monolayers through a condensation reaction using 1-ethyl-3-(3-dimethylaminopropyl)-car-bodiimide with N-hydroxy-succinimide(EDC/NHS).In the two methods of immobilization,one utilizes a two-step process to firstly form an aromatic siloxane base layer and subsequently attach the viologen derivative through an amide linkage by post-amidation.The other employs a direct ester linkage between the hydroxyl groups of the ITO surface and the car-boxyl group of the viologen derivative.The latter method was also applied to immobilize a ferrocenyl group at a very short distance from the ITO surface.Potential-modulated UV-visible transmission absorption spectral measurement techniques with oblique incidence of plane-polarized light were employed to determine the orientation of the longitudinal axis of the reduced form of the viologen.The frequency dependence data of the potential-modulated transmission absorption signals were utilized to analyze the electron transfer kinetics.The performance of the two viologen-modified electrodes was com-pared to that of an ITO modified by post-amidation to the most commonly used base layer prepared with 3-aminopropyl triethoxysilane.关键词
氧化还原活性单层/铟锡氧化物电极/吸收光谱/分子取向/EDC/NHSKey words
Redox-active monolayer/ITO electrode/Absorption spectroscopy/Molecular orientation/EDC/NHS引用本文复制引用
相乐隆正,中居沙映,与夫龙介,小仁翔太..后酰胺化和直接酯化法制备铟锡氧化物基氧化还原活性单层膜及其光谱电化学特性分析[J].电化学（中英文）,2025,31(6):51-63,13.基金项目
We thank financial supports by the Grant-in-Aid of Scientific Research of Challenging Research(Explor-atory)(JP23K17738)to TS from MEXT of Japan and by the 41st grant of research from Nippon Sheet Glass Foundation for Materials Science and Engineering to TS.We also thank Dr.Hong-Xiang Wang(Nagasaki University)for her help in translating the abstract from English to Chinese. （Explor-atory）
