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Bioelectrochemistry and Electrochemical Sensing

通过后酰胺化和直接酯化在 ITO 上制备的氧化还原活性单层膜及其光谱电化学特性分析

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  • 长崎大学 a综合生产科学研究科物質科学部門,b工学研究科化学・物質工学専攻,c综合生产科学研究科海洋未来科学専攻,长崎市文教町1番14号,长崎县,日本,852-8521
相乐 隆正,中居 沙映,养父 龙介,荒神 匠汰

网络出版日期: 2025-02-26

Redox-active Monolayers on ITO Prepared by Post-amidation and Direct Esterification and their Spectroelectrochemical Characterization

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  • a Professor T. Sagara* Division of Chemistry and Materials Science, Graduate School of Integrated Science and Technology (Engineering Branch), Nagasaki University, Bunkyo 1-14, Nagasaki 852-8521, Japan b S. Nakai and R. Yofu Chemistry and Materials Science course, Graduate School of Engineering, Nagasaki University, Bunkyo 1-14, Nagasaki 852-8521, Japan c S. Kojin Program for Frontiers of Marine Science, Graduate School of Integrated Science and Technology, Nagasaki University, Bunkyo 1-14, Nagasaki 852-8521, Japan
Takamasa Sagara , Sae Nakai , Ryusuke Yofu , and Shota Kojin

Online published: 2025-02-26

摘要

光学透明电极上的具有氧化还原活性的单层是光谱电化学传感的典型平台。源于其多维传感信号的可用性,需要使此平台更加复杂精致。同时监测氧化还原电流和与氧化态变化同步的颜色变化可显著提高灵敏度和选择性。本研究旨在阐明用有序取向的紫精(viologen)单层修饰铟锡氧化物(ITO)电极的方法。通过使用 1-乙基-3-(3-二甲基氨基丙基)-碳二亚胺与 N-羟基琥珀酰亚胺(EDC/NHS)的缩合反应,开发出了将带有羧基的viologen分子固定以形成组装单层的新方法。在两种固定化方法中,一种方法采用两个步骤,首先形成芳香族硅氧烷基底层,然后通过后酰胺化作用,以酰胺连接的方式将viologen衍生物固定在基底层上。另一种方法是在 ITO 表面的羟基和viologen衍生物的羧基之间直接建立酯连接。后一种方法还用于在距离 ITO 表面很短的距离固定二茂铁基。利用平面偏振光斜入射的电位调制紫外-可见透射吸收光谱测量技术,确定了还原型viologen的纵轴方向。利用电位调制透射吸收信号的频率依赖性数据分析了电子转移动力学。还对这两种固定方法做成的viologen修饰电极的性能与用 3-氨基丙基三乙氧基硅烷(3-aminopropyl triethoxysilane)制备的最常用基底层进行后酰胺化修饰的 ITO电极的性能进行了比较。

本文引用格式

相乐 隆正, 中居 沙映, 养父 龙介, 荒神 匠汰 . 通过后酰胺化和直接酯化在 ITO 上制备的氧化还原活性单层膜及其光谱电化学特性分析[J]. 电化学, 0 : 0 . DOI: 10.61558/2993-074X.3530

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 sensitivity 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 carboxyl group to form assembled monolayers through a condensation reaction using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide with N-hydroxy-succinimide (EDC/NHS). In the two methods of immobilization, one utilizes a two-step process to first 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 carboxyl 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 compared to that of an ITO modified by post-amidation to the most commonly used base layer prepared with 3-aminopropyl triethoxysilane.
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