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

doi:10.61558/2993-074X.3530

电化学（中英文） ›› 2025, Vol. 31 ›› Issue (6): 2417002. 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

相乐隆正^a^,^*(), 中居沙映^b, 养父龙介^b, 荒神匠汰^c

^a长崎大学综合生产科学研究科物质科学部門，长崎市文教町1番14号，长崎县，日本，852-8521
^b长崎大学工学研究科化学?物质工学专攻，长崎市文教町1番14号，长崎县，日本，852-8521
^c长崎大学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

收稿日期:2025-01-08 修回日期:2025-02-14 接受日期:2025-02-16 发布日期:2025-02-26 出版日期:2025-06-28

Redox-Active Monolayers on ITO Prepared by Post-Amidation and Direct Esterification and Their Spectroelectrochemical Characterization

Takamasa Sagara^a^,^*(), Sae Nakai^b, Ryusuke Yofu^b, Shota Kojin^c

^aDivision of Chemistry and Materials Science, Graduate School of Integrated Science and Technology (Engineering Branch), Nagasaki University, Bunkyo 1-14, Nagasaki 852-8521, Japan
^bChemistry and Materials Science course, Graduate School of Engineering, Nagasaki University, Bunkyo 1-14, Nagasaki 852-8521, Japan
^cProgram for Frontiers of Marine Science, Graduate School of Integrated Science and Technology, Nagasaki University, Bunkyo 1-14, Nagasaki 852-8521, Japan

Received:2025-01-08 Revised:2025-02-14 Accepted:2025-02-16 Online:2025-02-26 Published:2025-06-28
Contact: *Takamasa Sagara, E-mail: sagara@nagasaki-u.ac.jp

1. 2417002-Redox-Active Monolayers on ITO Prepared by Post-Amidation and Direct Esterification and Their Spectroelectrochemical Characterization-Supporting Information.pdf(155KB)

摘要/Abstract

摘要：

光学透明电极上构筑具有氧化还原活性的单层结构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，需要使用更加复杂精致的平台。此外，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。本研究旨在探索采用有序取向的紫精单层修饰铟锡氧化物（ITO）电极的方法及相关特性。通过利用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紫精分子固定以形成组装单层的新方法。两种固定化方法中，一种方法涉及两个步骤，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紫精衍生物固定在基底层上。另一种方法是在ITO表面的羟基和紫精衍生物的羧基之间直接建立酯连接。后一种方法还可用于ITO表面近距离固定二茂铁基。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，确定了还原型紫精的纵轴方向。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，并进一步比较了两种固定方法制备的紫精修饰电极与用3-氨基丙基三乙氧基硅烷制备的最常用基底层进行后酰胺化修饰的ITO电极的性能。

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/NHS

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 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 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.

Key words: Redox-active monolayer, ITO electrode, Absorption spectroscopy, Molecular orientation, EDC/NHS

相乐隆正, 中居沙映, 养父龙介, 荒神匠汰. 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): 2417002.

Takamasa Sagara, Sae Nakai, Ryusuke Yofu, Shota Kojin. Redox-Active Monolayers on ITO Prepared by Post-Amidation and Direct Esterification and Their Spectroelectrochemical Characterization[J]. Journal of Electrochemistry, 2025, 31(6): 2417002.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.61558/2993-074X.3530

https://electrochem.xmu.edu.cn/CN/Y2025/V31/I6/2417002

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参考文献 36

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Surface layer	ITO/APhS-amide-viologen	ITO/surface ester-viologen	ITO/APTES-amide-viologen
E^0'/V vs. E_{Ag/AgCl/sat-KCl}	-0.399	-0.383	-0.450
ΔE_p/mV	38	50	0
Γ /mol·cm^-2	2.6 × 10^-10	3.3× 10^-10	1.0 × 10^-10
f_dimer/%	64	85	97
α/degree	32	33	40
k_s/s^-1	80	70 9	300 ± 100

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

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