标题： 氧化还原反应在纳米孔中的光学伏安法与光子离子显微术 显示英文标题

标题： Optical Voltammetry of redox processes inside a nanohole with Opto-iontronic microscopy

摘要： 循环伏安法（CV）是电化学中用于表征电化学反应最常用的方法，通常涉及宏观电极。 在这里，我们展示了一种称为光离子显微镜的新光学CV技术，能够在纳米尺度上监测电化学过程。 通过将光学显微镜与纳米孔电极相结合，我们提高了在小于阿托升（$(100 \text{~nm})^{3}$）体积内检测氧化还原反应的灵敏度。 该技术使用全内反射（TIR）照明、双电层调制、循环伏安法和锁相检测，以探测纳米孔内的离子动力学。 我们将这种方法应用于研究与二甲基铁杂茂（Fc(MeOH)$_2$）氧化还原反应相关的EDL（充放电）。 实验结果与理论泊松-能斯特-普朗克-巴特勒-沃尔默（PNP-BV）模型进行了验证，提供了关于参与光学对比的反应物种离子浓度变化的见解。 这项工作为在纳米限制环境中进行高灵敏度、无标记的电化学反应分析开辟了机会，具有在纯纳米晶体生长和监测以及可能的单分子电化学中的潜在应用。 显示英文摘要

摘要： Cyclic Voltammetry (CV) is the most commonly used method in electrochemistry to characterize electrochemical reactions, usually involving macroscopic electrodes. Here we demonstrate a novel optical CV technique called Opto-iontronic Microscopy, which is capable of monitoring electrochemical processes at the nanoscale. By integrating optical microscopy with nanohole electrodes, we enhance sensitivity in detecting redox reactions within volumes as small as an attoliter ($(100 \text{~nm})^{3}$). This technique uses total internal reflection (TIR) illumination, Electric-double-layer modulation, cyclic voltammetry, and lock-in detection, to probe ion dynamics inside nanoholes. We applied this method to study EDL (dis)charging coupled to ferrocenedimethanol (Fc(MeOH)$_2$) redox reactions. Experimental results were validated against a theoretical Poisson-Nernst-Planck-Butler-Volmer (PNP-BV) model, providing insights into ion concentration changes of reaction species that contribute to the optical contrast. This work opens up opportunities for high-sensitivity, label-free analysis of electrochemical reactions in nanoconfined environments, with potential applications in pure nanocrystal growth and monitoring, and potentially single-molecule electrochemistry.