Ultrasensitive Plasmon-Enhanced Infrared Spectroelectrochemistry
Ultrasensitive Plasmon-Enhanced Infrared Spectroelectrochemistry
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DOI：
10.1002/anie.202319246
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发表时间：
2024-01-19
影响因子：
16.6
通讯作者：
Xia，Xing-Hua
中科院分区：
文献类型：
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作者：
Li，Jin;Wu，Dan;Xia，Xing-Hua
红外光谱电化学（EC-IR）是一种探索电化学反应机理的前沿操作方法。然而，由于缺乏高增强基底，现有EC-IR平台的灵敏度有限，这对界面分子的检测提出了挑战。在这里，我们提出了一种创新的等离子体增强红外光谱电化学（EC-PEIRS）平台来克服这种灵敏度限制。具有IR信号增强的等离子体天线通过单层石墨烯电连接，同时保持光路完整性，用作电极和IR基板。在EC-PEIRS平台上研究了[Fe（CN）6]3−/[Fe（CN）6]4−氧化还原反应和电化学CO2还原反应（CO2 RR），得到了显著的信号增强。值得注意的是，增强的IR信号能够重建氧化还原反应的电化学曲线，并揭示CO2 RR机制。这项研究提出了一种很有前途的技术，可以促进对不同应用中界面事件的深入理解。
IR spectroelectrochemistry (EC‐IR) is a cutting‐edge operando method for exploring electrochemical reaction mechanisms. However, detection of interfacial molecules is challenged by the limited sensitivity of existing EC‐IR platforms due to the lack of high‐enhancement substrates. Here, we propose an innovative plasmon‐enhanced infrared spectroelectrochemistry (EC‐PEIRS) platform to overcome this sensitivity limitation. Plasmonic antennae with ultrahigh IR signal enhancement are electrically connected via monolayer graphene while preserving optical path integrity, serving as both the electrode and IR substrate. The [Fe(CN)6]3−/[Fe(CN)6]4−redox reaction and electrochemical CO2reduction reaction (CO2RR) are investigated on the EC‐PEIRS platform with a remarkable signal enhancement. Notably, the enhanced IR signals enable a reconstruction of the electrochemical curve of the redox reactions and unveil the CO2RR mechanism. This study presents a promising technique for boosting the in‐depth understanding of interfacial events across diverse applications.