Surface enhanced Raman scattering (SERS) is a powerful technique based on the intensification of the Raman signal because of the interaction of a molecule with a nanostructured metal surface. Electrochemically roughened silver has been widely used as SERS substrate in the qualitative detection of analytes at the ultra-trace level. However, its potential for quantitative analysis has not been widely exploited yet. In this work, the combination of time-resolved Raman spectroelectrochemistry with silver screen-printed electrodes (SPE) is proposed as a novel methodology for the preparation of SERS substrates. The in situ activation of a SERS substrate is performed simultaneously with the analytical detection of a probe molecule, controlling the process related to the preparation of the substrate and performing the analytical measurement in real time. The results show the good performance of silver SPE as electrochemically-induced surface-enhanced Raman scattering substrates. Raman spectra were recorded at fairly low integration times (250 ms), obtaining useful spectroelectrochemical information of the processes occurring at the SPE surface with excellent time-resolution. By recording the microscopic surface images at different times during the experiment, we correlated the different data obtained: structural, optical and electrochemical. Finally, the in situ activation process was used to obtain a suitable in situ SERS signal for ferricyanide and tris(bipyridine)ruthenium (II) quantification. The detection of the analytes at concentrations of a few tens of nM was possible with a low integration time (2 s) and good precision, demonstrating the exceptional performance of the Raman spectroelectrochemical method and the possibility to use cost-effective screen-printed electrodes for applications where a high sensitivity is needed.

由于分子与纳米结构金属表面的相互作用，表面增强拉曼散射（SERS）是一项基于拉曼信号增强的强大技术。电化学粗糙化的银已被广泛用作超痕量分析物定性检测中的SERS底物。但是，其定量分析的潜力尚未得到广泛利用。在这项工作中，提出了时间分辨拉曼光谱电化学与银丝网印刷电极（SPE）的结合作为制备SERS衬底的新方法。在原位SERS底物的激活与探针分子的分析检测同时进行，控制与底物制备有关的过程，并实时进行分析测量。结果表明，银SPE作为电化学诱导的表面增强拉曼散射基质具有良好的性能。拉曼光谱以相当低的积分时间（250毫秒）记录下来，从而以优异的时间分辨率获得了在SPE表面发生的过程的有用的光谱电化学信息。通过在实验期间的不同时间记录微观表面图像，我们将获得的不同数据进行了关联：结构，光学和电化学。最后，使用原位活化过程获得合适的原位SERS信号用于铁氰化物和三（联吡啶）钌（II）定量。可以以短的积分时间（2 s）和良好的精密度检测几十nM浓度的分析物，这证明了拉曼光谱电化学方法的出色性能以及使用经济高效的丝网印刷电极进行分析的可能性需要高灵敏度的应用。