Electrolyte-Layer-Tunable ATR-SEIRAS for Simultaneous Detection of Adsorbed and Dissolved Species in Electrochemistry

A balanced detection of both adsorbates and dissolved species is very important for the clarification of the electrochemical reaction mechanism yet remains a major challenge for different modes of electrochemical infrared (IR) spectroscopy. Among others, conventional attenuated total reflection-surface-enhanced IR absorption spectroscopy (ATR-SEIRAS) is far less sensitive to low-concentration solution species than to surface species. We report herein an electrochemical wide-frequency ATR-SEIRAS with a novel thin-layer flow cell design, fulfilling the simultaneous detection of the variations of surface and solution species. This setup consists of a silicon wafer (with one side micromachined and the other side metallized), a thin-layer electrolyte structure with tunable thickness and flow rate, and a tilt-correction system based on laser collimation, enabling a well-controlled mass transport within the electrolyte layer and the spectral differentiation of solution species from adsorbates. Using acidic methanol oxidation on a Pt film electrode as a model system, besides SEIRA bands for adsorbed CO and formate intermediates, IR spectral signals for dissolved products CO2, formic acid, and methyl formate can be readily identified for a quiescent electrolyte layer of similar to 20 mu m, which are otherwise undetected with conventional ATR-SEIRAS, as indicated by the trend of spectral features with increasing thickness or flow rate.

Automated summary

A balanced detection of both adsorbates and dissolved species is crucial for understanding the electrochemical reaction mechanism, but it remains challenging for different modes of electrochemical infrared spectroscopy. In this study, we report a novel electrochemical wide-frequency ATR-SEIRAS with a thin-layer flow cell design, enabling the simultaneous detection of surface and solution species.