Lawrence Berkeley National Laboratory

Attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) is a powerful method for probing interfacial chemical processes. However, SEIRAS-active nanostructured metallic thin films for the in situ analysis of electrochemical phenomena are often unstable under biased aqueous conditions. In this work, we present a surface-enhancing structure based on etched black Si internal reflection elements with Au-coatings for in situ electrochemical ATR-SEIRAS. Using electrochemical potential-dependent adsorption and desorption of 4-methoxypyridine on Au, we demonstrate that black Si-based substrates offer advantages over commonly used structures, such as electroless-deposited Au on Si and electrodeposited Au on ITO-coated Si, due to the combination of high stability, sensitivity, and conductivity. These characteristics are especially valuable for time-resolved measurements where stable substrates are required over extended times. Furthermore, the low sheet resistance of Au layers on black Si reduces the RC time constant of the electrochemical cell, enabling a significantly higher time resolution compared to that of traditional substrates. Thus, we employ black Si-based substrates in conjunction with rapid- and step-scan Fourier transform infrared (FTIR) spectroscopy to investigate the adsorption and desorption kinetics of 4-methoxypyridine during in situ electrochemical potential steps. Adsorption is shown to be diffusion-limited, which allows for the determination of the mean molecular area in a fully established monolayer. Moreover, no significant changes in the peak ratios of vibrational modes with different orientations relative to the molecular axis are observed, suggesting a single adsorption mode and no alteration of the average molecular orientation during the adsorption process. Overall, this study highlights the enhanced performance of black Si-based substrates for both steady-state and time-resolved in situ electrochemical ATR-SEIRAS, providing a powerful platform for kinetic and mechanistic investigations of electrochemical interfaces.