Direct Determination of Plasmon Enhancement Factor and Penetration Depths in Surface Enhanced IR Absorption Spectroscopy.

Surface Enhanced Infrared Absorption Spectroscopy (SEIRAS) is a powerful tool for studying a wide range of surface and electrochemical phenomena. For most electrochemical experiments the evanescent field of an IR beam partially penetrates through a thin metal electrode deposited on top of an attenuated total reflection (ATR) crystal to interact with molecules of interest. Despite its success, a major problem that complicates quantitative interpretation of the spectra from this method is the ambiguity of the enhancement factor due to plasmon effects in metals. We developed a systematic method for measuring this, which relies upon independent determination of surface coverage by Coulometry of a surface-bound redox-active species. Following that, we measure the SEIRAS spectrum of the surface bound species, and from the knowledge of surface coverage, retrieve the effective molar absorptivity, εSEIRAS. Comparing this to the independently determined bulk molar absorptivity leads us to the enhancement factor f = εSEIRAS/εbulk. We report enhancement factors in excess of 1000 for the C-H stretches of surface bound ferrocene molecules. We additionally developed a methodical approach to measure the penetration depth of the evanescent field from the metal electrode into a thin film. Such systematic measure of the enhancement factor and penetration depth will help SEIRAS advance from a qualitative to a more quantitative method.

Phenol as a Tethering Group to Gold Surfaces: Stark Response and Comparison to Benzenethiol.

Understanding the adsorption of organic molecules on metals is important in numerous areas of surface science, including electrocatalysis, electrosynthesis, and biosensing. While thiols are commonly used to tether organic molecules on metals, it is desirable to broaden the range of anchoring groups. In this study, we use a combined spectroelectrochemical and computational approach to demonstrate the adsorption of 4-cyanophenols (CPs) on polycrystalline gold. Using the nitrile stretching vibration as a marker, we confirm the adsorption of CP on the gold electrode and compare our results with those obtained for the thiol counterpart, 4-mercaptobenzonitirle (MBN). Our results reveal that CP adsorbs on the gold electrode via the OH linker, as evidenced by the similarity in the direction and magnitude of the nitrite Stark shifts for CP and MBN. This finding paves the way for exploring new approaches to modify electrode surfaces for controlled reactivity. Furthermore, it highlights adsorption on metals as an important step in the electroreactivity of phenols.