Title

New Approach to Simultaneous In Situ Measurements of the air/liquid/solid interface using PM-IRRAS

Document Type

Article

Publication Date

3-16-2020

Department

Department of Chemistry, Department of Materials Science and Engineering

Abstract

Vibrational spectroscopy techniques have evolved to measure gases, liquids, and solids at surfaces and interfaces. In the field of surface-sensitive vibrational spectroscopy, infrared spectroscopy measures the adsorption on surfaces and changes from reactions. Previous polarized modulated-infrared reflection–absorption spectroscopy (PM-IRRAS) measurements at the gas/solid interface were developed to observe catalytic reactions near reaction conditions. Other PM-IRRAS measurements use liquid cells where the sample is submerged and compressed against a prism that has traditionally been used for electrochemical reactions. This article presents a new method that is used to observe in situ adsorption of molecules using PM-IRRAS at the gas/liquid/solid interface. We demonstrate the meniscus method by measuring the adsorption of octadecanethiol on gold surfaces. Characterization of self-assembled monolayers (SAMs), the “gold standard” for PM-IRRAS calibration measurements, was measured in ethanol solutions. The condensed-phase (air/liquid) interface in addition to the liquid/solid interface was measured simultaneously in solution. These are compared with liquid attenuated total reflectance (ATR)-Fourier transform infrared (FTIR) spectroscopy measurements to confirm the presence of the SAM and liquid ethanol. A model of the three-phase system is used to approximate the thickness of the liquid ethanol layer and correlate these values to signal attenuation using PM-IRRAS. This proof-of-concept study enables the measurement of reactions at the gas/liquid/solid interface that could be adapted for other reactions at the electrode and electrolyte interfaces with applications in environmental science and heterogeneous catalysis.

Publication Title

Langmuir

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