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Utility of Polarization Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS) in Surface and In-situ Studies: New Data Processing and Presentation Approach

Abstract

Infrared spectroscopy is a powerful non-destructive technique for identification and quantification of organic molecules widely used in scientific studies. For many years, there have been efforts to adopt the technique for in situ monitoring of reactions. From these efforts polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) was developed three decades ago. Unfortunately, because of the complexity in data processing and interpretation, PM-IRRAS had been avoided in lieu of the single potential alteration infrared spectroscopy (SPAIRS) and subtractively normalized interfacial Fourier transform infrared (SNIFTIR). In this work, we present a new approach for PM-IRRAS data processing and presentation, which provides more insights for in situ and surface studies besides dramatically improving the S/N. In this new approach, we recommend three complementary methods of data treatment (equation 7, 9, and 10) as the new protocols for presenting PM-IRRAS data. These equations are robust in visualising surface processes at solid-liquid and solid-gas interphases. Equation 7 contrasts the surface adsorbed species with respect to isotropic background with or without the influence of the applied potential. Equation 9 highlights the surface potential-driven changes between the sample and reference spectra. Equation 10 focuses on bulk-phase (solution/gas and surface species) potential-driven changes between the sample and reference spectra, hence can be used to track the production of species, which desorb from the surface upon their formation. Examples of ethanol electrooxidation reaction are provided as a test system for in situ studies and PVP deposited on glassy carbon for thin-film studies to illustrate the utility of the new PM-IRRAS data handling protocol, which is poised to improve the understanding of chemistry and physics of surface processes.

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Publication details

The article was accepted on 05 Apr 2018 and first published on 06 Apr 2018


Article type: Paper
DOI: 10.1039/C8AN00572A
Citation: Analyst, 2018, Accepted Manuscript
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    Utility of Polarization Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS) in Surface and In-situ Studies: New Data Processing and Presentation Approach

    E. A. Monyoncho, V. Zamlynny, T. Woo and E. Baranova, Analyst, 2018, Accepted Manuscript , DOI: 10.1039/C8AN00572A

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