Probing Heterogeneity in Attenuated Total Reflection Surface-Enhanced Infrared Absorption Spectroscopy (ATR-SEIRAS) Response with Synchrotron Infrared Microspectroscopy.
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| Title: | Probing Heterogeneity in Attenuated Total Reflection Surface-Enhanced Infrared Absorption Spectroscopy (ATR-SEIRAS) Response with Synchrotron Infrared Microspectroscopy. |
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| Authors: | Tu, Kaiyang1,2 (AUTHOR), Morhart, Tyler A.1,2 (AUTHOR), Read, Stuart T.2 (AUTHOR), Rosendahl, Scott M.2 (AUTHOR), Burgess, Ian J.1 (AUTHOR) ian.burgess@usask.ca |
| Source: | Applied Spectroscopy. Sep2021, Vol. 75 Issue 9, p1198-1206. 9p. |
| Subjects: | Infrared absorption, Attenuated total reflectance, Infrared spectroscopy, Metallic films, Fourier transform spectrometers, Heterogeneity |
| Abstract: | The heterogeneity of metal island films electrodeposited on conductive metal oxide modified internal reflection elements is shown to provide a variable attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) response. A self-assembled monolayer of a ferrocene-terminated thiol monolayer (FcC11SH) was formed on the gold islands covering a single substrate, which was measured using both a conventional spectrometer and a custom-built horizontal microscope. Cyclic voltammetry and ATR-SEIRAS results reveal that the FcC11SH-modified substrate undergoes a reversible electron transfer and an associated re-orientation of both the ferrocene/ferrocenium headgroup and the hydrocarbon backbone. The magnitude of the absorption signal arising from the redox changes in the monolayer, as well as the IR signature arising from the ingress/egress of the perchlorate counterions, is shown to depend significantly on the size of the infrared beam spot when using a conventional Fourier transform infrared spectrometer. By performing equivalent measurements on a horizontal microscope, the primary cause of the differences in the signal level is found to be the heterogeneity in the density of gold islands on the conductive metal oxide. Graphical Abstract [ABSTRACT FROM AUTHOR] |
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| Database: | Engineering Source |
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