Femtomole Infrared Spectroscopy at the Electrified Metal–Solution Interface

• Published in: Analytical chemistry (Washington) Vol. 88; no. 19; pp. 9351 - 9354
• Main Authors: Morhart, Tyler A., Quirk, Amanda, Lardner, Michael J., May, Tim E., Rosendahl, Scott M., Burgess, Ian J.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 04.10.2016
• Subjects: Analytical chemistry; Apertures; Beams (radiation); Diffraction; Electrodes; Information dissemination; Infrared spectroscopy; Micrometers; Molecules; Signal to noise ratio; Spectra
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/acs.analchem.6b02840

Characterization of surface adsorbed species using infrared (IR) spectroscopy provides valuable information concerning interfacial chemical and physical processes. However, in situ infrared studies of surface areas approaching the IR diffraction limit, such as micrometer scale electrodes, require a hitherto unrealized means to obtain high signal-to-noise (S/N) spectra from femtomole quantities of adsorbed molecules. A major methodological breakthrough is described that couples the high brilliance of synchrotron-sourced infrared microscopy with attenuated total reflection surface enhanced infrared spectroscopy (ATR-SEIRAS). The method is shown to allow the spectral measurement of a monolayer of 4-methoxypyridine (MOP) adsorbed on a surface enhancing gold film electrode under fully operational electrochemistry conditions. A factor of 15 noise improvement is achieved with small apertures using synchrotron IR relative to a thermal IR source. The very low noise levels allow the measurement of high quality IR spectra of 2.5 fmol of molecules confined to a 125 μm2 beam spot.