Femtomole Infrared Spectroscopy at the Electrified Metal-Solution Interface.
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 μm2beam spot.
Department of Chemistry, University of Saskatchewan , Saskatoon, Saskatchewan S7N 5C9, Canada.
Tyler A
TA
Morhart
Department of Chemistry, University of Saskatchewan , Saskatoon, Saskatchewan S7N 5C9, Canada.
Amanda
A
Quirk
Department of Chemistry, University of Saskatchewan , Saskatoon, Saskatchewan S7N 5C9, Canada.
Michael J
MJ
Lardner
Canadian Light Source , Saskatoon, Saskatchewan S7N 2 V3, Canada.
Tim E
TE
May
Canadian Light Source , Saskatoon, Saskatchewan S7N 2 V3, Canada.
Scott M
SM
Rosendahl
Department of Chemistry, University of Saskatchewan , Saskatoon, Saskatchewan S7N 5C9, Canada.
Ian J
IJ
Burgess