Combining scanning electrochemical microscopy with infrared attenuated total reflection spectroscopy for in situ studies of electrochemically induced processes.

The combination of scanning electrochemical microscopy (SECM) with single-bounce attenuated total reflection Fourier-transformed infrared spectroscopy (FT-IR-ATR) has been developed for in situ studies on electrochemically induced processes at IR waveguide surfaces via evanescent field absorption spectroscopy. The feasibility of the combined microelectrochemical FT-IR setup was demonstrated by spectroscopically monitoring microstructured polymer depositions induced via feedback mode SECM using a 25 mum Pt disk ultramicroelectrode (UME). The surface of a ZnSe ATR crystal was initially coated with 2,5-di-(2-thienyl)-pyrrole (SNS) layer, which was then locally polymerized during Ru(bpy)(3)(2+) mediated feedback mode SECM experiments. The polymerization reaction was simultaneously monitored by recording absorption intensity changes of SNS specific IR bands, thereby providing information on the polymerization mechanism and on the percentage of surface modification.