Spectroelectrochemical microscopy: Spatially resolved spectroelectrochemistry of carrier-based ion-selective membranes

High-resolution spectroscopic imaging of the cross section of ion-selective membranes and the adjoining solution phases during real-time electrochemical measurement is termed as spectroelectrochemical microscopy (SpECM). The novel SpECM instrument utilizes wavelength-dispersive multispectral imaging of a thin membrane strip separating the two sides of a four-electrode thin-layer electrochemical cell. SpECM is aimed as a tool for optimizing the experimental conditions in mass transport-controlled ion-selective electrode membranes for improved detection limit. Some of the capabilities of the new technique are demonstrated using fix site, chromoionophore-based, pH-sensitive membranes as model systems. The experimental results are discussed in the light of the existing theory of fixed-site membranes. The quantitative expression for the time-dependent change of the free ionophore concentration across the ion-selective membrane showed close correlation to the recorded concentration profiles. © 2005 American Chemical Society