Fiber Optic Spectroelectrochemical Sensing for in situ Determination of Metal Ions

In situ chemical sensing techniques are increasingly used for a variety of applications, including industrial process control, on‐site environmental assessment, and detection of explosives and chemical and biological weapons. A common category of sensors for such purposes entails the use of optical fibers for making spectral measurements of target compounds or species derived from these compounds via physical, chemical, enzymatic, or immunologic reactions. A less common but potentially advantageous approach involves the electrochemical conversion of the analyte subsequent to its spectroscopic detection. These spectroelectrochemical schemes represent versatile, essentially reagent‐free analyses that could provide superior alternatives to existing methods. Reported here is a summary of progress made by the authors' group toward the development of fiber optic spectroelectrochemical sensors for in situ measurements. The aqueous copper (II)/copper (0) couple was chosen as a model system to investigate the merit of an analytical scheme involving (i) cathodic preconcentration of Cu²⁺ as Cu⁰ followed by (ii) anodic stripping of Cu⁰ to Cu²⁺, (iii) complexation of Cu²⁺ by an appropriate ligand, and finally (iv) absorbance determination of the copper–ligand complex or fluorescence determination of the unbound ligand. Results are encouraging and indicate the need for further refinement of the sensor's design and the experimental protocol in order to improve the method's sensitivity.