Electrochemically prepared and optimized membrane compositions for silver(I)‐responsive chalcogenide‐based ion‐selective electrodes

Through electrochemical modeling, an attempt has been made to correlate the composition, structure and stoichiometry of a number of thin electroplated silver chalcogenide (selenides and tellurides) all‐solid‐state membranes with their performance as Ag‐responsive ion‐selective electrodes. The conclusions drawn from the electrochemical membrane composition modeling could be of practical value to the pressed‐pellet technology as well. The results suggest that no binary silver chalcogenide, irrespective of its stoichiometry, could perform reliably in an all‐solid‐state configuration. On the contrary, hyperstoichiometric membranes featuring both intrinsic and extrinsic defects, e.g., Ag2+δSe1−xTex have proved to exhibit high sensitivity, potential reproducibility and selectivity (even to mercury) under both steady‐state and flow‐injection modes. The competitiveness of the newly developed electroplated membranes to conventional Ag2S pressed ones has been assessed.