Reagent Free Electrochemical-Based Detection of Silver Ions at Interdigitated Micro Electrodes Using in Situ pH Control

Abstract

Herein we report on the development of an electrochemical sensor for silver ions detection in tap water using anodic sweep voltammetry with in-situ pH control; enabled by closely spaced interdigitated electrode arrays. The in-situ pH control approach allowed the pH of a test solution to be tailored to pH 3 (experimentally determined as the optimal pH) by applying 1.65 V to a protonator electrode with the subsequent production of protons, arising from water electrolysis, dropping the local pH value. Using this approach, an initial proof-of-concept study for silver detection in sodium acetate was undertaken where 1.25 V was applied during deposition (to compensate for oxygen production) and 1.65 V during stripping. Using these conditions, calibration between 0.2 and 10 μM was established with the silver stripping peak ∼0.3 V. The calculated limit of detection was 13 nM. For the final application in tap water, 1.65 V was applied to a protonator electrode for both deposition and stripping of silver. The chloride ions, present in tap water (as a consequence of adding chlorine during the disinfection process) facilitated silver detection and caused the striping peak to shift catholically to ∼0.2 V. The combination of the complexation of silver ions with chloride and in-situ pH control resulted in a linear calibration range between 0.25 and 2 μM in tap water and a calculated limit of detection of 106 nM without the need to add acid or supporting electrolytes.