An ion-selective chemiresistive platform as demonstrated for the detection of nitrogen species in water

Abstract

The use of ion-selective electrodes (ISE) is a well-established technique for the detection of ions in aqueous solutions but requires the use of a reference electrode. Here, we introduce a platform of ion-selective chemiresistors for the detection of nitrogen species in water as an alternative method without the need for reference electrodes. Chemiresistors have a sensitive surface that is prone to damage during operation in aqueous solutions. By applying a layer of ion-selective membrane to the surface of the chemiresistive device, the surface becomes protected and highly selective. We demonstrate both anion-selective (NO₃⁻, NO₂⁻) and cation-selective (NH₄⁺) membranes. The nitrate sensors are able to measure nitrate ions in a range of 2.2–220 ppm with a detection limit of 0.3 ppm. The nitrite sensors respond between 67 ppb and 67 ppm of nitrite ions (64 ppb detection limit). The ammonium sensors can measure ammonium concentrations in a wide range from 10 ppb to 100 ppm (0.5 ppb detection limit). The fast responses to nitrate and nitrite are due to a mechanism involving electrostatic gating repulsion between negative charge carriers of the film and anions while ammonium detection arises from two mechanisms based on electrostatic gating repulsion and adsorption of ammonium ions at the surface of the p-doped chemiresistive film. The adsorption phenomenon slows down the recovery time of the ammonium sensor. This sensor design is a new platform to continuously monitor ions in industrial, domestic, and environmental water resources by robust chemiresistive devices.