Facile Electrochemical Approach Based on Hydrogen-Bonded MOFs-Derived Tungsten Ethoxide/Polypyrrole-Reduced GO Nanocrystal for ppb Level Ammonium Ions Detection

Abstract

Ammonium (NH4+) ions are a primary contaminant in the river and along the waterside near an agricultural area, therefore, necessitating sensitive detection of pollutants before irreversibly damaging environment. Herein, a new approach of metal-organic framework-derived tungsten ethoxide/polypyrrole-reduced graphene oxide (MOFs-W(OCH2CH3)6/Ppy-rGO) electrochemical sensors are introduced. Through a simple hydrothermal process, Ppy-rGO is linked to tungsten ethoxide as an organic linker. This creates the MOFs-W(OCH2CH3)6/Ppy-rGO nanocrystal through hydrogen bonding. The synergistic combination of tungsten ethoxide and Ppy-rGO provides three-fold advantages: stabilization of Ppy-rGO for extended usage, enabling detection of analytes at ambient temperature, and availability of multiple pathways for effective detection of analytes. This is demonstrated through excellent detection of NH4+ ions over a dynamic concentration range of 0.85 to 3.35 µM with a ppb level detection limit of 0.278 µM (9.74 ppb) and a quantitation limit of 0.843 µM (29.54 ppb). The increment in the concentration of NH4+ ions contributes to the increment in proton (H+) concentration. The increment in proton concentration in the solution will increase the bonding activity and thus increase the conductivity. The cyclic voltammetry curves of all concentrations of NH4+ analytes at the operating potential window between −1.5 and 1.5 V exhibit a quasi-rectangular shape, indicating consistent electronic and ionic transport. The distinctive resistance changes of the MOFs-W(OCH2CH3)6/Ppy-rGO to various NH4+ ion concentrations and ultrasensitive detection provide an extraordinary platform for its application in the agriculture industry.