Electrochemical sensing mechanism of ammonium ions over an Ag/TiO2 composite electrode modified by hematite

Abstract

Here, we demonstrate a new electrochemical sensing mechanism of ammonium ions (NH₄⁺) involving a two-electron oxygen reduction reaction (ORR) and a hydrazine reaction. The NH₄⁺ are electrooxidized to hydrazine by H₂O₂ derived from the ORR over a self-supporting Ag/TiO₂ nanotube array composite electrode modified by hematite (Ag/Fe₂O₃/TNTs). The Ag/Fe₂O₃/TNT sensor exhibits a high sensitivity of 1876 µA mM⁻¹ cm⁻² with a detection limit of 0.18 µM under non-alkaline conditions, a short response time of 3 s, good reproducibility, and fine selectivity among various interferents, and is also successfully used in real water bodies to display high accuracy. Furthermore, this new mechanism has a certain universality in a range of Ag (main catalyst)/transition metal oxide (cocatalyst)/TNT sensing systems. This work offers a new design basis for the urgently needed electrochemical ammonia nitrogen sensors.