CuAg nanoparticles formed in situ on electrochemically pre-anodized screen-printed carbon electrodes for the detection of nitrate and nitrite anions

CuAg nanoparticles (CuAgNPs) were electrochemically formed in situ on pre-anodized, screen-printed carbon electrodes (SPCEs) that possessed many oxygen-containing functional groups capable of adsorbing metal ions, namely Cu²⁺ and Ag⁺. Pre-anodization was achieved using continuous cyclic voltammetry in the range of potential 0.3–2.0 V under a scan rate of 50 mV/s. Cu²⁺ and Ag⁺ ions were adsorbed on the pre-anodized SPCE by immersing the electrode in solutions containing both metal ions, and then CuAgNPs were formed in situ via electrochemical reduction in a deaerated, neat NaClO₄ solution after the electrode was ultrasonicated to remove physically adsorbed metal ions. Although CuNPs showed higher activity than AgNPs toward both nitrate (NO₃ ⁻) and nitrite (NO₂ ⁻) ions, the instability of CuNPs hindered the application, so CuAgNPs were employed to achieve a compromise between sensitivity and stability. The SPCE/anodized/CuAgNP electrodes showed activity toward the electrochemical reduction of NO₃ ⁻ and NO₂ ⁻, respectively, with the limit of detection (LOD) of 15.6 μM (0.97 ppm) and 11.1 μM (0.51 ppm), which is sufficient to fit the allowed values (50 and 3 ppm, respectively) in drinking water as suggested by the World Health Organization (WHO).