Synthesis and Applications of Crown Ether-Linked Metal–Organic Framework Composite-Based Sensors for Stripping Voltammetric Determination of Lead

Abstract

The present work demonstrates the construction and electrochemical characterization of novel disposable screen-printed carbon sensors integrated with functionalized MIL-53-NH2 metal–organic framework cross-linked with crown ethers and calixarene macrocyclic compounds for sensitive differential pulse voltammetric determination of lead ions in tap, surface water and biological fluid samples. The electroanalytical parameters were optimized regarding the nature of the electrode modifier, supporting electrolyte, the working pH value, scan rate, deposition potential, deposition time, reproducibility of measurement and the operational lifetime. Working electrodes dropcasted with MIL-53-NH2-dibenzo-24-crown-8-ether nanocomposite (MOFCE24) showed the proper performance within the lead concentration ranging from 13.75 to 217.83 ppb with LOD and LOQ values of 3.18 and 9.62 ppb, respectively. The synergistic effect of the metal–organic frameworks as transducer and dibenzo 24-crown-8-ether as sensing elements accelerates the electron transfer process at the electrode surface and improves the sensor selectivity through complexation of the lead ions with the crown ether moiety. The fabricated sensors showed high measuring reproducibility with long operational life time (60 days), which can be attributed to the formation of cross-linked ionophore/metal–organic framework with limited leaching of the sensing element in the measuring solution. The introduced sensors were utilized for the onsite voltammetric determination of lead in environmental and biological samples with acceptable average recoveries comparable with the graphite furnace atomic absorption spectrometric method.