MWCNT-OH/graphene composite sensor for nonenzymatic detection of paraoxon-ethyl in agricultural samples

In this study, we developed electrochemical sensors based on the composite of hydroxylated multiwalled carbon nanotubes (MWCNT-OH) and graphene for paraoxon-ethyl detection as pesticide residues in agricultural products. Chemical treatment was employed to produce MWCNT-OH from pristine MWCNT and its composite with graphene was subsequently characterized using FTIR, Raman spectroscopy, FESEM-EDX, TEM, and XPS techniques. The MWCNT-OH/graphene composite was employed as an electrode modifier on the glassy carbon electrode (GCE) surface, and its electroanalytical performances were studied using differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) techniques. It was revealed the optimum composition ratio between MWCNT-OH and graphene was 2:8, for paraoxon-ethyl detection at pH 7. This could be attributed to the enhanced electrocatalytic activity in the MWCNT-OH/graphene composite which displayed a linear range of paraoxon-ethyl concentration as 0.1–100 µM with a lower detection limit of 10 nM and a good sensitivity of 1.60 µA µM cm⁻². In addition, the proposed sensor shows good reproducibility, stability, and selectivity in the presence of 10 different interfering compounds including other pesticides. Ultimately, this proposed sensor was tested to determine the paraoxon-ethyl concentrations in green apples and cabbage as samples of agricultural products. The obtained concentrations of paraoxon-ethyl from this proposed sensor show no significant difference with standard spectrophotometric techniques suggesting this sensing platform might be further developed as a rapid detection of pesticide residue in agricultural products.