Non-enzymatic electrochemical impedance sensor for selective detection of electro-inactive organophosphate pesticides using Zr-MOF/ZrO2/MWCNT ternary composite

The existence of multiple pesticide residues in fruits and vegetables constitutes a direct peril to living organisms. Therefore, it is crucial to develop a low-cost screening method for determining organophosphate pesticides (OPPs) in food samples. This study describes the solvothermal synthesis of a ternary composite comprising multi-walled carbon nanotubes (MWCNT), zirconium oxide, and a zirconium-metal-organic framework (Zr-MOF). The ternary composite was characterised using XRD, FESEM, FTIR, and BET. The ternary composite provides a large surface area (1158 m2/g) compared with the pristine Zr-MOF (868 m2/g). The composite-modified glassy carbon electrode was used to determine nine pesticides, including organophosphate (malathion, dimethoate, chlorpyrifos, monocrotophos, and glyphosate) and non-organophosphate (thiophanate methyl, carbendazim, atrazine, and 2,4, D). In particular, various chemical combinations of OPPs were selected, such as S-P=S, P=S, P=O, and non-OPPs such as C=S (with sulphur), and without sulphur. The sensor results show that the sensor selectivity is high for OPPs containing both phosphorus and sulphur molecules. The low detection limit of the sensor was 2.02, 2.8, 2.5, 1.11, and 2.01 nM for malathion, chlorpyrifos, dimethoate, monocrotophos, and glyphosate, respectively. The electrode exhibited significant chemical stability (93%) after 100 cycles, good repeatability, and a long shelf life. The sensor is reliable for qualitative real-time applications.