Electrochemical analysis of glyphosate using porous biochar surface corrosive nZVI nanoparticles

Glyphosate [N-(phosphonomethyl)glycine] is a widely used phosphonate herbicide for different agricultural purposes. Due to its widespread use, suspected toxicity, and ubiquitous bioaccumulation, it is one of the most harmful contaminants found in drinking water. This demands efficient sensing and removal of glyphosate from contaminated water. Here, we report the decoration of novel and highly porous biochar with nanozero-valent iron (nZVI) nanoparticles to develop an efficient electrochemical sensor for the trace detection of glyphosate. The as-synthesized composite was thoroughly characterized by various state-of-the-art instrumental techniques. The electron micrographs of the composite materials revealed the cavity-like structure and the abundant loading of nZVI nanoparticles. FTIR and XPS analyses confirmed the presence of oxygen-rich functionalities and Fe(0) in the composite nanostructure. Electrochemical analysis through CV, LSV, and DPV techniques suggested efficient sensing activity with a limit of detection as low as 0.13 ppm. Furthermore, the chronopotentiometric response suggested excellent and superior stability for long-term applications. To gain more insight into the interaction between glyphosate and the composite material, DFT calculations were carried out. The Frontier Molecular Orbital study (FMO), Molecular Electrostatic Potentials (MEPs), and Density of States (DOS) suggest an increase in the electron density, an increase in the DOS, and a decrease in the HOMO-LUMO band gap by combining nZVI nanoparticles and biochar. The results suggest more facile electron transfer from the composite for trace detection of glyphosate. As a proof of concept, we have demonstrated that real-time analysis of milk, apple juice, and the as-synthesized composite shows promising results for glyphosate detection with an excellent recovery rate.