Removal of chlorpyrifos, thiamethoxam, and tebuconazole from water using green synthesized metal hexacyanoferrate nanoparticles

Abstract

The low-cost and highly efficient pesticides are largely used in residential, agricultural, and commercial applications. Their prevalent occurrence, bioaccumulation, and chronic toxicity to living beings have raised environmental concern and call for their whole eradication, especially from water. By virtue of semiconducting nature and high surface area, nanomaterials have become efficient adsorbent and photocatalyst in removal of toxins. To confirm this, the potential of highly crystalline metal hexacyanoferrates (MHCFs) of Zn, Cu, Co, and Ni was evaluated in deprivation of selected hazardous pesticides, viz., chlorpyrifos (CP), thiamethoxam (TH), and tebuconazole (TEB). Sharp nanocubes of ZnHCF (~ 100 nm), distorted nanocubes of CuHCF (~ 100 nm), and nanospheres of CoHCF and NiHCF (< 10 nm) were synthesized via green route using Sapindus mukorossi (raw ritha). At 50 mg L⁻¹ of pesticide, 15 mg of MHCF photocatalyst, neutral pH and sunlight irradiation, selected agrochemicals were degraded to maximum extent (91–98%) by ZnHCF followed by CuHCF (85–91%), NiHCF (73–85%), and CoHCF (70–83%). This might be because of highest zeta potential and BET surface area of ZnHCF. The highest adsorption of CP (83–98%) followed by TH (76–95%) and TEB (70–91%) on acidic surface of catalysts might be related to access of free electrons in their structures. On treatment with MHCF photocatalyst, targets underwent mineralization along with formation of some minor and non-toxic by-products such as (Z) but-2-enal, 3-aminopropanoic acid, and pyridin-3-ol, identified after mass spectrometric analysis of reaction mixture. Based on them, degradation pathways have been proposed to reveal the potential of MHCF for solar photocatalytic removal of organic pollutants in environment.