Photocatalytic degradation of imidacloprid in the flat-plate photoreactor under UVA and simulated solar irradiance conditions-The influence of operating conditions, kinetics and degradation pathway

This work reports the effectiveness of TiO2 photocatalysts modified by defect engineering methods. The prepared photocatalysts were characterized by X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (DRS), photoluminescence (PL) measurements and electron spin resonance (ESR) technique. The immobilized photocatalyst layer was prepared using an abrasive material as a support and a mineral binder. To the best of our knowledge, this is the first time that such type of the immobilized photocatalytic layer has been prepared and tested. A home-made flat-plate photoreactor (FPP) with artificial light sources was used for the degradation of an aqueous solution of imidacloprid using an immobilized TiO2. The effects of different operating variables such as irradiation source, recirculation flow rate, irradiated surface area and photoreactor volume on the photocatalytic performances were investigated. The hydrodynamic behavior of the flat-plate photoreactor (FPP) was studied utilizing a residence time distribution (RTD) technique using the axial dispersion model. Based on kinetic measurements it was found that the photocatalytic degradation of imidacloprid under the conditions used in this study can be described by a complex kinetic model that follows pseudo-zero order kinetics at the beginning of the degradation, and with the progress of the reaction at higher irradiation times changes to the pseudo-first order. Liquid chromatography - quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) was used to identify imidacloprid degradation by-products as a function of irradiation time. Theoretical modeling of the geometry and electronic structure of imidacloprid in aqueous solution was performed using density functional theory (DFT) calculation. Based on the results of theoretical simulations and experimental measurements, the possible pathway for photodegradation of imidacloprid in aqueous phase after irradiation with UVA was proposed and discussed.