Management of caffeine in wastewater using MOF and perovskite materials: optimization, kinetics, and adsorption isotherm modelling

Abstract

Pharmaceuticals and personal care products (PPCPs) have been increasingly used all over the world and they have been reported on water cycle and cause contamination. Among these pharmaceuticals is caffeine (CAF). In this work, CAF removal from aqueous samples by metal–organic framework (UIO-66) and perovskite (La_0.7Sr_0.3FeO₃) was achieved. Detailed studies on the preparation of MOFs and perovskite oxides compounds have been presented. Extensive characterizations such as X-Ray diffraction (XRD), field emission scanning electron microscope (FESEM), Fourier transform infrared spectra (FT-IR), N₂ adsorption–desorption isotherms were also carried out to assure proper formation and to better understand the physico-chemical behavior of the synthesized samples before and after adsorption. Batch experiments of CAF adsorption onto both MOFs and perovskite were performed to compare the effectiveness of both materials on the removal competence of the CAF residue at different conditions including the effect of pH, initial concentration, and contact time. It was observed that the adsorption capacity of CAF by MOF increased with increasing acidity. On the other hand, the adsorption capacity of perovskite is stable in pH 4–10. The maximum adsorption capacities of UiO-66 and perovskite toward CAF are high as 62.5 mg g⁻¹ and 35.25 mg g⁻¹, respectively. Equilibrium isotherms were investigated by numerous models: Langmuir, Freundlich, Temkin, Redlich-Peterson, Sips, Langmuir-Freundlich, Toth, Kahn, Baudu, and Fritz Schlunder. Moreover, the kinetics of the CAF@MOF and CAF@Perovskite systems have been studied by five kinetic models (Pseudo-1st -order (PFO), Pseudo-2nd -order (PSO), Mixed 1st, 2nd-order, Intraparticle diffusion and Avrami). The best model described the adsorption of CAF onto both of MOF and perovskite was the mixed 1st, 2nd-order model. The metal–organic framework and perovskite were applied to quickly extract CAF from water samples successfully. The maximum removal percentage obtained for MOF and perovskite was 0.89% and 0.94% respectively within 30 min contact time which suggests that these materials are considered as promising adsorbents for CAF.