Boosting the catalytic activity of natural magnetite for wet peroxide oxidation

This work explores the modification of naturally occurring magnetite by controlled oxidation (200-400 °C, air atmosphere) and reduction (300-600 °C, H₂ atmosphere) treatments with the aim of boosting its activity in CWPO. The resulting materials were fully characterized by XRD, XPS, TGA, TPR, SEM, and magnetization measurements, allowing to confirm the development of core-shell type structures. The magnetite core of the solid remained unchanged upon the treatment whereas the Fe(II)/Fe(III) ratio of the shell was modified (e.g. 0.42, 0.11 and 0.63 values were calculated for pristine Fe₃O₄, Fe₃O₄-O400, and Fe₃O₄-R400, respectively). The performance of the catalysts was tested in the CWPO of sulfamethoxazole (SMX) (5 mg L^-1) under ambient conditions and circumneutral pH (pH₀ = 5), using the stoichiometric dose of H₂O₂ (25 mg L^-1) and a catalyst load of 1 g L^-1. The key role of the ferrous species on the mineral shell was evidenced. Whereas the oxidation of magnetite led to significantly slower degradation rates of the pollutant, its reduction gave rise to a dramatic increase, achieving the complete removal of SMX in 1.5 h reaction time with the optimum catalyst (Fe₃O₄-R400) compared to the 3.5 h required with the pristine mineral. A reaction mechanism was proposed for SMX degradation, and a kinetic equation based on the Eley-Rideal model was accordingly developed. This model successfully fitted the experimental results. The stability of Fe₃O₄-R400 was evaluated upon five sequential runs. Finally, the versatility of the catalytic system was proved in real environmentally relevant water matrices.