Theoretical-experimental study of Fe–ZrO2 and Co–ZrO2. Oxidative degradation of methyl orange azo dye

In recent years, advanced oxidation processes (AOPs) based on the generation of sulfate radicals (SO 4 ●- ) (SR-AOPs) have emerged as an innovative method for the decontamination of water and wastewater. In this study, Fe(II) and Co(II) catalysts supported on ZrO₂ were synthesized and employed as an activator for PMS and PS for the degradation of methyl orange. The general objective is to gain detailed insight into the interaction between oxidants and supported metal catalysts at the molecular level. Experimental results and density functional theory (DFT) calculations were employed to analyze the potential activation mechanism of the oxidants. The support was prepared via coprecipitation, and metal ion deposition was achieved through incipient wetness impregnation. The characterization of the catalysts was conducted through atomic absorption spectrometry, X-ray diffraction and Fourier-transform infrared spectroscopy. The findings indicated that PMS was the most efficient oxidant, with Co–ZrO 2 emerging as the most effective catalyst (77% MO mineralization), compared to Fe–ZrO 2 , which exhibited a lower degree of mineralization (37.6%) under the specified experimental conditions. The use of PS as an oxidant resulted in low levels of degradation for both catalysts. The remarkable catalytic efficacy of the Co–ZrO₂/PMS system was elucidated through the application of density functional theory (DFT) calculations. These revealed that the adsorption energy of the oxidants on Co–ZrO₂ is lower than that on Fe–ZrO₂, which could facilitate the subsequent release of radicals to the reaction medium. • AOPs based on the generation of sulfate radicals have emerged as an innovative method. • We have investigated the use of peroxymonosulphate (PMS) and persulphate (PS) anions as oxidizing agents. • We have studied two transition metals -Co and Fe supported on ZrO 2 as catalysts. • A combination of experimental and theoretical simulation techniques was employed, with the latter based on DFT methods.