MgCr2O4 Nanospinel for Efficient Organic Dye Pollutants Degradation: A Comparison of Photocatalysis, Fenton-like, and Photo-Fenton-like Reactions

MgCr2O4 nanospinel samples were synthesized using a modified Pechini method, followed by controlled calcination. The resulting materials were evaluated in terms of crystal structure, particle morphology, and optical and electronic properties. Their oxidative activity towards the degradation of organic dyes was investigated via photocatalysis, Fenton-like, and photon-Fenton-like processes. Various analytical techniques were employed to characterize the samples, including X-ray diffraction (XRD) with Rietveld refinements, infrared (IR) spectroscopy, UV–Vis spectroscopy, colorimetry, and transmission and high-resolution transmission electron microscopy (TEM/HRTEM). Structural characterization revealed that MgCr2O4 crystallized after calcination at 600 ${}^{\circ }$C, and Rietveld refinements confirmed cubic Fd-3m symmetry. IR spectra confirmed the short-range order through the presence of vibrational modes assigned to CrO6^2- octahedra. UV–Vis spectroscopy indicated mixed Cr valences (Cr³+/Cr⁶+) for samples calcined at temperatures below 900 ${}^{\circ }$C, with Cr⁶+ eliminated at higher temperatures, confirmed by electron paramagnetic resonance (EPR) spectroscopy. This suggests that an oxidation reaction occurred due to oxygen vacancies in the lattice. Optical bandgap (Eg) increased with temperature. Samples calcined at low temperatures were dark green and became more saturated at temperatures above 900 ${}^{\circ }$C, suggesting photoresponse to visible light, as indicated by the Eg values. The oxidative activity of the nanospinels in degrading the dyes methylene blue (MB) and rhodamine B (RhB) under visible light depended on the nature of the dye, the catalyst concentration, and the use of H2O2 in the process to improve the formation of hydroxyl radicals (•OH), as confirmed by photohydroxylation of terephthalic acid (TA). The highest degradation rate was observed in the photo-Fenton-like process, with 96% and 97% degradation of RhB and MB dyes in 60 min, reaching a kinetic rate constant (${\mathit{K}}_{app}$) of 0.055 min${}^{-1}$ and 0.051 min${}^{-1}$, respectively. This study highlights the importance of controlling various parameters to promote the formation of reactive oxygen species (ROS) required for oxidative degradation by nanospinels.