Effect of temperature and copper doping on the heterogeneous Fenton-like activity of Cu$_x$Fe$_{3-x}$O$_4$ nanoparticles

Abstract: Ferrite nanoparticles serve as potent heterogeneous Fenton-like catalysts, producing reactive oxygen species (ROS) for decomposing organic pollutants. We investigated the impact of temperature and copper content on the catalytic activity of nanoparticles with different oxidation states of iron. Via solvothermal synthesis, we fabricated copper-doped magnetite (Cu$x$Fe${3-x}$O$_4$) with a Fe$^{2+}$/Fe ratio ~0.33 for the undoped system. Using a microwave-assisted method, we produced copper-doped oxidized ferrites, yielding a Fe$^{2+}$/Fe ratio of ~0.11 for the undoped nanoparticles. The ROS generated by the catalyst were identified and quantified by electron paramagnetic resonance, while optical spectroscopy allowed us to evaluate its effectiveness for the degradation of a model organic dye. At room temperature, the magnetite nanoparticles exhibited the most $\cdot$OH radical production and achieved almost 90% dye discoloration in 2 hours. This efficiency decreased with increasing Cu concentration, concurrently with a decrease in $\cdot$OH generation. Conversely, above room temperature, Cu-doped nanoparticles significantly enhance the dye degradation, reaching 100% discoloration at 90$^\circ$C. This enhancement is accompanied by a systematic increase in the kinetic constants, obtained from reaction equations, with Cu doping. This study highlights the superior stability and high-temperature catalytic advantages of copper ferrite holding promise for enhancing the performance of nanocatalysts for decomposing organic contaminants.