RESUMO
Two compositions of graphene oxide-magnetite nanocomposites were studied as catalysts in the heterogeneous Fenton process. Transmission electron microscopy and X-ray diffraction revealed that the graphene oxide sheets were covered with nanoparticles of magnetite, with an average crystallite size of 7 nm. Infrared spectroscopy analysis indicated that the phases interacted through covalent Fe-O-C bonds. The composites presented significantly improved catalytic activity, compared to pure magnetite, with a synergistic effect of up to a factor of 17.1 for the Fenton degradation of caffeine, achieving total removal after 90 min. This synergistic effect was a consequence of the interaction between the phases, resulting in improved mass transfer of caffeine to the catalyst surface, adsorption and efficient degradation, with enhanced HO⢠generation. The surface reaction constant increased by up to three orders of magnitude, demonstrating the important role of graphene oxide in the degradation kinetics of the heterogeneous Fenton process. The surface-bonded hydroxyl radicals were responsible for caffeine degradation, achieving 9.4 µmol L-1. After five degradation cycles, a loss of Fe-O-C bonds and increase in oxygenated groups were associated with a small decrease of caffeine removal efficiency, from 98 to 82%, without significant iron leaching, in the dark, and with low consumption of hydrogen peroxide.
Assuntos
Cafeína , Nanocompostos , Grafite , Fenômenos Magnéticos , FísicaRESUMO
The red Fe(2+)-phenanthroline complex is the basis of a classical spectrophotometric method for determination of iron. Due to the toxicity of this complexing agent, direct disposal of the wastewaters generated in analytical laboratories is not environmentally safe. This work evaluates the use of the solar photo-Fenton process for the treatment of laboratory wastewaters containing phenanthroline. Firstly, the degradation of phenanthroline in water was evaluated at two concentration levels (0.1 and 0.01%, w/v) and the efficiencies of degradation using ferrioxalate (FeOx) and ferric nitrate were compared. The 0.01% w/v solution presented much higher mineralization, achieving 82% after 30min of solar irradiation with both iron sources. The solar photo-Fenton treatment of laboratory wastewater containing, in addition to phenanthroline, other organic compounds such as herbicides and 4-chlorophenol, equivalent to 4,500mgL(-1) total organic carbon (TOC) resulted in total degradation of phenanthroline and 25% TOC removal after 150min, in the presence of either FeOx or ferric nitrate. A ratio of 1:10 dilution of the residue increased mineralization in the presence of ferrioxalate, achieving 38% TOC removal after 120min, while use of ferric nitrate resulted in only 6% mineralization over the same period.