Oxalate enhanced degradation of Orange II in heterogeneous UV-Fenton system catalyzed by Fe3O4@γ-Fe2O3 composite.

Oxalate enhanced mechanism of Fe3O4@γ-Fe2O3 was developed to provide novel insight into catalytic process regulation of iron oxide catalysts in heterogeneous UV-Fenton system. And the iron oxide composite of Fe3O4@γ-Fe2O3 was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), fourier transform infrared (FTIR) spectroscopy and nitrogen adsorption-desorption isotherms. The results showed that large amount of iron could be leached from catalyst in the presence of oxalate, which promoted the homogeneous UV-Fenton reactions in solution. Orange II degradation could be significantly enhanced with the increase of the ratio of homogeneous UV-Fenton process to heterogeneous UV-Fenton process. The optimum concentration of oxalate determined by experiment was 0.5 mM in oxalate enhanced heterogeneous UV-Fenton system. On this condition, the pseudo-first-order rate constant value of Orange II degradation was 0.314 min-1, which was 2.3 times as high as that in heterogeneous UV-Fenton system. The removal rates of color and TOC were 100% and 86.6% after 20 min and 120 min treatment, respectively. In addition, the iron ions in solution could be almost completely adsorbed back to the catalyst surface in later degradation stages of Orange II. During the recycle experiments, the results showed that the increase of pH in solution and the sorption of intermediates on the catalyst surface would hinder oxalate enhanced process and lead to a decrease of degradation rate of Orange II in oxalate enhanced heterogeneous UV-Fenton system.