Oxalate enhanced mechanism of Fe 3 O 4 @γ-Fe 2 O 3 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 Fe 3 O 4 @γ-Fe 2 O 3 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.
An enhanced method of hydroxyl radical generation was studied to lead a better understanding of the catalytic mechanism of α-FeOOH in UV-Fenton system. The catalyst was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, nitrogen adsorption–desorption isotherms and scanning electron microscope. The Orange II degradation and hydroxyl radical concentration under different conditions were studied in detail. The results showed that the hydroxyl radical was mainly oxidizing species for Orange II degradation. And the hydroxyl radical generation included both homogeneous and heterogeneous UV-Fenton processes. In heterogeneous UV-Fenton system, the additional oxalate could increase the ratio of homogeneous UV-Fenton process for hydroxyl radical generation. In oxalate enhanced system, the peak value of hydroxyl radical concentration would increase to 11.314 μmol/L which was nearly twice as it in heterogeneous UV-Fenton system (5.978 μmol/L). The k values of Orange II discoloration and mineralization increased to 0.386 min −1 and 0.044 min −1 , which were 1.169 and 0.692 times as that in heterogeneous UV-Fenton system (0.178 min −1 and 0.026 min −1 ). After treatment, the total iron ions concentration decreased to 2.357 μmol/L in oxalate enhanced system. The results indicated that additional oxalate was a promising enhanced method for hydroxyl radical generation in heterogeneous UV-Fenton system with α-FeOOH as catalyst.
As a highly active photocatalyst, g-C 3 N 4 /TiO 2 heterojunction nanocomposites were in situ synthesized by simple ultrasonic mixing and calcination by using TiO 2 and melamine as precursors. The morphology and structure of the prepared photocatalysts were characterized by field emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, UV-Vis diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. The photocatalytic activities of g-C 3 N 4 /TiO 2 nanocomposites to degrade Orange II (AO7) under visible light irradiation were evaluated. Results showed that the photocatalytic rate of the prepared g-C 3 N 4 /TiO 2 photocatalyst to degrade AO7 was about three times than that of pristine TiO 2 and g-C 3 N 4 . The g-C 3 N 4 /TiO 2 composite with a ratio of 1:4 had the highest degradation efficiency for AO7 solution. Its degradation efficiency under acidic conditions was significantly higher than that under alkaline conditions. The enhancement of photocatalytic activity can be attributed to the formation of heterojunctions between g-C 3 N 4 and TiO 2 , which leads to rapid charge transfer and the efficient separation of photogenerated electron-hole pairs. The recycling experiment indicated that the photocatalyst of g-C 3 N 4 /TiO 2 nanocomposites still maintained good photochemical stability and recyclability after five cycles; this finding was important for its practical applications. A series of free radical trapping experiments showed that •O 2 − played a crucial role in the degradation of AO7.
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