Enhanced ozonation of dichloroacetic acid in aqueous solution using nanometer ZnO powders

Nanometer zinc oxide （ZnO） powders were used as a catalyst to enhance the ozonation for the degradation of dichloroacetic acid （DCAA） in aqueous solution. The batch experiments were carded out to investigate the effects of key factors such as catalyst dosage, ozone dosage, solution pH and tert-butyl alcohol （t-BuOH） on the degradation efficiency of DCAA. Density functional theory （DFT） was adopted to explore the mechanism of generating hydroxyl radical （＇OH） on the ZnO surface. The results showed that adsorption and ozonation processes were not effective for DCAA removal, and the addition of ZnO catalyst improved the degradation efficiency of DCAA during ozonation, which caused an increase of 22.8% for DCAA decomposition compared to the case of ozonation alone after 25 min. Under the same experimental conditions, the DCAA decomposition was enhanced by increasing catalyst dosage from 100 to 500 mg/L and ozone dosage from 0.83 to 3.2 mg/L. The catalytic ozonation process is more pronounced than the ozonation process alone at pH 3.93, 6.88, and 10. With increasing the concentration of t-BuOH from 10 to 200 rag/L, the degradation of DCAA was significantly inhibited in the process of catalytic ozonation, indicating that ZnO catalytic ozonation followed ＂OH reaction mechanism. Based on the experimental results and DFT analysis, it is deduced that the generation of ＂OH on the ZnO surface is ascribed to the adsorption of molecule ozone followed by the interaction of adsorbed ozone with active sites of the catalyst surface. It is also concluded that ZnO may be an effective catalyst for DCAA removal, which could promote the formation of .OH derived from the catalytic decomposition of ozone.