Ozonation of oxalate in aqueous phase was performed with a commercial activated carbon（AC）in this work. The effect of AC dosage and solution pH on the contribution of hydroxyl radicals（HOU） in bulk solution and oxidation on the AC surface to the removal of oxalate was studied. We found that the removal of oxalate was reduced by tert-butyl alcohol（tBA） with low dosages of AC,while it was hardly affected by tBA when the AC dosage was greater than 0.3 g/L. tBA also inhibited ozone decomposition when the AC dosage was no more than 0.05 g/L, but it did not work when the AC dosage was no less than 0.1 g/L. These observations indicate that HOUin bulk solution and oxidation on the AC surface both contribute to the removal of oxalate. HOU oxidation in bulk solution is significant when the dosage of AC is low, whereas surface oxidation is dominant when the dosage of AC is high. The oxalate removal decreased with increasing pH of the solution with an AC dosage of 0.5 g/L. The degradation of oxalate occurs mainly through surface oxidation in acid and neutral solution, but through HOUoxidation in basic bulk solution. A mechanism involving both HOUoxidation in bulk solution and surface oxidation was proposed for AC enhanced ozonation of oxalate.
Linlin XingYongbing XieDaisuke MinakataHongbin CaoJiadong XiaoYi ZhangJohn C. Crittenden
Photocatalytic ozonation of phenol and oxalic acid （OA） was conducted with a Ag^＋/TiO2 catalyst and different pathways were found for the degradation of different compounds. Ag^＋ greatly promoted the photocatalytic degradation of contaminants due to its role as an electron scavenger. It also accelerated the removal rate of OA in ozonation and the simultaneous process for its complex reaction with oxalate. Phenol could be degraded both in direct ozonation and photolysis, but the TOC removal rates were much higher in the simultaneous processes due to the oxidation of hydroxyl radicals resulting from synergetic effects. The sequence of photo-illumination and ozone exposure in the combined process showed quite different effects in phenol degradation and TOC removal. The synergetic effects in different combined processes were found to be highly related to the properties of the target pollutants. The color change of the solution and TEM result confirmed that Ag＋ was easily reduced and deposited on the surface of Tit2 under photo-illumination, and dissolved again into solution in the presence of ozone. This simple cycle of enrichment and distribution of Ag^＋ can greatly benefit the design of advanced oxidation processes, in which the sequences of ozone and photo-illumination can be varied according to the needs for catalyst recycling and the different properties of pollutants.
A double layered, one-pot hydrothermal method was adopted in this work to prepare transition metal ions （Fe3＋, Ni2＋, Cu2＋ and Co2＋） doped TiO〉 The morphology and chemical properties of TiO2 and the status of metal ions were characterized with XRD, TEM, BET, UV-Vis and XPS analysis. TEM images show that the obtained TiO2 was very uniform with an average particle size of 10.4 nm. XPS, TEM and XRD results show that transitional metals were doped onto TiO2 in the form of ions. Photocatalytic decomposition of oxalic acid under UV illumination and methylene blue degradation under visible light on these materials were conducted, respectively. The results reveal that Cu2＋-TiO2 and C02＋-TiO2 showed a highest activity under UV and visible light illumination, respectively, and they were both more active than commercial P25 TiO2. With this special design of double layers, the hydrolysis of titanium precursor in the system with water can be easily controlled and metal ions are simply doped. This strategy can be further applied to synthesize metal ion doped TiO2 using various metal precursors with controllable amounts, and thus lead to better optimization of highly active photocatalyst.
CHEN YingYingXIE YongBingYANG JunCAO HongBinLIU HuiZHANG Yi
