Photocatalytic ozonation-based degradation of phenol by ZnO—TiO_(2)nanocomposites in spinning disk reactor

Spinning disk reactor(SDR)has emerged as a novel process intensification photocatalytic reactor,and it has higher mass transfer efficiency and photon utilization for the degradation of toxic organic pollutants by advanced oxidation processes(AOPs).In this study,ZnO—TiO_(2)nanocomposites were prepared by solgel method,and coated on the disk of SDR by impregnation-pull-drying-calcination method.The performance of catalyst was characterized by X-ray diffraction,scanning electron microscope,X-ray photoelectron spectroscopy,photoluminescence and ultraviolet—visible diffuse reflectance spectroscopy.Photocatalytic ozonation in SDR was used to remove phenol,and various factors on degradation effect were studied in detail.The results showed that the rate of degradation and mineralization reached 100%and 83.4%under UV light irradiation after 50 min,compared with photocatalysis and ozonation,the removal rate increased by 69.3%and 34.7%,and mineralization rate increased by 56.7%and 62.9%,which indicated that the coupling of photocatalysis and ozonation had a synergistic effect.The radical capture experiments demonstrated that the active species such as photogenerated holes(h^(+)),hydroxyl radicals(·OH),superoxide radical(·O_(2)-)were responsible for phenol degradation,and·OH played a leading role in the degradation process,while h+and·O_(2)^(-)played a non-leading role.

Reaction mechanism and metal ion transformation in photocatalytic ozonation of phenol and oxalic acid with Ag^+/TiO_2

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.

Liquid phase heterogeneous photocatalytic ozonation of phenol in liquid-solid fluidized bed:Simplified kinetic modeling

The isotherms of original AC （activated carbon） and photocatalysts （TiO2-AC） calcined at 500 ℃ for phenol were measured. The results showed a reversible adsorption of phenol onto both kinds of particles at 25 ℃, and could be fitted well to the Freundlich adsorption equation for the dilute solution. Five oxidation processes, namely O3, O3 [UV, O3/UV/AC, O2/UV/TiO2 and O3/UV/TiO2, for phenol degradation in fluidized bed were evaluated and compared, and the photocatalytic ozonation was found to give the highest phenol conversion because of the combined actions of homogenous ozonafion in the liquid phase, heterogeneous ozonation on the surface of the catalyst support, i.e. activated carbon, and heterogeneous photocatalytic oxidation on the TiO2 catalyst surface. With the simplified kinetic model, photolytic ozonation was confirmed to predominantly take place on the particle surface in comparison with the heterogeneous and homogeneous photolytic ozonation. Additionally, the heterogeneous photocatalytic oxidation constant was found to be enhanced by 3.73 times in photocatlaytic ozonation process with ozone as the scavenger compared to the photocatalytic oxidation process with oxygen as the scavenger.

Distinct synergetic effects in the ozone enhanced photocatalytic degradation of phenol and oxalic acid with Fe^(3+)/TiO_2 catalyst

In this work. phenol and oxalic acid （OA） degradation in an ozone and photocatalysis integrated process was intensively conducted with Fe3 ＋/TiO2 catalyst. The ferrioxalate complex formed between Fe3＋ and oxalate accelerated the removal of OA in the ozonation, photolysis and photocatalytic ozonation process, for its high reactivity with ozone and UV. Phenol was degraded in ozonation and photolysis with limited TOC removal rates, but much higher TOC removal was achieved in photocatalytic ozonation due to the generation of-OH. The sequence of UV light and ozone in the sequential process also influences the TOC removal, and ozone is very powerful to oxidize intermediates catechol and hydroquinone to maleic acid. Fenton or photo-Fenton reactions only played a small part in Fe3＋/TiO2 catalyzed processes, because Fe＋ was greatly reduced but not regenerated in many cases. The synergetic effect was found to be highly related with the property of the target pollutants. Fe3 ＋/TiO2 catalyzed system showed the highest ability to destroy organics, but the TiO2 catalyzed system showed little higher synergy.

Influence of Calcination Temperature on TiO_2 Nanotubes’Catalysis for TiO_2/UV/O_3 in Landfill Leachate Solution

The influence of calcination temperature on TiO2 nanotubes＇ catalysis for TiO2/UV/03 was investigated. TiO2 nanotubes （TNTs） were prepared via the sol-gel method and calcined at 300--700 ℃, which were labeled as TNTs-300, TNTs-400, TNTs-500, TNTs-600 and TNTs-700, respectively. TNTs were characterized by transmission electron microscopy （TEM） and X-ray diffraction （XRD）. It is found that TNTs calcined at 400 ℃ showed the best thermal stability. When the calcination temperature increased from 400 ℃ to 700 ℃, the special structure of tubes was destroyed and gradually converted into nanorods and/or particles. The transformation from anatase to rutile occurred at 600 ℃, and the rutile phase was enhanced when the calcination temperature was increased to over 600 ℃. The calcina- tion temperature＇s influence on TNTs＇ adsorption activity for for TiO2/UV/O3 was investigated in landfill leachate solution chemical oxygen demand （COD） and catalytic activity In landfill leachate solution, the adsorption activity of COD decreased in the reduced order of TNTs-300, TNTs-400, TNTs-500, TNTs-600 and TNTs-700. In photocatalytic ozonation, TNTs-400 showed the best catalytic activity while TNTs-700 exhibited the worst. In other three processes, the COD removal of TNTs-300/UV/O3 was higher than those of TNTs-500/UV/O3 and TNTs-600/UV/O3 in the first 20 rain, and then became close to those of the latter two in the following 40 rain. Compared with TNTs-300 and TNTs- 400, TNTs-600 had the best anti-fouling activity, while TNTs-500 and TNTs-700 had lower anti-fouling activity than the former three. In photocatalytic ozonation, the calcination temperature of 400 ℃ was appropriate when TNTs were obtained at the synthesis temperature of 105 ℃.