Shaogui Yang

Mechanistic Study of Visible-Light-Induced Photodegradation of 4-Chlorophenol by TiO2−xNx with Low Nitrogen Concentration

TiO2−x Nx powders with low N-doping concentrations (0.021<𝑥<0.049) were prepared by annealing commercial TiO2 (P-25) under an NH3 flow at 550°C. Regardless of UV or visible case, the photoactivities of the samples decreased as x increased, and TiO1.979N0.021 showed the highest activity for the 4-chlorophenol (4-CP) decomposition under the visible-light irradiation. The visible-light response for N-doped TiO2 could arise from an N-induced midgap level, formed above the valence band (O 2p). Electron spin resonance (ESR) measurements and the radical scavenger technologies gave the combined evidence that the active species (•OH and O2•−) are responsible for the photodecomposition of 4-CP over TiO2−xNx under the visible irradiation. A possible photocatalytic mechanism was discussed in detail.

Ametryn degradation by aqueous chlorine: kinetics and reaction influences.

The chemical oxidation of the herbicide ametryn was investigated by aqueous chlorination between pH 4 and 10 at a temperature of 25 degrees C. Ametryn was found to react very rapidly with aqueous chlorine. The reaction kinetics can be well described by a second-order kinetic model. The apparent second-order rate constants are greater than 5 x 10(2)M(-1)s(-1) under acidic and neutral conditions. The reaction proceeds much more slowly under alkaline conditions. The predominant reactions were found to be the reactions of HOCl with neutral ametryn and the charged ametryn, with rate constants equal to 7.22 x 10(2) and 1.58 x 10(3)M(-1)s(-1), respectively. The ametryn degradation rate increases with addition of bromide and decreases with addition of ammonia during the chlorination process. Based on elementary chemical reactions, a kinetic model of ametryn degradation by chlorination in the presence of bromide or ammonia ion was also developed. By employing this model, we estimate that the rate constants for the reactions of HOBr with neutral ametryn and charged ametryn were 9.07 x 10(3) and 3.54 x 10(6)M(-1)s(-1), respectively. These values are 10- to 10(3)-fold higher than those of HOCl, suggesting that the presence of bromine species during chlorination could significantly accelerate ametryn degradation.

Rapid photocatalytic destruction of pentachlorophenol in F–Si-comodified TiO2 suspensions under microwave irradiation

A novel photocatalysis material, F-Si-comodified TiO(2) (FST) powder, was synthesized by ultrasound-assisted hydrolysis. The prepared material was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-visible absorption spectroscopy, respectively. XRD analysis indicated that the phase of FST was pure anatase and Si atoms suppressed the growth of titania crystalline, XPS spectra showed that FST was composed of Ti, O, Si and F element, the band gap energy of FST calculated according to the spectrum of UV-vis absorption was 3.26 eV. The electron spin resonance (ESR) spin-trapping technique using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as the spin-trap reagent has been applied to detect free radical intermediates generated from FST. ESR results showed the concentration of the active species (OH) on FST is higher than those on F-doping TiO(2) (FT), Si-modifying TiO(2) (ST) and P25 titania. The degradation of pentachlorophenol (PCP) in the microwave-assisted photocatalysis (MAPC) process was faster than other processes including microwave-assisted direct photolysis (MADP), microwave process alone (MP) and dark process (DP). The photocatalytic activity of FST is much higher than that of ST, FT and P25 titania. It may be attributed to its strong capacity of absorption to the UV-vis irradiation and more hydroxyl radical on surface of FST. In MPAC process, 40 mg L(-1) PCP was completely degraded in 20 min and its corresponding mineralization efficiency was 71%, the pH of solutions decreased from 10.3 to 6.47 and the dechlorination was completed in 12 min. The intermediates products of PCP in MAPC process identified by GC/MS were trichlorophenols (TCP), tetrachlorophenols (TTCP) and tetrachlorocatechol (TTCC) and the possible mechanism of PCP degradation is proposed.

Enhanced photocatalytic activity for titanium dioxide by co-modifying with silica and fluorine

F-Si-co-modified TiO(2) (FST) samples with different ratios of fluorine to titanium (R(F)) and silica to titanium (R(x)), were successfully synthesized by ultrasound-assisted hydrolysis. The structure and properties of the as-prepared codoped titania were characterized by means of XRD, TEM, XPS, BET, UV-Vis diffuse reflectance spectra and ESR. XRD analysis showed that Si and F atoms prevented phase transition of anatase to rutile and suppressed the growth of titania crystalline. ESR results showed that the concentration of the active species (.OH) on 1%-FST(R(x)=10%) was higher than that on other FST samples and P25 titania. The improvement in photocatalytic activity relative to titania can be achieved by co-modifying fluorine and silica to fabricate FST composite material. The photocatalytic activity of FST powders for decomposition of methyl orange was affected by the content of fluorine and the content of silica. When the ratios of R(F) and R(x) were 1 and 10%, respectively, 1%-FST(R(x)=10%) shows the best among photocatalytic activity, which is much superior to P25 under UV-Vis irradiation. The possible reasons for the high photocatalytic activity of the FST powders were proposed in the paper. In addition, the stability of the FST powders in photocatalytic process was confirmed based on the XPS analysis.

Photoelectrocatalytic treatment of pentachlorophenol in aqueous solution using a rutile nanotube-like TiO2/Ti electrode

Taking pentachlorophenol (PCP) as a reference, we investigated the photoelectrocatalytic degradation of organic pollutants using a rutile nanotube-like TiO(2)/Ti film electrode. The nanotube-like TiO2 electrode was prepared by first oxidizing the surface of a titanium sheet to form rutile TiO2 and then treating it to form the tubular structure in NaOH aqueous solution. The occurrence of PCP degradation was indicated by the decrease in pH, concentration of PCP and TOC, and by the formation of chloride ions. The photoelectrochemical (PEC) efficiency of the nanotube-like TiO2/Ti electrode has been determined in terms of degradation of PCP and the incident photo-to-current conversion efficiency (IPCE). The experimental results showed that PCP could be degraded more efficiently by a photoelectrocatalytic process than by a photocatalytic or electrochemical oxidation alone. A significant photoelectrochemical synergetic effect was observed. The kinetic constant of PEC degradation of PCP using a nanotube-like TiO2 electrode was over 60% higher than that using a TiO2 film electrode. It is noted that chloride ion and hydrogen ion concentration increased with irradiation time in the PEC degradation of PCP; PCP was gradually mineralized and the complete minimization of PCP took more time than its degradation.

Fabrication of nanomaterial models and their applications in water treatment

In this paper, our previous work on the fabrication of four models involving nanometer-size TiO2 and their environmental applications are reviewed. The material characterization and the ability to remove pollutants in water for four models are examined. The obtained models have exhibited excellent photo electrocatalytic activity, high photoconversion efficiency, superior charge separating ability and remarkable improvement of membrane flux, respectively, and been proven to be of great interest for use in water treatment.