The roles of reactive species in micropollutant degradation in the UV/free chlorine system.

The UV/free chlorine process forms reactive species such as hydroxyl radicals (HO(•)), chlorine atoms (Cl(•)), Cl2(•-), and O(•-). The specific roles of these reactive species in aqueous micropollutant degradation in the UV/chlorine process under different conditions were investigated using a steady-state kinetic model. Benzoic acid (BA) was chosen as the model micropollutant. The steady-state kinetic model developed fitted the experimental data well. The results showed that HO(•) and Cl(•) contributed substantially to BA degradation, while the roles of the other reactive species such as Cl2(•-) and O(•-) were negligible. The overall degradation rate of BA decreased as the pH increased from 6 to 9. In particular, the relative contributions of HO(•) and Cl(•) to the degradation changed from 34.7% and 65.3% respectively at pH 6 to 37.9% and 62% respectively at pH 9 under the conditions evaluated. Their relative contributions also changed slightly with variations in chlorine dosage, BA concentration and chloride concentration. The scavenging effect of natural organic matter (NOM) on Cl(•) was relatively small compared to that on HO(•), while bicarbonate preferentially reduced the contribution of Cl(•). This study is the first to demonstrate the contributions of different reactive species to the micropollutant degradation in the UV/chlorine system under environmentally relevant conditions.

Structuring ß-Ga2O3 photonic crystal photocatalyst for efficient degradation of organic pollutants.

Coupling photocatalysts with photonic crystals structure is based on the unique property of photonic crystals in confining, controlling, and manipulating the incident photons. This combination enhances the light absorption in photocatalysts and thus greatly improves their photocatalytic performance. In this study, Ga2O3 photonic crystals with well-arranged skeleton structures were prepared via a dip-coating infiltration method. The positions of the electronic band absorption for Ga2O3 photonic crystals could be made to locate on the red edge, on the blue edge, and away from the edge of their photonic band gaps by changing the pore sizes of the samples, respectively. Particularly, the electronic band absorption of the Ga2O3 photonic crystal with a pore size of 135 nm was enhanced more than other samples by making it locate on the red edge of its photonic band gap, which was confirmed by the higher instantaneous photocurrent and photocatalytic activity for the degradation of various organic pollutants under ultraviolet light irradiation. Furthermore, the degradation mechanism over Ga2O3 photonic crystals was discussed. The design of Ga2O3 photonic crystals presents a prospective application of photonic crystals in photocatalysis to address light harvesting and quantum efficiency problems through manipulating photons or constructing photonic crystal structure as groundwork.

Optimizing treatment of benzoic acid by ozone process with recyclable catalyst of magnetism.

This study is to optimize the multi-quality performance of magnetic catalyst/ozone process by combining a technique for order performance by similarity to ideal solution (TOPSIS) with the Taguchi method, which simultaneously has the best decomposition rate constant of benzoic acid and removal rate constant of total organic carbon (TOC). The optimal experimental parameters were pH of 7, initial concentration of 75 ppm and catalyst loading of 0.05 g/L. More than 93% of the magnetic catalyst was easily separated and redispersed for reuse by the magnetic force due to the paramagnetic behaviours of the prepared SiO2/Fe3O4. It is believed that through the joint efforts improvement, design and manufacturing, new separation and recycling technologies will be available and more easily recyclable magnetic catalysts will be developed in the future.

Quantification of surface area and intrinsic mass transfer coefficient for ultrasound-assisted dissolution process of a sparingly soluble solid dispersed in aqueous solutions.

The efficacy of power ultrasound of 20 kHz in enhancing the volumetric mass transfer coefficient was investigated in this study. Breakage and dissolution of sparingly soluble benzoic acid dispersed in either water or 24% aqueous glycerol was monitored as a function of time and ultrasound power input. Particle size measurements were carried out at intermediate times during the experiment to estimate the mean particle size and surface area. Linear combination of lognormal distributions was found to fit the experimental particle size distribution data. The De Brouckere mean diameters (d(43)) obtained from the particle size distributions decreased with increase in the ultrasonic power level. Empirical correlations were developed for the evolution of surface area as a function of ultrasonic energy input per unit mass. The effect of ultrasound on the intrinsic mass transfer coefficient (k(c)) could be decoupled from the volumetric mass transfer coefficient (k(c)a) as the surface area was also estimated. Different approaches involving either constant or variable intrinsic mass transfer coefficients were employed when carrying out the delineation. Mass transfer rates were enhanced due to both higher ultrasound induced intrinsic convective mass transfer coefficient and additional surface area created from particle breakage. To delineate the effects of particle breakage from solid dissolution, experiments were also carried out under non-mass transfer conditions by pre-saturating the solvents with benzoic acid. Both the solid-liquid systems examined in the present study attained saturation concentration when the ultrasonic energy input per unit mass was approximately 60 kJ/kg, irrespective of the ultrasonic power level setting.

Synthesis, characterization, and photocatalytic activity of TiO(2-x)N(x) nanocatalyst.

Nitrogen-doped titanium dioxide powders were prepared by wet method, that is, the hydrolysis of acidic tetra-butyl titanate using aqueous ammonia solution, followed by calcination at temperatures about 350 degrees C. The catalysts exhibited photocatalytic activity in the visible light region owing to N-doping. The light absorption onset of TiO(2-x)N(x) was shifted to the visible region at 459 nm compared to 330 nm of pure TiO(2). An obvious decrease in the band gap was observed by the optical absorption spectroscopy, which resulted from N2p localized states above the valence band of TiO(2-x)N(x) (compared to TiO(2)). The TiO(2-x)N(x) catalyst was characterized to be anatase with oxygen-deficient stoichiometry by X-ray diffraction (XRD), surface photovoltage spectroscopy (SPS) and X-ray photoelectron spectroscopy (XPS). The binding energy of N1s measured by XPS characterization was 396.6 eV (TiN bonds, beta-N) and 400.9 eV (NN bonds, gamma-N(2)), respectively. The photocatalytic activity of TiO(2-x)N(x) under visible light was induced by the formation of beta-N in the structure. Photocatalytic decomposition of benzoic acid solutions was carried out in the ultraviolet and visible (UV-vis) light region, and the TiO(2-x)N(x) catalyst showed higher activity than pure TiO(2).

Pilot scale mineralization of organic acids by electro-Fenton process plus sunlight exposure.

The viability of the electro-Fenton degradation of aqueous solutions of benzoic acid, 2,4-dichlorophenoxyacetic acid and oxalic acid has been studied at 20 A using a pilot flow reactor containing an anode and an oxygen diffusion cathode, both of 100 cm(2) section. Pollutants were preferentially oxidized by hydroxyl radicals formed in solution from reaction of Fe(2+) with electrogenerated H(2)O(2), allowing mineralization of benzoic acid and 2,4-D. For oxalic acid no electrochemical mineralization was observed. After electrolysis, samples of the different effluents were exposed to sunlight (Helielectro-Fenton process) and almost complete mineralization was reached after ca. 30-50 min without additional cost. Effects of parameters such as electrolysis time, pH and solar irradiation time on the process efficiencies were studied.

Macro kinetic studies for photocatalytic degradation of benzoic acid in immobilized systems.

Semiconductor photocatalytic process has been studied extensively in recent years due to its intriguing advantages in environmental remediation. In this study, a two-phase swirl-flow monolithic-type reactor is used to study the kinetics of photocatalytic degradation of benzoic acid in immobilized systems. Transport contributions into the observed degradation rates were determined when catalyst is immobilized. Intrinsic kinetic rate constants and its dependence on light intensity and catalyst layer thickness, values of adsorption equilibrium constant, internal as well as external mass transfer parameters were determined. The simultaneous effect of catalyst loading and light intensity and optimum catalyst layer thickness were also determined experimentally. Reaction rate constants and overall observed degradation rates were compared with slurry systems.