Mingcan Cui

Uniform core–shell structured magnetic mesoporous TiO2 nanospheres as a highly efficient and stable sonocatalyst for the degradation of bisphenol-A

Uniform core–shell structured magnetic mesoporous TiO2 (Fe3O4@SiO2@mTiO2) nanospheres were fabricated via a kinetically controlled Stober method. A silica interlayer with a thickness of ∼25 nm was introduced as a passivation barrier to prevent photodissociation, as well as increase the thermal stability of the core–shell materials. After crystallizing at 600 °C under nitrogen, the resultant nanospheres (Fe3O4@SiO2@mTiO2-600) possessed well-defined core–shell structures with a high magnetic susceptibility (∼17.0 emu g−1) and exhibited uniform mesopores (∼5.2 nm), large BET surface area (∼216 m2 g−1) and large pore volume (∼0.20 cm3 g−1). More importantly, the magnetic mesoporous TiO2 was demonstrated for the first time as a highly efficient and stable sonocatalyst for the degradation of bisphenol-A. The pseudo first-order-reaction constant of the magnetic mesoporous TiO2 was measured to be 0.164 min−1, which is 1.49 and 2.27 times higher than that of P25 and ultrasound alone, respectively. The remarkable performance is attributed to the fast mass diffusion, large adsorption rate and enhanced hydroxyl-radical-production rate of the nanospheres. More importantly, the catalyst can be easily recycled within 2 minutes using an external magnetic field, and a constant catalytic activity is retained even after eight cycles. This study paves a promising way for the design and synthesis of magnetically separable sonocatalysts for the degradation of organic pollutants, which is of significant importance for practical applications from both environmental and industrial points of view.

Sonophotolytic diethyl phthalate (DEP) degradation with UVC or VUV irradiation

This study investigated the degradation of diethyl phthalate (DEP) by sonolytic, photolytic and sonophotolytic processes. Two types of UV lamps, UVC (254 nm) and VUV (185 nm+254 nm), were combined with ultrasound (283 kHz). The pseudo-first order degradation rate constants were in the order of 10(-1)-10(-3) min(-1) depending on the processes. The sonolytic DEP degradation rate increased with increasing applied power. Photolytic or sonophotolytic degradation of DEP when using a VUV lamp appeared to be effective because the photo ІІ (UVC/VUV) resulted in a significantly faster degradation than the photo І (UVC) processes due to the higher photon energy and higher hydroxyl radical generation by homolysis of water by VUV. Significant degradation and mineralization (TOC) of DEP were observed with the combined sonophotolytic processes. Moreover, synergistic effects of 1.68 and 1.23 were exhibited at DEP degradation of the sonophoto I and sonophoto II processes, respectively. This was attributed to the UV-induced dissociation of hydrogen peroxide (H(2)O(2)) generated by the application of US to hydroxyl radicals. Therefore, US in sonophotolytic processes can play an important role in enhancing DEP degradation. Moreover, the sonophoto ІІ process is more effective on the mineralization and biodegradability of DEP.

Application of Box-Behnken design with response surface methodology for modeling and optimizing ultrasonic oxidation of arsenite with H2O2

AbstractA combined ultrasound (US)/H2O2 process was used to oxidize arsenite to arsenate, yielding a synergistic effect value of 1.26. This showed that the combined process could be an effective method of oxidizing arsenite, instead of using either ultrasonic or H2O2 oxidation processes. This combined process was successfully modeled and optimized using a Box-Behnken design with response surface methodology (RSM). The effects of the US power density, the initial concentration of arsenite, and the H2O2 concentration on the sonochemical oxidation efficiency of arsenite were investigated. Analysis of variance indicated that the proposed quadratic model successfully interpreted the experimental data with coefficients of determination of R2 = 0.95 and adjusted R2 = 0.91. Through this model, we can predict and control the oxidation efficiency under different conditions. Furthermore, the optimal conditions for the oxidation of arsenite were found to be a US power density of 233.26 W L−1, an initial arsenite concentration of 0.5 mg L−1, and an H2O2 concentration of 74.29 mg L−1. The predicted oxidation efficiency obtained from the RSM under the optimal conditions was 88.95%. A confirmation test of the optimal conditions verified the validity of the model, yielding an oxidation efficiency of 90.1%.

Enhanced removal of dichloroacetonitrile from drinking water by the combination of solar-photocatalysis and ozonation

In this study, the photocatalytic ozonation process using either UV lamps with a wavelength close to a solar wavelength (UVsolar) or natural solar light was established to study the effects of the major operating parameters on the removal of a toxic disinfection by-product (DBP), dichloroacetonitrile (DCAN), from drinking water. Based on the test results of a bench system, the UVsolar/TiO2/O3 process had the highest DCAN-removal rate among the advanced oxidation processes (AOPs). The optimal TiO2 and ozone doses were 1gL(-1) and 1.13gL(-1)h(-1), respectively, while room temperature (20°C) produced the highest rate constant in the kinetic tests. The kinetic rate constants linearly increased when the UVsolar intensity increased in the range 4.6-25Wm(-2); however, it increased less at intensities higher than 25Wm(-2). The test results of the outdoor system showed that the solar/TiO2/O3 process provided complete removal of DCAN that was two times faster and had about 4.6 times higher energy efficiency than with solar/TiO2. As a green oxidation technique, solar photocatalytic ozonation could be a good alternative for treating recalcitrant and toxic organic pollutants, because it has high oxidation potential and low energy consumption compared to conventional AOPs.

A continuous pilot-scale system using coal-mine drainage sludge to treat acid mine drainage contaminated with high concentrations of Pb, Zn, and other heavy metals

A series of pilot-scale tests were conducted with a continuous system composed of a stirring tank reactor, settling tank, and sand filter. In order to treat acidic drainage from a Pb-Zn mine containing high levels of heavy metals, the potential use of coal-mine drainage sludge (CMDS) was examined. The pilot-scale tests showed that CMDS could effectively neutralize the acidic drainage due to its high alkalinity production. A previous study revealed that calcite and goethite contained in CMDS contributed to dissolutive coprecipitation and complexation with heavy metals. The continuous system not only has high removal efficiencies (97.2-99.8%), but also large total rate constants (K(total), 0.21-10.18h(-1)) for all heavy metals. More specifically, the pilot system has a much higher Zn(II) loading rate (45.3gm(-3)day(-1)) than other reference systems, such as aerobic wetland coupled with algal mats and anoxic limestone drains. The optimum conditions were found to be a CMDS loading of 280gL(-1) and a flow rate of 8Lday(-1), and the necessary quantity of CMDS was 91.3gL(-1)day(-1), as the replacement cycle of CMDS was determined to be 70 days.

Kinetic and thermodynamic studies of the adsorption of heavy metals on to a new adsorbent: coal mine drainage sludge

In this study, we investigated the application of sludge waste obtained from a coal mine drainage treatment facility that treats acid mine drainage (designated as AMD) from metal‐mine water. The coal mine drainage sludge (designated as CMDS), which contained 70% goethite and 30% calcite, was utilized as a sorption material for Cu(II) and Zn(II) removal from an aqueous solution of metallic mine drainage. The equilibriums and kinetics were investigated during a series of batch adsorption experiments. The Langmuir model was used to fit the equilibrium data, resulting in the best fits. The removal efficiencies were controlled by solution pH, temperature, initial concentration of heavy metal, sorbent amount and contact time. The pseudo‐second‐order kinetic model was used to fit the kinetic data, providing a good correlation with the experimental data. The results of a thermodynamic study showed that the activation energies (EA) were 3.75 and 1.75 kJ mol−1 for the adsorption of Cu(II) and Zn(II) on to CMDS at pH 5.5. These values of activation energy could correspond to physisorption. The positive values obtained for both the standard enthalpy change, Δ0, and the standard entropy change, ΔS0, suggest that the adsorption of Cu(II) and Zn(II) on to the CMDS was an endothermic reaction and that randomness increased at the solid–liquid interface during the adsorption of Cu(II) and Zn(II) on to the CMDS. The adsorption process also followed a pseudo‐second‐order kinetic model.

Enhancement in mineralization of a number of natural refractory organic compounds by the combined process of sonolysis and ozonolysis (US/O3)

As an advanced oxidation process, the combination of sonolysis (US)/ozonolysis (O(3)) was investigated on the treatment of tannic acid (TA) and humic acid (HA). In this study, biodegradable chemicals were found by the molecular weight and GC-MS analysis method, and mineralization rate and synergetic effects were also studied. For the water samples prior to the treatment of US/O(3), ratios of molecular size higher than 5000 and 2000 Da for HA and TA, detected by the ultra filtration method, were 90.25% and 89.53%, respectively. However, after 0.5h of reacting, this ratio rapidly reduced to 3% and 4%, and the ratios of molecules for HA and TA less than 500 Da rapidly increased from 0.8% to 41% and from 0.65% to 39%, respectively. In the results of chemical oxygen demand (COD(Cr)) and total organic carbon (TOC) reductions, the US/O(3) process also showed synergetic effect by US/O(3) for COD(Cr) of HA and TA were 19% and 11%, and those for TOC of HA and TA were 0% and 1%, respectively. The major by-products of the oxidation process included formaldehyde, acetone, hydroxylamine, etc. Biological decomposable materials could be indirectly inferred by measuring the molecular weights and intermediates.

Potential application of sludge produced from coal mine drainage treatment for removing Zn(II) in an aqueous phase

Various analyses of physico-chemical characteristics and batch tests were conducted with the sludge obtained from a full-scale electrolysis facility for treating coal mine drainage in order to find the applicability of sludge as a material for removing Zn(II) in an aqueous phase. The physico-chemical analysis results indicated that coal mine drainage sludge (CMDS) had a high specific surface area and also satisfied the standard of toxicity characteristic leaching procedure (TCLP) because the extracted concentrations of certain toxic elements such as Pb, Cu, As, Hg, Zn, and Ni were much less than their regulatory limits. The results of X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) showed that the CMDS mainly consists of goethite (70%) and calcite (30%) as a weight basis. However, the zeta potential analysis represented that the CMDS had a lower isoelectric point of pH (pHIEP) than that of goethite or calcite. This might have been caused by the complexation of negatively charged anions, especially sulfate, which usually exists with a high concentration in coal mine drainage. The results of Fourier transform infrared (FT-IR) spectrometry analysis revealed that Zn(II) was dominantly removed as a form of precipitation by calcite, such as smithsonite [ZnCO3] or hydrozincite [Zn5(CO3)2(OH)6]. Recycling sludge, originally a waste material, for the removal process of Zn(II), as well as other heavy metals, could be beneficial due to its high and speedy removal capability and low economic costs.

Effects of Hydrogen Peroxide and Frequency for the Sonochemical Degradation of Aqueous Phenol

The effect of hydrogen peroxide and frequency on the degradation of phenol was investigated in this study. The concentrations of phenol and hydrogen peroxide were 0.05 and 0.0018 mM, respectively. When a high frequency of sonication (1 MHz) was irradiated to a phenol solution, the efficiency of decomposition of phenol was about 95% within 120 min. At a low frequency, the phenol degradation was slower than at a high frequency, while the degradation of the total organic carbon at a low frequency was nearly the same as that at a high frequency. Hydrogen peroxide was formed due to the dissipation of water. Through a comparison, it can be seen that the order of degradation rates of phenol and the formation rate of hydrogen peroxide were not the same. The relationship between the degradation rate of compounds and the formation rate of hydrogen peroxide was not clear. With the addition of hydrogen peroxide in phenol solution, the phenol concentration was almost completely degradable within 30 min. In the case of total organic carbon (TOC), the concentration was degraded by 50%. Therefore, for the decomposition of total organic carbon, the addition of hydrogen peroxide or other catalysts was required.

Synergistic sonoelectrochemical removal of substituted phenols: implications of ultrasonic parameters and physicochemical properties.

The effects of ultrasonic conditions and physicochemical properties on the synergistic degradation in synthetic solution were investigated. A wide range of ultrasound frequencies, including 35, 170, 300, 500 and 700 kHz, and ultrasonic power densities, including 11.3, 22.5 and 31.5 W/L were used. It was revealed that the physical effect of ultrasound plays a major role in synergistic mechanism and 35 kHz was found to be the most effective frequency due to its more vigorous physical effect induced by high implosive energy released from collapse of cavitation bubbles. The highest ultrasonic power density (31.5 W/L) showed the highest synergy index as it increases the number of cavitation bubbles and the energy released when they collapse. The synergy indexes of various substituted phenols under identical condition were investigated. These results were correlated with physicochemical properties, namely octanol-water partition coefficient (Log K OW), water solubility (SW), Henrys law constant (KH) and water diffusivity (DW). Among these parameters, Log K OW and DW were found to have substantial effects on synergy indexes.