Synergistic degradation of methyl orange in an ultrasound intensified photocatalytic reactor

An original ultrasound (US) directly intensified photocatalytic reactor was designed to degrade azo dye pollutant methyl orange (MeO) using Degussa TiO(2) as the photocatalyst. The sonolytic, photocatalytic and sonophotocatalytic degradation of MeO in the new reactor and the synergistic effect between sonolysis and photocatalysis were investigated. Effects of operation parameters i.e., US power, TiO(2) dosage, liquid circulation velocity and air flow rate on degradation efficiency were investigated and optimized. The results showed that all parameters have optimal values for the sonophotocatalytic degradation of MeO, and the optimum conditions for the new process are US power 600 W, TiO(2) dosage 3g/L, liquid circulation velocity 4.05×10(-2) m/s and air flow rate 0.2 L/min. Under the optimum conditions, 91.52% MeO had been degraded within 1h, and the combination of sonolysis and TiO(2) photocatalysis exhibited an obvious synergetic effect.     

Degradation of orange-G by advanced oxidation processes

The degradation and mineralization of orange-G (OG) in aqueous solutions by means of ultrasound irradiation at a frequency of 213 kHz and its combination with a heterogeneous photocatalyst (TiO₂) were investigated. The effects of various operational parameters such as, the concentration of the dye and solution pH on the degradation efficiency were studied. The degradation of the dye followed first-order like kinetics under the conditions examined. The sonolytic degradation of OG was relatively higher at pH 5.8 than that at pH 12. However, an alkaline pH was favoured for the photocatalytic degradation of OG using TiO₂. Total organic carbon (TOC) measurements were also carried out in order to evaluate the mineralization efficiency of OG using sonolysis, photocatalysis and sonophotocatalysis. The hybrid technique of sonophotocatalytic degradation was compared with the individual techniques of photocatalysis and sonolysis. A simple additive effect was observed during the sonophotocatalytic oxidation of OG using TiO₂ indicating that the combined treatment offers no synergistic enhancement. TOC results also support the additive effect in the dual treatment process.     

Sonolytic degradation of endocrine disrupting chemical 4-cumylphenol in water

The sonolytic degradation of endocrine disrupting compound 4-cumylphenol (4-CyP) in aqueous solution was investigated. The influence of operating parameters for sonication process such as 4-CyP initial concentration, frequency, power, pH, temperature and saturating gas was examined. The extent of degradation was inversely proportional to the initial substrate concentration. The rate of 4-CyP degradation was frequency dependent. The degradation rate increased proportionally with increasing ultrasonic power from 20 to 100 W and temperature in the range of 20-50°C. The most favorable degradation pH was acidic media. Destruction in the presence of saturating gas follows the order: argon>air>nitrogen. The 4-CyP degradation was inhibited in the presence of nitrogen gas owing to the free radical scavenging effect in vapor phase within the bubbles of cavitation. The ultrasonic degradation of 4-CyP was clearly promoted in the presence of bromide anions and the promoting effect on degradation increased with increasing bromide concentration. At low 4-CyP concentration (0.05 mg L(-1)), bicarbonate ion drastically enhanced the rate of 4-CyP degradation. Experiments conducted using pure and natural water demonstrated that the sonolytic treatment was more efficient in the natural water compared to pure water.     

Mn掺杂ZnS量子点与孔雀石绿和隐性孔雀石绿的相互作用

研究了Mn掺杂ZnS量子点与孔雀石绿和隐性孔雀石绿的相互作用。首先采用水热法以壳聚糖为基质,利用成核掺杂原理制备量子点,然后分别采用紫外-可见吸收和荧光光谱技术研究了量子点与孔雀石绿和隐性孔雀石绿的相互作用。结果表明,向初始浓度为20 mg·L~(-1)孔雀石绿溶液中加入200 mg·L~(-1)量子点,60 min孔雀石绿的去除率约为82%,量子点可以光催化降解孔雀石绿,其反应过程符合假一级动力学的假设;量子点对隐性孔雀石绿具有荧光猝灭作用,猝灭作用为动态猝灭,相互作用力为氢键和范德华力,吉布斯自由能小于零,量子点与隐性孔雀石绿的相互作用是一个自发的过程。因此,量子点可以用于光催化降解孔雀石绿和快速无毒检测隐性孔雀石绿。     

Sonolysis of aqueous 4-nitrophenol at low and high pH

The sonolysis of 4-nitrophenol in argon-saturated aqueous solution has been studied at 321 kHz. In order to evaluate separately the effect of OH radicals that are formed in the cavitational bubble and part of which react in the aqueous phase with this substrate, radiolytic studies in N2O-saturated solutions were carried out for comparison. A detailed product study of the sonolysis of 4-nitrophenol solutions shows that at pH 10, where 4-nitrophenol is deprotonated (pKa = 7.1), its sonolytic degradation is fully accounted for by OH-radical-induced reactions in the aqueous phase. At this pH, the sonolytic yield of H2O2 resulting from OH radical recombination in the solution, measured as a function of the 4-nitrophenol concentration, is reduced in line with the scavenging capacity of the 4-nitrophenolate. In contrast, at pH 4 the formation of H2O2 is already fully suppressed when the solution is 7 x 10(-4) mol dm-3 in 4-nitrophenol, and oxidative-pyrolytic degradation predominates, as exemplified by the large yields of CO and CO2 which are accompanied by a large H2 yield. The basis of this difference in behavior is a hydrophobic enrichment of 4-nitrophenol (which is undissociated at pH 4) at the interface of the cavitational bubble by a factor of about 80. The pH dependence of the yields of the pyrolytic products reflects the hydrolytic equilibrium concentration of 4-nitrophenol. The paper also demonstrates that the complexity of this sonochemical system precludes its use a gauge to determine the temperature in the interior of the cavitational bubble.     

Treatment of dye wastewater by using photo-catalytic oxidation with sonication

The degradation of Acid Orange 52 in aqueous solutions was investigated by using three processes (photocatalysis, sonolysis, and photocatalysis with sonication). In the case of photocatalysis, although the concentration of Acid Orange 52 decreased to 35% in 480 min, the color of the solution was not disappeared. In the case of sonolysis, it was decomposed completely in 300 min, but the total organic carbon concentration decreased down by only about 13% in 480 min. In the case of photocatalysis with sonication, the concentration of Acid Orange 52 reached to 0 in 240 min and the total organic carbon concentration decreased by about 87% in 480 min. These results indicate that the ultrasonic irradiation enhanced the photocatalytic degradation. The addition of chloride ion (50 ppm) into Acid Orange 52 solution decreased the decomposition efficiency for photocatalysis. In the cases of sonolysis and photocatalysis with sonication, the decomposition efficiency did not change significantly by the addition of chloride ion. These results indicate that chloride ion disturbs the photocatalysis of dye, but the decomposition of dye using the irradiation of ultrasound is not influenced by chloride ion. From these results, it is considered that the photocatalysis with sonication is most effective for the decomposition of dye in the three processes in this study.     

A systematic study of the degradation of dimethyl phthalate using a high-frequency ultrasonic process

A comprehensive study of the sonochemical degradation of dimethyl phthalate (DMP) was carried out using high-frequency ultrasonic processes. The effects of various operating parameters were investigated, including ultrasonic frequency, power density, initial DMP concentration, solution pH and the presence of hydrogen peroxide. In general, a frequency of 400 kHz was the optimum for achieving the highest DMP degradation rate. The degradation rate was directly proportional to the power density and inversely related to the initial DMP concentration. It was interesting to find that faster removal rate was observed under weakly acidic condition, while hydrolysis effect dominated in extreme-basic condition. The addition of hydrogen peroxide can increase the radical generation to some extent. Furthermore, both hydroxylation of the aromatic ring and oxidation of the aliphatic chain appear to be the major mechanism of DMP degradation by sonolysis based on LC/ESI-MS analysis. Among the principle reaction intermediates identified, tri- and tetra-hydroxylated derivatives of DMP, as well as hydroxylated monomethyl phthalates and hydroxylated phthalic acid were reported for the first time in this study. Reaction pathways for DMP sonolysis are proposed based on the detected intermediates.     

Sonochemical and photosonochemical degradation of 4-chlorophenol in aqueous media

The degradation of 4-chlorophenol (4-CP) in aqueous media by 516 kHz ultrasonic irradiation was investigated in order to clarify the degradation mechanism. The degradation of concentrated 4-CP solution by means of ultrasound, UV irradiation and their combined application was also studied. The obtained results indicate that *OH radical are the primary reactive species responsible for 4-CP ultrasonic degradation. Very little 4-CP degradation occurs if the sonolysis is carried out in the presence of the *OH radical scavenger tert-butyl alcohol, also indicating that little or no pyrolysis of the compound occurs. The dominant degradation mechanism is the reaction of substrate with *OH radicals at the gas bubble-liquid interface rather than high temperature direct pyrolysis in ultrasonic cavities. This mechanism can explain the lower degradation rate of the ionic form of 4-CP that is partly due to the rapid dissociation of *OH radicals in alkaline solutions. The sonochemical destruction of concentrated 4-CP aqueous solution is obtained with low rate. Coupling photolysis with ultrasound irradiation results in increased efficiency compared to the individual processes operating at common conditions. Interestingly, the photosonochemical decomposition rate constant is greater than the additive rate constants of the two processes. This may be the result of three different oxidative processes direct photochemical action, high frequency sonochemistry and reaction with ozone produced by UV irradiation of air, dissolved in liquid phase because of the geyser effect of ultrasound streaming. Additionally, the photodecomposition, at 254 nm, of hydrogen peroxide produced by ultrasound generating *OH radical can partly explain the destruction enhancement.     

Degradation of aqueous solution of potassium iodide and sodium cyanide in the presence of carbon tetrachloride

The degradation of potassium iodide, carbon tetrachloride and sodium cyanide has been studied using an ultrasounic probe of 20 kHz frequency. In the case of potassium iodide and sodium cyanide, the rate of degradation was much higher in presence of CCl4. The location of the ultrasonic horn showed a significant effect in the degradation of CCl4.     

Improvement in sonochemical degradation of 4-chlorophenol by combined use of Fenton-like reagents

Studies on the sonolysis of a wide range of organic compounds have demonstrated that ultrasonic irradiation has potential for decomposition of organic pollutants in hazardous wastewater. However, the ultrasonic irradiation alone cannot provide high enough rate of decomposition to be used practically. One of the solutions to increase the degradation efficiency is to combine the ultrasound application with other advanced chemical oxidation processes (AOPs). In this study, in order to increase the efficiency of ultrasonically assisted degradation of organic pollutants in water, we examined effects of three kinds of solid Fe-containing catalysts, namely iron powder, basic oxygen furnace (BOF) slag and mill scale on the degradation rate of 4-CP (4-chlorophenol) in aqueous solutions containing hydrogen peroxide. In the experiments, 4-CP was considered as a model organic compound. All three Fe-containing matters when react with hydrogen peroxide are involved in the Fenton-like reaction system, which is one of the promising AOPs. The results showed that both the iron powder and mill scale additions can accelerate the degradation of 4-CP, although the effect is dependent on the solution pH. All 4-CP could be decomposed for 2 min at pH=3 and for 1h at pH=5.6. On the other hand, the BOF slag had no catalysis effect on the 4-CP degradation because of higher concentration of calcium and lower concentration of iron.     

Sonolysis of an aqueous mixture of trichloroethylene and chlorobenzene

The effect of the initial concentration on the ultrasonic degradation of two volatile organic compounds trichloroethylene (TCE) and chlorobenzene (CB) was investigated. At higher concentrations, slower sonolysis rates were obtained due to the lowering of the average specific heat ratio gamma of the gas inside the cavitation bubbles. Furthermore, the effect of different concentrations of CB on the sonolysis of 3.34 mM TCE and the effect of different concentrations of TCE on the sonolysis of 3.44 mM CB was examined. The presence of CB lowered the sonolysis rate of TCE, while the sonolysis rate of CB did not decrease by TCE addition. An even higher sonolysis rate was obtained for 3.44 mM CB in the presence of 0.84 mM TCE than without TCE. The explanation for the different effects of both volatile organics on each other's sonolysis rate is thought to be the difference in reaction rate of TCE and CB with the radicals formed during sonolysis. The effect of TCE on the sonolysis rate of CB by lowering the gamma value is compensated by an increased indirect degradation of CB by radicals formed out of TCE. The decreased thermal degradation and the increased indirect radical degradation of CB in the presence of TCE is demonstrated by determining the kinetics of the degradation products styrene and dichlorobenzene.     

Sonochemical degradation of martius yellow dye in aqueous solution

The sonolytic degradation of the textile dye martius yellow, also known as either naphthol yellow or acid orange 24, was studied at various initial concentrations in water. The degradation of the dye followed first-order kinetics under the conditions examined. Based on gas chromatographic results and sonoluminescence measurements of sonicated aqueous solutions of the dye, it is concluded that pyrolysis does not play a significant role in its degradation. The chromatographic identification of hydroxy added species indicates that an OH radical induced reaction is the main degradation pathway of the dye. Considering the non-volatility and surface activity of the dye, the degradation of the dye most probably takes place at the bubble/solution interface. The quantitative and qualitative formation of the degradation intermediates and final products were monitored using HPLC and ESMS. The analytical results suggest that the sonolytic degradation of the dye proceeds via hydroxylation of the aryl ring and also by C-N bond cleavage of the chromophoric ring, either through OH radical attack or through another unidentified process. The identification of various intermediates and end products also imply that the degradation of martius yellow proceeds through multiple reaction pathways. Total organic carbon (TOC) analyses of the dye solutions at various times following sonication revealed that sonolysis was effective in the initial degradation of the parent dye but very slow in achieving mineralization. The slow rate of mineralization is likely to be due to the inability of many of the intermediate products such as, the carboxylic acids, to accumulate at the bubble (air/water) interface and undergo decomposition due to their high water solubility (low surface activity).     

Ultrasonic degradation of aqueous carboxymethylcellulose: effect of viscosity, molecular mass, and concentration

It is well established that prolonged exposure of solutions of macromolecules to high-energy ultrasonic waves produces a permanent reduction in viscosity. It is generally agreed as well and also this study proved the hydrodynamic forces to have the primary importance in degradation. According to this study the sonolytic degradation of aqueous carboxymethylcellulose polymer or polymer mixtures is mainly depended on the initial dynamic viscosity of the polymer solution when the dynamic viscosity values are in the area range enabling intense cavitation. The higher was the initial dynamic viscosity the faster was the degradation. When the initial dynamic viscosities of the polymer solutions were similar the sonolytic degradation was dependent on the molecular mass and on the concentration of the polymer. The polymers with high molecular mass or high polymer concentration degraded faster than the polymers having low molecular mass or low polymer concentration. The initial dynamic viscosities were adjusted using polyethyleneglycol.     

Sonolytic hydrolysis of peptides in aqueous solution upon addition of catechol

The sonolytic hydrolysis of peptides with addition of phenolic reagents to aqueous solutions is described. Sonolysis of an aqueous solution of peptides to which catechol (o-dihydroxybenzene) had been added resulted in hydrolytic products reflecting the amino acid sequence without any side reactions, while sonolysis without any additives resulted in oxidation analytes and degradation products caused by side reactions. Although the use of additives such as resorcinol (m-dihydroxybenzene), hydroquinone (p-dihydroxybenzene) and phenol was also effective in producing sequence related products, several degradation products were produced by side reactions. A characteristic of the sonolysis of peptides is that the N-terminal side of proline, Xxx-Pro, is more susceptible than other amino acid residues to the process. This characteristic of sonolysis is superior to that of acid hydrolysis in which cleavage at the C-terminal side of proline, Pro-Xxx is difficult, and where dehydration products result due to side reactions.     

Sonolysis of chlorobenzene in aqueous solution: organic intermediates

The ultrasonic degradation of 1.72 mM chlorobenzene was investigated. The sonolysis of chlorobenzene followed first-order kinetics. The influence of the pH of the aqueous solution and the effect of the saturating gás, air or argon, was measured. No pH effect was noticed, and saturation with the monoatomic argon accelerated the degradation. Furthermore, the addition of the radical scavenger benzoate demonstrated that no significant degradation took place in the bulk solution. For air-saturated solutions, the following organic degradation products were identified: methane, acetylene, butenyne, butadiyne, benzene, chlorophenols, phenylacetylene and other chlorinated and non-chlorinated monocyclic and dicyclic hydrocarbons. For argon-saturated solutions, the same products were found, except for the chlorophenols. The presence of the chlorophenols in the case of air-saturation only demonstrated the interaction between the radicals formed and oxygen, and no direct degradation by OH. radicals. The kinetics of several organic degradation products and chloride were determined for the sonolysis of air- and argon-saturated solutions.     

Effect of pH on the ultrasonic degradation of ionic aromatic compounds in aqueous solution

The sonolysis of 4-nitrophenol (4-NP) and aniline in O2-saturated aqueous solutions was performed at 610 kHz with ultrasonic power of 25 W and aqueous temperature of 15 +/- 1 degrees C. The initial rate of degradation of both 4-NP and aniline in sonolysis of aqueous media follows pseudo-first-order reaction kinetics. Investigation of the H2O2 generation rate in phosphate buffer media (0.01 M) over the range of pH 2-9 revealed a maximum yield at pH approximately 3.2. The pH, which results in modification of the physical properties (including charge) of molecules with ionisable functional groups, plays an important role in the sonochemical degradation of chemical contaminants. For hydrophilic substrates, the neutral species more easily diffuse to and accumulate at the hydrophobic interface of liquid-gas bubbles in comparison with their corresponding ionic forms. As a consequence, the degradation rate of 4-NP under ultrasonic irradiation decreases with increasing pH. In contrast, the disappearance rate of aniline exhibits a maximum under alkaline conditions due to the high solubility of the ionic anilinium ion and the (potentially) preferential movement of the uncharged form to the interface. Additionally, the rate of reaction of the uncharged aniline molecule (which dominates at pH > 4.6) with hydroxyl radicals is reported to be about three times as fast as the rate of reaction of the cationic anilinium species.     

Development of dispersed-type sonophotocatalytic process using piezoelectric effect caused by ultrasonic resonance

Recently, degradation of persistent organic pollutants (POPs) with low biodegradability in the environment and in industrial and municipal wastewaters has gained importance. In this study, a dispersed-type sonophotocatalysis (SP) process, which is a combination of sonolysis and photocatalysis with dispersed light sources, has been proposed for the effective and energy-efficient degradation of POPs. In this method, the piezoelectric effect caused by ultrasonic resonance in a piezoelectric element is used for producing luminescence in a LED. A luminescent device composed of eight UV-LEDs and a piezoelectric element was designed for dispersion of UV light in water; this device was confirmed to show luminescence under ultrasonic irradiation. Sonophotocatalytic degradation experiments were carried out using several such devices, and the results were compared with those obtained in sonolysis, photocatalysis, and fixed-type SP. The comparison showed that the degradation rate constants in fixed-type and dispersed-type SP were larger than the sum of the rate constants obtained for sonolysis and photocatalysis; further, the synergetic effect caused by the combination of sonolysis and photocatalysis was 7.5% and 18% in fixed-type and dispersed-type SP, respectively.     

OH-radical formation by ultrasound in aqueous solution--Part II: Terephthalate and Fricke dosimetry and the influence of various conditions on the sonolytic yield

Terephthalate and Fricke dosimetry have been carried out to determine the sonolytic energy yields of the OH free radical and of its recombination product H2O2 in aqueous solutions under various operating conditions (nature of operating gas, power, frequency, temperature). For example, in the sonolysis of Ar-saturated terephthalate solutions at room temperature, a frequency of 321 kHz, and a power of 170 W kg-1, the total yield [G(.OH) + 2 G(H2O2)], equals 16 x 10(-10) mol J-1. This represents the total of .OH that reach the liquid phase from gas phase of the cavitating bubble. The higher the solute concentration, the lower the H2O2 production as more of the OH free radicals are scavenged, in competition with their recombination. Fricke dosimetry, in the absence and presence of Cu2+ ions, shows that the yield of H atom reaching the liquid phase is much lower, with G(H.) of the order of 3 x 10(-10) mol J-1. These sonolytic yields are smaller in solutions that are at the point of gas saturation, and increase to an optimum as the initial sonication-induced degassing and effervescence subsides. The probing of the sonic field has shown that the rate of sonolytic free-radical formation may vary across the sonicated volume depending on frequency and power input.     

Ultrasound-assisted removal of malachite green from aqueous solution by dead pine needles

The dead needles of Aleppo pine (Pinus halepensis) were tested as a possible sorbent for the removal of malachite green from aqueous solutions in the absence and presence of ultrasound. Batch process was employed for sorption kinetic and equilibrium studies. Sorption experiments indicated that the sorption capacity was dependent of operating variables. Both the rate and the amount of malachite green sorption are markedly increased in the presence of the ultrasonic field. The dye removal with the assistance of ultrasound was enhanced with the increase of sorbate initial concentration and temperature, and with the decrease of sorbent dosage and ionic strength. The combination of stirring and ultrasound leads to an improvement of the removal of dye. The sorption kinetics was controlled by the intraparticle diffusion. The intraparticle diffusion coefficient increased 1.7 times in the presence of ultrasound and up to 3.6 times in the combined process. The sorption capacity, estimated according to the Freundlich model, indicates that ultrasound enhanced the sorption properties of the sorbent. The effect of ultrasound on the improvement of dye sorption is due to a variety of physical and mechanical effects as well as to thermal properties. The combination of ultrasound and stirring for the sorption process was shown to be of interest for the treatment of wastewaters contaminated with malachite green.     

Sonochemical degradation of chlorophenols in water

Sonochemical degradation of dilute aqueous solutions of 2-, 3- and 4-chlorophenol and pentachlorophenol has been investigated under air or argon atmosphere. The degradation follows first-order kinetics in the initial state with rates in the range 4.5-6.6 microM min-1 under air and 6.0-7.2 microM min-1 under argon at a concentration of 100 microM of chlorophenols. The rate of OH radical formation from water is 19.8 microM min-1 under argon and 14.7 microM min-1 under air in the same sonolysis conditions. The sonolysis of chlorophenols is effectively inhibited, but not completely, by the addition of t-BuOH, which is known to be an efficient OH radical scavenger in aqueous sonolysis. This suggests that the main degradation of chlorophenols proceeds via reaction with OH radicals; a thermal reaction also occurs, although its contribution is small. The addition of appropriate amounts of Fe(II) ions accelerates the degradation. This is probably due to the regeneration of OH radicals from hydrogen peroxide, which would be formed from recombination of OH radicals and which may contribute a little to the degradation. The ability to inhibit bacterial multiplication of pentachlorophenol decreases with ultrasonic irradiation.