Ultrasonic waste-water treatment: incidence of ultrasonic frequency on the rate of phenol and carbon tetrachloride degradation

Organic compounds in aqueous solution submitted to an ultrasonic irradiation behave differently according to their physical and chemical properties. In this work, hydrogen peroxide formation and the degradation rate of phenol and carbon tetrachloride have been studied at different frequencies: 20, 200, 500 and 800 kHz. Whatever the frequency, it is easier to decompose CCl₄ than phenol by means of ultrasonic wave. It is shown that the rates of reactions involving hydroxyl radicals (hydrogen peroxide formation and phenol degradation) have a maximum value at 200 kHz. The best yield observed at 200 kHz for the phenol degradation may be the result of better HO radicals availability outside of the bubble of cavitation. The degradation rate for carbon tetrachloride which decomposes into the bubble of cavitation increases with frequency. Calculating the reaction rate for one ultrasonic period shows that the efficiency of one ultrasonic cycle decreases as frequency increases.     

Simple sonochemical synthesis of novel grass-like vanadium disulfide: A viable non-enzymatic electrochemical sensor for the detection of hydrogen peroxide

Design and fabrication of novel inorganic nanomaterials for the low-level detection of food preservative chemicals significant is of interest to the researchers. In the present work, we have developed a novel grass-like vanadium disulfide (GL-VS₂) through a simple sonochemical method without surfactants or templates. As-prepared VS₂ was used as an electrocatalyst for reduction of hydrogen peroxide (H₂O₂). The crystalline nature, surface morphology, elemental compositions and binding energy of the as-prepared VS₂ were analyzed by X-ray diffraction, Raman spectroscopy, field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The electrochemical studies show that the GL-VS₂ modified glassy carbon electrode (GL-VS₂/GCE) has a superior electrocatalytic activity and lower-reduction potential than the response observed for unmodified GCE. Furthermore, the GL-VS₂/GCE displayed a wide linear response range (0.1–260 μM), high sensitivity (0.23 μA μM⁻¹ cm⁻²), lower detection limit (26 nM) and excellent selectivity for detection of H₂O₂. The fabricated GL-VS₂/GCE showed excellent practical ability for detection of H₂O₂ in milk and urine samples, revealing the real-time practical applicability of the sensor in food contaminants.     

Enhanced sonochemical degradation of azure B dye by the electroFenton process

The degradation of azure B dye (C₁₅H₁₆ClN₃S; AB) has been studied by Fenton, sonolysis and sono-electroFenton processes employing ultrasound at 23 kHz and the electrogeneration of H₂O₂ at the reticulated vitreous carbon electrode. It was found that the dye degradation followed apparent first-order kinetics in all the degradation processes tested. The rate constant was affected by both the pH of the solution and initial concentration of Fe²⁺, with the highest degradation obtained at pH between 2.6 and 3. The first-order rate constant decreased in the following order: sono-electroFenton > Fenton > sonolysis. The rate constant for AB degradation by sono-electroFenton is ∼10-fold that of sonolysis and ∼2-fold the one obtained by Fenton under silent conditions. The chemical oxygen demand was abated ∼68% and ∼85% by Fenton and sono-electroFenton respectively, achieving AB concentration removal over 90% with both processes.     

Ultrasonic degradation of Rhodamine B in the presence of hydrogen peroxide and some metal oxide

In this research, degradation of Rodamine B in the presence of (hydrogen peroxide), (hydrogen peroxide + ultrasound), (hydrogen peroxide + aluminum oxide), (hydrogen peroxide + aluminum oxide + ultrasound with different ultrasound power), (hydrogen peroxide + iron oxide) and (hydrogen peroxide + iron oxide + ultrasound with different ultrasound power) were investigated at 25 °C. The apparent rate constants for the examined systems were calculated by pseudo-first-order kinetics. The results indicate that the rate of degradation was accelerated by ultrasound. The rate of degradation was increased by increasing power ultrasound. The efficiency of the (hydrogen peroxide + iron oxide + ultrasound) system for degradation of Rodamine B was higher than the others examined.     

The size of active bubbles for the production of hydrogen in sonochemical reaction field

The sonication of aqueous solution generates microscopic cavitation bubbles that may growth and violently collapse to produce highly reactive species (i.e. OH, HO₂ and H₂O₂), hydrogen and emit light, sonoluminescence. The bubble size is a key parameter that influences the chemical activity of the system. This wok aims to study theoretically the size of active bubbles for the production of hydrogen in ultrasonic cavitation field in water using a single bubble sonochemistry model. The effect of several parameters such as frequency of ultrasound, acoustic intensity and liquid temperature on the range of sonochemically active bubbles for the production of hydrogen was clarified. The numerical simulation results showed that the size of active bubbles is an interval which includes an optimum value at which the production rate of H₂ is maximal. It was shown that the range of ambient radius for an active bubble as well as the optimum bubble radius for the production of hydrogen increased with increasing acoustic intensity and decreased with increasing ultrasound frequency and bulk liquid temperature. It was found that the range of ambient bubble radius dependence of the operational conditions followed the same trend as those reported experimentally for sonoluminescing bubbles. Comparison with literature data showed a good agreement between the theoretical determined optimum bubble sizes for the production of hydrogen and the experimental reported sizes for sonoluminescing bubbles.     

Ultrasonic degradation, mineralization and detoxification of diclofenac in water: Optimization of operating parameters

The 20 kHz ultrasound-induced degradation of non-steroidal, anti-inflammatory drug diclofenac (DCF) was investigated. Several operating conditions, such as power density (25–100 W/L), substrate concentration (2.5–80 mg/L), initial solution pH (3.5–11), liquid bulk temperature and the type of sparging gas (air, oxygen, argon), were tested concerning their effect on DCF degradation (as assessed measuring absorbance at 276 nm) and hydroxyl radicals generation (as assessed measuring H₂O₂ concentration). Sample mineralization (in terms of TOC and COD removal), aerobic biodegradability (as assessed by the BOD₅/COD ratio) and ecotoxicity to Daphnia magna and Artemia salina were followed too.DCF conversion is enhanced at increased applied power densities and liquid bulk temperatures, acidic conditions and in the presence of dissolved air or oxygen. The reaction rate increases with increasing DCF concentration in the range 2.5–5 mg/L but it remains constant in the range 40–80 mg/L, indicating different kinetic regimes (i.e. first and zero order, respectively). H₂O₂ production rates in pure water are higher than those in DCF solutions, implying that decomposition basically proceeds through hydroxyl radical reactions. Mineralization is a slow process as reaction by-products are more stable than DCF to total oxidation; nonetheless, they are also more readily biodegradable. Toxicity to D. magna increases during the early stages of the reaction and then decreases progressively upon degradation of reaction by-products; nevertheless, complete toxicity elimination cannot be achieved at the conditions in question. Neither the original nor the treated DCF samples are toxic to A. salina.     

超声空化状态对苯酚降解的影响

给出不同空化状态下超声波降解苯酚溶液的实验结果,比较了相应的声压级频谱和合成声强。研究了苯酚溶液的浓度,二阶铁盐,超声辐射时间对苯酚降解率的影响,讨论了不同空化状态下的声压级频谱特征。     

Detection of hydrogen peroxide with graphyne

The effect of hydrogen peroxide on the electronic properties of graphyne has been investigated to explore the possibility of using graphyne based biosensor. We have used density functional theory to study the electronic properties of γ-graphyne in the presence of different number of hydrogen peroxide. The optimal adsorption position, orientation, and distance of hydrogen peroxide adsorbed on the graphyne sheet have been determined by calculating adsorption energy. It is found that γ-graphyne which is an intrinsic semiconductor becomes an n-type semiconductor due to the presence of hydrogen peroxide. The energy band gap of γ-graphyne is decreased by increasing the number of hydrogen peroxide. The results demonstrate that γ-graphyne is a promising candidate for biosensor application because of its electrical sensitivity to hydrogen peroxide.     

A novel sodium iodide and ammonium molybdate co-catalytic system for the efficient synthesis of 2-benzimidazoles using hydrogen peroxide under ultrasound irradiation

The reaction of aldehydes and o-phenylenediamine for the preparation of 2-benzimidazoles has been studied using hydrogen peroxide as an oxidant under ultrasound irradiation at room temperature in this paper. The combination of substoichiometric sodium iodide and ammonium molybdate as co-catalysts, together with using small amounts of hydrogen peroxide, makes this transformation very efficient and attractive under ultrasound. Thus, a mild, green and efficient method is established to carry out this reaction in high yield.     

The effects of ultrasound on micromixing

The Villermaux–Dushman reaction is a widely used technique to study micromixing efficiencies with and without sonication. This paper shows that ultrasound can interfere with this reaction by sonolysis of potassium iodide, which is excessively available in the Villermaux–Dushman solution, into triiodide ions. Some corrective actions, to minimize this interference, are proposed. Furthermore, the effect of ultrasonic frequency, power dissipation, probe tip surface area and stirring speed on micromixing were investigated. The power and frequency seem to have a significant impact on micromixing in contrast to the stirring speed and probe tip surface area. Best micromixing was observed with a 24 kHz probe and high power intensities. Experiments with different frequencies but a constant power intensity, emitter surface, stirring speed, cavitation bubble type and reactor design showed best micromixing for the highest frequency of 1135 kHz. Finally, these results were used to test the power law model of Rahimi et al. This model was not able to predict micromixing accurately and the addition of the frequency, as an additional parameter, was needed to improve the simulations.     

Temperature dependence and the effect of hydrogen peroxide on ITO/poly-ZnO Schottky diodes fabricated by laser evaporation

Transparent and efficient poly-ZnO ultraviolet Schottky diodes grown at different temperatures with indium-tin-oxide (ITO) as the metallic contact layer were fabricated with hydrogen peroxide (H₂O₂) applied as a surface treatment at 70 °C for 20 min. Analysis via field-emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) demonstrated that the ZnO films underwent gradual oxidation and that H₂O₂ treatment resulted in an interfacial ZnO₂ layer that covered the ZnO surface. I–V measurements indicated that the ideality factor and the Schottky barrier height improved with increasing shunt resistance, and the trade-off between film quality and the degree of oxidation revealed that films grown at 400 °C exhibited the best diode characteristics.     

过氧化氢加酒精补燃气体发生器实验研究

 介绍了过氧化氢催化分解气体加酒精补燃以提高气体发生器排气温度的理论计算和分析方法,并建立了一套实验研究装置。 装置中质量分数为90%的过氧化氢溶液由高压气挤推,通过催化床完成催化分解,产生高温气体;质量分数为97%的酒精溶液经由分布喷嘴喷入过氧化氢分解气体中发生自燃,从而提高气体温度。实验研究了采用不同酒精喷入形式和参数对气体发生器排气温度均匀性的影响。结果表明：利用沿气体发生器燃烧室周向分布的多喷嘴进行酒精喷注,并与高浓度过氧化氢催化分解气体进行混合燃烧的方法,能够有效提高气体发生器的排气温度,并得到均匀的排气温度场。     

Role of activated carbon features on the photocatalytic degradation of phenol

In this work we have investigated the role of porous carbon material used as a photocatalyst and a catalyst support in the carbon/titania composite in the photodegradation of phenol, and compared the results to those of bare titanium oxide. The immobilization of titania on an activated carbon provoked acceleration of the degradation rate under UV irradiation, which is likely to be attributed to the porosity of the carbon support. The identification of the degradation intermediates detected in the solution showed that the presence of the carbon support affects the nature of phenol degradation mechanism through the formation of different intermediates. Additionally, phenol photodecomposition rate over the carbon support outperformed that attained in the carbon/titania composite, suggesting an important self-photoactivity of the carbon support.     

Physical insights into the sonochemical degradation of recalcitrant organic pollutants with cavitation bubble dynamics

This paper tries to discern the mechanistic features of sonochemical degradation of recalcitrant organic pollutants using five model compounds, viz. phenol (Ph), chlorobenzene (CB), nitrobenzene (NB), p-nitrophenol (PNP) and 2,4-dichlorophenol (2,4-DCP). The sonochemical degradation of the pollutant can occur in three distinct pathways: hydroxylation by OH radicals produced from cavitation bubbles (either in the bubble–bulk interfacial region or in the bulk liquid medium), thermal decomposition in cavitation bubble and thermal decomposition at the bubble–liquid interfacial region. With the methodology of coupling experiments under different conditions (which alter the nature of the cavitation phenomena in the bulk liquid medium) with the simulations of radial motion of cavitation bubbles, we have tried to discern the relative contribution of each of the above pathway to overall degradation of the pollutant. Moreover, we have also tried to correlate the predominant degradation mechanism to the physico-chemical properties of the pollutant. The contribution of secondary factors such as probability of radical–pollutant interaction and extent of radical scavenging (or conservation) in the medium has also been identified. Simultaneous analysis of the trends in degradation with different experimental techniques and simulation results reveals interesting mechanistic features of sonochemical degradation of the model pollutants. The physical properties that determine the predominant degradation pathway are vapor pressure, solubility and hydrophobicity. Degradation of Ph occurs mainly by hydroxylation in bulk medium; degradation of CB occurs via thermal decomposition inside the bubble, degradation of PNP occurs via pyrolytic decomposition at bubble interface, while hydroxylation at bubble interface contributes to degradation of NB and 2,4-DCP.     

Effect of nitrate ions on the efficiency of sonophotochemical phenol degradation

A sonophotochemical oxidation process has been used for the treatment of an aqueous solution of phenol. The aim of this work is to evaluate the effect of nitrate ions on hydroxyl radical production and on phenol oxidation. It has been demonstrated that ultrasound can produce NOx (nitrate and nitrite), with a production rate of 2.2 μM min⁻¹. The photolysis of nitrate can significantly improve the hydroxyl radical production. The apparent rate constant for hydroxyl radical production increased from 0.0015 min⁻¹ to 0.0073 min⁻¹ while increasing initial nitrate concentration from 0 to 0.5 mM. The concentration of hydroxyl radical was directly proportional to the initial nitrate concentration. Using US/UV process, the apparent reaction rate constant of phenol degradation in the presence of nitrate reached 0.020 min⁻¹, which was relatively lower than the value obtained (0.027 min⁻¹) in the absence of nitrate. It appeared that, nitrate ions can inhibit the sonochemical degradation of organic compounds such as phenol.     

Evidences of ultraviolet visible spectra of hydrogen sulfide scavenging trans-crotonaldehyde induced by hydrogen peroxide through mitochondria of rat heart

Evidences of ultraviolet visible spectra of hydrogen sulfide scavenging trans-crotonaldehyde (TCA) induced by hydrogen peroxide through mitochondria were probed for the first time. TCA was induced by hydrogen peroxide through mitochondria. When sodium hydrosulfide as hydrogen sulfide donor, comparison with control, ultraviolet visible spectra of TCA decrease were clear. Hydrogen sulfide released by garlic was detected by ultraviolet visible spectroscopy. When garlic as hydrogen sulfide donors, the ultraviolet visible spectra of TCA decrease were very obvious. The findings are strongly recommended that garlic as safe, stable, and controllable hydrogen sulfide donor become a promising drug which is worthy of further study.     

The torsion potential function of hydrogen peroxide and disulfan molecules

A method for constructing the torsion potential function of hydrogen peroxide and disulfan molecules which takes into account the magnitudes of intramolecular interactions is suggested. The new representation of the potential is used to calculate the torsion spectra of the molecules indicated. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 450–452, July–August, 2000.     

Degradation of endocrine disruptor bisphenol A by ultrasound-assisted electrochemical oxidation in water

Micropollutants are becoming an increasing problem for the environment and wastewater treatment. One example is Bisphenol A (BPA), an endocrinic disruptor, which is widely used in plastic production. Due to its endocrine disrupting effects on aquatic (micro-)organisms and its ubiquity, in surface- and wastewater alike, adequate treatment techniques are necessary.In this study, the degradation of BPA by a sonoelectrochemical hybrid system was investigated, using a low frequency (24 kHz) ultrasound horn and two boron doped diamond electrodes. It was found that by the combination of the individual processes, i.e. ultrasound and electrochemical oxidation, more than 90% of BPA could be removed within 30 min at an initial concentration of 1 mg L⁻¹. Moreover, synergistic effects were discovered and a considerable improvement compared to the individual processes could be achieved by using a potential of 5 V, whereas synergistic effects were absent at a potential of 10 V. This study provides investigation of ultrasound amplitude, potential and electrode positioning on BPA degradation. The reaction was found to follow pseudo first order kinetics with a rate constant of 0.089 min⁻¹. Samples were analysed by high pressure liquid chromatography (HPLC) using a diode array detector. Moreover, the presence and distribution of hydroxyl radicals within the reactor was visualized by using sonochemiluminescence.     

Ultrasound (US), Ultraviolet light (UV) and combination (US + UV) assisted semiconductor catalysed degradation of organic pollutants in water: Oscillation in the concentration of hydrogen peroxide formed in situ

Application of Advanced Oxidation Processes (AOP) such as sono, photo and sonophoto catalysis in the purification of polluted water under ambient conditions involve the formation and participation of Reactive Oxygen Species (ROS) like OH, HO₂, O₂⁻, H₂O₂ etc. Among these, H₂O₂ is the most stable and is also a precursor for the reactive free radicals. Current investigations on the ZnO mediated sono, photo and sonophoto catalytic degradation of phenol pollutant in water reveal that H₂O₂ formed in situ cannot be quantitatively correlated with the degradation of the pollutant. The concentration of H₂O₂ formed does not increase corresponding to phenol degradation and reaches a plateau or varies in a wave-like fashion (oscillation) with well defined crests and troughs, indicating concurrent formation and decomposition. The concentration at which decomposition overtakes formation or formation overtakes decomposition is sensitive to the reaction conditions. Direct photolysis of H₂O₂ in the absence of catalyst or the presence of pre-equilibrated (with the adsorption of H₂O₂) catalyst in the absence of light does not lead to the oscillation. The phenomenon is more pronounced in sonocatalysis, the intensity of oscillation being in the order sonocatalysis > photocatalysis ⩾ sonophotocatalysis while the degradation of phenol follows the order sonophotocatalysis > photocatalysis > sonocatalysis > sonolysis > photolysis. In the case of sonocatalysis, the oscillation continues for some more time after discontinuing the US irradiation indicating that the reactive free radicals as well as the trapped electrons and holes which interact with H₂O₂ have longer life time (memory effect).     

The effects of liquid height/volume,initial concentration of reactant and acoustic power on sonochemical oxidation

Even though much knowledge on acoustic cavitation and its application has been accumulated over the past decades, further research is still required to develop industrial uses of acoustic cavitation. It is because the available information is mainly based on small-scale sonoreactors and the design and optimization of sonoreactors for large-scale applications have not been widely studied. In this study, the effects of liquid height/volume, initial concentration of the reactant and input acoustic power on sonochemical oxidation reactions including iodide ion oxidation, As(III) oxidation, and hydrogen peroxide generation were investigated using a 291 kHz sonoreactor with various liquid height/volumes (50, 100, 200, 300, 500, and 1000 mL) and input powers (23, 40, and 82 W). As the liquid height/volume and the input power changed, the power density varied from 23 to 1640 W/L and the maximum cavitation yields of triiodide ion for 23, 40, and 82 W were observed at 0.05, 0.1, and 0.2/0.3 L, respectively. It was found that low power was more effective for the small volume and the large volume required high power level and the moderate power density, approximately 400 W/L, was suggested for the sonochemical oxidation of iodide ion in the 291 kHz sonoreactor in this study. Similar results were observed in the generation of hydrogen peroxide and the sonochemical oxidation of As(III) to As(V). It was also revealed that KI dosimetry could be applicable for the estimation of the sonochemical reactions of non-volatile compounds such as As(III).