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1.
Sonochemical degradation of 4-chlorophenol, phenol, catechol and resorcinol was studied under Ar at 200 kHz in the absence and presence of Na2SO4 or NaCl. The rates of sonochemical degradation in the absence of salts decreased in the order 4-chlorophenol > phenol > catechol > resorcinol and this order was in good agreement with the order of log P (partition coefficient) value of each phenolic compound. The effects of salts on the rates of sonochemical degradation consisted of no effect or slight negative or positive effects. We discussed these unclear results based on two viewpoints: one was based on the changes in pseudo hydrophobicity and/or diffusion behavior of phenolic compounds and the other was based on the changes in solubility of Ar gas. The measured log P value of each phenolic compound slightly increased with increasing salt concentration. In addition, the dynamic surface tension for 4-chlorophenol aqueous solution in the absence and presence of Na2SO4 or NaCl suggested that phenolic compounds more easily accumulated at the interface region of bubbles at higher salt concentration. These results indicated that the rates of sonochemical degradation should be enhanced by the addition of salts. On the other hand, the calculated Ar gas solubility was confirmed to decrease with increasing salt concentration. The yield of H2O2 formed in the presence of Na2SO4 or NaCl decreased with increasing salt concentration. These results suggested that sonochemical efficiency decreased with decreasing gas amount in aqueous solution: a negative effect of salts was observed. Because negative and positive effects were induced simultaneously, we concluded that the effects of salts on the rates of sonochemical degradation of phenolic compounds became unclear. The products formed from sonochemical degradation of 4-chlorophenol were also characterized by HPLC analysis. The formation of phenol and 4-chloro-1,3-dihydroxy benzene was confirmed and these concentrations were affected by the presence of salts.  相似文献   

2.
The study is an extension of our previous work on sonolytic and sonocatalytic decomposition of Diclofenac-Na (DCF) to depict and highlight further operation parameters of significance, and to assess the effect of a novel home-made catalyst made of magnetic nanoparticles of zero-valent iron (ZVI). It was found that high-frequency was more effective than power ultrasound (20 kHz), and the efficiency was a maximum at 861 kHz, acetate-buffered pH 3.0 and air bubbling provided that samples were prepared from a pre-heated stock solution to enhance solubility of the compound. As such, 40-min sonication rendered nearly complete transformation of DCF to intermediate products that were more biodegradable than itself, but with little mineralization of organic carbon. Catalytic sono-treatment showed that the effect of the catalyst was largest in a non-buffered acidic solution and the rate of DCF elimination increased with increasing concentrations of solids up to a “critical” mass, above which it declined via the coalescence of particles and bubbles. Sonocatalysis using the “effective” solid mass also enhanced the overall degradation or mineralization of the compound as portrayed by the accumulation of chloride and nitrate ions in solution after prolonged contact. The production of excess H2O2 during catalysis with ZVI was attributed to the presence of additional and major routes of OH and/or H2O2 formation (other than water pyrolysis). The initial rate of DCF degradation in the presence of nanoparticles was found highly sensitive to the mass of solids in solution, declining sharply as the mass exceeded a “critical” effective level. A catalyst efficacy factor was defined as a function of the initial mass ratio of Fe0 to DCF and found to be one order of magnitude larger than that obtained by using commercial microparticles with a threefold larger Fe content. The result signifies that the role of aqueous Advanced Fenton reactions (Fe0/H2O2) was less significant in the presence of nanoparticles relative to that of heterogeneous reactions with reactive Fe and oxygen species on the massive surface areas with enriched reaction/adsorption and nucleation sites.  相似文献   

3.
TiO2 nanoparticles were synthesized via the laser pyrolysis of titanium tetrachloride-based gas-phase mixtures. In the obtained nanopowders, a mixture of anatase and rutile phases with mean particle size of about 14 nm was identified. Using the thermal heated laser nanopowders, mechanically stable films were produced by immobilizing titania nanopowders on glass substrates (the doctor blading method followed by compression). The photocatalytic activity of the prepared films was tested by the degradation of 4-chlorophenol in an aqueous solution under UV-illumination. By referring to known commercial samples (Degussa P25) similarly prepared, higher photocatalytic efficiency was found for the laser-prepared samples.  相似文献   

4.
In this work, the influence of CCl4 on the sonochemical decolorization of anthraquinonic dye Acid Blue 25 (AB25) in aqueous medium was investigated using high frequency ultrasound (1700 kHz). This frequency, reputed ineffective, was tested in order to introduce the ultrasound waves with high frequency in the field of degradation or removal of dyes from wastewater, due to its limited use in this field, and to increase the application of high frequency ultrasound wave in the field of environmental protection. The effects of various parameters such as the concentration of CCl4, frequency (22.5 and 1700 kHz), solution pH, temperature and tert-butyl alcohol adding on the decolorization rate of AB25 was studied. The obtained results clearly demonstrated the significant intensification of AB25 decolorization in the presence of CCl4. The enhancement effect of CCl4 increased by decreasing temperature and by increasing the CCl4 concentration. The pH has a significant influence on the bleaching of dye both in the absence and presence of CCl4. The three investigated dosimeter methods (KI oxidation, Fricke reaction and H2O2 production) well corroborate the improvement of the sonochemical effects in the presence of CCl4. The best sonochemical decolorization rate of AB25 in aqueous solution both in the absence and presence of CCl4 is observed to occur at 1700 kHz compared to 22.5 kHz. The sonochemical oxidation of CCl4 generates oxidizing species in the liquid phase that are highly beneficial for oxidation of hydrophilic and non-volatile pollutant, such as dyes, because they are less susceptible to free radical attack due to lower stability of the generated free radicals.  相似文献   

5.
Removal of 2-chlorophenol by ultrasonic waves (sonolysis), inorganic catalyst, and a combination of the two processes was tested and compared with each technique. In sonolysis, 2-chlorophenol mostly degraded indirectly in the bulk of solution by the radicals produced in the cavitation process. In catalyst treatment, the removal was performed in the presence of Al2O3, TiO2 and CuO. The highest removal was achieved in the presence of TiO2 for this pollutant. In the combined method an enhancement was observed for the removal of 2-chlorophenol. This could be attributed primarily to the continuous cleaning and chemical activation of the catalyst by acoustic cavitation. The mass transfer between the liquid phase and the catalyst and also the surface area of the catalyst are accelerated by the ultrasonic waves. The removal of 2-chlorophenol was performed under different intensities of irradiation, temperatures and quantities of catalyst. Some experiments were conducted in the presence of a Fenton reagent. In kinetic point of view, the removal of pollutant showed a pseudo-first order behavior. The combined method had a higher rate coefficient than sonolysis and catalyst treatment individually. Under some conditions, the presence of ultrasound has increased the rate coefficient of removal to about 10 times that in the absence of ultrasound.  相似文献   

6.
An ultrasound-assisted method was used for synthesizing nanosized Pt-graphene oxide (GO)-TiO2 photocatalyst. The Pt-GO-TiO2 nanoparticles were characterized by diffused reflectance spectroscopy, X-ray diffraction, N2 BET adsorption-desorption measurements, atomic force microscopy and transmission electron microscopy. The photocatalytic and sonophotocatalytic degradation of a commonly used anionic surfactant, dodecylbenzenesulfonate (DBS), in aqueous solution was carried out using Pt-GO-TiO2 nanoparticles in order to evaluate the photocatalytic efficiency. For comparison purpose, sonolytic degradation of DBS was carried out. The Pt-GO-TiO2 catalyst degraded DBS at a higher rate than P-25 (TiO2), prepared TiO2 or GO-TiO2 photocatalysts. The mineralization of DBS was enhanced by a factor of 3 using Pt-GO-TiO2 compared to the P-25 (TiO2). In the presence of GO, an enhanced rate of DBS oxidation was observed and, when doped with platinum, mineralization of DBS was further enhanced. The Pt-GO-TiO2 catalyst also showed a considerable amount of degradation of DBS under visible light irradiation. The initial solution pH had an effect on the rate of photocatalytic oxidation of DBS, whereas no such effect of initial pH was observed in the sonochemical or sonophotocatalytic oxidation of DBS. The intermediate products formed during the degradation of DBS were monitored using electrospray mass spectrometry. The ability of GO to serve as a solid support to anchor platinum particles on GO-TiO2 is useful in developing new photocatalysts.  相似文献   

7.
Pb2+离子可以作为高效的催化剂用于降解糖为乳酸, 但是为了降低暴露Pb2+离子于环境中的风险,最好的办法是把铅固定在一个固体催化剂上.报道了一个简单的制备Pb(PbO2)/石墨烯复合固体催化剂的方法,可以得到石墨烯负载的纳米铅催化剂,铅颗粒的尺寸在2~5 nm.获得的催化剂可以在水中用于降解葡萄糖、果糖甚至纤维素,产物主要为乳酸.对于果糖、乳酸的产率为58.7% (433 K,2.5 MPa N2);当直接使用纤维素为原料,无额外酸、碱催化剂时,乳酸的产率可以达到31.7%.  相似文献   

8.
This work describes the results of investigations carried out to examine the adsorption kinetics of 4-chlorophenol (4-CP) from aqueous solution containing tert-butyl alcohol (10%, v/v) onto granular activated carbon (GAC) in the presence of ultrasound of different high frequencies (516, 800 and 1660 kHz) and acoustic powers (15.2, 21.5, 31.1 and 38.3 W). The main objective of this study is to describe the mechanism of ultrasound-assisted adsorption rather than the enhancement of adsorption capacity. Sonochemical degradation of 4-CP was studied in the absence and presence of tert-butyl alcohol. The sonolysis of 4-CP is effectively inhibited by the addition of tert-butyl alcohol (10%, v/v) and very little 4-CP degradation occurs, indicating that little or no pyrolysis of the compound occurs. Without addition of tert-butyl alcohol, after 300 min and at 1660 kHz, the removal of 4-CP in the presence of ultrasound for an acoustic power of 38.3 W was nearly total (99%), but in the conventional method only 60% was eliminated. In this case, the removal of 4-CP by GAC in the ultrasound-assisted technique is due to both adsorption and ultrasonic degradation, but the removal by simple stirring is only due to adsorption, which makes a direct comparison unacceptable. In order to distinguish sonochemical degradation and adsorption of 4-CP onto GAC and to make an exact and practical comparison of the adsorption in the absence and presence of ultrasound, kinetic adsorption experiments were conducted using aqueous solution containing 10% (v/v) tert-butyl alcohol. The obtained results show that both adsorption rate and adsorbed amount were significantly enhanced and improved in the presence of ultrasound for all the studied frequencies and powers. The enhancement of adsorption is favored by increasing ultrasonic power. Adsorption kinetic data were modeled using the liquid-film mass transfer equation and intraparticle diffusion model. The values of the intraparticle diffusion coefficient obtained in the presence of ultrasound are greater than that obtained in the absence of ultrasound. In the initial period of adsorption, where external mass transfer is assumed to predominate, liquid-film mass transfer coefficients significantly increased by the assistance of ultrasound. These results indicate that ultrasound enhances the mass transport in the pores as well as across the boundary layer. This effect increased with increasing ultrasonic power for the three studied frequencies. The average order for the studied ultrasonic waves according to the initial adsorption rate, the intraparticle diffusion coefficient and the liquid-film mass transfer coefficient is 516 kHz>800 kHz>1660 kHz.  相似文献   

9.
By the direct coprecipitation of the aqueous solution of iron salt and tetramethylammonium hydroxide solution the stable iron ferrite nanoparticles were formulated. These nanoparticles were found to have uniform sizes of about 7 nm, and also showed no coalescence in the aqueous solution for a few months. The superparamagnetic behavior of these nanoparticles was checked by a vibrating sample magnetometer. Also, the temperature dependence of saturation magnetization of nanoparticles was observed using a superconducting quantum interface device magnetometer. The relaxation times of T1 and T2 of hydrogen proton in the colloidal aqueous solution of magnetic nanoparticles were measured using a nuclear magnetic resonance spectrometer for the wide range of concentration of nanoparticles in the aqueous solution. The inverse of relaxation times was observed to be directly dependent on the concentration of nanoparticles.  相似文献   

10.
In this paper, the photocatalytic degradation of Reactive Black 5 (RB5) was investigated with ferrite bismuth synthesized via ultrasound under direct sunlight irradiation. The intensity of absorption peaks of RB5 gradually decreased by increasing the irradiation time and finally vanished in 50 min in acidic medium. The formation of new intermediate was observed in basic medium. The relative concentration of RB5 in solution and on the surface of ferrite bismuth (BiFeO3) nanoparticles was considered during the experiment in acidic and basic media. The effects of various parameters such as amount of catalyst, concentration of dye, and pH of the solution have been studied on the dye degradation. The adsorption isotherm and the kinetic of photocatalytic degradation of RB5 were investigated. The adsorption constants in the dark and in the presence of sunlight irradiation were compared. The photocatalytic degradation mechanism of RB5 has been evaluated through the addition of some scavengers to the solution. In addition, the stability and reusability of the catalyst were examined in this work.  相似文献   

11.
Degradation of C.I. Direct Black 168 from aqueous solution using Fenton-like reactions combining ultrasound was investigated. In the presence of H2O2, the effect of the heterogeneous catalysts, such as fly ash, kaolinite or diatomaceous earth on the degradation of Direct Black 168 was observed under ultrasound. The fly ash was the most efficient catalyst. It is apparent that ultrasound can prompt the reaction to take place and give in higher degradation. In the combination of ultrasound and fly ash/H2O2, the effect of different system variables namely concentration of the dye, dosage of fly ash, concentration of H2O2, pH of solution and the addition of NaCl were studied. 99.0% removal ratio was achieved at initial concentration 100 mg/L, pH 3.0, and dosage of fly ash 2.0 g/L, as well as 2.94 mM H2O2. NaCl exhibited only a minor effect on the dye removal.  相似文献   

12.
A recyclable heterogeneous catalyst has been successfully developed for application in a Fenton-type advanced oxidation process without adding external H2O2. LaFeO3 was prepared from Fe(NO3)3·9H2O and La(NO3)·6H2O by a simple sol-gel method and its catalytic efficiency was evaluated for mineralization of 4-chlorophenol using a Fenton-like process. The mineralization process was carried out under ultrasonication in presence of heterogeneous LaFeO3 catalyst with H2O2 that was produced during ultrasonication. The mineralization process was monitored through total organic carbon (TOC) analysis. Very importantly, utmost 5-fold synergism was evidenced by the ultrasound mediated LaFeO3-catalyzed system. Besides, more than twofold synergism was observed by combining the ultrasound assisted LaFeO3 catalytic process and potassium persulfate (KPS) assisted advanced oxidation process. It is worth to mention that complete mineralization (∼96%) of 4-chlorophenol (initial concentration of 1.25 × 10−4 M) was observed within 1 h in the presence of LaFeO3 (0.5 g L−1) and KPS (1.0 mmol) under ultrasonication (40 kHz). Even after four cycles, the activity of LaFeO3 remained intact which proved its recyclability. Extremely reusable heterogeneous LaFeO3 catalyst makes the system more interesting from both economic and environmental points of view.  相似文献   

13.
In this article, we report a facile approach for the synthesis of an inexpensive catalyst of bimetallic Hg/Pd alloys comprising nanoparticles with various structures using a unique ultrasonic reaction that is conducted without the use of any reducing agent. The nanoparticles of Hg/Pd alloys (HgPd and Hg2Pd5) were achieved for the first time by sonicating an aqueous solution of Palladium (II) nitrate with metallic liquid mercury, as evidenced by XRD. EDS further confirmed the presence of Pd and Hg elements in the alloy. The surface morphology and structure of the nanoparticles have been systematically investigated by HRSEM, HRTEM and SAED pattern. In order to explore the catalytic activity of the as-synthesized nanoalloys, the catalytic reduction of 4-nitrophenol and a few other nitrophenol derivatives were investigated. Excellent catalytic activity was obtained for Hg/Pd (1:1) alloy, and the rate constant for the reduction of 4-NP with Hg/Pd at room temperature was found to be 58.4 × 10−3 s−1, which is possibly the highest ever reported. The catalyst exhibited superior stability and reusability when compared with those reported in the literature for other catalysts based on noble metals.  相似文献   

14.
A simplified method for synthesis of polyacrylic acid-bound iron oxide magnetic nanoparticles (Fe3O4@PAA NPs) was reported. The as-prepared nanoparticles were characterized by TEM, FT-IR, VSM and XRD. Characterization results indicated that PAA was successfully introduced onto the surface of Fe3O4 and did not cause any changes in magnetic property. The Fe3O4@PAA NPs were used to adsorb rhodamine 6G (R6G) as a model basic dye pollutant from aqueous solution. Kinetics data and adsorption isotherms were better fitted by pseudo-second-order kinetic model and Langmuir isotherm, respectively. The adsorption equilibrium could be reached at about 20 min, showing that the as-prepared adsorbent exhibited extremely rapid adsorption rate. The aqueous solution of the Yellow River was chosen as the test sample, and the results showed that the magnetic adsorbent was efficient for the removal of the basic dye in the real sample.  相似文献   

15.
In this paper, a novel approach was successfully developed for advanced catalyst Ag-deposited silica-coated Fe3O4 magnetic nanoparticles, which possess a silica coated magnetic core and growth active silver nanoparticles on the outer shell using n-butylamine as the reductant of AgNO3 in ethanol. The as-synthesized nanoparticles have been characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), Fourier transform infrared spectra (FT-IR), vibration sample magnetometer (VSM), and have been exploited as a solid phase catalyst for the reduction of p-nitrophenol in the presence of NaBH4 by UV-vis spectrophotometry. The obtained products exhibited monodisperse and bifunctional with high magnetization and excellent catalytic activity towards p-nitrophenol reduction. As a result, the as-obtained nanoparticles showed high performance in catalytic reduction of p-nitrophenol to p-aminophenol with conversion of 95% within 14 min in the presence of an excess amount of NaBH4, convenient magnetic separability, as well as remained activity after recycled more than 6 times. The Fe3O4@SiO2-Ag functional nanostructure could hold great promise for various catalytic reactions.  相似文献   

16.
《Current Applied Physics》2020,20(2):249-254
The main drawbacks of anatase titanium dioxide (TiO2) nanoparticles for being used as a photocatalyst are due to the rapid charge recombination of the electron-hole pairs and the wide band gap energy, limiting its photocatalysis application. To enhance photocatalytic activity, structure modification was performed here. Heterogeneous nanostructure of Dy-doped TiO2 nanoparticles hybrid with Monoclinic TiO2 nanobelts (Dy/TNBs) was fabricated via hydrothermal method. Annealing temperature was varied to investigate its effect on phase composition and morphology of the as-prepared TiO2 catalyst. Phase composition and morphology were studied by XRD and SEM, respectively. The effect of amount of catalyst loaded on the degradation efficiency of methylene blue (MB) dye in aqueous solution under UV and fluorescence illumination was investigated. The results showed that pure monoclinic TiO2 nanobelts (TNBs) was achieved at 450 °C. Enhanced photocatalytic activity under both UV and fluorescence irradiation was found on Dy/TNB samples. The optimum Dy dosage providing the highest MB degradation rates under both irradiation sources was 0.1 mol%.  相似文献   

17.
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.  相似文献   

18.
Numerical simulations of sonochemical production and oriented attachment of BaTiO3 nanocrystals are performed in aqueous solution with pH 14. It is suggested that most significant effect of ultrasound is the dissolution of Ti-based gel in aqueous solution. It results in the dissolution-precipitation mechanism in the production of BaTiO3 nanoparticles, while with mechanical stirring without ultrasound it is the in situ mechanism that BaTiO3 is gradually formed on Ti-based gel. The oriented attachment of spherical BaTiO3 nanocrystals occurs by van der Waals torque (Casimir torque). Large aggregates of nanocrystals do not attach with each other as the repulsive double layer interaction is stronger for larger aggregates. For smaller spherical nanocrystals, the alignment of the crystal axes is less accurate due to more significant rotational Brownian motion of the nanocrystals.  相似文献   

19.
Mn–Zn ferrite nanoparticles (Mn1−xZnxFe2O4) are synthesized by a hydrothermal precipitation approach using metal sulfate solution and aqueous ammonia. The analysis methods of XRPD, TEM, TGA, and VSM are used to characterize the magnetic nanoparticles. Through the characterization of the precipitated nanoparticles, the effects of the reacting component proportions and preparation techniques on the Curie temperature, the magnetization, and the size distribution of Mn–Zn ferrite nanoparticles are discussed. Furthermore, the Mn–Zn ferrite nanoparticles are used to prepare ferrofluid. Variation of the magnetic properties of the ferrite nanoparticles with the composition content x of Zn and the magnetic moment of the nanoparticles are discussed.  相似文献   

20.
The sonocatalytic degradation of EDTA (C0 = 5 10−3 M) in aqueous solutions was studied under 345 kHz (Pac = 0.25 W mL−1) ultrasound at 22–51 °C, Ar/20%O2, Ar or air, and in the presence of metallic titanium (Ti0) or core-shell Ti@TiO2 nanoparticles (NPs). Ti@TiO2 NPs have been obtained using simultaneous action of hydrothermal conditions (100–214 °C, autogenic pressure P = 1.0–19.0 bar) and 20 kHz ultrasound, called sonohydrothermal (SHT) treatment, on Ti0 NPs in pure water. Ti0 is composed of quasi-spherical particles (30–150 nm) of metallic titanium coated with a metastable titanium suboxide Ti3O. SHT treatment at 150–214 °C leads to the oxidation of Ti3O and partial oxidation of Ti0 and formation of nanocrystalline shell (10–20 nm) composed of TiO2 anatase. It was found that Ti0 NPs do not exhibit catalytic activity in the absence of ultrasound. Moreover, Ti0 NPs remain inactive under ultrasound in the absence of oxygen. However, significant acceleration of EDTA degradation was achieved during sonication in the presence of Ti0 NPs and Ar/20%O2 gas mixture. Coating of Ti0 with TiO2 nanocrystalline shell reduces sonocatalytic activity. Pristine TiO2 anatase nanoparticles do not show a sonocatalytic activity in studied system. Suggested mechanism of EDTA sonocatalytic degradation involves two reaction pathways: (i) sonochemical oxidation of EDTA by OH/HO2 radicals in solution and (ii) EDTA oxidation at the surface of Ti0 NPs in the presence of oxygen activated by cavitation event. Ultrasonic activation most probably occurs due to the local heating of Ti0/O2 species at cavitation bubble/solution interface.  相似文献   

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