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1.
Zerovalent iron (ZVI) has been demonstrated to be suitable for the dehalogenation of environmental pollutants such as chloroethenes. The construction of ZVI reactive barriers by conventional engineering measures is expensive and limited to shallow aquifers. The use of nanosized ZVI particles opens new opportunities to construct ZVI barriers with less invasive techniques. However, nanosized particles of pure ZVI are pyrophoric and react spontaneously with atmospheric oxygen.In this study, nanosized air-stable ZVI particles were produced by applying ultrasound to a solution of Fe(CO)5 in edible oil. The resulting iron nanoparticles were dispersed in a carbon matrix, and coated with a non-crystalline carbon layer of approx. 2.5 nm. Although, these nanoparticles are non-pyrophoric and stable in air, dechlorination of tetrachloroethene was demonstrated in synthetic aqueous medium and in polluted groundwater. Additionally, hydrogen was formed. Due to the larger surface area, significantly higher mass-normalized reaction rates of the novel carbon-coated nanoparticles were obtained as compared to conventional bulk ZVI material. Surface normalized pseudo-first-order-reaction rates of kSA = 3.49 × 10?3 L h?1 m?2 and 2.33 × 10?2 L h?1 m?2 were calculated for the nano-ZVI and the bulk ZVI, respectively. Dechlorination reaction products of the novel nano-ZVI were trichloroethene, cis-dichloroethene, vinyl chloride, ethene, and ethane.  相似文献   

2.
In this study, synergistic degradation of antibiotic norfloxacin (NOR) was obtained in a novel sonochemical ultrasound/zero-valent iron/tetraphosphate system (US/ZVI/TPP). Compared to three common organic ligands (EDTA, EDDS, and DTPA), TPP could perform more excellently in activation of O2 to produce reactive oxidative species (ROS) and lead to efficient Fenton-like oxidative degradation of NOR in the sonochemical in situ chemical oxidation (ISCO) system. An optimized initial condition was obtained as 10 mg/L NOR, 0.3 mM TPP, 1 g/L ZVI and initial pH 7, and the US/ZVI/TPP system would effectively degrade NOR with relative low dosage of ZVI and ligand as well as broad pH work range 3–9. It was found that three ROS (OH, O2 and H2O2) instead of OH only would participate in the NOR degradation, while the in situ generation of H2O2 during the series of Fe-TPP reactions should be more critical. Fourteen organic intermediates and four inorganic products were detected during the NOR decomposition, suggesting that two main degradation pathways would occur under OH oxidation via cleavage of the piperazine ring and defluorination of the benzene ring, respectively. Finally, an integrated reaction mechanism in the US/ZVI/TPP system was proposed including solid-liquid interfacial iron corrosion as well as bulk homogenous oxygen activation and Fenton reactions, wherein US would play mechanically and chemically promotional roles. Besides, triple-repeated treatments suggested the relative long-term re-usage of ZVI particles and low effluent dissolved iron (<0.6 mg/L).  相似文献   

3.
The heterogeneous catalytic reaction of H2O2 with iron oxides is an important reaction for the environment since both H2O2 and iron oxides are common constituents of natural and atmospheric waters. In this work, three ferrihydrites, labeled Fh-1, -2 and -3, were prepared by different procedures. Fh-1 was prepared by adding alkali solution to ferric solution under stirring. In the preparation of Fh-2, the mixing procedure of the two solutions was reversed. Fh-3 was obtained by adding alkali solution and ferric solution simultaneously into a certain amount of water. The heterogeneous catalytic reaction of H2O2 with three ferrihydrites in aqueous solution was investigated in detail. The results demonstrated that the apparent reaction rate was affected by the preparation procedure of ferrihydrite besides pH, temperature and the dose of catalyst. The activation energy of the decomposition reaction of H2O2 was determined to be 76.13, 59.41 and 68.05 kJ mol?1 for Fh-1, -2 and -3, respectively. The activation enthalpy of the reaction were determined to be 73.59, 56.56 and 65.76 kJ mol-1 and the activation entropy of the reaction were determined to be ?69.65, ?119.67 and ?90.58 J mol?1 K?1, respectively.  相似文献   

4.
The study is about the degradation of a widely used pharmaceutical and personal care product-salicylic acid by sonocatalysis, and the experimental design of the reaction system. The first part of the study consists of sonication (572 kHz) in the presence of zero-valent iron (ZVI) with or without H2O2 to select and optimize the operational parameters as frequency, time, initial solute concentration, dose of reagents and pH. The second part consists of the use of response surface methodology and multiple regression to develop an experimental design modeland to assess the individual and interactive effects of pH, power (Po), ZVI dose and H2O2. The results showed that the optimal conditions predicted by the model without defining any restrictions are: pH = 2.0, Po = 120 W, ZVI = 24 mg L−1, which provide total salicyclic acid and 48% TOC decay. However, the prediction implies intensive consumption of energy and reagents, and must therefore be modified by restricting the value of TOC decay to a lower value and that of pH to a higher one. Cross-validation tests showed that the prediction accuracy of the model was considerably high with 5.0–9.4% deviation from the experimental data.  相似文献   

5.
This study synthesized Fe3O4 nanoparticles of 30–40 nm by a sonochemical method, and these particles were uniformly dispersed on the reduced graphene oxide sheets (Fe3O4/RGO). The superparamagnetic property of Fe3O4/RGO was evidenced from a saturated magnetization of 30 emu/g tested by a sample-vibrating magnetometer. Based on the testing results, we proposed a mechanism of ultrasonic waves to explain the formation and dispersion of Fe3O4 nanoparticles on RGO. A biosensor was fabricated by modifying a glassy carbon electrode with the combination of Fe3O4/RGO and hemoglobin. The biosensor showed an excellent electrocatalytic reduction toward H2O2 at a wide, linear range from 4 × 10?6 to 1 × 10?3 M (R2 = 0.994) as examined by amperometry, and with a detection limit of 2 × 10?6 M. The high performance of H2O2 detection is attributed to the synergistic effect of the combination of Fe3O4 nanoparticles and RGO, promoting the electron transfer between the peroxide and electrode surface.  相似文献   

6.
Sonocatalytic performance of pyrite nanoparticles was evaluated by the degradation of sulfasalazine (SSZ). Pyrite nanoparticles were produced via a high energy mechanical ball milling (MBM) in different processing time from 2 h to 6 h, in the constant milling speed of 320 rpm. X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX), Fourier transform infrared spectroscopy (FT-IR) analysis and Brunauer–Emmett–Teller (BET) confirmed the production of pyrite nanoparticles during 6 h of ball milling with the average size distribution of 20–80 nm. The effects of various operational parameters including pH value, catalyst amount (mg/L), SSZ concentration (mg/L), ultrasonic frequency (kHz) and reaction time on the SSZ removal efficiency were examined. The obtained results showed that the maximum removal efficiency of 97.00% was obtained at pH value of 4, catalyst dosage of 0.5 g/L, SSZ concentration of 10 mg/L and reaction time of 30 min. Experimental results demonstrated that the kinetic of the degradation process can be demonstrated using Langmuir–Hinshelwood (L-H) kinetic model. The effect of different inorganic ions such as Cl, CO32− and SO42− was investigated on the L-H reaction rate (kr) and adsorption (Ks) constants. Results showed that the presence of the mentioned ions significantly influenced the L-H constants. The impact of ethanol as a OH radical scavenger and some enhancers including H2O2 and K2S2O8 was investigated on the SSZ removal efficiency. Accordingly, the presence of ethanol suppressed SSZ degradation due to the quenching of OH radicals and the addition of K2S2O8 and H2O2 increased the SSZ removal efficiency, due to the formation of SO4 and additional OH radicals, respectively. Under the identical conditions of operating parameters, pyrite nanoparticles maintained their catalytic activity during four consecutive runs.  相似文献   

7.
The paper presents the synthesis and catalytic activity of CuFe2O4 nanoparticles. The CuFe2O4 nanoparticles have been prepared by sonochemical route under low power ultrasonic irradiation (UI) and using silent stirring at room temperature only (ST) along with co-precipitation method, without using any additive/capping agent. The synthesized magnetic nanoparticles were successfully used and compared for the synthesis of 4H-chromene-3-carbonitrile derivatives. The CuFe2O4 nanoparticles obtained by sonochemical route exhibit higher catalytic activity because of small size (0.5–5 nm), high surface area (214.55 m2/g), high thermal stability up to 700 °C, recyclability and reusability due to its magnetic characteristics than CuFe2O4 nanoparticles obtained by room temperature silent stirring. The synthesized CuFe2O4 nanoparticles were characterized by FT-IR, SEM–EDX, HR-TEM, XRD, TGA/DTA/DTG, BET, VSM techniques. The present method is of great interest due to its salient features such as environmentally compatible, efficient, short reaction time, chemoselectivity, high yield, cheap, moisture insensitive, green and recyclable catalyst which make it sustainable protocol.  相似文献   

8.
《Ultrasonics sonochemistry》2014,21(5):1787-1796
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).  相似文献   

9.
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   

10.
《Current Applied Physics》2010,10(2):708-714
A facile strategy for controlling sizes and stabilities of gold nanoparticles synthesized by aqueous reduction method was experimentally examined and reported. When pH of the solution of HAuCl4 and Na3C6H5O7 was controlled by introducing either NaOH or HCl with different concentration, the zeta potential of suspension of gold nanoparticles changed accordingly. With the strategy using a control of pH in a range of 5–9, the zeta potential of synthesized gold nanoparticles was regulated in a range of −60 to −40 mV, resulting in a stable red suspension of gold nanoparticles. Under a condition with pH < 5.0, gold nanoparticles could agglomerate after being kept quiescently for a day due to an adsorption of H+ on their surface, which in turn enhanced the attractive van der Waals interaction. On the other hand, synthesis of gold nanoparticles with pH > 9.1 would provide a lower amount of gold nanoparticles due to the formation of NaAuO2. Based on these results, a potential mechanism of gold nanoparticle synthesis was also discussed.  相似文献   

11.
Heterostructured CdS-pillared H2Ti3O7 nanohybrids were prepared by the self-assembly of exfoliated trititanate nanosheets and CdS nanosol particles under the electrostatic interactions. It was revealed that the present nanohybrids were mesoporous with specific surface areas of about 90 m2 g−1. The nanohybrids exhibited high photocatalytic activity and good recurrence stability in the H2 evolution from water splitting. When the preparation molar ratio of H2Ti3O7/CdS was 2:1, the nanohybrid reached a high H2-evolution rate of 1523 μmol h−1 g−1 under a 300 W Xe lamp irradiation, which was 13 times higher than the bare CdS. Apart from the wider spectral responsive range, the superior photocatalytic performance of the nanohybrids was predominantly attributed to the efficient photogenerated charge separation between the trititanate nanosheets and the encapsulated CdS nanoparticles.  相似文献   

12.
This report describes the detection and dosimetry of gamma ray emitted from Thallium-201 (201Tl) and Technetium-99m (99mTc) based on chemiluminescence technique. H2O2 produced by two gamma emitter radioisotopes of 201Tl and 99mTc were quantitatively measured by chemiluminescence method. Upon producing H2O2 in a luminol alkaline solution, in the presence of diperiodatocuprate, as catalyst a chemical reaction was accrued and consequently the emitted light was measured. The determined H2O2 concentration was correlated with the gamma ray detection and dosimetry. The sensitivity of chemiluminescence technique for 201Tl and 99mTc dosimetry was determined to be 0.20 and 0.08 MBq/l (Mega Becquerel per liter) respectively (R.S.D. = %5, N = 3). The plotted calibration curves showed detection limits of 3.24 and 1.76 MBq/l for 201Tl and 99mTc, respectively.  相似文献   

13.
Hydrogen peroxide (H2O2) and hydroperoxy (HO2) reactions present in the H2O2 thermal decomposition system are important in combustion kinetics. H2O2 thermal decomposition has been studied behind reflected shock waves using H2O and OH diagnostics in previous studies (Hong et al. (2009) [9] and Hong et al. (2010) [6,8]) to determine the rate constants of two major reactions: H2O2 + M  2OH + M (k1) and OH + H2O2  H2O + HO2 (k2). With the addition of a third diagnostic for HO2 at 227 nm, the H2O2 thermal decomposition system can be comprehensively characterized for the first time. Specifically, the rate constants of two remaining major reactions in the system, OH + HO2  H2O + O2 (k3) and HO2 + HO2  H2O2 + O2 (k4) can be determined with high-fidelity.No strong temperature dependency was found between 1072 and 1283 K for the rate constant of OH + HO2  H2O + O2, which can be expressed by the combination of two Arrhenius forms: k3 = 7.0 × 1012 exp(550/T) + 4.5 × 1014 exp(?5500/T) [cm3 mol?1 s?1]. The rate constants of reaction HO2 + HO2  H2O2 + O2 determined agree very well with those reported by Kappel et al. (2002) [5]; the recommendation therefore remains unchanged: k4 = 1.0 × 1014 exp(?5556/T) + 1.9 × 1011+exp(709/T) [cm3 mol?1 s?1]. All the tests were performed near 1.7 atm.  相似文献   

14.
《Ultrasonics sonochemistry》2014,21(5):1629-1634
MnO2 was synthesized by sonochemical reduction of MnO4 in water under Ar atmosphere at 20 °C, where the effects of solution pH on the reduction of MnO4 were investigated. The obtained XRD results showed that poor crystallinity δ-MnO2 was formed at pH 2.2, 6.0 and 9.3. When solution pH was increased from 2.2 to 9.3, the morphologies of δ-MnO2 changed from aggregated sheet-like or needle-like structures to spherical nanoparticles and finally to cubic or polyhedron nanoparticles. After further irradiation, MnO2 was readily reduced to Mn2+. It was confirmed that H2O2 and H atoms formed in the sonolysis of water acted as reductants for both reduction for MnO4 to MnO2 and MnO2 to Mn2+. The optimum irradiation time for the effective synthesis of MnO2 was 13 min at pH 2.2, 9 min at pH 6.0, 8 min at pH 9.3, respectively.  相似文献   

15.
《Ultrasonics sonochemistry》2014,21(5):1881-1885
In this work, the decolorization of C.I. Reactive Blue 181 (RB181), an anthraquinone dye, by Ultrasound and Fe2+ H2O2 processes was investigated. The effects of operating parameters, such as Fe2+ dosage, H2O2 dosage, pH value, reaction time and temperature were examined. Process optimisation [pH, ferrous ion (Fe2+), hydrogen peroxide (H2O2), and reaction time], kinetic studies and their comparison were carried out for both of the processes. The Sono-Fenton process was performed by indirect sonication in an ultrasonic water bath, which was operated at a fixed 35-kHz frequency. The optimum conditions were determined as [Fe2+] = 30 mg/L, [H2O2] = 50 mg/L and pH = 3 for the Fenton process and [Fe2+] = 10 mg/L, [H2O2] = 40 mg/L and pH = 3 for the Sono-Fenton process. The colour removals were 88% and 93.5% by the Fenton and Sono-Fenton processes, respectively. The highest decolorization was achieved by the Sono-Fenton process because of the production of some oxidising agents as a result of sonication. The paper also discussed kinetic parameters. The decolorization kinetic of RB181 followed pseudo-second-order reaction (Fenton study) and Behnajady kinetics (Sono-Fenton study).  相似文献   

16.
《Solid State Ionics》2006,177(26-32):2407-2411
Electrical conduction of Sr-doped LaP3O9 ([Sr]/{[La] + [Sr]} = 2–10 mol%) was investigated under 0.4–5 kPa of p(H2O) and 0.01–100 kPa of p(O2) or 0.3–3 kPa of p(H2) at 573–973 K. Sr-doped LaP3O9 showed apparent H/D isotope effect on conductivity regardless of the Sr-doping level under both H2O/O2 oxidizing and H2/H2O reducing conditions at investigated temperatures. Conductivities of the material were almost independent of p(O2) and p(H2O). These results demonstrated that the Sr-doped LaP3O9 exhibited protonic conduction under wide ranges of p(O2), p(H2O) and temperature. The conductivity of the Sr-doped LaP3O9 increased with increasing Sr concentration up to its solubility limit, ca. 3 mol%, while the further Sr-doping slightly degraded the conductivity. These indicate that Sr2+ substitution for La3+ leads to proton dissolution into the material and induced protonic conduction. Conductivities of the 3 mol% Sr-doped sample were 2 × 10- 6–5 × 10 4 S cm 1 at 573–973 K.  相似文献   

17.
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   

18.
Fe3O4/hydroxyapatite/graphene quantum dots (Fe3O4/HAP/GQDs) nanocomposite was synthesized and used as a novel magnetic adsorbent. This nanocomposite was characterized using scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, and magnetization property. The Fe3O4/HAP/GQDs was applied to pre-concentrate copper residues in Thai food ingredients (so-called “Tom Yum Kung”) prior to determination by inductively coupled plasma-atomic emission spectrometry. Based on ultrasound-assisted extraction optimization, various parameters affecting the magnetic solid-phase extraction, such as solution pH, amount of magnetic nanoparticles, adsorption and desorption time, and type of elution solvent and its concentration were evaluated. Under optimal conditions, the linear range was 0.05–1500 ng mL−1 (R2 > 0.999), limit of detection was 0.58 ng mL−1, and limit of quantification was 1.94 ng mL−1. The precision, expressed as the relative standard deviation of the calibration curve slope (n = 5), for intra-day and inter-day analyses was 0.87% and 4.47%, respectively. The recovery study of Cu for real samples was ranged between 83.5% and 104.8%. This approach gave the enrichment factor of 39.2, which guarantees trace analysis of Cu residues. Therefore, Fe3O4/HAP/GQDs can be a potential and suitable candidate for the pre-concentration and separation of Cu from food samples. It can easily be reused after treatment with deionized water.  相似文献   

19.
Fe3O4 magnetic nanoparticles (Fe3O4 MNPs) with much improved peroxidase-like activity were successfully prepared through an advanced reverse co-precipitation method under the assistance of ultrasound irradiation. The characterizations with XRD, BET and SEM indicated that the ultrasound irradiation in the preparation induced the production of Fe3O4 MNPs possessing smaller particle sizes (16.5 nm), greater BET surface area (82.5 m2 g?1) and much higher dispersibility in water. The particle sizes, BET surface area, chemical composition and then catalytic property of the Fe3O4 MNPs could be tailored by adjusting the initial concentration of ammonia water and the molar ratio of Fe2+/Fe3+ during the preparation process. The H2O2-activating ability of Fe3O4 MNPs was evaluated by using Rhodamine B (RhB) as a model compound of organic pollutants to be degraded. At pH 5.4 and temperature 40 °C, the sonochemically synthesized Fe3O4 MNPs were observed to be able to activate H2O2 and remove ca. 90% of RhB (0.02 mmol L?1) in 60 min with a apparent rate constant of 0.034 min?1 for the RhB degradation, being 12.6 folds of that (0.0027 min?1) over the Fe3O4 MNPs prepared via a conventional reverse co-precipitation method. The mechanisms of the peroxidase-like catalysis with Fe3O4 MNPs were discussed to develop more efficient novel catalysts.  相似文献   

20.
Hierarchical structured Co-doped SnO2 nanoparticles are prepared by a low temperature hydrothermal process. The structural and surface morphologies of the SnO2 and Sn1?xCoxO2 nanoparticles are studied by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The Sn1?xCoxO2 nanoparticles form with a tetragonal rutile structure during the hydrothermal process without further calcination. The pseudocapacitance behavior of the Sn1?xCoxO2 nanoparticles is characterized by cyclic voltammetry (CV) in 1.0 M H2SO4 electrolyte. The specific capacitance (SC) is found to increase with an increase in cobalt content. A maximum SC of 840 F g?1 is obtained for a Sn0.96Co0.04O2 composite at a 10 mV s?1 scan rate.  相似文献   

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