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1.
Zerovalent iron (ZVI) has drawn intense interest as an effective and inexpensive tool to enhance degradation of various environmental contaminants. Reduction of Cr(VI) to Cr(III) by ZVI merits environmental concern as a hazardous species is transformed into a non-hazardous one. Objectives of this research were to assess kinetics and capacity of Cr(VI) reduction by different sources of ZVIs, of which chemical parameters can base in situ application of ZVI to treat Cr(VI) contaminated water. Reduction kinetics were first-order and rapid showing that 50% of the initial Cr(VI) was reduced within 7.0 to 347 min depending on Cr(VI) concentration, temperature and ZVI source. The reduction rates were increased with decreasing the initial Cr(VI) concentrations and increasing the reaction temperatures. The J ZVI (Shinyo Pure Chemical Co., Japan) was more effective in Cr(VI) reduction than PU (Peerless Metal Powders, USA). The maximum reduction capacities of J and PU ZVIs at 25°C were 0.045 and 0.042 mmol g−1 Fe0, respectively. A relatively higher value of the net reaction energy (E a ) indicated that Cr(VI) reduction by ZVI was temperature dependent and controlled by surface properties of ZVI. Chemical parameters involved in the Cr(VI) reduction by ZVI such as temperature quotient, kinetic rates, and stoichiometry indicated that the ZVI might be effective for in situ treatment of the Cr(VI) containing wastewater.  相似文献   

2.
《分离科学与技术》2012,47(2):290-299
A novel adsorbent: Fe2+-modified vermiculite was prepared in a two-step reaction. Adsorption experiments were carried out as a function of pH, contact time, and concentration of Cr(VI). It was found that Fe2+-modified vermiculite was particularly effective for the removal of Cr(VI) at pH 1.0. The adsorption of Cr(VI) reached equilibrium within 60 min, and the pseudo-second-order kinetic model best described the adsorption kinetics. The adsorption data follow the Langmuir model more than the Freundlich model. At pH 1.0, the maximum Cr(VI) sorption capacity (Q max ) was 87.72 mg · g?1. Desorption of Cr(VI) from Fe2+-modified vermiculite using NaOH treatment exhibited a higher desorption efficiency by more than 80%. The sorption mechanisms including electrostatic interaction and reduction were involved in the Cr (VI) removal. The results showed that Fe2+-modified vermiculite can be used as a new adsorbent for Cr(VI) removal which has a higher adsorption capacity and a faster adsorption rate.  相似文献   

3.
This work experimentally investigates Cr(VI) reduction to Cr(III) using waste scrap iron in the form of zerovalent iron (ZVI) collected from the mechanical workshop of the Institute, both in batch and continuous operation. The reduction of Cr(VI) to Cr(III) was found to be complete (~100%) depending on the experimental conditions. Lower pH values favour Cr(VI) reduction. Two concurrent reactions take place, that is reduction of Cr(VI) by Fe0 (ZVI) and by Fe2+ generated due to H+ corrosion of iron. Maximum around 22%, 11% and 2% Cr(III) remained dissolved in solution while the experiments were carried out at initial pH of 2, 4.67 and 7. Higher ZVI loading increases Cr(VI) reduction rate, however, consumption of iron is noted to be higher. The results indicate that the bed is exhausted rapidly at higher pH, initial Cr(VI) concentration and flow rate. This is attributable to predominance passivation of ZVI surface forming Cr(III)–Fe(III)‐oxide layer. SEM analysis of ZVI before and after the experiments confirms formation of passive oxide on iron surface is responsible for deterioration of Cr(VI) reduction efficiency due to its blanketing effect.  相似文献   

4.
The development of visible-light photocatalysts with desirable material characteristics and efficient performance is an existing challenge for photocatalysis community. Herein, we report on the synthesis of silver nanoparticles (AgNPs) modified porous silicon (PSi) nanopowder and its effective use in the photo-reduction of hexavalent chromium Cr(VI) to trivalent Cr(III) under direct visible light irradiation in the presence of citric acid. The PSi was prepared via simple stain etching of Si microparticles in HF/HNO3 aqueous solution, followed by the deposition of AgNPs onto PSi by the immersion plating technique. The developed photocatalyst composed of PSi with <20 nm mesoporous structure, decorated with crystalline 15-50 nm AgNPs. Photocatalytic experiments using unmodified Si microparticles, either PSi or sonicated one, indicated inactive catalytic behavior toward the photo-reduction of Cr(VI). Remarkable photo-reduction efficiency (97.4%) was achieved after 180 minutes irradiation using the AgNPs/PSi sample. The efficient photo-reduction capability of AgNPs/PSi photocatalyst is attributed to the enhanced separation between photo-generated electrons and holes (e-h+) enabling better utilization of light, as revealed from the photoluminescence measurement. Additionally, the presence of citric acid in solution promoted greatly the photo-reduction reaction as it acted as a hole scavenger, suppressing further the rate of e-h+ recombination through rapid consumption of photo-generated holes. Excellent reusability of the current photocatalyst was evidenced by performing cyclic five runs with minimal reactivity loss. Results of synthesis, characterization, photocatalytic activity and reaction mechanism are thoroughly addressed and discussed.  相似文献   

5.
The conventional chemical reduction of Cr(VI) to Cr(III) and subsequent Cr(OH)3 precipitation are expensive due to the use of large amounts of chemicals and the generation of chemical sludges. An attempt was carried out for microbial Cr(VI) removal in an anaerobic chemostat fed with an acetate-containing synthetic medium. With 26 mg Cr(VI) dm−3 in the influent, almost complete removal of Cr(VI) was achieved at dilution rates of 0·15 and 0·32 day−1 at 20°C and at 35°C, respectively. The optimum Cr(VI) mass loading and the specific Cr(VI) applied rates were found to be 5 mg Cr(VI) dm−3 day−1 and 0·02 mg Cr(VI) mg−1 VSS day−1, respectively. Either the influent Cr(VI) concentration or the dilution rate could be adjusted to maintain an efficient removal of Cr(VI) in a continuous operation. Since the Cr(VI)-reducing activity is associated with the biomass concentration in the system, recycling the effluent solids is essential for practical application. In a batch reactor with the biomass collected from the chemostat, NaAc degradation appeared to be proportional to Cr(VI) reduction with the ratio of 9 mg C mg−1 Cr(VI) at 35°C. As reactions proceeded, the oxidation–reduction potential correspondingly decreased and both pH and alkalinity increased. © 1997 SCI.  相似文献   

6.
Construction of heterojunctions with matching energy band structures between two semiconductors displays great potential in promoting the separation and transfer of photogenerated charge carriers and is one of the effective strategies for obtaining high active photocatalysts. In this study, a type-II heterojunction photocatalyst was designed and prepared using Bi2Fe4O9 (BFO) nanoparticles and hydrothermal-treated red phosphorus (HRP). The photocatalytic performance test exhibited that the 3%BFO/HRP composite photocatalyst with 3% mass fraction of BFO rapidly and efficiently photoreduced Cr(VI), and the reduction was completed within 25 min, with a rate constant of 0.15 min−1, which was 15 times higher than that of pure HRP. Further mechanistic investigation revealed that the photocatalytic activity was enhanced due to the tight heterojunction between BFO and HRP, thereby effectively promoting carrier transfer, destroying the carrier recombination, and reducing the charge-transfer resistance of composite catalyst. Mott–Schottky diagrams and UV-vis diffuse reflectance spectroscopy data indicated the theoretical feasibility of establishing a close contact between BFO and HRP. X-ray photoelectron spectroscopy provided evidence for the way in which interfacial charges were transferred. This work provides a new possibility to construct heterojunction photocatalysts for the rapid and efficient reduction of Cr(VI).  相似文献   

7.
Adherent polypyrrole films were electropolymerized from a tosylic acid solution onto an aluminium substrate and used for the reduction of Cr(VI). The reduction of Cr(VI) to the trivalent state was found to proceed by pseudo-first-order kinetics with an activation energy barrier of 15.13 kJ mol–1. This catalyst could be regenerated by reducing the composite at a sufficiently negative potential, in the absence of Cr(VI). However, it was found that the catalyst functioned also through a self-sustained regeneration mechanism. In this mechanism, Cr(VI) was reduced by PPy0 to generate PPy+, but the PPy+ was subsequently reduced to PPy0 by oxidation of the aluminium substrate, thus regeneration of the catalytic PPy0 surface giving rise to a synergistic action between the polypyrrole and the aluminium substrate.  相似文献   

8.
Hexavalent chromium (Cr(VI)) adsorption from aqueous solutions on magnetically modified multi-wall carbon nanotubes (M-MWCNT) and activated carbon (M-AC) was investigated. M-MWCNT and M-AC were prepared by co-precipitation method with Fe2+:Fe3+ salts as precursors. The magnetic adsorbents were characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA) and scanning electron microscope (SEM). The effects of amount of adsorbents, contact time, initial pH, temperature and the initial concentration of Cr(VI) solution were determined. The adsorption equilibrium, kinetics, thermodynamics and desorption of Cr(VI) were investigated. Equilibrium data fitted well with the Langmuir isotherm for both of the adsorbents. The theoretical adsorption capacities are 14.28 mg/g of M-MWCNT and 2.84 mg/g of M-AC. Cr(VI) adsorption kinetics was modeled with pseudo-second order model, intra-particle diffusion model and Bangham model. Thermodynamic parameters were calculated and ΔG°, ΔH° and ΔS° indicate that the adsorption of Cr(VI) onto M-MWCNT and M-AC was exothermic and spontaneous in nature. Results revealed that M-MWCNT is an easily separated effective adsorbent for Cr(VI) adsorption from aqueous solution.  相似文献   

9.
《Ceramics International》2020,46(8):12255-12268
In recent times cost-effective advanced materials with dual applications in photocatalytic water treatment and electrochemical sensing have been explored and developed. Herein we report facile solution combustion synthesis of ZnO/Fe2O3 (ZF) type-II heterojunction for electrochemical sensing of dopamine and visible assisted photocatalytic reduction of carcinogenic Cr(VI) into Cr(III). Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to evaluate the compatibility of the electrodes for DA sensing. Furthermore, DPV curves revealed that ZF2 (ZnO: Fe2O3- 3:0.5) modified GCEs possessed 0.27 μM and 0.7 μM of LOD and LOQ with good linear range from 3 μM to 30 μM. Overall, reproducibility and interference studies confirm the efficient use of material for DA sensing. The junction ZF2 shows best performance with 88% Cr(VI) photo-reduction under visible light in 90 min and 100% reduction with tartaric acid as sacrificial agent (utilizing holes) in just 45 min. The effect of sacrificial agents and scavengers suggest the photogenerated electrons were major active species followed by O2. The CB edges have enough potential for rapid reduction of hexavalent chromium under visible light and solar light. The photoluminescence and electrochemical impedance suggest lowered recombination, high charge separation and charge transfer capacity in the heterojunction. The transfer of electrons from conduction band of Fe2O3 to that of ZnO having high enough negative potential to reduce Cr(VI), thus utilizing the CB potential of wide band gap ZnO for rapid visible photocatalysis. In addition shortcomings as low conductivity Fe2O3 and high band gap of ZnO are both minimized in the junction. This study confirmed that popular semiconductors as ZnO and Fe2O3 have enough potential in dual role as electrochemical sensors and visible photocatalysts with best performance by optimizing the conditions and ratios.  相似文献   

10.
The photocatalytic reduction of Cr(VI) to the less toxic Cr(III) is presented in the presence of the polyoxometalates (POM) PW12O403− or SiW12O404− as photocatalyst and an organic substrate (salicylic acid or propan-2-ol) as electron donor. Cr(VI), as dichromate, is reduced to Cr(III), according to the 6:1 stoichiometry of PW12O404− versus Cr2O72− indicated from experiments in the dark. Increase of POM or salicylic acid (SA) concentration accelerates, till a saturation value, both the reduction of metal and the oxidation of the organic, suggesting that these two conjugate reactions act synergistically. The photocatalytic action of POM is not so important in the case of highly concentrated solutions of organics that exhibit direct photochemical reduction of Cr(VI), i.e. propan-2-ol (i-prOH), while it becomes important at low concentrations of i-prOH, especially for organics that do not react directly photochemically with Cr(VI), such as SA. Increase of Cr(VI) concentration enhances consumption of SA and Cr(VI) till an optimum value, due to inner filter effect. The method is suitable for a range of chromium concentration from 5–100 ppm achieving complete reduction of Cr(VI) to Cr(III) up to non-detected traces (>98%). The presence of oxygen does not influence the efficiency of SA and Cr(VI) consumption. In contrast to the semiconductor-based heterogeneous photocatalysis, the POM-based homogeneous process seems superior in the frame that: (i) it remains catalytic throughout illumination by providing more active sites and (ii) among the two POM used, the one that is more efficient in the degradation of the organic, that is PW12O403− compared to SiW12O404−, is also more efficient in reducing Cr(VI), due to a kinetic effect, and a compromise is not needed.  相似文献   

11.
MIL-53(Fe)/polyaniline (PANI) composite was prepared by in situ depositing PANI on the surface of MIL-53(Fe) and their catalytic performances on the simultaneous removal of RhB and Cr(VI) were investigated. The elimination efficiency of both RhB and Cr(VI) reached more than 98% under pH=2 where hydrochloric acid and citric acid were used to adjust the pH. The results indicated that MIL-53(Fe)/PANI revealed an obvious pH response to the degradation of RhB, while citric acid promoted the Cr(VI) photoreduction. UV-Vis spectra, EIS, and photocurrent response experiments showed that MIL-53(Fe)/PANI had a better light response and carrier migration ability than MIL-53(Fe). The transient absorption spectra also exhibited that the lifetimes of photo-generated carriers were prolonged after the conductive polymer deposition on the MIL-53(Fe) surface. Scavenger experiments demonstrated that the main active species were ·O2- and OH. Combined with activity evaluation results, and the possible photocatalytic mechanism of MIL-53(Fe)/PANI on RhB oxidation and Cr(VI) reduction was proposed. The addition of conductive polymer can effectively improve the light response of the catalyst under acidic conditions, and meanwhile citric acid also provided a new mediation for the synergistic degradation of multiple pollutants. Good activity and stability of the catalysts made the scale-up purification of acid water feasible under UV-Vis light.  相似文献   

12.
Fe3O4 @C nano-adsorption was prepared by a simple one-step solvothermal synthesis method using Fe (NO3)3 、cyclodextrin as raw materials, meanwhile urea as an alkali source. The obtained samples were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, scanning electron microscopy, and Brunauer-Emmett-Teller. The adsorption behavior of the Fe3O4@C toward Cr (VI) and Congo red was also studied. The core-shell structure Fe3O4@C exhibited large specific surface area of 112.91?m2 g?1. The prepared Fe3O4@C samples demonstrated typical ferromagnetic behavior and high removal capacity in removing the toxic Cr (VI) ions and organic pollutant CR from wastewater, together with facile magnetic separability and good recyclability. Equilibrium adsorption performance was conducted by using the Langmuir and Freundlich model and Freundlich model could simulate the adsorption process of Congo red and Cr (VI) better. The maximum adsorption capacity of Cr (VI) and Congo red was 33.35?mg?g?1 and 262.72?mg?g?1 by calculation.  相似文献   

13.
Palladised biomass of Desulfovibrio desulfuricans ATCC 29577 (bio‐Pd(0)) effected reduction of Cr(VI) to Cr(III) under conditions where biomass alone or chemically‐prepared Pd(0) were ineffective. Reduction of 500 µmol dm?3 Cr(VI) by 0.4 mg cm?3 bio‐Pd(0) (Pd : biomass ratio of 1:1) was achieved from 1 mol dm?3 formate/acetate buffer at pH 1–7 at room temperature; the optimum pH was 3.0. The ratio of mass of Pd : dry mass of biomass, and the need for finely ground bio‐Pd(0) were important parameters for optimal Cr(VI) reduction, with a ratio of 1:1 giving 100% reduction of 500 µmol dm?3 Cr(VI) within 6 h at room temperature, decreasing to 30 min following heat treatment of the Pd(0)‐loaded biomass. The reduced Cr was recovered quantitatively as soluble Cr(III) at pH 3.0 with no poisoning of the bioinorganic catalyst with respect to continued reduction of Cr(VI). © 2002 Society of Chemical Industry  相似文献   

14.
《分离科学与技术》2012,47(18):2900-2909
The goal of this work was to evaluate the effectiveness of iron and boron-doped-diamond (BDD) as cathodic electrodes on the reduction of Cr(VI) in synthetic and wastewater samples. The pH and electrolyte composition were varied, and the effect on the Cr(VI) reduction rate was measured. The optimized conditions from the synthetic water Cr(VI) reduction experimental data, were tasted on electroplating wastewater. The results indicated that both a pH of 2 and the use of NaCl as an electrolyte significantly increase the Cr(VI) reduction rate for all synthetic systems, especially the iron-BDD system. The Cr(VI) reduction rate in Fe-BDD systems was also affected by nitrate and sulfate ions. In the case of electroplating wastewater, Cr(VI) reduction by BDD cathodes was faster than with iron cathodes, achieving a complete reduction of 180 mg Cr(VI)/L in 25 min, with 40% less sludge produced. The elemental composition of sludge was analyzed using SEM/EDS and X-ray spectroscopy to confirm that iron and chromium precipitated out of the solution. The sludge had a chemical composition of (31.9%) Fe2O3, (29.6%) FeOOH, (21%) FeO, and (17.4%) FeSO4. Therefore, BDD as an electrode material effectively reduces Cr(VI) in electroplating wastewater, and can be effectively scaled up to industrial applications.  相似文献   

15.
Palladized biomass of Desulfovibrio vulgaris (Bio‐Pd(0)) reduced Cr(VI) to Cr(III) at an initial rate four‐fold higher than chemically‐prepared Pd(0) metal. Optimal Cr(VI) reduction by suspended Bio‐Pd(0) occurred at pH 3, whereas pH did not affect the rate of Cr(VI) reduction by Bio‐Pd(0) immobilized in agar beads. The rate of Cr(VI) reduction was concentration‐dependent below 300 µmol dm?3, and application of enzyme kinetics, considering Bio‐Pd(0) as an ‘artificial enzyme’, gave an apparent Km (Kmapp) of approx. 650 µmol dm?3 and Vmax of 1667 nmol h?1 mg Pd(0) for suspended Bio‐Pd(0). The potential of Bio‐Pd(0) as a method for the treatment of Cr(VI)‐wastes is discussed. Copyright © 2005 Society of Chemical Industry  相似文献   

16.
CeO2 powders were synthesized via a solution combustion method. The product was characterized by X-ray diffraction scanning electron microscope, and BET surface area analysis. The results indicated that the CeO2 powders present a foaming state with a surface area of 28.17 m2 g–1. The adsorption performance of the CeO2 powders was tested toward the removal of typical pollutants of Cr(VI) and Congo red (CR). The results showed that the adsorption of Cr(VI) and CR onto CeO2 powders followed the Langmuir isotherm model and pseudo-second-order kinetics, with an adsorption capacity of 5.69 mg g–1 and 35.51 mg g–1, respectively.  相似文献   

17.
Fe3O4 coated glycine doped polypyrrole magnetic nanocomposite (Fe3O4@gly-PPy NC) was prepared via coating of suspended Fe3O4 nanoparticles with gly-PPy. FE-SEM and HR-TEM images indicated that Fe3O4 nanoparticles were encapsulated by precipitating gly-PPy moieties. Chromium(VI) adsorption followed a Langmuir isotherm with maximum capacity of 238–303 mg/g for a temperature range of 25–45 °C at pH 2. The adsorption process was governed by the ionic interaction and the reduction of Cr(VI) to Cr(III) by the PPy moiety. Results showed that NCs are effective adsorbents for the removal of Cr(VI) from wastewater and can be separated by external magnetic field from the reactor.  相似文献   

18.
BACKGROUND: Hexavalent chromium (Cr(VI)) is toxic to humans, animals and plants. Conventional treatment technologies reduce Cr(VI) to the less toxic and mobile Cr(III), but these methods are usually expensive and generate secondary waste. Microbial Cr(VI) reduction has recently gained attention as a detoxification process, since it enables Cr(VI) reduction through relatively cheap and simple methods. The aim of this work was to investigate the mechanism and the performance of biological Cr(VI) reduction using mixed cultures originated from industrial sludge under continuous operation with recirculation in a pilot‐scale trickling filter. RESULTS: Biological Cr(VI) reduction was studied using a pilot‐scale trickling filter filled with plastic media under continuous operation with recirculation and the use of indigenous bacterial population. The effect of the organic carbon (electron donor) concentration was examined for constant Cr(VI) influent concentration at about 5.5 mg L?1 and volumetric flow rates ranging from 60 to 900 mL min?1. The highest reduction rate achieved was 1117 g Cr(VI) m?2 d?1 for a volumetric flow rate of 900 mL min?1. The system's reduction capacity was significantly affected by chromate loadings, resulting in frequent backwashing of the filter. The determination of the reduction mechanism was also studied using batch cultures of free suspended cells and culture supernatant. CONCLUSION: The high reduction rates combined with the low operating cost indicate that the above technology can be a viable solution for the treatment of industrial chromate effluents. Copyright © 2008 Society of Chemical Industry  相似文献   

19.
This work is aimed at obtaining and calibrating a dynamical model of the electrochemical reduction of Cr(VI) in a tubular continuous reactor with a spiral wire shaped anode at different conditions of pH (1.0 to 2.0) and residence times. An industrial wastewater sampled from a Mexican electroplating industry with about 1000 mg dm?3 of Cr(VI) was used for the experiments. It was found that pH exerts a strong influence on the performance of electrochemical reduction of Cr(VI). Thus at a wastewater influent pH = 1.0 and a residence time in the reactor of 38.5 min it is possible to reduce the Cr(VI) concentration from 1000 to 0.37 mg dm?3. However at an influent pH higher than 1.5, an effluent Cr(VI) concentration lower than 0.5 mg dm?3 cannot be obtained. A more complete dynamic model was applied incorporating pH and the dispersion effects that affect the electrochemical Cr(VI) removal. The model, which adequately describes the performance of the electrochemical process, can be used to optimize the performance of this kind of reactor with more reliability. Copyright © 2007 Society of Chemical Industry  相似文献   

20.
Poly(aniline-co-o-aminophenol) (PANOA)-modified glassy carbon electrode (GCE) was first used to investigate the electrocatalytic reduction of dichromate in a NaCl solution of pH 5.0. The results of cyclic voltammograms and UV–vis spectra demonstrated that the reduction of Cr(VI) occurred at PANOA-modified GCE. The FT-IR, ESR and XPS results showed that the Cr(VI) can be doped in the PANOA films and can convert to less-toxic Cr(III). The doping level Cr/N was 78.2% and trace amount of Cl (0.42%) was detected in the doped PANOA, which indicated that the doping process is effective and PANOA had rather good ion selectivity in the 0.10 M NaCl supporting electrolyte. The factors influenced the reduction were also considered. Various initial concentrations of Cr(VI) had different removal rates. The maximum removal rate of Cr(VI) at 20 mg L−1 (32.3%) was better than that of at 5 mg L−1 (22.9%). The solution pH had little effect on Cr(VI) reduction and doping process of the PANOA because PANOA had good electrochemical activity and stability in a wide range of pHs (from pH 4 to pH 8).  相似文献   

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