Diclofenac(DCF)is one of the most frequently detected pharmaceuticals in groundwater,posing a great threat to the environment and human health due to its toxicity.To mitigate the DCF contamination,experiments on DCF d...Diclofenac(DCF)is one of the most frequently detected pharmaceuticals in groundwater,posing a great threat to the environment and human health due to its toxicity.To mitigate the DCF contamination,experiments on DCF degradation by the combined process of zero-valent iron nanoparticles(nZVI)and nano calcium peroxide(nCaO_(2))were performed.A batch experiment was conducted to examine the influence of the adding dosages of both nZVI and nCaO_(2)nanoparticles and pH value on the DCF removal.In the meantime,the continuous-flow experiment was done to explore the sustainability of the DCF degradation by jointly adding nZVI/nCaO_(2)nanoparticles in the reaction system.The results show that the nZVI/nCaO_(2)can effectively remove the DCF in the batch test with only 0.05 g/L nZVI and 0.2 g/L nCaO_(2)added,resulting in a removal rate of greater than 90%in a 2-hour reaction with an initial pH of 5.The degradation rate of DCF was positively correlated with the dosage of nCaO_(2),and negatively correlated with both nZVI dosage and the initial pH value.The order of significance of the three factors is identified as pH value>nZVI dosage>nCaO_(2)dosage.In the continuous-flow reaction system,the DCF removal rates remained above 75%within 150 minutes at the pH of 5,with the applied dosages of 0.5 g/L for nZVI and 1.0 g/L for nCaO_(2).These results provide a theoretical basis for the nZVI/nCaO_(2)application to remove DCF in groundwater.展开更多
The present research investigated a novel route for the synthesis of nanoparticle zero-valent iron(NZVI)utilizing an aqueous extract of green tea waste as a reductant with ferric chloride.Also,the supported nanopartic...The present research investigated a novel route for the synthesis of nanoparticle zero-valent iron(NZVI)utilizing an aqueous extract of green tea waste as a reductant with ferric chloride.Also,the supported nanoparticle zerovalent iron was synthesized using natural silty clay as a support material(SC-NZVI).The NZVI and SC-NZVI were characterized by infrared spectroscopy(FTIR),scanning electron microscope(SEM),X-ray diffraction(XRD),Brunauer–Emmett–Teller(BET),and zeta potential(ζ).The interpretation of the results demonstrated that the polyphenol and other antioxidants in green tea waste can be used as reduction and capping agents in NZVI synthesis,with silty clay an adequate support.Additionally,the experiments were carried out to explore phenol adsorption by NZVI and SC-NZVI.To determine the optimum conditions,the impact of diverse experimental factors(i.e.,initial pH,adsorbent dose,temperature,and concentration of phenol)was studied.Langmuir,Freundlich,and Tempkin isotherms were used as representatives of adsorption equilibrium.The obtained results indicated that the adsorption processes for both NZVI and SC-NZVI well fitted by the Freundlich isotherm model.The appropriateness of pseudofirstorder and pseudosecondorder kinetics was investigated.The experimental kinetics data were good explained by the second-order model.The thermodynamic parameters(ΔH0,ΔS0,andΔG0)for NZVI and SC-NZVI were determined.The maximum removal rates of phenol at optimum conditions,when adsorbed onto NZVI and SC-NZVI,were found to be 94.8%and 90.1%,respectively.展开更多
In this study, novel core-shell SiO<sub>2</sub>-coated iron nanoparticles (SiO<sub>2</sub>-nZVI) were synthesized using a one-step Stoeber method. The Malachite green degradation abilities of t...In this study, novel core-shell SiO<sub>2</sub>-coated iron nanoparticles (SiO<sub>2</sub>-nZVI) were synthesized using a one-step Stoeber method. The Malachite green degradation abilities of the nanoparticles were investigated. The effects of ethanol/distilled water volume ratio, presence and absence of PEG, tetraethyl orthosilicate (TEOS) dosage, and hydrolysis time used in the nanoparticles preparation process were investigated. The results indicated that the SiO<sub>2</sub>-coated iron nanoparticles had the highest reduction activity when the particles synthesized with ethanol/H<sub>2</sub>O ratio of 2:1, PEG of 0.15 ml, TEOS of 0.5 ml and the reaction time was 4 h. The SiO<sub>2</sub>-nZVI nanoparticles were characterized using Transmission Electron Microscopy (TEM), Energy Dispersive Spectrometry (EDS) and powder X-Ray Diffraction (XRD). The results showed that the average particles diameter of the SiO<sub>2</sub>-nZVI was 20 - 30 nm. The thickness of the outside SiO<sub>2</sub> film is consistent and approximately 10 nm. The results indicated that the nanoparticles coated completely with a transparent SiO<sub>2</sub>-film. Such nanoparticles could have wide applications in dye decolorization.展开更多
This study addresses the synthesis of nanoscale zero-valent iron(n ZVI) in the presence of natural bentonite(B-n ZVI) using green tea extract. The natural bentonite and B-n ZVI were then applied for the removal of pho...This study addresses the synthesis of nanoscale zero-valent iron(n ZVI) in the presence of natural bentonite(B-n ZVI) using green tea extract. The natural bentonite and B-n ZVI were then applied for the removal of phosphorus from aqueous solutions at various concentrations, p H levels and contact time. The desorption of phosphorus(P) from adsorbents was done immediately after sorption at the maximum initial concentration using the successive dilution method. The characterization of FTIR, SEM, and XRD indicated that n ZVI was successfully loaded to the surface of natural bentonite. The sorption of phosphorus on B-n ZVI was observed to be p H-dependent, with maximum phosphorus removal occurring at the p H range of 2 to 5. The results demonstrate that the maximum sorption capacities of natural bentonite and B-n ZVI were 4.61 and 27.63 mg·g^(-1), respectively.Langmuir, Freundlich, and Redlich–Peterson models properly described the sorption isotherm data. For either adsorbent, desorption isotherms did not coincide with their corresponding sorption isotherms, suggesting the occurrence of irreversibility and hysteresis. The average percentages of retained phosphorus released from natural bentonite and B-n ZVI were 80% and 9%, respectively. The results indicated that sorption kinetics was best described by the pseudo-second-order model. The present study suggests that B-n ZVI could be used as a suitable adsorbent for the removal of phosphorus from aqueous solutions.展开更多
In this study, iron nano-particles were used to remediate malathion contaminated soil in the concentration range of 1 - 10 μg?g–1. The zero valent iron nano-particles were prepared by reducing ferric chloride soluti...In this study, iron nano-particles were used to remediate malathion contaminated soil in the concentration range of 1 - 10 μg?g–1. The zero valent iron nano-particles were prepared by reducing ferric chloride solution with sodium boro- hydride for remediation of the soil. The optimized quantity of iron nano particles was found to be 0.1 g?kg–1 of soil con- taminated with 10 μg?g–1 of malathion. Malathion was determined in the soil after leaching to water at pH 8.2 and fol- lowed by its oxidation with slight excess of N-bromosuccinimide (NBS). The unconsumed NBS was estimated by measuring the decrease in the color intensity of rhodamine B. Degradation product formed during the oxidation of ma-lathion by zero valent iron was monitored by the Attenuated Total Reflectance Fourier Transform Infrared Spectros- copy (ATR-FTIR). The results clearly showed that quantitative oxidation of malathion was achieved within eight min- utes after the addition of zero valent iron nano particles.展开更多
In this study, bimetallic nanoscale zero-valent iron particles（nZVI）, including copper/nanoscale zero-valent iron particles（Cu/nZVI） and nickel/nanoscale zero-valent iron particles（Ni/nZVI）, were synthesized by ...In this study, bimetallic nanoscale zero-valent iron particles（nZVI）, including copper/nanoscale zero-valent iron particles（Cu/nZVI） and nickel/nanoscale zero-valent iron particles（Ni/nZVI）, were synthesized by one-step liquid-phase reduction and applied for oxytetracycline（OTC） removal. The effects of contact time and initial p H on the removal efficiency were studied. The as-prepared nanoscale particles were characterized by scanning electron microscopy（SEM）, energy dispersive spectroscopy（EDS） and X-ray diffraction（XRD）. Finally, the degradation mechanisms of OTC utilizing the as-prepared nanoparticles were investigated by using X-ray photoelectron spectroscopy（XPS） and mass spectrometry（MS）. Cu/n ZVI presented remarkable ability for OTC degradation and removed71.44% of OTC（100 mg/L） in 4 hr, while only 62.34% and 31.05% of OTC was degraded by Ni/nZVI and nZVI respectively. XPS and MS analysis suggested that OTC was broken down to form small molecules by ·OH radicals generated from the corrosion of Fe0. Cu/nZVI and Ni/n ZVI have been proved to have potential as materials for application in OTC removal because of their significant degradation ability toward OTC.展开更多
Effects of nanoscale iron oxide particles on textural structure,reduction,carburization and catalytic behavior of precipitated iron catalyst in Fischer-Tropsch synthesis（FTS） are investigated.Nanostructured iron cat...Effects of nanoscale iron oxide particles on textural structure,reduction,carburization and catalytic behavior of precipitated iron catalyst in Fischer-Tropsch synthesis（FTS） are investigated.Nanostructured iron catalysts were prepared by microemulsion method in two series.Firstly,Fe2O3 ,CuO and La2O3 nanoparticles were prepared separately and were mixed to attain Fe/Cu/La nanostructured catalyst（sep-nano catalyst）;Secondly nanostructured catalyst was prepared by co-precipitation in a water-in-oil microemulsion method（mix-nano catalyst）.Also,conventional iron catalyst was prepared with common co-precipitation method.Structural characterizations of the catalysts were performed by TEM,XRD,H2 and CO-TPR tests.Particle size of iron oxides for sep-nano and mix-nano catalysts,which were determined by XRD pattern（Scherrer equation） and TEM images was about 20 and 21.6 nm,respectively.Catalyst evaluation was conducted in a fixed-bed stainless steel reactor and compared with conventional iron catalyst.The results revealed that FTS reaction increased while WGS reaction and olefin/paraffin ratio decreased in nanostructured iron catalysts.展开更多
Effects of nano-particle size on hydrocarbon production rates and distributions for precipitated Fe/Cu/La catalysts in Fischer-Tropsch synthesis were investigated.Nano-structured iron catalyst was prepared by micro-em...Effects of nano-particle size on hydrocarbon production rates and distributions for precipitated Fe/Cu/La catalysts in Fischer-Tropsch synthesis were investigated.Nano-structured iron catalyst was prepared by micro-emulsion method.The concept of two superimposed AndersonSchulz-Flory （ASF） distributions has been applied for the representation of the effects of reaction conditions and nano-particles size on kinetics parameters and product distributions.These results reveal that by reducing the particle size of catalyst,the break in ASF distributions was decreased.Also useful different kinetics equations for synthesis of C3 to C9 and C10 to C22 were determined by using α1 and α2 chain growth probabilities.展开更多
A nano-structured iron catalyst for syngas conversion to hydrocarbons in Fischer-Tropsch synthesis（FTS） was prepared by micro-emulsion method.Compositions of bulk iron phase and phase transformations of carbonaceous...A nano-structured iron catalyst for syngas conversion to hydrocarbons in Fischer-Tropsch synthesis（FTS） was prepared by micro-emulsion method.Compositions of bulk iron phase and phase transformations of carbonaceous species during catalyst deactivation in FTS reaction were characterized by temperature-programmed surface reaction with hydrogen（TPSR-H 2 ）,and XRD techniques.Many carbonaceous species on surface and bulk of the nano-structured iron catalysts were completely identified by combined TPSR-H 2 and XRD spectra and which were compared with those recorded on conventional co-precipitated iron catalyst.The results reveal that the catalyst deactivation results from the formation of inactive carbide phases and surface carbonaceous species like graphite,and it will be increased when the particle size of iron oxides was reduced in FTS iron catalyst.展开更多
Nitrobenzene has been considered as a significant groundwater contaminant due to its wide usage in explosives, insecticides, herbicides, pharmaceuticals and dyes. Nitrobenzene is of environmental concern because of it...Nitrobenzene has been considered as a significant groundwater contaminant due to its wide usage in explosives, insecticides, herbicides, pharmaceuticals and dyes. Nitrobenzene is of environmental concern because of its toxicity. In the presence of zero-valent iron （ZVI）, reduction of the nitro group is the dominant transformation process for nitrobenzene. A series of experiments were carried out to investigate the kinetics of nitrobenzene reduction by ZVI and the effects of pH and ZVI particle size on nitrobenzene removal in groundwater. The results indicated that nitrobenzene could be reduced to aniline by ZVI; the reduction of nitrobenzene by ZVI followed a pseudo first-order kinetics; the observed nitrobenzene reduction rate constant （k obs ） was 0.0006 min^-1 and the half-life of nitrobenzene （t 1/2 ） was 115.5 min; the mass balance achieved 87.5% for nitrobenzene reduction by the 1 mm ZVI particle and the final removal efficiency was 80.98%. In addition, the pH and ZVI particle size were found to exhibit significant influences on the nitrobenzene reduction. The observed nitrobenzene reduction rate constant linearly decreased with increase pH and the data fitted on polynomial regression equation for the observed nitrobenzene reduction rate constant and ZVI particle size. Therefore, use of ZVI based permeable reactive barrier technology to remedy nitrobenzene contaminated groundwater was feasible.展开更多
The addition of nano zero-valent iron(nZVI)is a promising technology for the in situ remediation of soil.Unfortunately,the mobility and,consequently,the reactivity of nZVI particles in contaminated areas decrease due ...The addition of nano zero-valent iron(nZVI)is a promising technology for the in situ remediation of soil.Unfortunately,the mobility and,consequently,the reactivity of nZVI particles in contaminated areas decrease due to their rapid aggregation.In this study,we determined how nZVI particles can be stabilized using different types of biochar(BC)as a support(BC@nZVI).In addition,we investigated the transport behavior of the synthesized BC@nZVI particles in a column filled with porous media and their effectiveness in the removal of BDE209(decabromodiphenyl ether)from soil.The characterization results of N2 Brunauer-Emmett-Teller(BET)surface area analyses,scanning electron microscopy(SEM),X-ray diffraction(XRD)and Fourier transform infrared spectroscopy(FTIR)indicated that nZVI was successfully loaded into the BC.The sedimentation test results and the experimental breakthrough curves indicated that all of the BC@nZVI composites manifested better stability and mobility than did the bare-nZVI particles,and the transport capacity of the particles increased with increasing flow velocity and porous medium size.Furthermore,the maximum concentrations of the column effluent for bagasse-BC@nZVI(B-BC@nZVI)were 19%,37%and 48%higher than those for rice straw-BC@nZVI(R-BC@nZVI),wood chips-BC@nZVI(W-BC@nZVI)and corn stalks-BC@nZVI(C-BC@nZVI),respectively.A similar order was found for the removal and debromination efficiency of decabromodiphenyl ether(BDE209)by the aforementioned particles.Overall,the attachment of nZVI particles to BC significantly increased the reactivity,stability and mobility of B-BC@nZVI yielded,and nZVI the best performance.展开更多
Arsenic(As)and antimony(Sb)are usually coexistent in mine wastes and pose a great threat to human health.The As immobilization by nano zero-valent iron(n ZVI)is promising,however,the stabilization for co-occurring As ...Arsenic(As)and antimony(Sb)are usually coexistent in mine wastes and pose a great threat to human health.The As immobilization by nano zero-valent iron(n ZVI)is promising,however,the stabilization for co-occurring As and Sb is not known.Herein,the immobilization and transformation of As and Sb in n ZVI-treated sediments were evaluated using complementary leaching experiments and characterization techniques.Raw sediment samples from a gold-antimony deposit revealed the co-existence of ultrahigh As and Sb at 50.3 and 14.9 g/kg,respectively.Leaching results show that As was more efficiently stabilized by n ZVI than Sb,which was primarily due to the soluble fraction that was readily absorbed by n ZVI of As was higher.As the n ZVI treatment proceeds,the oxidation and reduction of As and Sb occur simultaneously as evidenced by XPS analysis.The primary oxidant,hydroxyl radicals,was detected by EPR studies,proving the occurrence of n ZVI induced Fenton reaction.This study sheds light on differences in the interaction and immobilization of n ZVI with Sb and As in co-contaminated sediments.展开更多
The aim of this work is to optimize iron nanoparticle production in stirred tank reactors equipped with two classical impellers:Rushton and four-pitched blade turbines,which are largely used in batch industrial synthe...The aim of this work is to optimize iron nanoparticle production in stirred tank reactors equipped with two classical impellers:Rushton and four-pitched blade turbines,which are largely used in batch industrial synthesis and efficient scale-up.The main operative parameters of nanoparticle synthesis are the precursor initial concentration,reducing agent/precursor molar ratio,impeller-tank clearance,and impeller rotational velocity.These parameters were varied during the synthesis to find the optimal operating values based on the Fe(0)(%)production,zeta potential,particle size distribution,and powder X-ray diffraction pattern obtained.We found that the optimal operating conditions for nanoparticle production were an impeller velocity of 1500 rpm,initial iron precursor concentration of 20 mM,molar ratio of reducing agent to iron precursor of 3 mol/mol,and impeller clearance of 0.25 and 0.4 times the vessel diameter for Rushton and four-pitched blade impellers,respectively.Setting these conditions achieved a total conversion of 0.94-0.98 and yielded a product with a unimodal size distribution and average diameters in the range 30-50 nm.The computational fluid dynamics results agreed with the expectations,and the obtained mixing Damkohler numbers show that the process is mixed controlled.展开更多
Nitroaromatic explosives are major pollutants produced during wars that cause serious environmental and health problems. The removal of a typical nitroaromatic explosive, 2,4,6-trinitrotoluene(TNT), from aqueous solut...Nitroaromatic explosives are major pollutants produced during wars that cause serious environmental and health problems. The removal of a typical nitroaromatic explosive, 2,4,6-trinitrotoluene(TNT), from aqueous solution, was conducted using a new recyclable magnetic nano-adsorbent(Fe@SiO_(2) –NH_(2)). This adsorbent was prepared by grafting amino groups onto Fe@SiO_(2) particles with a well-defined core-shell structure and demonstrated monodispersity in solution. The removal performance of the nano-adsorbent towards TNT was found to be 2.57 and 4.92 times higher than that towards two analogous explosives, 2,4-dinitrotoluene(2,4-DNT) and 2-nitrotoluene(2-NT), respectively, under neutral conditions. The difference in the removal performance among the three compounds was further compared in terms of the effects of different conditions(pH value, ionic strength, humic acid concentration, adsorbent modification degree and dosage, etc.) and the electrostatic potential distributions of the three compounds. The most significant elevation is owing to modification of amino on Fe@SiO_(2) which made a 20.7% increase in adsorption efficiency of TNT. The experimental data were well fit by the pseudo-second-order kinetic model and the Freundlich adsorption isotherm model, indicating multilayer adsorption on a heterogeneous surface. The experimental results and theoretical considerations show that the interactions between Fe@SiO_(2) –NH_(2) NPs and TNT correspond to dipole-dipole and hydrophobic interactions. These interactions should be considered in the design of an adsorbent. Furthermore, the adaptability to aqueous environment and excellent regeneration capacity of Fe@SiO_(2) –NH_(2) NPs makes these remediation materials promising for applications.展开更多
基金the National Natural Science Foundation of China(42077176,41601514)Shanghai“Science and Technology Innovation Action Plan”Project(19230742400,19ZR1459300)+1 种基金Shanghai Peak Discipline Project(0200121005/053,2019010202)State Key Laboratory of Petroleum Pollution Control(PPC2016019)。
文摘Diclofenac(DCF)is one of the most frequently detected pharmaceuticals in groundwater,posing a great threat to the environment and human health due to its toxicity.To mitigate the DCF contamination,experiments on DCF degradation by the combined process of zero-valent iron nanoparticles(nZVI)and nano calcium peroxide(nCaO_(2))were performed.A batch experiment was conducted to examine the influence of the adding dosages of both nZVI and nCaO_(2)nanoparticles and pH value on the DCF removal.In the meantime,the continuous-flow experiment was done to explore the sustainability of the DCF degradation by jointly adding nZVI/nCaO_(2)nanoparticles in the reaction system.The results show that the nZVI/nCaO_(2)can effectively remove the DCF in the batch test with only 0.05 g/L nZVI and 0.2 g/L nCaO_(2)added,resulting in a removal rate of greater than 90%in a 2-hour reaction with an initial pH of 5.The degradation rate of DCF was positively correlated with the dosage of nCaO_(2),and negatively correlated with both nZVI dosage and the initial pH value.The order of significance of the three factors is identified as pH value>nZVI dosage>nCaO_(2)dosage.In the continuous-flow reaction system,the DCF removal rates remained above 75%within 150 minutes at the pH of 5,with the applied dosages of 0.5 g/L for nZVI and 1.0 g/L for nCaO_(2).These results provide a theoretical basis for the nZVI/nCaO_(2)application to remove DCF in groundwater.
文摘The present research investigated a novel route for the synthesis of nanoparticle zero-valent iron(NZVI)utilizing an aqueous extract of green tea waste as a reductant with ferric chloride.Also,the supported nanoparticle zerovalent iron was synthesized using natural silty clay as a support material(SC-NZVI).The NZVI and SC-NZVI were characterized by infrared spectroscopy(FTIR),scanning electron microscope(SEM),X-ray diffraction(XRD),Brunauer–Emmett–Teller(BET),and zeta potential(ζ).The interpretation of the results demonstrated that the polyphenol and other antioxidants in green tea waste can be used as reduction and capping agents in NZVI synthesis,with silty clay an adequate support.Additionally,the experiments were carried out to explore phenol adsorption by NZVI and SC-NZVI.To determine the optimum conditions,the impact of diverse experimental factors(i.e.,initial pH,adsorbent dose,temperature,and concentration of phenol)was studied.Langmuir,Freundlich,and Tempkin isotherms were used as representatives of adsorption equilibrium.The obtained results indicated that the adsorption processes for both NZVI and SC-NZVI well fitted by the Freundlich isotherm model.The appropriateness of pseudofirstorder and pseudosecondorder kinetics was investigated.The experimental kinetics data were good explained by the second-order model.The thermodynamic parameters(ΔH0,ΔS0,andΔG0)for NZVI and SC-NZVI were determined.The maximum removal rates of phenol at optimum conditions,when adsorbed onto NZVI and SC-NZVI,were found to be 94.8%and 90.1%,respectively.
文摘In this study, novel core-shell SiO<sub>2</sub>-coated iron nanoparticles (SiO<sub>2</sub>-nZVI) were synthesized using a one-step Stoeber method. The Malachite green degradation abilities of the nanoparticles were investigated. The effects of ethanol/distilled water volume ratio, presence and absence of PEG, tetraethyl orthosilicate (TEOS) dosage, and hydrolysis time used in the nanoparticles preparation process were investigated. The results indicated that the SiO<sub>2</sub>-coated iron nanoparticles had the highest reduction activity when the particles synthesized with ethanol/H<sub>2</sub>O ratio of 2:1, PEG of 0.15 ml, TEOS of 0.5 ml and the reaction time was 4 h. The SiO<sub>2</sub>-nZVI nanoparticles were characterized using Transmission Electron Microscopy (TEM), Energy Dispersive Spectrometry (EDS) and powder X-Ray Diffraction (XRD). The results showed that the average particles diameter of the SiO<sub>2</sub>-nZVI was 20 - 30 nm. The thickness of the outside SiO<sub>2</sub> film is consistent and approximately 10 nm. The results indicated that the nanoparticles coated completely with a transparent SiO<sub>2</sub>-film. Such nanoparticles could have wide applications in dye decolorization.
文摘This study addresses the synthesis of nanoscale zero-valent iron(n ZVI) in the presence of natural bentonite(B-n ZVI) using green tea extract. The natural bentonite and B-n ZVI were then applied for the removal of phosphorus from aqueous solutions at various concentrations, p H levels and contact time. The desorption of phosphorus(P) from adsorbents was done immediately after sorption at the maximum initial concentration using the successive dilution method. The characterization of FTIR, SEM, and XRD indicated that n ZVI was successfully loaded to the surface of natural bentonite. The sorption of phosphorus on B-n ZVI was observed to be p H-dependent, with maximum phosphorus removal occurring at the p H range of 2 to 5. The results demonstrate that the maximum sorption capacities of natural bentonite and B-n ZVI were 4.61 and 27.63 mg·g^(-1), respectively.Langmuir, Freundlich, and Redlich–Peterson models properly described the sorption isotherm data. For either adsorbent, desorption isotherms did not coincide with their corresponding sorption isotherms, suggesting the occurrence of irreversibility and hysteresis. The average percentages of retained phosphorus released from natural bentonite and B-n ZVI were 80% and 9%, respectively. The results indicated that sorption kinetics was best described by the pseudo-second-order model. The present study suggests that B-n ZVI could be used as a suitable adsorbent for the removal of phosphorus from aqueous solutions.
文摘In this study, iron nano-particles were used to remediate malathion contaminated soil in the concentration range of 1 - 10 μg?g–1. The zero valent iron nano-particles were prepared by reducing ferric chloride solution with sodium boro- hydride for remediation of the soil. The optimized quantity of iron nano particles was found to be 0.1 g?kg–1 of soil con- taminated with 10 μg?g–1 of malathion. Malathion was determined in the soil after leaching to water at pH 8.2 and fol- lowed by its oxidation with slight excess of N-bromosuccinimide (NBS). The unconsumed NBS was estimated by measuring the decrease in the color intensity of rhodamine B. Degradation product formed during the oxidation of ma-lathion by zero valent iron was monitored by the Attenuated Total Reflectance Fourier Transform Infrared Spectros- copy (ATR-FTIR). The results clearly showed that quantitative oxidation of malathion was achieved within eight min- utes after the addition of zero valent iron nano particles.
基金supported by grants from Tai Shan Scholar Foundation(No.ts 201511003)
文摘In this study, bimetallic nanoscale zero-valent iron particles（nZVI）, including copper/nanoscale zero-valent iron particles（Cu/nZVI） and nickel/nanoscale zero-valent iron particles（Ni/nZVI）, were synthesized by one-step liquid-phase reduction and applied for oxytetracycline（OTC） removal. The effects of contact time and initial p H on the removal efficiency were studied. The as-prepared nanoscale particles were characterized by scanning electron microscopy（SEM）, energy dispersive spectroscopy（EDS） and X-ray diffraction（XRD）. Finally, the degradation mechanisms of OTC utilizing the as-prepared nanoparticles were investigated by using X-ray photoelectron spectroscopy（XPS） and mass spectrometry（MS）. Cu/n ZVI presented remarkable ability for OTC degradation and removed71.44% of OTC（100 mg/L） in 4 hr, while only 62.34% and 31.05% of OTC was degraded by Ni/nZVI and nZVI respectively. XPS and MS analysis suggested that OTC was broken down to form small molecules by ·OH radicals generated from the corrosion of Fe0. Cu/nZVI and Ni/n ZVI have been proved to have potential as materials for application in OTC removal because of their significant degradation ability toward OTC.
文摘Effects of nanoscale iron oxide particles on textural structure,reduction,carburization and catalytic behavior of precipitated iron catalyst in Fischer-Tropsch synthesis（FTS） are investigated.Nanostructured iron catalysts were prepared by microemulsion method in two series.Firstly,Fe2O3 ,CuO and La2O3 nanoparticles were prepared separately and were mixed to attain Fe/Cu/La nanostructured catalyst（sep-nano catalyst）;Secondly nanostructured catalyst was prepared by co-precipitation in a water-in-oil microemulsion method（mix-nano catalyst）.Also,conventional iron catalyst was prepared with common co-precipitation method.Structural characterizations of the catalysts were performed by TEM,XRD,H2 and CO-TPR tests.Particle size of iron oxides for sep-nano and mix-nano catalysts,which were determined by XRD pattern（Scherrer equation） and TEM images was about 20 and 21.6 nm,respectively.Catalyst evaluation was conducted in a fixed-bed stainless steel reactor and compared with conventional iron catalyst.The results revealed that FTS reaction increased while WGS reaction and olefin/paraffin ratio decreased in nanostructured iron catalysts.
文摘Effects of nano-particle size on hydrocarbon production rates and distributions for precipitated Fe/Cu/La catalysts in Fischer-Tropsch synthesis were investigated.Nano-structured iron catalyst was prepared by micro-emulsion method.The concept of two superimposed AndersonSchulz-Flory （ASF） distributions has been applied for the representation of the effects of reaction conditions and nano-particles size on kinetics parameters and product distributions.These results reveal that by reducing the particle size of catalyst,the break in ASF distributions was decreased.Also useful different kinetics equations for synthesis of C3 to C9 and C10 to C22 were determined by using α1 and α2 chain growth probabilities.
文摘A nano-structured iron catalyst for syngas conversion to hydrocarbons in Fischer-Tropsch synthesis（FTS） was prepared by micro-emulsion method.Compositions of bulk iron phase and phase transformations of carbonaceous species during catalyst deactivation in FTS reaction were characterized by temperature-programmed surface reaction with hydrogen（TPSR-H 2 ）,and XRD techniques.Many carbonaceous species on surface and bulk of the nano-structured iron catalysts were completely identified by combined TPSR-H 2 and XRD spectra and which were compared with those recorded on conventional co-precipitated iron catalyst.The results reveal that the catalyst deactivation results from the formation of inactive carbide phases and surface carbonaceous species like graphite,and it will be increased when the particle size of iron oxides was reduced in FTS iron catalyst.
基金supported by the National High Technology Research and Development Program(863) of China(No.2007AA06A410)the Water Pollution Control and Management Project(No.2008ZX07207-007-05)the National Natural Science Foundation of China(No.40802055)
文摘Nitrobenzene has been considered as a significant groundwater contaminant due to its wide usage in explosives, insecticides, herbicides, pharmaceuticals and dyes. Nitrobenzene is of environmental concern because of its toxicity. In the presence of zero-valent iron （ZVI）, reduction of the nitro group is the dominant transformation process for nitrobenzene. A series of experiments were carried out to investigate the kinetics of nitrobenzene reduction by ZVI and the effects of pH and ZVI particle size on nitrobenzene removal in groundwater. The results indicated that nitrobenzene could be reduced to aniline by ZVI; the reduction of nitrobenzene by ZVI followed a pseudo first-order kinetics; the observed nitrobenzene reduction rate constant （k obs ） was 0.0006 min^-1 and the half-life of nitrobenzene （t 1/2 ） was 115.5 min; the mass balance achieved 87.5% for nitrobenzene reduction by the 1 mm ZVI particle and the final removal efficiency was 80.98%. In addition, the pH and ZVI particle size were found to exhibit significant influences on the nitrobenzene reduction. The observed nitrobenzene reduction rate constant linearly decreased with increase pH and the data fitted on polynomial regression equation for the observed nitrobenzene reduction rate constant and ZVI particle size. Therefore, use of ZVI based permeable reactive barrier technology to remedy nitrobenzene contaminated groundwater was feasible.
基金The National Key Research and Development Program of China(2018YFC1802802)the Guangdong Technology Research Center for Ecological Management and Remediation of Water Systems(2014B090904077).
文摘The addition of nano zero-valent iron(nZVI)is a promising technology for the in situ remediation of soil.Unfortunately,the mobility and,consequently,the reactivity of nZVI particles in contaminated areas decrease due to their rapid aggregation.In this study,we determined how nZVI particles can be stabilized using different types of biochar(BC)as a support(BC@nZVI).In addition,we investigated the transport behavior of the synthesized BC@nZVI particles in a column filled with porous media and their effectiveness in the removal of BDE209(decabromodiphenyl ether)from soil.The characterization results of N2 Brunauer-Emmett-Teller(BET)surface area analyses,scanning electron microscopy(SEM),X-ray diffraction(XRD)and Fourier transform infrared spectroscopy(FTIR)indicated that nZVI was successfully loaded into the BC.The sedimentation test results and the experimental breakthrough curves indicated that all of the BC@nZVI composites manifested better stability and mobility than did the bare-nZVI particles,and the transport capacity of the particles increased with increasing flow velocity and porous medium size.Furthermore,the maximum concentrations of the column effluent for bagasse-BC@nZVI(B-BC@nZVI)were 19%,37%and 48%higher than those for rice straw-BC@nZVI(R-BC@nZVI),wood chips-BC@nZVI(W-BC@nZVI)and corn stalks-BC@nZVI(C-BC@nZVI),respectively.A similar order was found for the removal and debromination efficiency of decabromodiphenyl ether(BDE209)by the aforementioned particles.Overall,the attachment of nZVI particles to BC significantly increased the reactivity,stability and mobility of B-BC@nZVI yielded,and nZVI the best performance.
基金financial This work was supported by the National Key Basic Research Program of China(No.2020YFC1807800)the National Natural Science Foundation of China(Nos,41877378 and 42077299)the Major Program of Shandong Natural Science Foundation,China(No.ZR2020ZD34)。
文摘Arsenic(As)and antimony(Sb)are usually coexistent in mine wastes and pose a great threat to human health.The As immobilization by nano zero-valent iron(n ZVI)is promising,however,the stabilization for co-occurring As and Sb is not known.Herein,the immobilization and transformation of As and Sb in n ZVI-treated sediments were evaluated using complementary leaching experiments and characterization techniques.Raw sediment samples from a gold-antimony deposit revealed the co-existence of ultrahigh As and Sb at 50.3 and 14.9 g/kg,respectively.Leaching results show that As was more efficiently stabilized by n ZVI than Sb,which was primarily due to the soluble fraction that was readily absorbed by n ZVI of As was higher.As the n ZVI treatment proceeds,the oxidation and reduction of As and Sb occur simultaneously as evidenced by XPS analysis.The primary oxidant,hydroxyl radicals,was detected by EPR studies,proving the occurrence of n ZVI induced Fenton reaction.This study sheds light on differences in the interaction and immobilization of n ZVI with Sb and As in co-contaminated sediments.
文摘The aim of this work is to optimize iron nanoparticle production in stirred tank reactors equipped with two classical impellers:Rushton and four-pitched blade turbines,which are largely used in batch industrial synthesis and efficient scale-up.The main operative parameters of nanoparticle synthesis are the precursor initial concentration,reducing agent/precursor molar ratio,impeller-tank clearance,and impeller rotational velocity.These parameters were varied during the synthesis to find the optimal operating values based on the Fe(0)(%)production,zeta potential,particle size distribution,and powder X-ray diffraction pattern obtained.We found that the optimal operating conditions for nanoparticle production were an impeller velocity of 1500 rpm,initial iron precursor concentration of 20 mM,molar ratio of reducing agent to iron precursor of 3 mol/mol,and impeller clearance of 0.25 and 0.4 times the vessel diameter for Rushton and four-pitched blade impellers,respectively.Setting these conditions achieved a total conversion of 0.94-0.98 and yielded a product with a unimodal size distribution and average diameters in the range 30-50 nm.The computational fluid dynamics results agreed with the expectations,and the obtained mixing Damkohler numbers show that the process is mixed controlled.
基金supported by the National Natural Science Foundation of China(No.21677177)the Science Foundation of China University of Petroleum-Beijing(No.2462020XKJS04)+1 种基金the Beijing Municipal Science&Technology Commission(No.Z181100005318002)the China Postdoctoral Science Foundation(No.2018M631491)。
文摘Nitroaromatic explosives are major pollutants produced during wars that cause serious environmental and health problems. The removal of a typical nitroaromatic explosive, 2,4,6-trinitrotoluene(TNT), from aqueous solution, was conducted using a new recyclable magnetic nano-adsorbent(Fe@SiO_(2) –NH_(2)). This adsorbent was prepared by grafting amino groups onto Fe@SiO_(2) particles with a well-defined core-shell structure and demonstrated monodispersity in solution. The removal performance of the nano-adsorbent towards TNT was found to be 2.57 and 4.92 times higher than that towards two analogous explosives, 2,4-dinitrotoluene(2,4-DNT) and 2-nitrotoluene(2-NT), respectively, under neutral conditions. The difference in the removal performance among the three compounds was further compared in terms of the effects of different conditions(pH value, ionic strength, humic acid concentration, adsorbent modification degree and dosage, etc.) and the electrostatic potential distributions of the three compounds. The most significant elevation is owing to modification of amino on Fe@SiO_(2) which made a 20.7% increase in adsorption efficiency of TNT. The experimental data were well fit by the pseudo-second-order kinetic model and the Freundlich adsorption isotherm model, indicating multilayer adsorption on a heterogeneous surface. The experimental results and theoretical considerations show that the interactions between Fe@SiO_(2) –NH_(2) NPs and TNT correspond to dipole-dipole and hydrophobic interactions. These interactions should be considered in the design of an adsorbent. Furthermore, the adaptability to aqueous environment and excellent regeneration capacity of Fe@SiO_(2) –NH_(2) NPs makes these remediation materials promising for applications.
