Nanoscale zero-valent iron particles(NZVI) produced by using green tea(GT) extract as a reductant can remove Cr(Ⅵ) from water effectively,which can be utilized in groundwater remediation.In order to define the reacti...Nanoscale zero-valent iron particles(NZVI) produced by using green tea(GT) extract as a reductant can remove Cr(Ⅵ) from water effectively,which can be utilized in groundwater remediation.In order to define the reaction mechanism and removal effect in the aquifer,in this study,GT-NZVI particles were prepared and measured by some characterization methods to define their surface performance,and then batch and one-dimensional experiments were carried out to reveal the reaction properties of GT-NZVI and Cr(Ⅵ) in groundwater.The results showed that the prepared GT-NZVI particles were regular spherical with a diameter of 10-20 nm,which could disperse in water stably.The main component of GT-NZVI wasα-Fe with superficial polyphenols as a stabilizer.GT-NZVI suspension had good ability to reduce the Cr(Ⅵ) to Cr(Ⅲ) in water.When the concentration of GT-NZVI was 1 g/L,the removal efficiency of Cr(Ⅵ)with an initial concentration of 100 mg/L reached 92.8% in 1 h reaction.In column tests,GT-NZVI passed through the natural sand column successfully with an average outflow percentage of 71.2%.The simulated in-situ reaction zone(IRZ) with GT-NZVI was used to remediate Cr(Ⅵ) contaminated groundwater.The oufflow concentration of Cr(Ⅵ) kept in 0.14-0.32 mg/L corresponding to the outflow rate below 0.32%within 15 days,and the removal efficiency of Cr(Ⅵ) by IRZ with GT-NZVI decreased with the increase of aquifer medium particle size,groundwater flow rate and ionic strength.Most of Cr(Ⅲ) as reduzate was adsorbed or immobilized on the surface or in the lattice of GT-NZVI,which indicated effective immobilization for chromium.展开更多
Considering the need for efficiently and rapidly treating oily wastewater while preventing secondary pollution,the nanoscale zero-valent iron(nZVI)was supported on biochar prepared by using a spent mushroom substrate(...Considering the need for efficiently and rapidly treating oily wastewater while preventing secondary pollution,the nanoscale zero-valent iron(nZVI)was supported on biochar prepared by using a spent mushroom substrate(SMS),to produce an iron-carbon composite(SMS-nZVI).The ability of the SMS-nZVI to treat wastewater containing high concentration of oil was then comprehensively evaluated.The morphology,structure,and other properties of the composite were characterized by using scanning electron microscopy,transmission electron microscopy,the Brunauer-Emmett-Teller nitrogen sorption analysis,and the Fourier transform infrared spectroscopy.The results show that the biochar prepared by using the SMS can effectively prevent the agglomeration of nZVI and increase the overall specific surface area,thereby enhancing the absorption of petroleum by the composite.Experiments reveal that compared with the SMS and nZVI,the SMS-nZVI composite removes petroleum faster and more efficiently from wastewater.Under optimized conditions involving an nZVI to biochar mass ratio of 1:5 and a pH value of 4,the efficiency for removal of petroleum from wastewater with an initial petroleum concentration of 1000 mg/L could reach 95%within 5 h.Based on a natural aging treatment involving exposure to air for 30 d,the SMS-nZVI composite retained an oil removal rate of higher than 62%,and this result could highlight its stability for practical applications.展开更多
As nitrobenzene(NB)is structurally stable and difficult to degrade due to the presence of an electron withdrawing group(nitro group).The sequential nanoscale zero valent iron-persulfate(NZVI-Na_(2)S_(2)O_(8))process w...As nitrobenzene(NB)is structurally stable and difficult to degrade due to the presence of an electron withdrawing group(nitro group).The sequential nanoscale zero valent iron-persulfate(NZVI-Na_(2)S_(2)O_(8))process was proposed in this study for the degradation NB-containing wastewater.The results showed that the NB degradation efficiency and the total organic carbon removal efficiency in the sequential NZVINa_(2)S_(2)O_(8)process were 100%and 49.25%,respectively,at a NB concentration of 200 mg L^(-1),a NZVI concentration of 0.75 g L^(-1),a Na_(2)S_(2)O_(8)concentration of 26.8 mmol L^(-1),an initial pH of 5,and a reaction time of 30 min,which were higher than those(88.53%and 35.24%,respectively)obtained in the NZVI/Na_(2)S_(2)O_(8)process.Sulfate radicals(SO_(4)·-)and hydroxyl radicals(·OH)generated in the reaction were identified directly by electron paramagnetic resonance spectroscopy and indirectly by radical capture experiments,and it was shown that both SO_(4)^(·-)and·OH played a major role in the sequential NZVI-Na_(2)S_(2)O_(8)process.The possible pathways involved in the reduction of NB to aniline(AN)and the further oxidative degradation of AN were determined by gas chromatography-mass spectrometry.展开更多
Knowledge on corrosion behaviors and kinetics of nanoscale zero-valent iron(nZVI)in aquatic environment is particularly significant for understanding the reactivity,longevity and stability of nZVI,as well as providing...Knowledge on corrosion behaviors and kinetics of nanoscale zero-valent iron(nZVI)in aquatic environment is particularly significant for understanding the reactivity,longevity and stability of nZVI,as well as providing theoretical guidance for developing a cost-effective nZVI-based technology and designing large-scale applications.Herein,this review gives a holistic overview on the corrosion behaviors and kinetics of nZVI in water.Firstly,Eh-pH diagram is introduced to predict the thermodynamics trend of iron corrosion.The morphological,structural,and compositional evolution of(modified-)nZVI under different environmental conditions,assisted with microscopic and spectroscopic evidence,is then summarized.Afterwards,common analytical methods and characterization technologies are categorized to establish time-resolved corrosion kinetics of nZVI in water.Specifically,stable models for calculating the corrosion rate constant of nZVI as well as electrochemical methods for monitoring the redox reaction are discussed,emphasizing their capabilities in studying the dynamic iron corrosion processes.Finally,in the future,more efforts are encouraged to study the corrosion behaviors of nZVI in long-term practical application and further build nanoparticles with precisely tailored properties.We expect that our work can deepen the understanding of the nZVI chemistry in aquatic environment.展开更多
To improve the adsorption and catalytic performance of heterogeneous Fenton-like catalysts for oil wastes,amino acids were used to modify nanoscale zero-valent iron(AA@Fe^(0)),which were applied in the Fenton-like deg...To improve the adsorption and catalytic performance of heterogeneous Fenton-like catalysts for oil wastes,amino acids were used to modify nanoscale zero-valent iron(AA@Fe^(0)),which were applied in the Fenton-like degradation of organic solvents(tributyl phosphate and n-dodecane,named TBP and DD).Twelve amino acids,i.e.,glycine(Gly),alanine(Ala),leucine(Leu),proline(Pro),phenylalanine(Phe),methionine(Met),cysteine(Cys),asparagine(Asn),serine(Ser),glutamic acid(Glu),lysine(Lys)and arginine(Arg),were selected and calculated by density functional theory(DFT).The optimized structure,charge distribution,the highest occupied molecular orbital(HOMO),the lowest unoccupied molecular orbital(LUMO),interaction region indicator(IRI)isosurface map and adsorption energy of AA@Fe^(0),AA@Fe^(0)-TBP and AA@Fe^(0)-DD were studied,which indicated that Fe is more likely to approach and charge transfer with-COO and-NH_(3) on theα-carbon of amino acids.There is strong attraction between Fe and–COO,and Van der Waals force between Fe and-NH_(3),respectively.In the interaction of AA@Fe^(0)with TBP and DD,Van der Waal force plays an important role.AA@Fe^(0)was synthesized in laboratory and characterized to investigate physicochemical properties.In Fenton-like degradation of organic solvents,the change of COD in water phase during the degradation process as well as the volume of the organic phase after the reaction were investigated.The results of calculations combined with experiments showed that Ser-modified Fe^(0)performed the best in these amino acids,with 98%removal of organic solvents.A possible catalytic mechanism was proposed in which amino acids acted a linking role between Fe and organic solvents,activating H_(2)O_(2)to generate hydroxyl radicals for the degradation of organic solvents.展开更多
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
Carbothermal reduction using biochar(BC)is a green and effective method of synthesizing BCsupported nanoscale zero-valent iron(nanoFe^(0))composites.However,the effect of BC surface area on the structure,distribution,...Carbothermal reduction using biochar(BC)is a green and effective method of synthesizing BCsupported nanoscale zero-valent iron(nanoFe^(0))composites.However,the effect of BC surface area on the structure,distribution,and performance such as the heavy metal uptake capacity of nanoFe^(0)particles remains unclear.Soybean stover-based BCs with different surface areas(1.7−1472 m^(2)/g)were prepared in this study.They have been used for in-situ synthesis BCs-supported nanoFe^(0)particlesthrough carbothermal reduction of ferrous chloride.The BCs-supported nanoFe^(0)particles were found to be covered with graphene shells and dispersed onto BC surfaces,forming the BC-supported graphene-encapsulated nanoFe^(0)(BC-G@Fe^(0))composite.These graphene shells covering the nanoFe^(0)particles were formed because of gaseous carbon evolved from biomass carbonization reacting with iron oxides/iron salts.Increasing BC surface area decreased the average diameters of nanoFe^(0)particles,indicating a higher BC surface area alleviated the aggregation of nanoFe^(0)particles,which resulted in higher heavy metal uptake capacity.At the optimized condition,BC-G@Fe^(0)composite exhibited uptake capacities of 124.4,121.8,254.5,and 48.0 mg/g for Cu^(2+),Pb^(2+),Ag^(+),and As^(3+),respectively(pH 5,25℃).Moreover,the BC-G@Fe^(0)composite also demonstrated high stability for Cu^(2+)removal from the fixed-bed continuous flow,in which 1 g of BC-G@Fe^(0)can work for 120 h in a 4 mg/L Cu^(2+)flow continually and clean 28.6 L Cu^(2+)contaminated water.Furthermore,the BC-G@Fe^(0)composite can effectively immobilize the bioavailable As^(3+)from the contaminated soil,i.e.,5%(w)of BC-G@Fe^(0)composite addition can immobilize up to 92.2%bioavailable As^(3+)from the contaminated soil.展开更多
Sodium citrate(SC)is a widely-used food and industrial additive with the properties of com-plexation and microbial degradation.In the present study,nano-zero-valent iron reaction system(SC-nZVI@BC)was successfully est...Sodium citrate(SC)is a widely-used food and industrial additive with the properties of com-plexation and microbial degradation.In the present study,nano-zero-valent iron reaction system(SC-nZVI@BC)was successfully established by modifying nanoscale zero-valent iron(nZVI)with SC and biochar(BC),and was employed to remove Cr(Ⅵ)from aqueous solu-tions.The nZVI,SC-nZVI and SC-nZVI@BC were characterized and compared using X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),thermogravimetric analy-ses(TGA),vibrating sample magnetometer(VSM),scanning electron microscope(SEM),X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS).The results showed that nZVI was successfully loaded on the biochar,and both the agglomeration and surface pas-sivation problems of nanoparticles were well resolved.The dosage of SC,C∶Fe,initial pH and Cr(Ⅵ)concentration demonstrated direct effects on the removal efficiency.The maximum Cr(Ⅵ)removal rate and the removal capacity within 60 min were 99.7%and 199.46 mg/g,respectively(C∶Fe was 1∶1,SC dosage was 1.12 mol.%,temperature was 25℃,pH=7,and the original concentration of Cr(Ⅵ)was 20 mg/L).The reaction confirmed to follow the pseudo-second-order reaction kinetics,and the order of the reaction rate constant k was as follows:SC-nZVI@BC>nZVI@BC>SC-nZVI>nZVI.In addition,the mechanism of Cr(Ⅵ)removal by SC-nZVI@BC mainly involved adsorption,reduction and co-precipitation,and the reduction of Cr(Ⅵ)to Cr(Ⅲ)by nano Fe0 played a vital role.Findings from the present study demon-strated that the SC-nZVI@BC exhibited excellent removal efficiency toward Cr(Ⅵ)with an improved synergistic characteristic by SC and BC.展开更多
Integrating nanoscale zero-valent iron(nZVI) with biological treatment processes holds the promise of inheriting significant advantages from both environmental nano-and biotechnologies. nZVI and microbes can perform i...Integrating nanoscale zero-valent iron(nZVI) with biological treatment processes holds the promise of inheriting significant advantages from both environmental nano-and biotechnologies. nZVI and microbes can perform in coalition in direct contact and act simultaneously, or be maintained in separate reactors and operated sequentially. Both modes can generate enhanced performance for wastewater treatment and environmental remediation. nZVI scavenges and eliminates toxic metals, and enhances biodegradability of some recalcitrant contaminants while bioprocesses serve to mineralize organic compounds and further remove impurities from wastewater. This has been demonstrated in a number of recent works that nZVI can substantially augment the performance of conventional biological treatment for wastewaters from textile and nonferrous metal industries. Our recent laboratory and field tests show that COD of the industrial effluents can be reduced to a record-low of 50 ppm. Recent literature on the theory and applications of the nZVI-bio system is highlighted in this mini review.展开更多
Pathogenic enteric viruses pose a significant risk to human health.Nanoscale zero-valent iron(nZVI),a novel material for environmental remediation,has been shown to be a promising tool for disinfection.However,the exi...Pathogenic enteric viruses pose a significant risk to human health.Nanoscale zero-valent iron(nZVI),a novel material for environmental remediation,has been shown to be a promising tool for disinfection.However,the existing research has typically utilized MS2 or f2 bacteriophages to investigate the antimicrobial properties of nZVI,and the resistance difference between bacteriophages,which is important for the application of disinfection technologies,is not yet understood.Here,MS2 and PhiX174 containing RNA and DNA,respectively,were used as model viruses to investigate the resistances to nZVI.The bacteriophage inactivation mechanisms were also discussed using TEM images,protein,and nucleic acid analysis.The results showed that an initial concentration of 10^(6)PFU/mL of MS2 could be completely inactivated within 240 min by 40 mg/L nZVI at pH 7,whereas the complete inactivation of PhiX174 could not be achieved by extending the reaction time,increasing the nZVI dosage,or changing the dosing means.This indicates that the resistance of phage PhiX174 to nZVI was much stronger than that of MS2.TEM images indicated that the viral particle shape was distorted,and the capsid shell was ruptured by nZVI.The damage to viral surface proteins in both phages was examined by three-dimensional fluorescence spectrum and sodium dodecyl sulfate polyacrylamide gel electrophoresis(SDS-PAGE).However,the nucleic acid analysis demonstrated that the nucleic acid of MS2,but not PhiX174,was destroyed.It indicated that bacteriophage inactivation was mainly attributed to the damage of nucleic acids.展开更多
Chlorophenols(CPs),as important contami-nants in groundwater,are toxic and difficult to biode-grade.Recentlynanoscalezero-valentironreceivedagreat deal of attention because of its excellent performance in treating rec...Chlorophenols(CPs),as important contami-nants in groundwater,are toxic and difficult to biode-grade.Recentlynanoscalezero-valentironreceivedagreat deal of attention because of its excellent performance in treating recalcitrant compounds.In this study,nanoscale zero-valent iron particles were prepared using chemical reduction,and the reductive transformations of three kinds of chlorinated phenols(2-CP,3-CP,and 4-CP)by nanoscale zero-valent iron under different conditions were investigated.The transformation process of the CPs was shown to be dechlorination first,then cleavage of the benzene ring.The removal efficiency of the CPs varied as follows:2-CP.3-CP.4-CP.The reactivity of CPs was associated with their energy of lowest unoccupied molecular orbit(E LUMO).With the increase in initial concentrations of CPs,removal efficiency decreased a little.But the quantities of CPs reduced increased evidently.Temperature had influence on not only the removal efficiency,but also the transformation pathway.At higher temperatures,dechlorination occurred prior to benzene ring cleavage.At lower temperatures,however,the oxidation product was formed more easily.展开更多
Biochar supported nano-scale zerovalent iron(nZVI/BC)for persulfate(PS)activation has been studied extensively for the degradation of pollutants on the lab scale,but it was rarely applied in practical soil remediation...Biochar supported nano-scale zerovalent iron(nZVI/BC)for persulfate(PS)activation has been studied extensively for the degradation of pollutants on the lab scale,but it was rarely applied in practical soil remediation in the field.In this research,we developed a facile ball-milling method for the mass production of nZVI/BC,which was successfully applied to activate persulfate for the remediation of organic polluted soil on an in-situ pilot scale.In-situ high-pressure injection device was developed to inject nZVI/BC suspension and PS solution into the soil with a depth of 0-70 cm.The removal efficiency of target pollutants such as 2-ethylnitrobenzene(ENB,1.47-1.56 mg/kg),biphenyl(BP,0.19-0.21 mg/kg),4-(methylsulfonyl)toluene(MST,0.32-0.43 mg/kg),and 4-phenylphenol(PP,1.70-2.46 mg/kg)at different soil depths was 99.7%,99.1%,99.9%and 99.7%,respectively,after 360 days of remediation.The application of nZVI/BC significantly increased the degradation rates of contaminants by 11-322%,ascribed to its relatively higher efficiency of free radical generation than that of control groups.In addition,it was found that nZVI/BC-PS inhibited soil urease and sucrase enzyme activities by 1-61%within 55 days due to the oxidative stress for microbes induced by free radicals,while these inhibition effects disappeared with remediation time prolonged(>127 days).Our research provides a useful implementation case of remediation with nZVI/BC-PS activation and verifies its feasibility in practical contaminated soil remediation.展开更多
Great efforts have been made to remove sulfur from fossil fuels to protect the environment.We proposed synthesis of high efficiency oxidation desulfurization(ODS)catalysts by encapsulating nano zero valent iron(nZVI)i...Great efforts have been made to remove sulfur from fossil fuels to protect the environment.We proposed synthesis of high efficiency oxidation desulfurization(ODS)catalysts by encapsulating nano zero valent iron(nZVI)in self-catalyzed carbon nanotubes.The synthetic strategy features facile hydrothermal and pyrolysis process.The specific surface area,pore structure,and microstructure of the catalysts were characterized by series techniques,and the catalytic ability was evaluated by the reduction of sulfur after oxidation and reflux-extraction.The optimized nZVI@CNT catalyst exhibits outstanding catalytic performance(within 120 min,the oxidative removal rate of DBT reached 96%)and enhanced stability(a 80%retention of initial performance after six cycles.),revealing the effective optimization and modulation between carbon nanotubes and iron particles.This excellent ODS activity originated from the defects of N-doped nanotubes as well as excellent particle dispersion and material transport capacity,which excites highly active free radicals with the assistance of H_(2)O_(2).In addition,the unique two-dimensional tube channel and mesoporous structure promoted the diffusion and transfer of reactants and electrons,leading to high density of active sites.The different experimental conditions confirmed that the material is a bifunctional catalyst integrating adsorption and catalysis.This work provides an creative ideas for the rational design and synthesis of advanced ODS catalysts for fuel oil.展开更多
基金the Open Project Program of Hebei Province Collaborative Innovation Center for Sustainable Utilization of Water Resources and Optimization of Industrial Structure(Grants Nos.XTZX202108)the National Key Research and Development Program of China(Grants Nos.2019YFC1805300)。
文摘Nanoscale zero-valent iron particles(NZVI) produced by using green tea(GT) extract as a reductant can remove Cr(Ⅵ) from water effectively,which can be utilized in groundwater remediation.In order to define the reaction mechanism and removal effect in the aquifer,in this study,GT-NZVI particles were prepared and measured by some characterization methods to define their surface performance,and then batch and one-dimensional experiments were carried out to reveal the reaction properties of GT-NZVI and Cr(Ⅵ) in groundwater.The results showed that the prepared GT-NZVI particles were regular spherical with a diameter of 10-20 nm,which could disperse in water stably.The main component of GT-NZVI wasα-Fe with superficial polyphenols as a stabilizer.GT-NZVI suspension had good ability to reduce the Cr(Ⅵ) to Cr(Ⅲ) in water.When the concentration of GT-NZVI was 1 g/L,the removal efficiency of Cr(Ⅵ)with an initial concentration of 100 mg/L reached 92.8% in 1 h reaction.In column tests,GT-NZVI passed through the natural sand column successfully with an average outflow percentage of 71.2%.The simulated in-situ reaction zone(IRZ) with GT-NZVI was used to remediate Cr(Ⅵ) contaminated groundwater.The oufflow concentration of Cr(Ⅵ) kept in 0.14-0.32 mg/L corresponding to the outflow rate below 0.32%within 15 days,and the removal efficiency of Cr(Ⅵ) by IRZ with GT-NZVI decreased with the increase of aquifer medium particle size,groundwater flow rate and ionic strength.Most of Cr(Ⅲ) as reduzate was adsorbed or immobilized on the surface or in the lattice of GT-NZVI,which indicated effective immobilization for chromium.
基金This study was supported by the State Key Laboratory of Petroleum and Petrochemical Contaminant Control and Treatment,the Open Project(Authorization:PPC2019021)the Research and Promotion Project of Key Technologies for Safety and Environmental Protection of CNPC(2017D-4013)the PetroChina Technology Innovation Fund Research Project(Authorization:2017D-5007-0601,2018D-5007-0605).
文摘Considering the need for efficiently and rapidly treating oily wastewater while preventing secondary pollution,the nanoscale zero-valent iron(nZVI)was supported on biochar prepared by using a spent mushroom substrate(SMS),to produce an iron-carbon composite(SMS-nZVI).The ability of the SMS-nZVI to treat wastewater containing high concentration of oil was then comprehensively evaluated.The morphology,structure,and other properties of the composite were characterized by using scanning electron microscopy,transmission electron microscopy,the Brunauer-Emmett-Teller nitrogen sorption analysis,and the Fourier transform infrared spectroscopy.The results show that the biochar prepared by using the SMS can effectively prevent the agglomeration of nZVI and increase the overall specific surface area,thereby enhancing the absorption of petroleum by the composite.Experiments reveal that compared with the SMS and nZVI,the SMS-nZVI composite removes petroleum faster and more efficiently from wastewater.Under optimized conditions involving an nZVI to biochar mass ratio of 1:5 and a pH value of 4,the efficiency for removal of petroleum from wastewater with an initial petroleum concentration of 1000 mg/L could reach 95%within 5 h.Based on a natural aging treatment involving exposure to air for 30 d,the SMS-nZVI composite retained an oil removal rate of higher than 62%,and this result could highlight its stability for practical applications.
基金supported by the Specialized Research Fund for Sanjin Scholars Program of Shanxi Province(201707)Key Research and Development Plan of Shanxi Province(201903D321059)Shanxi Scholarship Council of China(HGKY2019071)。
文摘As nitrobenzene(NB)is structurally stable and difficult to degrade due to the presence of an electron withdrawing group(nitro group).The sequential nanoscale zero valent iron-persulfate(NZVI-Na_(2)S_(2)O_(8))process was proposed in this study for the degradation NB-containing wastewater.The results showed that the NB degradation efficiency and the total organic carbon removal efficiency in the sequential NZVINa_(2)S_(2)O_(8)process were 100%and 49.25%,respectively,at a NB concentration of 200 mg L^(-1),a NZVI concentration of 0.75 g L^(-1),a Na_(2)S_(2)O_(8)concentration of 26.8 mmol L^(-1),an initial pH of 5,and a reaction time of 30 min,which were higher than those(88.53%and 35.24%,respectively)obtained in the NZVI/Na_(2)S_(2)O_(8)process.Sulfate radicals(SO_(4)·-)and hydroxyl radicals(·OH)generated in the reaction were identified directly by electron paramagnetic resonance spectroscopy and indirectly by radical capture experiments,and it was shown that both SO_(4)^(·-)and·OH played a major role in the sequential NZVI-Na_(2)S_(2)O_(8)process.The possible pathways involved in the reduction of NB to aniline(AN)and the further oxidative degradation of AN were determined by gas chromatography-mass spectrometry.
基金supported by the National Natural Science Foundation of China (No.52200184)the Fundamental Research Funds for Central Universities (No.12060096014)。
文摘Knowledge on corrosion behaviors and kinetics of nanoscale zero-valent iron(nZVI)in aquatic environment is particularly significant for understanding the reactivity,longevity and stability of nZVI,as well as providing theoretical guidance for developing a cost-effective nZVI-based technology and designing large-scale applications.Herein,this review gives a holistic overview on the corrosion behaviors and kinetics of nZVI in water.Firstly,Eh-pH diagram is introduced to predict the thermodynamics trend of iron corrosion.The morphological,structural,and compositional evolution of(modified-)nZVI under different environmental conditions,assisted with microscopic and spectroscopic evidence,is then summarized.Afterwards,common analytical methods and characterization technologies are categorized to establish time-resolved corrosion kinetics of nZVI in water.Specifically,stable models for calculating the corrosion rate constant of nZVI as well as electrochemical methods for monitoring the redox reaction are discussed,emphasizing their capabilities in studying the dynamic iron corrosion processes.Finally,in the future,more efforts are encouraged to study the corrosion behaviors of nZVI in long-term practical application and further build nanoparticles with precisely tailored properties.We expect that our work can deepen the understanding of the nZVI chemistry in aquatic environment.
基金supported by the National Natural Science Foundation of China (No.22176067)。
文摘To improve the adsorption and catalytic performance of heterogeneous Fenton-like catalysts for oil wastes,amino acids were used to modify nanoscale zero-valent iron(AA@Fe^(0)),which were applied in the Fenton-like degradation of organic solvents(tributyl phosphate and n-dodecane,named TBP and DD).Twelve amino acids,i.e.,glycine(Gly),alanine(Ala),leucine(Leu),proline(Pro),phenylalanine(Phe),methionine(Met),cysteine(Cys),asparagine(Asn),serine(Ser),glutamic acid(Glu),lysine(Lys)and arginine(Arg),were selected and calculated by density functional theory(DFT).The optimized structure,charge distribution,the highest occupied molecular orbital(HOMO),the lowest unoccupied molecular orbital(LUMO),interaction region indicator(IRI)isosurface map and adsorption energy of AA@Fe^(0),AA@Fe^(0)-TBP and AA@Fe^(0)-DD were studied,which indicated that Fe is more likely to approach and charge transfer with-COO and-NH_(3) on theα-carbon of amino acids.There is strong attraction between Fe and–COO,and Van der Waals force between Fe and-NH_(3),respectively.In the interaction of AA@Fe^(0)with TBP and DD,Van der Waal force plays an important role.AA@Fe^(0)was synthesized in laboratory and characterized to investigate physicochemical properties.In Fenton-like degradation of organic solvents,the change of COD in water phase during the degradation process as well as the volume of the organic phase after the reaction were investigated.The results of calculations combined with experiments showed that Ser-modified Fe^(0)performed the best in these amino acids,with 98%removal of organic solvents.A possible catalytic mechanism was proposed in which amino acids acted a linking role between Fe and organic solvents,activating H_(2)O_(2)to generate hydroxyl radicals for the degradation of organic solvents.
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.
基金the USDA National Institute of Food and Agriculture(NIFA),grant No.2020–65210–30763.
文摘Carbothermal reduction using biochar(BC)is a green and effective method of synthesizing BCsupported nanoscale zero-valent iron(nanoFe^(0))composites.However,the effect of BC surface area on the structure,distribution,and performance such as the heavy metal uptake capacity of nanoFe^(0)particles remains unclear.Soybean stover-based BCs with different surface areas(1.7−1472 m^(2)/g)were prepared in this study.They have been used for in-situ synthesis BCs-supported nanoFe^(0)particlesthrough carbothermal reduction of ferrous chloride.The BCs-supported nanoFe^(0)particles were found to be covered with graphene shells and dispersed onto BC surfaces,forming the BC-supported graphene-encapsulated nanoFe^(0)(BC-G@Fe^(0))composite.These graphene shells covering the nanoFe^(0)particles were formed because of gaseous carbon evolved from biomass carbonization reacting with iron oxides/iron salts.Increasing BC surface area decreased the average diameters of nanoFe^(0)particles,indicating a higher BC surface area alleviated the aggregation of nanoFe^(0)particles,which resulted in higher heavy metal uptake capacity.At the optimized condition,BC-G@Fe^(0)composite exhibited uptake capacities of 124.4,121.8,254.5,and 48.0 mg/g for Cu^(2+),Pb^(2+),Ag^(+),and As^(3+),respectively(pH 5,25℃).Moreover,the BC-G@Fe^(0)composite also demonstrated high stability for Cu^(2+)removal from the fixed-bed continuous flow,in which 1 g of BC-G@Fe^(0)can work for 120 h in a 4 mg/L Cu^(2+)flow continually and clean 28.6 L Cu^(2+)contaminated water.Furthermore,the BC-G@Fe^(0)composite can effectively immobilize the bioavailable As^(3+)from the contaminated soil,i.e.,5%(w)of BC-G@Fe^(0)composite addition can immobilize up to 92.2%bioavailable As^(3+)from the contaminated soil.
基金This work was supported by the National Natural Science Foundation of China(No.21976153).
文摘Sodium citrate(SC)is a widely-used food and industrial additive with the properties of com-plexation and microbial degradation.In the present study,nano-zero-valent iron reaction system(SC-nZVI@BC)was successfully established by modifying nanoscale zero-valent iron(nZVI)with SC and biochar(BC),and was employed to remove Cr(Ⅵ)from aqueous solu-tions.The nZVI,SC-nZVI and SC-nZVI@BC were characterized and compared using X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),thermogravimetric analy-ses(TGA),vibrating sample magnetometer(VSM),scanning electron microscope(SEM),X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS).The results showed that nZVI was successfully loaded on the biochar,and both the agglomeration and surface pas-sivation problems of nanoparticles were well resolved.The dosage of SC,C∶Fe,initial pH and Cr(Ⅵ)concentration demonstrated direct effects on the removal efficiency.The maximum Cr(Ⅵ)removal rate and the removal capacity within 60 min were 99.7%and 199.46 mg/g,respectively(C∶Fe was 1∶1,SC dosage was 1.12 mol.%,temperature was 25℃,pH=7,and the original concentration of Cr(Ⅵ)was 20 mg/L).The reaction confirmed to follow the pseudo-second-order reaction kinetics,and the order of the reaction rate constant k was as follows:SC-nZVI@BC>nZVI@BC>SC-nZVI>nZVI.In addition,the mechanism of Cr(Ⅵ)removal by SC-nZVI@BC mainly involved adsorption,reduction and co-precipitation,and the reduction of Cr(Ⅵ)to Cr(Ⅲ)by nano Fe0 played a vital role.Findings from the present study demon-strated that the SC-nZVI@BC exhibited excellent removal efficiency toward Cr(Ⅵ)with an improved synergistic characteristic by SC and BC.
基金supported by the Research and Development Program of Guangdong Province (No. 2020B0202080001)by the China Postdoctoral Science Foundation (No. 2019M651583)+1 种基金by the Education Commission of Shanghai (No. 0400106005)by the National Science Foundation of China (Nos. 21277102, 21003151)。
文摘Integrating nanoscale zero-valent iron(nZVI) with biological treatment processes holds the promise of inheriting significant advantages from both environmental nano-and biotechnologies. nZVI and microbes can perform in coalition in direct contact and act simultaneously, or be maintained in separate reactors and operated sequentially. Both modes can generate enhanced performance for wastewater treatment and environmental remediation. nZVI scavenges and eliminates toxic metals, and enhances biodegradability of some recalcitrant contaminants while bioprocesses serve to mineralize organic compounds and further remove impurities from wastewater. This has been demonstrated in a number of recent works that nZVI can substantially augment the performance of conventional biological treatment for wastewaters from textile and nonferrous metal industries. Our recent laboratory and field tests show that COD of the industrial effluents can be reduced to a record-low of 50 ppm. Recent literature on the theory and applications of the nZVI-bio system is highlighted in this mini review.
基金This work was supported by the National Natural Science Foundation of China(Grant Nos.51778618 and 52070192)which are greatly acknowledged.
文摘Pathogenic enteric viruses pose a significant risk to human health.Nanoscale zero-valent iron(nZVI),a novel material for environmental remediation,has been shown to be a promising tool for disinfection.However,the existing research has typically utilized MS2 or f2 bacteriophages to investigate the antimicrobial properties of nZVI,and the resistance difference between bacteriophages,which is important for the application of disinfection technologies,is not yet understood.Here,MS2 and PhiX174 containing RNA and DNA,respectively,were used as model viruses to investigate the resistances to nZVI.The bacteriophage inactivation mechanisms were also discussed using TEM images,protein,and nucleic acid analysis.The results showed that an initial concentration of 10^(6)PFU/mL of MS2 could be completely inactivated within 240 min by 40 mg/L nZVI at pH 7,whereas the complete inactivation of PhiX174 could not be achieved by extending the reaction time,increasing the nZVI dosage,or changing the dosing means.This indicates that the resistance of phage PhiX174 to nZVI was much stronger than that of MS2.TEM images indicated that the viral particle shape was distorted,and the capsid shell was ruptured by nZVI.The damage to viral surface proteins in both phages was examined by three-dimensional fluorescence spectrum and sodium dodecyl sulfate polyacrylamide gel electrophoresis(SDS-PAGE).However,the nucleic acid analysis demonstrated that the nucleic acid of MS2,but not PhiX174,was destroyed.It indicated that bacteriophage inactivation was mainly attributed to the damage of nucleic acids.
基金This work was supported by the National Natural Science Foundation of China(Grant Nos.50678089 and 50325824),which is greatly acknowledged.
文摘Chlorophenols(CPs),as important contami-nants in groundwater,are toxic and difficult to biode-grade.Recentlynanoscalezero-valentironreceivedagreat deal of attention because of its excellent performance in treating recalcitrant compounds.In this study,nanoscale zero-valent iron particles were prepared using chemical reduction,and the reductive transformations of three kinds of chlorinated phenols(2-CP,3-CP,and 4-CP)by nanoscale zero-valent iron under different conditions were investigated.The transformation process of the CPs was shown to be dechlorination first,then cleavage of the benzene ring.The removal efficiency of the CPs varied as follows:2-CP.3-CP.4-CP.The reactivity of CPs was associated with their energy of lowest unoccupied molecular orbit(E LUMO).With the increase in initial concentrations of CPs,removal efficiency decreased a little.But the quantities of CPs reduced increased evidently.Temperature had influence on not only the removal efficiency,but also the transformation pathway.At higher temperatures,dechlorination occurred prior to benzene ring cleavage.At lower temperatures,however,the oxidation product was formed more easily.
基金the National Key Research and Development Program of China(2018YFC1802006,2017YFA0207001)the National Natural Science Foundation of China(42022049,42130707,and 42107045)the 145 Program of Institute of Soil Science(ISSASIP2213).
文摘Biochar supported nano-scale zerovalent iron(nZVI/BC)for persulfate(PS)activation has been studied extensively for the degradation of pollutants on the lab scale,but it was rarely applied in practical soil remediation in the field.In this research,we developed a facile ball-milling method for the mass production of nZVI/BC,which was successfully applied to activate persulfate for the remediation of organic polluted soil on an in-situ pilot scale.In-situ high-pressure injection device was developed to inject nZVI/BC suspension and PS solution into the soil with a depth of 0-70 cm.The removal efficiency of target pollutants such as 2-ethylnitrobenzene(ENB,1.47-1.56 mg/kg),biphenyl(BP,0.19-0.21 mg/kg),4-(methylsulfonyl)toluene(MST,0.32-0.43 mg/kg),and 4-phenylphenol(PP,1.70-2.46 mg/kg)at different soil depths was 99.7%,99.1%,99.9%and 99.7%,respectively,after 360 days of remediation.The application of nZVI/BC significantly increased the degradation rates of contaminants by 11-322%,ascribed to its relatively higher efficiency of free radical generation than that of control groups.In addition,it was found that nZVI/BC-PS inhibited soil urease and sucrase enzyme activities by 1-61%within 55 days due to the oxidative stress for microbes induced by free radicals,while these inhibition effects disappeared with remediation time prolonged(>127 days).Our research provides a useful implementation case of remediation with nZVI/BC-PS activation and verifies its feasibility in practical contaminated soil remediation.
基金The authors acknowledge financial supports from National Natural Science Foundation of China(grant Nos.21776302,21776308 and 22278431)the Science Foundation of China University of Petroleum,Beijing(grant No.2462020YXZZ033)。
文摘Great efforts have been made to remove sulfur from fossil fuels to protect the environment.We proposed synthesis of high efficiency oxidation desulfurization(ODS)catalysts by encapsulating nano zero valent iron(nZVI)in self-catalyzed carbon nanotubes.The synthetic strategy features facile hydrothermal and pyrolysis process.The specific surface area,pore structure,and microstructure of the catalysts were characterized by series techniques,and the catalytic ability was evaluated by the reduction of sulfur after oxidation and reflux-extraction.The optimized nZVI@CNT catalyst exhibits outstanding catalytic performance(within 120 min,the oxidative removal rate of DBT reached 96%)and enhanced stability(a 80%retention of initial performance after six cycles.),revealing the effective optimization and modulation between carbon nanotubes and iron particles.This excellent ODS activity originated from the defects of N-doped nanotubes as well as excellent particle dispersion and material transport capacity,which excites highly active free radicals with the assistance of H_(2)O_(2).In addition,the unique two-dimensional tube channel and mesoporous structure promoted the diffusion and transfer of reactants and electrons,leading to high density of active sites.The different experimental conditions confirmed that the material is a bifunctional catalyst integrating adsorption and catalysis.This work provides an creative ideas for the rational design and synthesis of advanced ODS catalysts for fuel oil.
