During thewater treatment process,chlorination and ultraviolet(UV)sterilization can modify microplastics(MPs)and alter their physicochemical properties,causing various changes between MPs and other pollutants.In this ...During thewater treatment process,chlorination and ultraviolet(UV)sterilization can modify microplastics(MPs)and alter their physicochemical properties,causing various changes between MPs and other pollutants.In this study,the impact of chlorination and UV modification on the physicochemical properties of polystyrene(PS)and polyvinyl chloride(PVC)were investigated,and the adsorption behavior of pefloxacin(PEF)before and after modificationwas examined.The effect of pH,ionic strength,dissolved organicmatter,heavymetal ions and other water environmental conditions on adsorption behavior was revealed.The results showed that PS had a higher adsorption capacity of PEF than PVC,and the modification increased the presence of O-containing functional groups in the MPs,thereby enhancing the adsorption capacity of both materials.Chlorination had a more significant impact on the physicochemical properties of MPs compared to UV irradiation within the same time period,leading to better adsorption performance of chlorination.The optimal pH for adsorption was found to be 6,and NaCl,sodium alginate and Cu2+would inhibit adsorption to varying degrees,among which the inhibition caused by pH was the strongest.Chlorination and UV modification would weaken the inhibitory effect of environmental factors on the adsorption of PEF by MPs.The main mechanisms of adsorption involved electrostatic interaction and hydrogen bonding.The study clarified the effects of modification on the physicochemical properties of MPs,providing reference for subsequent biotoxicity analysis and environmental protection studies.展开更多
Sudden temperature drops cause soils in natural environments to freeze unidirectionally,resulting in soil expansion and deformation that can lead to damage to engineering structures.The impact of temperature-induced f...Sudden temperature drops cause soils in natural environments to freeze unidirectionally,resulting in soil expansion and deformation that can lead to damage to engineering structures.The impact of temperature-induced freezing on deformation and solute migration in saline soils,especially under extended freezing,is not well understood due to the lack of knowledge regarding the microscopic mechanisms involved.This study investigated the expansion,deformation,and water-salt migration in chlorinated saline soils,materials commonly used for canal foundations in cold and arid regions,under different roof temperatures and soil compaction levels through unidirectional freezing experiments.The microscopic structures of saline soils were observed using scanning electron microscopy(SEM)and optical microscopy.A quantitative analysis of the microstructural data was conducted before and after freezing to elucidate the microscopic mechanisms of water-salt migration and deformation.The results indicate that soil swelling is enhanced by elevated roof temperatures approaching the soil's freezing point and soil compaction,which prolongs the duration and accelerates the rate of water-salt migration.The unidirectional freezing altered the microstructure of saline soils due to the continuous temperature gradients,leading to four distinct zones:natural frozen zone,peak frozen zone,gradual frozen zone,and unfrozen zone,each exhibiting significant changes in pore types and fractal dimensions.Vacuum suction at the colder end of the soil structure facilitates the upward migration of salt and water,which subsequently undergoes crystallization.This process expands the internal pore structure and causes swelling.The findings provide a theoretical basis for understanding the evolution of soil microstructure in cold and arid regions and for the management of saline soil engineering.展开更多
With the continuous increase in the disposal volume of spent lithium-ion batteries(LIBs),properly recycling spent LIBs has become essential for the advancement of the circular economy.This study presents a systematic ...With the continuous increase in the disposal volume of spent lithium-ion batteries(LIBs),properly recycling spent LIBs has become essential for the advancement of the circular economy.This study presents a systematic analysis of the chlorination roasting kinetics and proposes a new two-step chlorination roasting process that integrates thermodynamics for the recycling of LIB cathode materials.The activation energy for the chloride reaction was 88.41 kJ/mol according to thermogravimetric analysis–derivative thermogravimetry data obtained by using model-free,model-fitting,and Z(α)function(αis conversion rate).Results indicated that the reaction was dominated by the first-order(F1)model when the conversion rate was less than or equal to 0.5 and shifted to the second-order(F2)model when the conversion rate exceeded 0.5.Optimal conditions were determined by thoroughly investigating the effects of roasting temperature,roasting time,and the mass ratio of NH_(4)Cl to LiCoO_(2).Under the optimal conditions,namely 400℃,20 min,and NH_(4)Cl/LiCoO_(2)mass ratio of 3:1,the leaching efficiency of Li and Co reached 99.43% and 99.05%,respectively.Analysis of the roasted products revealed that valuable metals in LiCoO_(2)transformed into CoCl_(2) and LiCl.Furthermore,the reaction mechanism was elucidated,providing insights for the establishment of a novel low-temperature chlorination roasting technology based on a crystal structure perspective.This technology can guide the development of LIB recycling processes with low energy consumption,low secondary pollution,high recovery efficiency,and high added value.展开更多
Recovery of rare earth elements(REEs)from bulk Nd-Fe-B scrap by chlorination with NH_(4)Cl as a chlorinating agent has been reported to be an energy efficient and environmentally friendly method.However,the reaction m...Recovery of rare earth elements(REEs)from bulk Nd-Fe-B scrap by chlorination with NH_(4)Cl as a chlorinating agent has been reported to be an energy efficient and environmentally friendly method.However,the reaction mechanism and phase evolution of the low-temperature selective chlorination process of Nd-Fe-B sludge are not clear.In this paper,we systematically investigated the lowtemperature selective chlorination process of Nd-Fe-B sludge with NH4Cl by combining thermokinetic theoretical calculations and experiments,and revealed its reaction mechanism.The phase evolution during chlorination was determined by X-ray diffraction(XRD),scanning electron microscopy(SEM)and ene rgy-dispersive X-ray spectroscopy(EDS)characterization as well as co mputational analysis of the phase stability diagram of the M-O-Cl system.To determine the optimum chlorination conditions,the effects of chlorinating agent dosage,reaction temperature and reaction time on the reaction were investigated.The results show that the rare earth components in Nd-Fe-B sludge are selectively chlorinated to RECl3and the formation of REOCl is avoided in the temperature range of 300-420℃,while the iron components are preferentially oxidized to Fe2O3.The selective chlorination reaction is consistent with the unreacted shrinking core model,and the rate-controlling step of the reaction is the internal diffusion process of NH4Cl through the transition layer of the reactant product to the surface of the Nd-Fe-B sludge.The complete chlorination of REEs is successfully achieved and 99.8%of REEs are selectively extracted into the leaching solution under optimal chlorination conditions(300℃,2.5 times of stoichiometric amount,4 h).展开更多
Following the COVID-19 outbreak,a vast array of chlorine disinfectants was used to eliminate the virus,leading to inevitable discharge into aquatic ecosystems.These environments also contain various anthropogenic micr...Following the COVID-19 outbreak,a vast array of chlorine disinfectants was used to eliminate the virus,leading to inevitable discharge into aquatic ecosystems.These environments also contain various anthropogenic micropollutants,such as pharmaceuticals,which pose threats to the survival and activities of biological communities.Consequently,the presence of discharged chlorine disinfectants and pharmaceuticals can simultaneously impact the structure and function of aquatic ecosystems.To investigate the combined effects of chlorine disinfectants and pharmaceuticals on the periphyton and zoobenthos(Limnodrilus hoffmeisteri)community composition and function,we conducted a 12-flume reactor experiment using sodium hypochlorite and representative pharmaceuticals(abundant in the Yangtze River)as influents.Results demonstrated that the discharge of chlorine disinfectants further altered the composition of river prokaryotic communities.Eukaryotic organisms within the periphyton exhibited greater resilience to chlorine exposure compared to prokaryotic communities.Metagenomic analysis revealed that prokaryotic communities with different compositions can execute similar functions,while RNA sequencing indicated that co-exposure promoted biological processes such as focal adhesion and ribosome synthesis,but inhibited activities related to nitrogen metabolism and resistance to folate antimicrobials.Additionally,co-exposure induced oxidative stress in L.hoffmeisteri,leading to stronger environmental adaptation.展开更多
The first example of Nd@C_(3)N_(4)-photoredox/chlorine dual catalyzed alkylation with unactivated alkanes as the alkyl sources has been developed,which allows for the synthesis of various 4-alkylated cyclic sulfonyl k...The first example of Nd@C_(3)N_(4)-photoredox/chlorine dual catalyzed alkylation with unactivated alkanes as the alkyl sources has been developed,which allows for the synthesis of various 4-alkylated cyclic sulfonyl ketimines.In this process,chlorine functions as both a redox and hydrogen atom transfer catalyst.The synergism of the reversible Nd^(2+)/Nd^(3+)and Cl^(ˉ)/Cl˙redox pairs significantly enhances overall photocatalytic efficiency.The in vitro anticancer activity of 4-alkylated products was evaluated by using the CCK8assay against both human choroidal melanoma(MUM-2B)and lung cancer(A549)cell.Compound 3da showed approximately triple the potency of 5-fluorouracil.展开更多
Benzotriazole(BTA)-based A_(2)-A_1-D-A_1-A_(2)type wide-bandgap(WBG)non-fullerene acceptors(NFAs)have shown promising potential in indoor photovoltaic,and in-depth investigation of their structure-property relationshi...Benzotriazole(BTA)-based A_(2)-A_1-D-A_1-A_(2)type wide-bandgap(WBG)non-fullerene acceptors(NFAs)have shown promising potential in indoor photovoltaic,and in-depth investigation of their structure-property relationship is of great significance.Herein,we explored the chlorination effect of the side chain on the terminals.We introduced Cl atoms into the benzyl side chains in parent BTA5 to synthesize two NFAs,BTA5-Cl with mono-chlorinated benzyl groups and BTA5-2Cl containing bi-chlorinated benzyl groups.We chose D18-Cl with deep-energy levels and strong crystallinity to pair with these three acceptors,affording high photovoltage and photocurrent.With the stepwise chlorination,the open-circuit voltage(V_(OC))values decrease from 1.28,1.22,to 1.20 V,while the corresponding power conversion efficiencies(PCEs)improve from 5.07%,9.15%,to 10.96%.Compared with BTA5-based OSCs,introducing Cl atoms downshifts the energy levels and slightly increases the non-radiative energy loss(0.14<0.17<0.19 e V),resulting in a sequential decrease in VO C.However,more chlorine atom replacements produce more effective exciton dissociation,higher charge transfer,and balanced carrier mobility in the blend films,ultimately achieving better PCEs.This work indicates that chlorination of the benzyl group on the terminals can improve the device's performance,implying good application potential in indoor photovoltaics.展开更多
Halogenated aromatic disinfection byproducts(DBPs)are gradually receiving attention due to their high detection frequency and usually higher toxicity than regulated DBPs.In this study,we established a solid phase extr...Halogenated aromatic disinfection byproducts(DBPs)are gradually receiving attention due to their high detection frequency and usually higher toxicity than regulated DBPs.In this study,we established a solid phase extraction(SPE)-LC-MS/MS method to simultaneously trace analyze 59 halogenated aromatic DBPs.The limits of detection and limits of quantification of halogenated aromatic DBPs ranged from 0.03 to 135.23 ng/L and from 0.1 to 450.76 ng/L,respectively.The range of recoveries and relative standard deviation(RSD)in river water were between 72.41%to 119.54%and 1.86%to 16.03%,respectively.Therefore,this method can be used to accurately analyze trace levels of halogenated aromatic DBPs in drinking water.The occurrence and transformation of halogenated aromatic DBPs were explored based on this method.In the chlorinated simulated source water and chlorinated river water,20 and 45 halogenated aromatic DBPs were determined,respectively.The active halogen species(HOCl,HOBr,and HOI)first reacted with natural organic matter(NOM)to form halogenated aromatic DBPs.Then,chlorine further reacted with the halogenated aromatic DBPs to convert them into small-molecule halogenated aliphatic DBPs through oxidation,electrophilic substitution,and hydrolysis reaction,etc.In the chlorinated simulated source water,chlorinated river water,and tap water,the toxicity contribution of bromoacetic acids(Br-HAAs)accounted for themajority(>71.16%).Given that halogenated aromatic DBPs are intermediate products of halogenated aliphatic DBPs,controlling the formation of halogenated aromatic DBPs is beneficial in decreasing the formation of halogenated aliphatic DBPs,thereby diminishing the toxicity of drinking water.展开更多
Due to the lack of effective screening systems in the rare earth waste recycling industry,the composition of rare earth elements in rare earth waste is complex and difficult to separate.In response to such problems,by...Due to the lack of effective screening systems in the rare earth waste recycling industry,the composition of rare earth elements in rare earth waste is complex and difficult to separate.In response to such problems,by studying the reaction behavior between various elements in rare earth waste and cobalt chloride,we propose a process path for the separation and recovery of iron,cerium and other rare earth elements using cobalt chloride roasting.The experiments on simulated wastes show that the leaching rates of the Nd,Sm,Gd,Pr can reach 98.31%,94.5%,93.87%and 72.05%under the optimal process conditions,respectively.Ce and iron remain in the leaching residue in the form of CeO_(2)and CoFe_(2)O_(4),respectively.And through a simple magnetic separation process,CeO_(2)and CoFe_(2)O_(4)can be enriched in non-magnetic leaching residue and magnetic leaching residue,respectively.The cerium content in the leaching residue composed of cobalt ferrite is only 1.95%.Therefore,this method is beneficial to the separation and high-value utilization of iron,cerium,and other rare earth elements in the waste system.The research results can provide theoretical reference for the low-cost and high-value recovery of rare earth secondary resources.展开更多
Seawater electrolysis offers a promising pathway to generate green hydrogen,which is crucial for the net-zero emission targets.Indirect seawater electrolysis is severely limited by high energy demands and system compl...Seawater electrolysis offers a promising pathway to generate green hydrogen,which is crucial for the net-zero emission targets.Indirect seawater electrolysis is severely limited by high energy demands and system complexity,while the direct seawater electrolysis bypasses pre-treatment,offering a simpler and more cost-effective solution.However,the chlorine evolution reaction and impurities in the seawater lead to severe corrosion and hinder electrolysis’s efficiency.Herein,we review recent advances in the rational design of chlorine-suppressive catalysts and integrated electrolysis systems architectures for chloride-induced corrosion,with simultaneous enhancement of Faradaic efficiency and reduction of electrolysis’s cost.Furthermore,promising directions are proposed for durable and efficient seawater electrolysis systems.This review provides perspectives for seawater electrolysis toward sustainable energy conversion and environmental protection.展开更多
Currently,ferrate(VI)oxidation technology(FOT)has been regarded as one of the most promising options for the degradation of emerging organic pollutants.However,the role and transformation of chloride ions(Cl^(−))in FO...Currently,ferrate(VI)oxidation technology(FOT)has been regarded as one of the most promising options for the degradation of emerging organic pollutants.However,the role and transformation of chloride ions(Cl^(−))in FOT have not been well explored.The current study aims to investigate the formation of chlorinated phenolic byproducts upon ferrate(VI)oxidation processes.The obtained results indicate that chlorides suffering ferrate(VI)attack will be transformed to active chlorine species(ACS),which will subsequently lead to the formation of highly toxic aromatic chlorinated byproducts.The identified byproducts include common chlorinated phenolic derivatives,as well as complex chlorinated oligomer byproducts with ether structures(mainly dimers and trimers).While the formation of common chlorophenols can be ascribed to the electrophilic substitution reactions mediated by ACS,the oligomer byproducts are generated via coupling reactions between chlorinated phenoxy radicals.ECOSAR software predicts that the generated chlorinated oligomer byproducts exhibit high ecotoxicological effects.As a whole,the above findings shed light on the potential risk of FOT in real practice.展开更多
Weight lost method was used to comparatively study the corrosion behavior of four different metals under the dosage of chlorine dioxide, chlorine and their mixture respectively. The experimental results indicated that...Weight lost method was used to comparatively study the corrosion behavior of four different metals under the dosage of chlorine dioxide, chlorine and their mixture respectively. The experimental results indicated that chlorine causes the most serious corrosion of carbon steel, and the higher the concentration of chlorine, the more serious the corrosion. On the contrary, metals corrosion is the least serious in the case of chlorine dioxide. The results further revealed that chlorine dioxide is the most effective water treatment reagent, making it the best choice to use extensively in circulated cooling water disinfection and corrosion control.展开更多
Based on the mechanism analysis of the polychlorination of long chain n-alkanes by photo-initiation,a kinetic model was developed. The model parameters were obtained by the method of non-linear fitting. The influences...Based on the mechanism analysis of the polychlorination of long chain n-alkanes by photo-initiation,a kinetic model was developed. The model parameters were obtained by the method of non-linear fitting. The influences of luminous intensity and concentration of molecular chlorine on the rate of polychlorination are demonstrated by the model. If the luminous intensity is adequate, the polychlorination rate of n-alkane is only controlled by the flow rate of molecular chlorine in a wide range of temperature, and the changes of temperature and luminous intensity have less effect on the reaction rate. In addition, the predictions of chlorine content of polychlorinated n-alkane calculated with the model agree very well with experimental results.展开更多
Chlorination roasting followed by water leaching process was used to extract lithium from lepidolite.The microstructure of the lepidolite and roasted materials were characterized by X-ray diffraction（XRD）.Various pa...Chlorination roasting followed by water leaching process was used to extract lithium from lepidolite.The microstructure of the lepidolite and roasted materials were characterized by X-ray diffraction（XRD）.Various parameters including chlorination roasting temperature,time,type and amount of chlorinating agents were optimized.The conditional experiments indicate that the best mass ratio of lepidolite to NaCl to CaCl2 is 1：0.6：0.4 during the roasting process.The extraction of lithium reaches peak value of 92.86% at 880 °C,potassium,rubidium,and cesium 88.49%,93.60% and 93.01%,respectively.The XRD result indicates that the major phases of the product after roasting lepidolite with mixture of chlorinating agents（CaCl2 and NaCl） are SiO2,CaF2,KCl,CaSiO3,CaAl2Si2O8,NaCl and NaAlSi3O8.展开更多
Behaviors of TiO2 in the alumina carbothermic reduction and chlorination process in vacuum at different temperatures were investigated experimentally by means of XRD,SEM and EDS.In the preparation of materials,the mol...Behaviors of TiO2 in the alumina carbothermic reduction and chlorination process in vacuum at different temperatures were investigated experimentally by means of XRD,SEM and EDS.In the preparation of materials,the molar ratio of Al2O3 to C was 1：4,and 10% TiO2 and excess AlCl3 were added.The results show that TiC is produced by C and TiO2 after TiO2 transforms from anatase into rutile gradually.In the temperature range of 1 763？1 783 K,the compounds of Ti and Al are not found in slags and condensate.The purity of aluminum reaches 98.35%,and TiO2 does not participate in alumina carbothermic reduction process and chlorination process in vacuum.展开更多
Cyclops of zooplankton propagated excessively in eutrophic water body and could not be effectively inactivated by the conventional disinfections process like chlorination due to its stronger resistance to oxidation. I...Cyclops of zooplankton propagated excessively in eutrophic water body and could not be effectively inactivated by the conventional disinfections process like chlorination due to its stronger resistance to oxidation. In this paper, a full-scale study of chlorine dioxide preoxidation cooperating with routine clarification process for Cyclops removal was conducted in a waterworks. The experimental results were compared with that of the existing prechlorination process in several aspects: including the Cyclops removal efficiencies of water samples taken from the outlets of sedimentation tank and sand filter and the security of drinking water and so on. The results showed that chlorine dioxide might be more effective to inactivate Cyclops than chlorine and Cyclops could be thoroughly removed from water by pre-dosing chlorine dioxide process. The GC-MS examination and Ames test further showed that the sort and amount of organic substance in the treated water by chlorine dioxide preoxidation were evidently less than that of prechlorination and the mutagenicity of drinking water treated by pre-dosing chlorine dioxide was substantially reduced compared with prechlorination.展开更多
Hazardous waste dechlorination reduces the potential of creating dioxins during the incineration process. To investigate the salt effect on waste dechlorination, molten hydroxides with a low melting temperature were u...Hazardous waste dechlorination reduces the potential of creating dioxins during the incineration process. To investigate the salt effect on waste dechlorination, molten hydroxides with a low melting temperature were utilized for the pre-dechlorination and decomposition of chlorine-containing organic wastes(COWs) including trichlorobenzene(TCB),perchloroethylene, hexachlorobenzene and chlordane. The results showed that a eutectic mixture of caustic sodium and potassium hydroxides(41 wt.% NaOH and 59 wt.% KOH) led to a low melting point below 300°C and a relatively high chlorine retention efficiency(CRE) with TCB as a representative COWs. The amounts of hydroxides, reaction time, and temperature all had notable influence on CRE. When the mass ratio of hydroxides to TCB reached 30:1,approximately 98.1% of the TCB was destroyed within 2.5 hr at 300°C with CRE of 71.6%.According to the residue analysis, the shapes of reaction residues were irregular with particles becoming swollen and porous. The benzene ring and C–Cl bonds disappeared, while carboxyl groups formed in the residues. The stripped chlorine was retained and condensed to form chloride salts, and the relative abundance of the chloride ions associated with the mass of TCB in residues increased from 0 to 75.0% within the 2.5 hr reaction time. The observed concentration of dioxins in residues was 5.6 ngTEQ/kg. A reaction pathway and possible additional reactions that occur in this dechlorination system were proposed. Oxidizing agents may attack TCB and facilitate hydrogenation/dechlorination reactions, making this process a promising and environmentally friendly approach for chlorine-containing organic waste treatment.展开更多
A method was developed for determination of chlorine and bromine in plant materials by ion chromatography using temperature programing-semi molten for sample preparation. Values of detection limits of the method found...A method was developed for determination of chlorine and bromine in plant materials by ion chromatography using temperature programing-semi molten for sample preparation. Values of detection limits of the method found were 1.0×10^-5 for CI and 1.3×10^-6 for Br. The measuring range of the method found were 0.3-20.0 mg/L for CI and 4,0-120,0 μg/L for Br. The results obtained agreed quite well with those reference values.展开更多
基金supported by the Shanxi Scholarship Council of China(No.2023-054)the Applied Basic Research Project of Shanxi Province,China(No.20210302123121)the National Natural Science Foundation of China(No.52170045).
文摘During thewater treatment process,chlorination and ultraviolet(UV)sterilization can modify microplastics(MPs)and alter their physicochemical properties,causing various changes between MPs and other pollutants.In this study,the impact of chlorination and UV modification on the physicochemical properties of polystyrene(PS)and polyvinyl chloride(PVC)were investigated,and the adsorption behavior of pefloxacin(PEF)before and after modificationwas examined.The effect of pH,ionic strength,dissolved organicmatter,heavymetal ions and other water environmental conditions on adsorption behavior was revealed.The results showed that PS had a higher adsorption capacity of PEF than PVC,and the modification increased the presence of O-containing functional groups in the MPs,thereby enhancing the adsorption capacity of both materials.Chlorination had a more significant impact on the physicochemical properties of MPs compared to UV irradiation within the same time period,leading to better adsorption performance of chlorination.The optimal pH for adsorption was found to be 6,and NaCl,sodium alginate and Cu2+would inhibit adsorption to varying degrees,among which the inhibition caused by pH was the strongest.Chlorination and UV modification would weaken the inhibitory effect of environmental factors on the adsorption of PEF by MPs.The main mechanisms of adsorption involved electrostatic interaction and hydrogen bonding.The study clarified the effects of modification on the physicochemical properties of MPs,providing reference for subsequent biotoxicity analysis and environmental protection studies.
基金supported by the Open Fund of State Key Laboratory of Frozen Soil Engineering (Grant No.SKLFSE201806)the National Natural Science Foundation of China (Grant No.42177155).
文摘Sudden temperature drops cause soils in natural environments to freeze unidirectionally,resulting in soil expansion and deformation that can lead to damage to engineering structures.The impact of temperature-induced freezing on deformation and solute migration in saline soils,especially under extended freezing,is not well understood due to the lack of knowledge regarding the microscopic mechanisms involved.This study investigated the expansion,deformation,and water-salt migration in chlorinated saline soils,materials commonly used for canal foundations in cold and arid regions,under different roof temperatures and soil compaction levels through unidirectional freezing experiments.The microscopic structures of saline soils were observed using scanning electron microscopy(SEM)and optical microscopy.A quantitative analysis of the microstructural data was conducted before and after freezing to elucidate the microscopic mechanisms of water-salt migration and deformation.The results indicate that soil swelling is enhanced by elevated roof temperatures approaching the soil's freezing point and soil compaction,which prolongs the duration and accelerates the rate of water-salt migration.The unidirectional freezing altered the microstructure of saline soils due to the continuous temperature gradients,leading to four distinct zones:natural frozen zone,peak frozen zone,gradual frozen zone,and unfrozen zone,each exhibiting significant changes in pore types and fractal dimensions.Vacuum suction at the colder end of the soil structure facilitates the upward migration of salt and water,which subsequently undergoes crystallization.This process expands the internal pore structure and causes swelling.The findings provide a theoretical basis for understanding the evolution of soil microstructure in cold and arid regions and for the management of saline soil engineering.
基金financially supported by the National Natural Science Foundation of China(No.52204310)the Guizhou Provincial Key Laboratory of Coal Clean Utilization(No.[2020]2001)+5 种基金the China Postdoctoral Science Foundation(Nos.2020TQ0059 and 2020M570967)the Natural Science Foundation of Liaoning Province(No.2021–MS–083)the Fundamental Research Funds for the Central Universities,China(No.N2125010)the Open Project Program of Key Laboratory of Metallurgical Emission Reduction&Resources Recycling(Anhui University of Technology),Ministry of Education(No.JKF22–02)the Foundation of Liupanshui Normal University(No.LPSSYZDZK202205)the Key Laboratory for Anisotropy and Texture of Materials,Ministry of Education,China。
文摘With the continuous increase in the disposal volume of spent lithium-ion batteries(LIBs),properly recycling spent LIBs has become essential for the advancement of the circular economy.This study presents a systematic analysis of the chlorination roasting kinetics and proposes a new two-step chlorination roasting process that integrates thermodynamics for the recycling of LIB cathode materials.The activation energy for the chloride reaction was 88.41 kJ/mol according to thermogravimetric analysis–derivative thermogravimetry data obtained by using model-free,model-fitting,and Z(α)function(αis conversion rate).Results indicated that the reaction was dominated by the first-order(F1)model when the conversion rate was less than or equal to 0.5 and shifted to the second-order(F2)model when the conversion rate exceeded 0.5.Optimal conditions were determined by thoroughly investigating the effects of roasting temperature,roasting time,and the mass ratio of NH_(4)Cl to LiCoO_(2).Under the optimal conditions,namely 400℃,20 min,and NH_(4)Cl/LiCoO_(2)mass ratio of 3:1,the leaching efficiency of Li and Co reached 99.43% and 99.05%,respectively.Analysis of the roasted products revealed that valuable metals in LiCoO_(2)transformed into CoCl_(2) and LiCl.Furthermore,the reaction mechanism was elucidated,providing insights for the establishment of a novel low-temperature chlorination roasting technology based on a crystal structure perspective.This technology can guide the development of LIB recycling processes with low energy consumption,low secondary pollution,high recovery efficiency,and high added value.
基金Project supported by the National Natural Science Foundation of China(52261037,52401251)Key Research Project of Jiangxi Province(20203ABC28W006)+2 种基金the Research Fund of Key Laboratory of Rare Earths,Chinese Academy of SciencesKey Laboratory of Ionic Rare Earth Re sources and Environment,Ministry of Natural Resources of the People's Republic of China(2022IRERE302)the Ganzhou Science and Technology Innovation Empowerment Youth"Jie bang Gua shuai"Project。
文摘Recovery of rare earth elements(REEs)from bulk Nd-Fe-B scrap by chlorination with NH_(4)Cl as a chlorinating agent has been reported to be an energy efficient and environmentally friendly method.However,the reaction mechanism and phase evolution of the low-temperature selective chlorination process of Nd-Fe-B sludge are not clear.In this paper,we systematically investigated the lowtemperature selective chlorination process of Nd-Fe-B sludge with NH4Cl by combining thermokinetic theoretical calculations and experiments,and revealed its reaction mechanism.The phase evolution during chlorination was determined by X-ray diffraction(XRD),scanning electron microscopy(SEM)and ene rgy-dispersive X-ray spectroscopy(EDS)characterization as well as co mputational analysis of the phase stability diagram of the M-O-Cl system.To determine the optimum chlorination conditions,the effects of chlorinating agent dosage,reaction temperature and reaction time on the reaction were investigated.The results show that the rare earth components in Nd-Fe-B sludge are selectively chlorinated to RECl3and the formation of REOCl is avoided in the temperature range of 300-420℃,while the iron components are preferentially oxidized to Fe2O3.The selective chlorination reaction is consistent with the unreacted shrinking core model,and the rate-controlling step of the reaction is the internal diffusion process of NH4Cl through the transition layer of the reactant product to the surface of the Nd-Fe-B sludge.The complete chlorination of REEs is successfully achieved and 99.8%of REEs are selectively extracted into the leaching solution under optimal chlorination conditions(300℃,2.5 times of stoichiometric amount,4 h).
基金supported by the National Natural Science Foundation of China(Nos.52293442,52300249,and 52388101)the Scientific Research Project of China Three Gorges Corporation(No.201903139).
文摘Following the COVID-19 outbreak,a vast array of chlorine disinfectants was used to eliminate the virus,leading to inevitable discharge into aquatic ecosystems.These environments also contain various anthropogenic micropollutants,such as pharmaceuticals,which pose threats to the survival and activities of biological communities.Consequently,the presence of discharged chlorine disinfectants and pharmaceuticals can simultaneously impact the structure and function of aquatic ecosystems.To investigate the combined effects of chlorine disinfectants and pharmaceuticals on the periphyton and zoobenthos(Limnodrilus hoffmeisteri)community composition and function,we conducted a 12-flume reactor experiment using sodium hypochlorite and representative pharmaceuticals(abundant in the Yangtze River)as influents.Results demonstrated that the discharge of chlorine disinfectants further altered the composition of river prokaryotic communities.Eukaryotic organisms within the periphyton exhibited greater resilience to chlorine exposure compared to prokaryotic communities.Metagenomic analysis revealed that prokaryotic communities with different compositions can execute similar functions,while RNA sequencing indicated that co-exposure promoted biological processes such as focal adhesion and ribosome synthesis,but inhibited activities related to nitrogen metabolism and resistance to folate antimicrobials.Additionally,co-exposure induced oxidative stress in L.hoffmeisteri,leading to stronger environmental adaptation.
基金supported by grants from the Provincial Natural Science Foundation of Hunan(No.2023JJ60335)。
文摘The first example of Nd@C_(3)N_(4)-photoredox/chlorine dual catalyzed alkylation with unactivated alkanes as the alkyl sources has been developed,which allows for the synthesis of various 4-alkylated cyclic sulfonyl ketimines.In this process,chlorine functions as both a redox and hydrogen atom transfer catalyst.The synergism of the reversible Nd^(2+)/Nd^(3+)and Cl^(ˉ)/Cl˙redox pairs significantly enhances overall photocatalytic efficiency.The in vitro anticancer activity of 4-alkylated products was evaluated by using the CCK8assay against both human choroidal melanoma(MUM-2B)and lung cancer(A549)cell.Compound 3da showed approximately triple the potency of 5-fluorouracil.
基金support from the National Natural Science Foundation of China(Nos.52373176,52073067)。
文摘Benzotriazole(BTA)-based A_(2)-A_1-D-A_1-A_(2)type wide-bandgap(WBG)non-fullerene acceptors(NFAs)have shown promising potential in indoor photovoltaic,and in-depth investigation of their structure-property relationship is of great significance.Herein,we explored the chlorination effect of the side chain on the terminals.We introduced Cl atoms into the benzyl side chains in parent BTA5 to synthesize two NFAs,BTA5-Cl with mono-chlorinated benzyl groups and BTA5-2Cl containing bi-chlorinated benzyl groups.We chose D18-Cl with deep-energy levels and strong crystallinity to pair with these three acceptors,affording high photovoltage and photocurrent.With the stepwise chlorination,the open-circuit voltage(V_(OC))values decrease from 1.28,1.22,to 1.20 V,while the corresponding power conversion efficiencies(PCEs)improve from 5.07%,9.15%,to 10.96%.Compared with BTA5-based OSCs,introducing Cl atoms downshifts the energy levels and slightly increases the non-radiative energy loss(0.14<0.17<0.19 e V),resulting in a sequential decrease in VO C.However,more chlorine atom replacements produce more effective exciton dissociation,higher charge transfer,and balanced carrier mobility in the blend films,ultimately achieving better PCEs.This work indicates that chlorination of the benzyl group on the terminals can improve the device's performance,implying good application potential in indoor photovoltaics.
基金supported by the National Natural Science Foundation of China(No.52300005)China Postdoctoral Science Foundation(No.2023TQ0098)+5 种基金Heilongjiang Postdoctoral Fund(No.LBH-Z23175)Heilongjiang Touyan Innovation Team Program(No.HIT-SE-01)the Crossover Fund of Medical Engineering Science of Harbin Institute of Technology(No.IR2021107)the National Natural Science Foundation of International(Regional)Cooperation and Exchange Project(No.51961125104)the State Key Laboratory of Urban Water Resource and Environment(Harbin Institute of Technology)(No.2022TS15)the Ecological and Environmental Protection Research Project of Heilongjiang Province(No.HST2022ST006).
文摘Halogenated aromatic disinfection byproducts(DBPs)are gradually receiving attention due to their high detection frequency and usually higher toxicity than regulated DBPs.In this study,we established a solid phase extraction(SPE)-LC-MS/MS method to simultaneously trace analyze 59 halogenated aromatic DBPs.The limits of detection and limits of quantification of halogenated aromatic DBPs ranged from 0.03 to 135.23 ng/L and from 0.1 to 450.76 ng/L,respectively.The range of recoveries and relative standard deviation(RSD)in river water were between 72.41%to 119.54%and 1.86%to 16.03%,respectively.Therefore,this method can be used to accurately analyze trace levels of halogenated aromatic DBPs in drinking water.The occurrence and transformation of halogenated aromatic DBPs were explored based on this method.In the chlorinated simulated source water and chlorinated river water,20 and 45 halogenated aromatic DBPs were determined,respectively.The active halogen species(HOCl,HOBr,and HOI)first reacted with natural organic matter(NOM)to form halogenated aromatic DBPs.Then,chlorine further reacted with the halogenated aromatic DBPs to convert them into small-molecule halogenated aliphatic DBPs through oxidation,electrophilic substitution,and hydrolysis reaction,etc.In the chlorinated simulated source water,chlorinated river water,and tap water,the toxicity contribution of bromoacetic acids(Br-HAAs)accounted for themajority(>71.16%).Given that halogenated aromatic DBPs are intermediate products of halogenated aliphatic DBPs,controlling the formation of halogenated aromatic DBPs is beneficial in decreasing the formation of halogenated aliphatic DBPs,thereby diminishing the toxicity of drinking water.
基金Project supported by China Baowu Low Carbon Metallurgy Innovation Foundation(BWLCF202121)Jiangxi Provincial Key Laboratory of Flash Green Development and Recycling(20193BCD40019)+1 种基金Academic and Technical Leaders of Major Disciplines in Jiangxi Province(20213BCJ22003)Yichun Science and Technology Plan Project(2023YBKJGG04)。
文摘Due to the lack of effective screening systems in the rare earth waste recycling industry,the composition of rare earth elements in rare earth waste is complex and difficult to separate.In response to such problems,by studying the reaction behavior between various elements in rare earth waste and cobalt chloride,we propose a process path for the separation and recovery of iron,cerium and other rare earth elements using cobalt chloride roasting.The experiments on simulated wastes show that the leaching rates of the Nd,Sm,Gd,Pr can reach 98.31%,94.5%,93.87%and 72.05%under the optimal process conditions,respectively.Ce and iron remain in the leaching residue in the form of CeO_(2)and CoFe_(2)O_(4),respectively.And through a simple magnetic separation process,CeO_(2)and CoFe_(2)O_(4)can be enriched in non-magnetic leaching residue and magnetic leaching residue,respectively.The cerium content in the leaching residue composed of cobalt ferrite is only 1.95%.Therefore,this method is beneficial to the separation and high-value utilization of iron,cerium,and other rare earth elements in the waste system.The research results can provide theoretical reference for the low-cost and high-value recovery of rare earth secondary resources.
基金supported by the National Natural Science Foundation of China(Nos.22208376,UA22A20429)Shandong Provincial Natural Science Foundation(Nos.ZR2024QB175,ZR2023LFG005)+1 种基金Qingdao New Energy Shandong Laboratory Open Project(QNESL OP 202303)Ministry of Education University-Industry Collaborative Education Program(No.230804132140429).
文摘Seawater electrolysis offers a promising pathway to generate green hydrogen,which is crucial for the net-zero emission targets.Indirect seawater electrolysis is severely limited by high energy demands and system complexity,while the direct seawater electrolysis bypasses pre-treatment,offering a simpler and more cost-effective solution.However,the chlorine evolution reaction and impurities in the seawater lead to severe corrosion and hinder electrolysis’s efficiency.Herein,we review recent advances in the rational design of chlorine-suppressive catalysts and integrated electrolysis systems architectures for chloride-induced corrosion,with simultaneous enhancement of Faradaic efficiency and reduction of electrolysis’s cost.Furthermore,promising directions are proposed for durable and efficient seawater electrolysis systems.This review provides perspectives for seawater electrolysis toward sustainable energy conversion and environmental protection.
基金supported by the Fundamental Research Funds for the Central Universities(Nos.KYCYXT2023001,and XUEKEN2022034).
文摘Currently,ferrate(VI)oxidation technology(FOT)has been regarded as one of the most promising options for the degradation of emerging organic pollutants.However,the role and transformation of chloride ions(Cl^(−))in FOT have not been well explored.The current study aims to investigate the formation of chlorinated phenolic byproducts upon ferrate(VI)oxidation processes.The obtained results indicate that chlorides suffering ferrate(VI)attack will be transformed to active chlorine species(ACS),which will subsequently lead to the formation of highly toxic aromatic chlorinated byproducts.The identified byproducts include common chlorinated phenolic derivatives,as well as complex chlorinated oligomer byproducts with ether structures(mainly dimers and trimers).While the formation of common chlorophenols can be ascribed to the electrophilic substitution reactions mediated by ACS,the oligomer byproducts are generated via coupling reactions between chlorinated phenoxy radicals.ECOSAR software predicts that the generated chlorinated oligomer byproducts exhibit high ecotoxicological effects.As a whole,the above findings shed light on the potential risk of FOT in real practice.
文摘Weight lost method was used to comparatively study the corrosion behavior of four different metals under the dosage of chlorine dioxide, chlorine and their mixture respectively. The experimental results indicated that chlorine causes the most serious corrosion of carbon steel, and the higher the concentration of chlorine, the more serious the corrosion. On the contrary, metals corrosion is the least serious in the case of chlorine dioxide. The results further revealed that chlorine dioxide is the most effective water treatment reagent, making it the best choice to use extensively in circulated cooling water disinfection and corrosion control.
文摘Based on the mechanism analysis of the polychlorination of long chain n-alkanes by photo-initiation,a kinetic model was developed. The model parameters were obtained by the method of non-linear fitting. The influences of luminous intensity and concentration of molecular chlorine on the rate of polychlorination are demonstrated by the model. If the luminous intensity is adequate, the polychlorination rate of n-alkane is only controlled by the flow rate of molecular chlorine in a wide range of temperature, and the changes of temperature and luminous intensity have less effect on the reaction rate. In addition, the predictions of chlorine content of polychlorinated n-alkane calculated with the model agree very well with experimental results.
文摘Chlorination roasting followed by water leaching process was used to extract lithium from lepidolite.The microstructure of the lepidolite and roasted materials were characterized by X-ray diffraction（XRD）.Various parameters including chlorination roasting temperature,time,type and amount of chlorinating agents were optimized.The conditional experiments indicate that the best mass ratio of lepidolite to NaCl to CaCl2 is 1：0.6：0.4 during the roasting process.The extraction of lithium reaches peak value of 92.86% at 880 °C,potassium,rubidium,and cesium 88.49%,93.60% and 93.01%,respectively.The XRD result indicates that the major phases of the product after roasting lepidolite with mixture of chlorinating agents（CaCl2 and NaCl） are SiO2,CaF2,KCl,CaSiO3,CaAl2Si2O8,NaCl and NaAlSi3O8.
基金Project (u0837604) supported by the Joint Funds of the National Natural Science Foundation of China and Yunnan ProvinceProject (20095314110003) supported by the Special Research Funds of the Doctor Subject of Higher School,China
文摘Behaviors of TiO2 in the alumina carbothermic reduction and chlorination process in vacuum at different temperatures were investigated experimentally by means of XRD,SEM and EDS.In the preparation of materials,the molar ratio of Al2O3 to C was 1：4,and 10% TiO2 and excess AlCl3 were added.The results show that TiC is produced by C and TiO2 after TiO2 transforms from anatase into rutile gradually.In the temperature range of 1 763？1 783 K,the compounds of Ti and Al are not found in slags and condensate.The purity of aluminum reaches 98.35%,and TiO2 does not participate in alumina carbothermic reduction process and chlorination process in vacuum.
文摘Cyclops of zooplankton propagated excessively in eutrophic water body and could not be effectively inactivated by the conventional disinfections process like chlorination due to its stronger resistance to oxidation. In this paper, a full-scale study of chlorine dioxide preoxidation cooperating with routine clarification process for Cyclops removal was conducted in a waterworks. The experimental results were compared with that of the existing prechlorination process in several aspects: including the Cyclops removal efficiencies of water samples taken from the outlets of sedimentation tank and sand filter and the security of drinking water and so on. The results showed that chlorine dioxide might be more effective to inactivate Cyclops than chlorine and Cyclops could be thoroughly removed from water by pre-dosing chlorine dioxide process. The GC-MS examination and Ames test further showed that the sort and amount of organic substance in the treated water by chlorine dioxide preoxidation were evidently less than that of prechlorination and the mutagenicity of drinking water treated by pre-dosing chlorine dioxide was substantially reduced compared with prechlorination.
基金supported by the National Natural Science Foundation of China(No.21677112)the Science and Technology Program of Ministry of Housing and Urban–Rural Development(No.2015-K7-021)
文摘Hazardous waste dechlorination reduces the potential of creating dioxins during the incineration process. To investigate the salt effect on waste dechlorination, molten hydroxides with a low melting temperature were utilized for the pre-dechlorination and decomposition of chlorine-containing organic wastes(COWs) including trichlorobenzene(TCB),perchloroethylene, hexachlorobenzene and chlordane. The results showed that a eutectic mixture of caustic sodium and potassium hydroxides(41 wt.% NaOH and 59 wt.% KOH) led to a low melting point below 300°C and a relatively high chlorine retention efficiency(CRE) with TCB as a representative COWs. The amounts of hydroxides, reaction time, and temperature all had notable influence on CRE. When the mass ratio of hydroxides to TCB reached 30:1,approximately 98.1% of the TCB was destroyed within 2.5 hr at 300°C with CRE of 71.6%.According to the residue analysis, the shapes of reaction residues were irregular with particles becoming swollen and porous. The benzene ring and C–Cl bonds disappeared, while carboxyl groups formed in the residues. The stripped chlorine was retained and condensed to form chloride salts, and the relative abundance of the chloride ions associated with the mass of TCB in residues increased from 0 to 75.0% within the 2.5 hr reaction time. The observed concentration of dioxins in residues was 5.6 ngTEQ/kg. A reaction pathway and possible additional reactions that occur in this dechlorination system were proposed. Oxidizing agents may attack TCB and facilitate hydrogenation/dechlorination reactions, making this process a promising and environmentally friendly approach for chlorine-containing organic waste treatment.
文摘A method was developed for determination of chlorine and bromine in plant materials by ion chromatography using temperature programing-semi molten for sample preparation. Values of detection limits of the method found were 1.0×10^-5 for CI and 1.3×10^-6 for Br. The measuring range of the method found were 0.3-20.0 mg/L for CI and 4,0-120,0 μg/L for Br. The results obtained agreed quite well with those reference values.
