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
It has been shown clinically that continuous removal of ischemia/reperfusion-induced reactive oxygen species is not conducive to the recovery of late stroke.Indeed,previous studies have shown that excessive increases ...It has been shown clinically that continuous removal of ischemia/reperfusion-induced reactive oxygen species is not conducive to the recovery of late stroke.Indeed,previous studies have shown that excessive increases in hypochlorous acid after stroke can cause severe damage to brain tissue.Our previous studies have found that a small amount of hypochlorous acid still exists in the later stage of stroke,but its specific role and mechanism are currently unclear.To simulate stroke in vivo,a middle cerebral artery occlusion rat model was established,with an oxygen-glucose deprivation/reoxygenation model established in vitro to mimic stroke.We found that in the early stage(within 24 hours)of ischemic stroke,neutrophils produced a large amount of hypochlorous acid,while in the recovery phase(10 days after stroke),microglia were activated and produced a small amount of hypochlorous acid.Further,in acute stroke in rats,hypochlorous acid production was prevented using a hypochlorous acid scavenger,taurine,or myeloperoxidase inhibitor,4-aminobenzoic acid hydrazide.Our results showed that high levels of hypochlorous acid(200μM)induced neuronal apoptosis after oxygen/glucose deprivation/reoxygenation.However,in the recovery phase of the middle cerebral artery occlusion model,a moderate level of hypochlorous acid promoted the proliferation and differentiation of neural stem cells into neurons and astrocytes.This suggests that hypochlorous acid plays different roles at different phases of cerebral ischemia/reperfusion injury.Lower levels of hypochlorous acid(5 and 100μM)promoted nuclear translocation ofβ-catenin.By transfection of single-site mutation plasmids,we found that hypochlorous acid induced chlorination of theβ-catenin tyrosine 30 residue,which promoted nuclear translocation.Altogether,our study indicates that maintaining low levels of hypochlorous acid plays a key role in the recovery of neurological function.展开更多
Wastewater electrolysis cells(WECs)for decentralized wastewater treatment/reuse coupled with H_(2) production can reduce the carbon footprint associated with transportation of water,waste,and energy carrier.This study...Wastewater electrolysis cells(WECs)for decentralized wastewater treatment/reuse coupled with H_(2) production can reduce the carbon footprint associated with transportation of water,waste,and energy carrier.This study reports Ir-doped NiFe_(2)O_(4)(NFI,~5 at%Ir)spinel layer with TiO_(2) overlayer(NFI/TiO_(2)),as a scalable heterojunction anode for direct electrolysis of wastewater with circumneutral pH in a single-compartment cell.In dilute(0.1 M)NaCl solutions,the NFI/TiO_(2) marks superior activity and selectivity for chlorine evolution reaction,outperforming the benchmark IrO_(2).Robust operation in near-neutral pH was confirmed.Electroanalyses including operando X-ray absorption spectroscopy unveiled crucial roles of TiO_(2) which serves both as the primary site for Cl−chemisorption and a protective layer for NFI as an ohmic contact.Galvanostatic electrolysis of NH4+-laden synthetic wastewater demonstrated that NFI/TiO_(2)not only achieves quasi-stoichiometric NH_(4)^(+)-to-N_(2)conversion,but also enhances H_(2)generation efficiency with minimal competing reactions such as reduction of dissolved oxygen and reactive chlorine.The scaled-up WEC with NFI/TiO_(2)was demonstrated for electrolysis of toilet wastewater.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
Based on first-principles calculation framework,the surface model,anodic dissolution,cathodic oxygen absorption reaction,and other related electrochemical corrosion models of Fe-Ce system were constructed,and the infl...Based on first-principles calculation framework,the surface model,anodic dissolution,cathodic oxygen absorption reaction,and other related electrochemical corrosion models of Fe-Ce system were constructed,and the influencing mechanism Ce doping on the corrosion resistance of Fe-Ce system in the Cl medium environment was analyzed.The results show that Ce doping on the first surface and subsurface inhibits the ionization of Fe atoms and greatly promotes the repassivation process of Fe matrix.Ce doping on the first layer is conducive to preventing the detachment of surface Fe atoms from Fe matrix and delaying the occurrence of corrosion.Ce atoms in the subsurface effectively increase the difficulty of Fe atoms detaching from the matrix at high Cl concentrations.When O diffusion is the controlling link of oxygen absorption reaction,Ce doping has no effects on the reaction rate of cathodic oxygen absorption.Ce doping enhances the electrochemical stability of Fe(100)1and reduces the anodic dissolution rate of Fe matrix,thereby improving its corrosion resistance.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
Reclaimed water for irrigation or hydroponic cultivation provides exposure pathways for per-and polyfluoroalkyl substances(PFAS)to enter the human food chain.This study employed hydroponic methods to investigate the b...Reclaimed water for irrigation or hydroponic cultivation provides exposure pathways for per-and polyfluoroalkyl substances(PFAS)to enter the human food chain.This study employed hydroponic methods to investigate the behavior of legacy PFAS and emerging chlorinated polyfluoroalkyl ether sulfonic acids(Cl-PFESAs)in lettuce grown under environment-related exposure levels and assessed the human exposure risks from consuming contaminated lettuce.Overall,PFAS in lettuce were concentration-dependent,with long-chain PFAS tending to accumulate in roots and short-chain PFAS accumulating more in shoots.The enrichment of PFAS in lettuce was jointly influenced by their chain length and polar functional groups.Specifically,the root concentration factors(RCFs)of PFAS generally increased with increasing chain length,and RCF values of most perfluoroalkanesulfonic acids(PFSAs)were significantly higher than those of perfluoroalkyl carboxylic acids(PFCAs)with the same chain length(p<0.01),while the translocation factors(TFs)exhibited opposite trends.RCF values of perfluorooctane sulfonate(PFOS)and its alternatives,Cl-PFESAs,were ranked as follows:8:2 Cl-PFESA(mean:139)>6:2 Cl-PFESA(28.6)>PFOS(25.7),which was attributed to the increased molecular size and hydrophobicity resulting from the insertion of ether bonds and additional CF2 in 8:2 Cl-PFESA.Notably,TF value of 8:2 Cl-PFESA(mean:0.007)was the smallest among all PFAS,indicating 8:2 Cl-PFESA was difficult to transfer to nutritional compartments.Adults and children would exceed the most conservative health-based reference dose(RfD)by consuming approximately 15.9–148 g and 7.92–74.0 g of contaminated lettuce per day,implying high health risks.展开更多
Direct electrolysis of seawater to produce green hydrogen is a more environmentally friendly process than freshwater electrolysis.The renewable energy sector exhibits tremendous interest in practical seawater electrol...Direct electrolysis of seawater to produce green hydrogen is a more environmentally friendly process than freshwater electrolysis.The renewable energy sector exhibits tremendous interest in practical seawater electrolysis techniques due to its substantial capacity to mitigate the need for freshwater consumption.With the low catalytic efficiency of the current seawater splitting process and the poor reliability of its operation,the process suffers from severe corrosion caused by chloride ions,as well as anodic competition between oxygen evolution and chlorine oxidation reactions.This review provides an overview of the latest electrocatalyst developments for promoting selectivity and stability in seawater electrolysis.Using the characterization and simulation results,as well as active machine learning,advanced electrocatalytic materials can be designed and developed,a research direction that will become increasingly important in the future.A variety of strategies are discussed in detail for designing advanced electrocatalysts in seawater electrolysis,including the surface protective layer,structural regulation by heteroatom doping and vacancies,porous structure,core-shell construction,and 3D hetero-structure construction to hinder chlorine evolution reactions.Finally,future perspectives and challenges for green hydrogen production from seawater electrolysis are also described.展开更多
In early 2019, Mozambique was struck by two cyclones, Cyclone Idai in Sofala Province and Cyclone Kenneth in Cabo Delgado Province. Outbreaks of cholera were declared soon after both cyclones in Beira and Pemba cities...In early 2019, Mozambique was struck by two cyclones, Cyclone Idai in Sofala Province and Cyclone Kenneth in Cabo Delgado Province. Outbreaks of cholera were declared soon after both cyclones in Beira and Pemba cities. In response to the emergencies and outbreaks, government and humanitarian partners collaborated to create a mobile phone based water quality monitoring program to monitor daily free residual chlorine (FRC) levels in the piped network in both locations and at accommodation centers created for internally displaced persons in Beira. Overall, 87% of the 1080 samples from the piped network in Beira had detectable FRC and at accommodation centers, 73% of the 179 samples collected had detectable FRC. In Pemba, 64% of the 114 total samples collected had detectable FRC. Data from the water quality monitoring programs allowed for the identification of trends that helped increase the effectiveness of the response, including identifying areas where chlorination could be strengthened with the installation of booster chlorinators, issues with the consistency of daily chlorine treatment, and sites where water availability was limited. The water quality monitoring activities were a result of productive collaboration and could be replicated after similar emergencies in cholera endemic areas to prevent and control outbreaks.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
Rechargeable chlorine-based battery recently emerged as a promising substitute for energy storage systems due to their high average operating voltage(~3.7 V)and large theoretical capacity of~754.9 mAh g-1.However,insu...Rechargeable chlorine-based battery recently emerged as a promising substitute for energy storage systems due to their high average operating voltage(~3.7 V)and large theoretical capacity of~754.9 mAh g-1.However,insufficient supply of chlorine(Cl_(2))and sluggish oxidation of NaCl to Cl_(2) limit its practical application.Covalent Organic Frameworks(COFs)have the potential to be ideal Cl_(2) host materials as Cl_(2) adsorbents for their abundant porosity and easily modifiable nature.In this work,the single atom Mn coordinated biomimetic phthalocyanine COFs are used for Cl_(2) capture and catalyst.The DFT reveals that ASMn and-NH_(2) significantly change the microenvironment around the active site,effectively promoting the oxidation of NaCl.When applied as the cathode material for Na-Cl_(2) batteries,the SAMn-COFs-NH2 electrode exhibits large reversible capacities and excellent high-rate cycling performances throughout 200 cycles based on the mechanism of highly reversible NaCl/Cl_(2) redox reactions.Even at the temperature as low as-40℃,the SAMn-COFs-NH2 cathode showed stable discharge ca-pacities at~1000 mAh g^(-1) over 50 cycles with a voltage plateau of~3.3 V.This work may provide new insights for the investigation of chlorine-based electrochemical redox mechanisms and the design of green nanoscaled electrodes for high-property chlorine-based batteries.展开更多
A mixed oxidant of chlorine dioxide(ClO_(2))and NaClO was often used in water treatment.A novel UVA-LED(_(365) nm)-activated mixed ClO_(2)/NaClO process was proposed for the degradation of micropollutants in this stud...A mixed oxidant of chlorine dioxide(ClO_(2))and NaClO was often used in water treatment.A novel UVA-LED(_(365) nm)-activated mixed ClO_(2)/NaClO process was proposed for the degradation of micropollutants in this study.Carbamazepine(CBZ)was selected as the target pollutant.Compared with the UVA_(365)/ClO_(2) process,the UVA_(365)/ClO_(2)/NaClO process can improve the degradation of CBZ,with the rate constant increasing from 2.11×10^(−4) sec^(−1) to 2.74×10^(−4) sec^(−1).In addition,the consumption of oxidants in the UVA_(365)/ClO_(2)/NaClO process(73.67%)can also be lower than that of UVA_(365)/NaClO(86.42%).When the NaClO ratio increased,both the degradation efficiency of CBZ and the consumption of oxidants can increase in the UVA_(365)/ClO_(2)/NaClO process.The solution pH can affect the contribution of NaClO in the total oxidant ratio.When the pH range of 6.0-8.0,the combination process can generate more active species to promote the degradation of CBZ.The change of active species with oxidant molar ratio was investigated in the UVA_(365)/ClO_(2)/NaClO process.When ClO_(2) acted as the main oxidant,HO·and Cl·were the main active species,while when NaClO was the main oxidant,ClO·played a role in the system.Both chloride ion(Cl^(-)),bicarbonate ion(HCO_(3)^(-)),and nitrate ion(NO_(3)^(-))can promote the reaction system.As the concentration of NaClO in the reaction solution increased,the generation of chlorates will decrease.The UVA_(365)/ClO_(2)/NaClO process can effectively control the formation of volatile disinfection by-products(DBPs),and with the increase of ClO_(2) dosage,the formation of DBPs can also decrease.展开更多
The underutilization of production capacity in recycling waste lithium-ion battery(LIB)highlights the demand for cost-effective and eco-friendly processes.This study challenges conventional practices by proposing a pr...The underutilization of production capacity in recycling waste lithium-ion battery(LIB)highlights the demand for cost-effective and eco-friendly processes.This study challenges conventional practices by proposing a product-oriented strategy that converts spent LIB into functional materials rather than only conventional metal salts.Phase evolution thermodynamics first identifies the conditions for selective extraction,enabling a novel oxygen-assisted chlorination roasting system.This single-step process achieves two transformative outcomes:lithium is converted to carbonate product,while cobalt is reconstructed into a functional catalyst serving as peroxymonosulfate activators.Specifically,99%of Li is recovered as lithium carbonate(99.6%purity),while upcycled catalyst demonstrates equivalent performance to commercial alternatives,achieving>98%efficiency in model reactions.Besides,system scaling analysis confirms dual sustainability advantages.Life-cycle assessment reveals a 61.5%reduction in carbon footprint compared to traditional recycling,while techno-economic analysis shows 50%higher profitability.This paradigm shift from simple metal recovery to functional material synthesis addresses both environmental and economic challenges in LIB recycling.Our findings demonstrate that this product design can enhance sustainability without compromising technical performance,providing a new slight for LIB recycling.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
Reducing the cost of RuO_(2)/TiO_(2)catalysts is still one of the urgent challenges in catalytic HCl oxidation.In the present work,a Ce-doped TiO_(2)supported RuO_(2)catalyst with a low Ru loading was developed,showin...Reducing the cost of RuO_(2)/TiO_(2)catalysts is still one of the urgent challenges in catalytic HCl oxidation.In the present work,a Ce-doped TiO_(2)supported RuO_(2)catalyst with a low Ru loading was developed,showing a high activity in the catalytic oxidation of HCl to Cl_(2).The results on some extensive characterizations of both Ce-doped TiO_(2)carriers and their supported RuO_(2)catalysts show that the doping of Ce into TiO_(2)can effectively change the lattice parameters of TiO_(2)to improve the dispersion of the active RuO_(2)species on the carrier,which facilitates the production of surface Ru species to expose more active sites for boosting the catalytic performance even under some harsh reaction conditions.This work provides some scientific basis and technical support for chlorine recycling.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supported by the Natural Science Foundation of Jiangsu Province of China,No.BK20211348(to SHQ)Xuzhou Basic Research Program,No.KC21030(to LYH)+1 种基金Leadership Program of Xuzhou Medical University,No.JBGS202203(to SHQ)Research Grant Council GRF of Hong Kong Special Administrative Region of China,No.17105220(to JGS)。
文摘It has been shown clinically that continuous removal of ischemia/reperfusion-induced reactive oxygen species is not conducive to the recovery of late stroke.Indeed,previous studies have shown that excessive increases in hypochlorous acid after stroke can cause severe damage to brain tissue.Our previous studies have found that a small amount of hypochlorous acid still exists in the later stage of stroke,but its specific role and mechanism are currently unclear.To simulate stroke in vivo,a middle cerebral artery occlusion rat model was established,with an oxygen-glucose deprivation/reoxygenation model established in vitro to mimic stroke.We found that in the early stage(within 24 hours)of ischemic stroke,neutrophils produced a large amount of hypochlorous acid,while in the recovery phase(10 days after stroke),microglia were activated and produced a small amount of hypochlorous acid.Further,in acute stroke in rats,hypochlorous acid production was prevented using a hypochlorous acid scavenger,taurine,or myeloperoxidase inhibitor,4-aminobenzoic acid hydrazide.Our results showed that high levels of hypochlorous acid(200μM)induced neuronal apoptosis after oxygen/glucose deprivation/reoxygenation.However,in the recovery phase of the middle cerebral artery occlusion model,a moderate level of hypochlorous acid promoted the proliferation and differentiation of neural stem cells into neurons and astrocytes.This suggests that hypochlorous acid plays different roles at different phases of cerebral ischemia/reperfusion injury.Lower levels of hypochlorous acid(5 and 100μM)promoted nuclear translocation ofβ-catenin.By transfection of single-site mutation plasmids,we found that hypochlorous acid induced chlorination of theβ-catenin tyrosine 30 residue,which promoted nuclear translocation.Altogether,our study indicates that maintaining low levels of hypochlorous acid plays a key role in the recovery of neurological function.
基金supported by the National Research Foundation of Korea(NRF)grants(2022R1A2C4001228,2022M3H4A4097524,2022M3I3A1082499,and 2021M3I3A1084818)the Technology Innovation Program(20026415)of the Ministry of Trade,Industry&Energy(MOTIE,Korea)the supports from Nanopac for fabrication of scaled-up reactor.
文摘Wastewater electrolysis cells(WECs)for decentralized wastewater treatment/reuse coupled with H_(2) production can reduce the carbon footprint associated with transportation of water,waste,and energy carrier.This study reports Ir-doped NiFe_(2)O_(4)(NFI,~5 at%Ir)spinel layer with TiO_(2) overlayer(NFI/TiO_(2)),as a scalable heterojunction anode for direct electrolysis of wastewater with circumneutral pH in a single-compartment cell.In dilute(0.1 M)NaCl solutions,the NFI/TiO_(2) marks superior activity and selectivity for chlorine evolution reaction,outperforming the benchmark IrO_(2).Robust operation in near-neutral pH was confirmed.Electroanalyses including operando X-ray absorption spectroscopy unveiled crucial roles of TiO_(2) which serves both as the primary site for Cl−chemisorption and a protective layer for NFI as an ohmic contact.Galvanostatic electrolysis of NH4+-laden synthetic wastewater demonstrated that NFI/TiO_(2)not only achieves quasi-stoichiometric NH_(4)^(+)-to-N_(2)conversion,but also enhances H_(2)generation efficiency with minimal competing reactions such as reduction of dissolved oxygen and reactive chlorine.The scaled-up WEC with NFI/TiO_(2)was demonstrated for electrolysis of toilet wastewater.
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Project supported by the National Natural Science Foundation of China(52364044,52204364)Scientific Research Special Project for First-Class Disciplines of Education Department of Inner Mongolia Autonomous Region(YLXKZX-NKD-001,YLXKZX-NKD-011)Basic Scientific Research Business Expenses of Colleges and Universities of Inner Mongolia Autonomous Region(2023QNJS011)。
文摘Based on first-principles calculation framework,the surface model,anodic dissolution,cathodic oxygen absorption reaction,and other related electrochemical corrosion models of Fe-Ce system were constructed,and the influencing mechanism Ce doping on the corrosion resistance of Fe-Ce system in the Cl medium environment was analyzed.The results show that Ce doping on the first surface and subsurface inhibits the ionization of Fe atoms and greatly promotes the repassivation process of Fe matrix.Ce doping on the first layer is conducive to preventing the detachment of surface Fe atoms from Fe matrix and delaying the occurrence of corrosion.Ce atoms in the subsurface effectively increase the difficulty of Fe atoms detaching from the matrix at high Cl concentrations.When O diffusion is the controlling link of oxygen absorption reaction,Ce doping has no effects on the reaction rate of cathodic oxygen absorption.Ce doping enhances the electrochemical stability of Fe(100)1and reduces the anodic dissolution rate of Fe matrix,thereby improving its corrosion resistance.
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 Fundamental Research Funds for Central Non-profit Scientific Institution(No.1610132022015)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0750200)the National Natural Science Foundation of China(No.22176198).
文摘Reclaimed water for irrigation or hydroponic cultivation provides exposure pathways for per-and polyfluoroalkyl substances(PFAS)to enter the human food chain.This study employed hydroponic methods to investigate the behavior of legacy PFAS and emerging chlorinated polyfluoroalkyl ether sulfonic acids(Cl-PFESAs)in lettuce grown under environment-related exposure levels and assessed the human exposure risks from consuming contaminated lettuce.Overall,PFAS in lettuce were concentration-dependent,with long-chain PFAS tending to accumulate in roots and short-chain PFAS accumulating more in shoots.The enrichment of PFAS in lettuce was jointly influenced by their chain length and polar functional groups.Specifically,the root concentration factors(RCFs)of PFAS generally increased with increasing chain length,and RCF values of most perfluoroalkanesulfonic acids(PFSAs)were significantly higher than those of perfluoroalkyl carboxylic acids(PFCAs)with the same chain length(p<0.01),while the translocation factors(TFs)exhibited opposite trends.RCF values of perfluorooctane sulfonate(PFOS)and its alternatives,Cl-PFESAs,were ranked as follows:8:2 Cl-PFESA(mean:139)>6:2 Cl-PFESA(28.6)>PFOS(25.7),which was attributed to the increased molecular size and hydrophobicity resulting from the insertion of ether bonds and additional CF2 in 8:2 Cl-PFESA.Notably,TF value of 8:2 Cl-PFESA(mean:0.007)was the smallest among all PFAS,indicating 8:2 Cl-PFESA was difficult to transfer to nutritional compartments.Adults and children would exceed the most conservative health-based reference dose(RfD)by consuming approximately 15.9–148 g and 7.92–74.0 g of contaminated lettuce per day,implying high health risks.
基金part of a research project, PIF 726175Alfaisal University and its Office of Research & Innovation for their continuous support throughout this study。
文摘Direct electrolysis of seawater to produce green hydrogen is a more environmentally friendly process than freshwater electrolysis.The renewable energy sector exhibits tremendous interest in practical seawater electrolysis techniques due to its substantial capacity to mitigate the need for freshwater consumption.With the low catalytic efficiency of the current seawater splitting process and the poor reliability of its operation,the process suffers from severe corrosion caused by chloride ions,as well as anodic competition between oxygen evolution and chlorine oxidation reactions.This review provides an overview of the latest electrocatalyst developments for promoting selectivity and stability in seawater electrolysis.Using the characterization and simulation results,as well as active machine learning,advanced electrocatalytic materials can be designed and developed,a research direction that will become increasingly important in the future.A variety of strategies are discussed in detail for designing advanced electrocatalysts in seawater electrolysis,including the surface protective layer,structural regulation by heteroatom doping and vacancies,porous structure,core-shell construction,and 3D hetero-structure construction to hinder chlorine evolution reactions.Finally,future perspectives and challenges for green hydrogen production from seawater electrolysis are also described.
文摘In early 2019, Mozambique was struck by two cyclones, Cyclone Idai in Sofala Province and Cyclone Kenneth in Cabo Delgado Province. Outbreaks of cholera were declared soon after both cyclones in Beira and Pemba cities. In response to the emergencies and outbreaks, government and humanitarian partners collaborated to create a mobile phone based water quality monitoring program to monitor daily free residual chlorine (FRC) levels in the piped network in both locations and at accommodation centers created for internally displaced persons in Beira. Overall, 87% of the 1080 samples from the piped network in Beira had detectable FRC and at accommodation centers, 73% of the 179 samples collected had detectable FRC. In Pemba, 64% of the 114 total samples collected had detectable FRC. Data from the water quality monitoring programs allowed for the identification of trends that helped increase the effectiveness of the response, including identifying areas where chlorination could be strengthened with the installation of booster chlorinators, issues with the consistency of daily chlorine treatment, and sites where water availability was limited. The water quality monitoring activities were a result of productive collaboration and could be replicated after similar emergencies in cholera endemic areas to prevent and control outbreaks.
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supported by the National Natural Science Foundation of China(32371809)the Zhejiang Public Welfare Public Research Program(LGC22B010001)the Fundamental Research Funds for the Provincial University of Zhejiang(2024TD002).
文摘Rechargeable chlorine-based battery recently emerged as a promising substitute for energy storage systems due to their high average operating voltage(~3.7 V)and large theoretical capacity of~754.9 mAh g-1.However,insufficient supply of chlorine(Cl_(2))and sluggish oxidation of NaCl to Cl_(2) limit its practical application.Covalent Organic Frameworks(COFs)have the potential to be ideal Cl_(2) host materials as Cl_(2) adsorbents for their abundant porosity and easily modifiable nature.In this work,the single atom Mn coordinated biomimetic phthalocyanine COFs are used for Cl_(2) capture and catalyst.The DFT reveals that ASMn and-NH_(2) significantly change the microenvironment around the active site,effectively promoting the oxidation of NaCl.When applied as the cathode material for Na-Cl_(2) batteries,the SAMn-COFs-NH2 electrode exhibits large reversible capacities and excellent high-rate cycling performances throughout 200 cycles based on the mechanism of highly reversible NaCl/Cl_(2) redox reactions.Even at the temperature as low as-40℃,the SAMn-COFs-NH2 cathode showed stable discharge ca-pacities at~1000 mAh g^(-1) over 50 cycles with a voltage plateau of~3.3 V.This work may provide new insights for the investigation of chlorine-based electrochemical redox mechanisms and the design of green nanoscaled electrodes for high-property chlorine-based batteries.
基金supported by the National Natural Science Foundation of China (No.52170006)。
文摘A mixed oxidant of chlorine dioxide(ClO_(2))and NaClO was often used in water treatment.A novel UVA-LED(_(365) nm)-activated mixed ClO_(2)/NaClO process was proposed for the degradation of micropollutants in this study.Carbamazepine(CBZ)was selected as the target pollutant.Compared with the UVA_(365)/ClO_(2) process,the UVA_(365)/ClO_(2)/NaClO process can improve the degradation of CBZ,with the rate constant increasing from 2.11×10^(−4) sec^(−1) to 2.74×10^(−4) sec^(−1).In addition,the consumption of oxidants in the UVA_(365)/ClO_(2)/NaClO process(73.67%)can also be lower than that of UVA_(365)/NaClO(86.42%).When the NaClO ratio increased,both the degradation efficiency of CBZ and the consumption of oxidants can increase in the UVA_(365)/ClO_(2)/NaClO process.The solution pH can affect the contribution of NaClO in the total oxidant ratio.When the pH range of 6.0-8.0,the combination process can generate more active species to promote the degradation of CBZ.The change of active species with oxidant molar ratio was investigated in the UVA_(365)/ClO_(2)/NaClO process.When ClO_(2) acted as the main oxidant,HO·and Cl·were the main active species,while when NaClO was the main oxidant,ClO·played a role in the system.Both chloride ion(Cl^(-)),bicarbonate ion(HCO_(3)^(-)),and nitrate ion(NO_(3)^(-))can promote the reaction system.As the concentration of NaClO in the reaction solution increased,the generation of chlorates will decrease.The UVA_(365)/ClO_(2)/NaClO process can effectively control the formation of volatile disinfection by-products(DBPs),and with the increase of ClO_(2) dosage,the formation of DBPs can also decrease.
基金supported by the Natural Science Foundation of Xiamen,China(3502Z202372038)the Opening Project of Key Laboratory of Solid Waste Treatment and Resource Recycle,Ministry of Education(23kfgk04)the Scientific Research Funds of Huaqiao University(Grant ID:20221XD053)。
文摘The underutilization of production capacity in recycling waste lithium-ion battery(LIB)highlights the demand for cost-effective and eco-friendly processes.This study challenges conventional practices by proposing a product-oriented strategy that converts spent LIB into functional materials rather than only conventional metal salts.Phase evolution thermodynamics first identifies the conditions for selective extraction,enabling a novel oxygen-assisted chlorination roasting system.This single-step process achieves two transformative outcomes:lithium is converted to carbonate product,while cobalt is reconstructed into a functional catalyst serving as peroxymonosulfate activators.Specifically,99%of Li is recovered as lithium carbonate(99.6%purity),while upcycled catalyst demonstrates equivalent performance to commercial alternatives,achieving>98%efficiency in model reactions.Besides,system scaling analysis confirms dual sustainability advantages.Life-cycle assessment reveals a 61.5%reduction in carbon footprint compared to traditional recycling,while techno-economic analysis shows 50%higher profitability.This paradigm shift from simple metal recovery to functional material synthesis addresses both environmental and economic challenges in LIB recycling.Our findings demonstrate that this product design can enhance sustainability without compromising technical performance,providing a new slight for LIB recycling.
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.
基金supported by Zhejiang Provincial Key R&D Project(No.2021C01056)the Programme of Introducing Talents of Discipline to Universities(No.D17008).
文摘Reducing the cost of RuO_(2)/TiO_(2)catalysts is still one of the urgent challenges in catalytic HCl oxidation.In the present work,a Ce-doped TiO_(2)supported RuO_(2)catalyst with a low Ru loading was developed,showing a high activity in the catalytic oxidation of HCl to Cl_(2).The results on some extensive characterizations of both Ce-doped TiO_(2)carriers and their supported RuO_(2)catalysts show that the doping of Ce into TiO_(2)can effectively change the lattice parameters of TiO_(2)to improve the dispersion of the active RuO_(2)species on the carrier,which facilitates the production of surface Ru species to expose more active sites for boosting the catalytic performance even under some harsh reaction conditions.This work provides some scientific basis and technical support for chlorine recycling.
