The Dexing porphyry deposit is the largest porphyry Cu–Mo–Au deposit in South China.Biotite composition can record the physicochemical conditions and evolution history of magmatic-hydrothermal system.Biotite from th...The Dexing porphyry deposit is the largest porphyry Cu–Mo–Au deposit in South China.Biotite composition can record the physicochemical conditions and evolution history of magmatic-hydrothermal system.Biotite from the Dexing porphyry deposit could be divided to three types:primary magmatic biotite(Bi-M),hydrothermal altered magmatic biotite(Bi-A)and hydrothermal biotite(Bi-H).The temperature of Bi-M and Bi-H range from 719 to 767℃ and 690 to 727℃,respectively.Both magmatic and hydrothermal biotite have high Fe^(3+)/Fe^(2+)ratios(from 0.18 to 0.24)and XMgvalues(from 0.57 to 0.66),indicating a high oxygen fugacity.BiM has F lower than Bi-A and Bi-H(up to 0.26 wt%),but has Cl(Cl=0.18–0.30 wt%)similar to Bi-A and Bi-H(Cl=0.21–0.35 wt%),suggesting that high Cl/F ratios of early hydrothermal fluid may result from the exsolution from high Cl magma.From potassic alteration zone to phyllic and propylitic alteration zones,Cl decreases with increasing Cu,whereas F increases roughly.Therefore,Cl mostly originate from magma,but enrichment of F possibly results from reaction of fluids and Neoproterozoic strata.Negative correlation between Cl and Cu indicates that Cl might act as an important catalyst during Cu mineralization process.Biotite from Dexing has similar halogen compositions to other porphyry Cu-/Mo deposits in the world.Chlorine contents of hydrothermal fluid may be critical for Cu transportation and enrichment,while consumption of Cl would promote Cu deposition.展开更多
The reactive halogens play key roles in the destruction of boundary layer ozone by catalytic reactions and provide a fast pathway to the sedimentation of elemental gaseous mercury.The presence of bromine oxides in the
The three halogen solids(Cl_(2),Br_(2),and I_(2))have the isostructural diatomic molecular phaseⅠwith a space group of Cmca at ambient pressure.At high pressure,they all go through an intermediate phaseⅤwith incomme...The three halogen solids(Cl_(2),Br_(2),and I_(2))have the isostructural diatomic molecular phaseⅠwith a space group of Cmca at ambient pressure.At high pressure,they all go through an intermediate phaseⅤwith incommensurate structures before eventually dissociating into the monatomic phaseⅡ.However,a new structural transition between phaseⅠandⅤwith anomalous bond-length behavior was observed in bromine under pressure,which,so far,has not been confirmed in iodine and chlorine.Here,we perform first-principles calculations for iodine and chlorine.The new structural transition was predicted to be common to all three halogens under pressure.The transition pressures might be systematically underestimated by the imperfect van der Waals correction method,but they follow the order Cl_(2)>Br_(2)>I_(2),which is consistent with other pressure-induced structural transitions such as metallization and the molecular-to-monatomic transition.展开更多
To constrain the ore-fluid source(s)of the Laoshankou Fe-Cu-Au deposit(Junggar orogen,NW China),we analyzed the fluid inclusion(FI)noble gas(Ar,Kr and Xe)and halogen(Cl,Br and I)compositions in the hydrothermal epidot...To constrain the ore-fluid source(s)of the Laoshankou Fe-Cu-Au deposit(Junggar orogen,NW China),we analyzed the fluid inclusion(FI)noble gas(Ar,Kr and Xe)and halogen(Cl,Br and I)compositions in the hydrothermal epidote and quartz.Four hypogene alteration/mineralization stages,including(I)pre-ore Ca-silicate,(II)early-ore amphibole-epidote-magnetite,(III)late-ore pyrite-chalcopyrite,and(IV)post-ore hydrothermal veining,have been identified at Laoshankou.Stage II FIs have salinity of 15.7 wt.%(NaCl eq.),I/Cl molar ratios of 75×10^(−6)-135×10^(−6),and Br/Cl molar ratios of 1.4×10^(−3)-2.1×10^(−3).The moderately-high seawatercorrected Br*/I ratios(0.5-1.5)and low 40ArE/Cl slope(-10−5)indicate the presence of sedimentary marine pore fluid,which was modified by seawater reacting with the Beitashan Fm.volcanic rocks.Stage III fluid is more saline than their stage II and IV counterparts,reaching up to 23.3 wt.%(NaCl+CaCl2 eq.)close to halite saturation(-26 wt.%).The fluid has I/Cl ratios of 75×10^(−6)-90×10^(−6) and Br/Cl ratios of 1.5×10^(−3)-1.8×10^(−3).Considering the increasing 40ArE/Cl trend toward bittern brine and the higher 36Ar content than air-saturated water(ASW),a bittern fluid source is inferred from seawater evaporation,which was modified by interaction with organic-rich marine sedimentary rocks.Stage IV FIs have lower temperature(110-228°C)and Br/Cl(0.90×10^(−3)-1.2×10^(−3)),but higher 36Ar content than ASW,indicative of dissolved evaporite or halite input.Considering also the lowδDfluid(−114‰to−144‰)andδ18Ofluid(2.1‰-3.5‰)values,meteoric water(with minor dissolved evaporites)likely dominated the stage IV fluid.The evaporites may have formed through continuous evaporation of the stage III surface-derived bittern.Involvement of non-magmatic fluids and different ore-fluid origins in stages II and III suggest that the ore-forming process was different from a typical magmatichydrothermal fluid-dominated skarn mineralization,which was previously proposed for Laoshankou.Our noble gas and halogen study at Laoshankou provide new insights on the fluid sources for the Paleozoic Fe−Cu(−Au)deposits in the Central Asian Orogenic Belt(CAOB),and our non-magmatic fluid source interpretation is consistent with the basin inversion setting for the mineralization.展开更多
HALOGENS, as mineralizer elements, have been attracting ever increasing attention of geological workers inpetrogenetically experimental and ore-forming fluid geochemical studies. However, little research workhas been ...HALOGENS, as mineralizer elements, have been attracting ever increasing attention of geological workers inpetrogenetically experimental and ore-forming fluid geochemical studies. However, little research workhas been done on the contents, variation characteristics and significance of halogens in solid ores(rocks). It is found in the study of the Danzhai Hg-Au deposit that (i) variations in the contents ofhalogens and their distribution regularities in solid rocks and ores can shed light on the formation of thedeposit; and (ii) halogens can serve the function of indicator elements in search of buried orebodies. 1 Main characteristics of the ore展开更多
Ensuring the health and safety of drinking water is crucial for both nations and their citizens.Since the 20th century,the disinfection of drinking water,effectively controlling pathogens in water sources,has become o...Ensuring the health and safety of drinking water is crucial for both nations and their citizens.Since the 20th century,the disinfection of drinking water,effectively controlling pathogens in water sources,has become one of the significant advances in public health.However,the disinfectants used in the process,such as chlorine and chlorine dioxide,react with natural organic matter in the water to produce disinfection by-products(DBPs).Most of these DBPs contain chlorine,and if the source water contains bromine or iodine,brominated or iodinated DBPs,collectively referred to as Halogenated disinfection byproducts(X-DBPs),are formed.Numerous studies have found that X-DBPs pose potential risks to human health and the environment,leading to widespread concern.Mass spectrometry has become an important means of discovering new types of X-DBPs.This paper focuses on the study of methods for analyzing X-DBPs in drinking water using mass spectrometry.展开更多
Metal–organic frameworks(MOFs)have attracted significant research interest in biomimetic catalysis.However,the modulation of the activity of MOFs by precisely tuning the coordination of metal nodes is still a signifi...Metal–organic frameworks(MOFs)have attracted significant research interest in biomimetic catalysis.However,the modulation of the activity of MOFs by precisely tuning the coordination of metal nodes is still a significant challenge.Inspired by metalloenzymes with well-defined coordination structures,a series of MOFs containing halogen-coordinated copper nodes(Cu-X MOFs,X=Cl,Br,I)are employed to elucidate their structure–activity relationship.Intriguingly,experimental and theoretical results strongly support that precisely tuning the coordination of halogen atoms directly regulates the enzyme-like activities of Cu-X MOFs by influencing the spatial configuration and electronic structure of the Cu active center.The optimal Cu–Cl MOF exhibits excellent superoxide dismutase-like activity with a specific activity one order of magnitude higher than the reported Cu-based nanozymes.More importantly,by performing enzyme-mimicking catalysis,the Cu–Cl MOF nanozyme can significantly scavenge reactive oxygen species and alleviate oxidative stress,thus effectively relieving ocular chemical burns.Mechanistically,the antioxidant and antiapoptotic properties of Cu–Cl MOF are achieved by regulating the NRF2 and JNK or P38 MAPK pathways.Our work provides a novel way to refine MOF nanozymes by directly engineering the coordination microenvironment and,more significantly,demonstrating their potential therapeutic effect in ophthalmic disease.展开更多
Perovskite solar cells(PSCs)are taking steps to commercialization.However,the halogen-reactive anode with high cost becomes a stumbling block.Here,the halogen migration in PSCs is utilized to in situ generate a unifor...Perovskite solar cells(PSCs)are taking steps to commercialization.However,the halogen-reactive anode with high cost becomes a stumbling block.Here,the halogen migration in PSCs is utilized to in situ generate a uniform tunneling layer between the hole transport materials and anodes,which enriches the options of anodes by breaking the Schottky barrier,enabling the regular PSCs with both high efficiency and stability.Specifically,the regular PSC that uses silver iodide as the tunneling layer and copper as the anode obtains a champion power conversion efficiency of 23.24%(certified 22.74%)with an aperture area of 1.04 cm^(2).The devices are stable,maintaining 98.6%of the initial effi-ciency after 500 h of operation at the maximum power point with continuous 1 sun illumination.PSCs with different tunneling layers and anodes are fabricated,which confirm the generality of the strategy.展开更多
The AOX (adsorbable organic halogens) problem in wool shrinkproofing effluents has attracted more attention in recent years. The probable origins and structures of AOX compounds were proved by the reaction of DCCA wit...The AOX (adsorbable organic halogens) problem in wool shrinkproofing effluents has attracted more attention in recent years. The probable origins and structures of AOX compounds were proved by the reaction of DCCA with the model substances of different amino acid residues. The GC-MS results indicated that available chlorine could chlorinate the side chain of tyrosine, histidine and trypotophan and generate AOX load in the effluent.展开更多
Chlorination occurred simultaneously with oxidationwhen wool was treated by chlorine-containing reagents.The adsorbable organic halogens(AOX) compounds were produced by the chlorination of amino acid residues,especial...Chlorination occurred simultaneously with oxidationwhen wool was treated by chlorine-containing reagents.The adsorbable organic halogens(AOX) compounds were produced by the chlorination of amino acid residues,especially tyrosine residue. The factors that might influence the reaction of dichloroisocyanuric acid (DCCA) with tyrosine residue were discussed. Higher temperature, appropriate pH value and lower concentration of chloride ion are favorable to decrease the percentage of chlorination. Determination of optimum process conditions would be helpful to control AOX compounds formation during wool chlorine pretreatment.展开更多
Organic halogens generated in the chlorlnatlon treatment of wool are proven to be acutely toxic to human beings. Legislation on environmental pollution has become more and more stringent in recent years. So the chlorl...Organic halogens generated in the chlorlnatlon treatment of wool are proven to be acutely toxic to human beings. Legislation on environmental pollution has become more and more stringent in recent years. So the chlorlnation treatment is faced with disuse. Alkaline hydrolysis is adopted to reduce the AOX (Absorbable Organic Halogen) concentrations in the effluents from the chlorlnatlontreatment under 40℃ and pH values 9, 10, 11 and 12. After treatment the reduction of AOX appears approximately 65%.展开更多
Halogenated methyl-phenyl ethers (anisoles) are ubiquitous organic compounds in the environment. In the present study, geometrical optimization and electrostatic potential calcu- lations have been performed for 42 hal...Halogenated methyl-phenyl ethers (anisoles) are ubiquitous organic compounds in the environment. In the present study, geometrical optimization and electrostatic potential calcu- lations have been performed for 42 halogenated anisoles at the HF/6-31G* level. A number of sta- tistically based parameters have been obtained. By multiple regression method, linear relationships between the gas-chromatographic relative retention time (RRT) and structural descriptors have been established for the training set of 32 halogenated anisoles. The result showed that the parameters derived from electrostatic potentials (ESPs) together with the molecular volume (Vmc) could be well used to express the quantitative structure-RRT relationships of halogenated anisoles. The best two-variable regression model gives a correlation coefficient of 0.980 and a standard deviation of 0.07, and the leave-one-out cross-validated correlation coefficient is 0.975. The goodness of the model has been further validated through exploring the predictive power for the testing set of 10 halogenated anisoles.展开更多
Noninvasive gluoose monitoring development is critical for diabetic patient continuous moni-toring.However,almost all the available devices are invasive and painful.Noninvasive methods such as using spectroscopy have ...Noninvasive gluoose monitoring development is critical for diabetic patient continuous moni-toring.However,almost all the available devices are invasive and painful.Noninvasive methods such as using spectroscopy have shown some good results.Unfortunately,the drawback was that the tungsten halogen lamps 1usage that is impractical if applied on human skin.This paper compared the light emitting diode(LED)to traditional tungsten halogen lamps as light source for glucose detection where the type of light source plays an important role in achieving a good spectrum quality.Glucose concentration measurement has been developed as part of noninvasive technique using optical spectroscopy.Small change and overlapping in tungsten halogen results need to replace it with a more convenient light source such as LED.Based on the result obtained,the performance of LED for absorbance spectrum gives a signifcantly different and is directly proportional to the glucose concentration.The result shows a linear trend and scucssully detects lowest at 60 to 160 mg/dL glucose concentration.展开更多
The oxygen evolution reaction(OER) plays a crucial role in many electrochemical energy technologies,and creating multiple beneficial factors for OER catalysis is desirable for achieving high catalytic efficiency.Here,...The oxygen evolution reaction(OER) plays a crucial role in many electrochemical energy technologies,and creating multiple beneficial factors for OER catalysis is desirable for achieving high catalytic efficiency.Here,we highlight a new halogen-chlorine(Cl)-anion doping strategy to boost the OER activity of perovskite oxides.As a proof-of-concept,proper Cl doping at the oxygen site of LaFeO3(LFO) perovskite can induce multiple favorable characteristics for catalyzing the OER,including rich oxygen vacancies,increased electrical conductivity and enhanced Fe-O covalency.Benefiting from these factors,the LaFeO2.9-δCl0.1(LFOCl) perovskite displays significant intrinsic activity enhancement by a factor of around three relative to its parent LFO.This work uncovers the effect of Cl-anion doping in perovskites on promoting OER performance and paves a new way to design highly efficient electrocatalysts.展开更多
Coordination tuning electronic structure of host materials is a quite effective strategy for activating and improving the intrinsic properties.Herein,halogen anion(X-)-incorporated β-FeOOH(β-FeOOH(X),X=F-,Cl-,and Br...Coordination tuning electronic structure of host materials is a quite effective strategy for activating and improving the intrinsic properties.Herein,halogen anion(X-)-incorporated β-FeOOH(β-FeOOH(X),X=F-,Cl-,and Br-) was investigated with a spontaneous adsorption process,which realized a great improvement of supercapacitor performances by adjusting the coordination geometry.Experiments coupled with theoretical calculations demonstrated that the change of Fe-O bond length and structural distortion of β-FeOOH,which is rooted in halogen ions embedment,led to the relatively narrow band gap.Because of the strong electronegativity of X-,the Fe element in β-FeOOH(X)s presented the unexpected high valence state(3+δ),which is facilitating to adsorb S032-species.Consequently,the designed β-FeOOH(X)s exhibited the good electric conductivity and enhanced the contact between electrode and electrolyte.When used as a negative electrode,the β-FeOOH(F) showed the excellent specific capacity of 391.9 F g-1 at 1 A g-1 current density,almost tenfold improvement compared with initial β-FeOOH,with the superior rate capacity and cyclic stability.This combinational design principle of electronic structure and electrochemical performances provides a promising way to develop advanced electrode materials for supercapacitor.展开更多
The ever-increasing demand for rechargeable batteries with high energy density,abundant resources,and high safety has pushed the development of various battery technologies based on cation,anion,or dual-ion transfer.T...The ever-increasing demand for rechargeable batteries with high energy density,abundant resources,and high safety has pushed the development of various battery technologies based on cation,anion,or dual-ion transfer.The use of halogen storage electrode materials has led to new concept battery systems such as halide-ion batteries(HIB)and dual-ion batteries(DIB).This review highlights the recent progress on these electrode materials,including metal(oxy)halides,layered double hydroxides,MXenes,graphite-based materials,and organic materials with carbon or nitrogen redox centers.The reversible electrochemical halogen storage of halide ions(e.g.,F^(−),Cl^(−),and Br^(−)),dual halogen(e.g.,Br_(m)Cl_(n) and [ICl_(2)]^(−)),or binary halide anions(e.g.,PF_(6)^(−),AlCl_(4)^(−),[ZnCl_(x)]^(2−x),and [MgCl_(x)]^(2−x)) in the electrodes is covered.The challenges and mechanisms of halogen storage in various electrode materials in HIBs and DIBs are summarized and analyzed,providing insights into the development of high-performance halogen storage electrode materials for rechargeable batteries.展开更多
In order to construct p-n homojunction of Cu20-based thin film solar cells that may increase its conversion efficiency, to synthesize n-type Cu20 with high conductivity is extremely crucial, and considered as a challe...In order to construct p-n homojunction of Cu20-based thin film solar cells that may increase its conversion efficiency, to synthesize n-type Cu20 with high conductivity is extremely crucial, and considered as a challenge in the near future. The doping effects of halogen on electronic structure of Cu20 have been investigated by density function theory calculations in the present work. Halogen dopants form donor levels below the bottom of conduction band through gaining or losing electrons, suggesting that halogen doping could make Cu20 have n-type conductivity. The lattice distortion, the impurity formation energy, the position, and the band width of donor level of Cu201-xHx (H = F, C1, Br, I) increase with the halogen atomic number. Based on the calculated results, chlorine doping is an effective n-type dopant for Cu20, owing to the lower impurity formation energy and suitable donor level.展开更多
In this paper . the reductive dehalogenation potency of haloarenes in mathanogenic sedirnent - watersystems was divided into two classes according to the length of acclimation period and degradation rate con-stants du...In this paper . the reductive dehalogenation potency of haloarenes in mathanogenic sedirnent - watersystems was divided into two classes according to the length of acclimation period and degradation rate con-stants during acclimation time. Based on the rn展开更多
基金supported by the Chinese National Science Fund for Distinguished Young Scholars to Dr.Gao Jian-Feng(42025301).
文摘The Dexing porphyry deposit is the largest porphyry Cu–Mo–Au deposit in South China.Biotite composition can record the physicochemical conditions and evolution history of magmatic-hydrothermal system.Biotite from the Dexing porphyry deposit could be divided to three types:primary magmatic biotite(Bi-M),hydrothermal altered magmatic biotite(Bi-A)and hydrothermal biotite(Bi-H).The temperature of Bi-M and Bi-H range from 719 to 767℃ and 690 to 727℃,respectively.Both magmatic and hydrothermal biotite have high Fe^(3+)/Fe^(2+)ratios(from 0.18 to 0.24)and XMgvalues(from 0.57 to 0.66),indicating a high oxygen fugacity.BiM has F lower than Bi-A and Bi-H(up to 0.26 wt%),but has Cl(Cl=0.18–0.30 wt%)similar to Bi-A and Bi-H(Cl=0.21–0.35 wt%),suggesting that high Cl/F ratios of early hydrothermal fluid may result from the exsolution from high Cl magma.From potassic alteration zone to phyllic and propylitic alteration zones,Cl decreases with increasing Cu,whereas F increases roughly.Therefore,Cl mostly originate from magma,but enrichment of F possibly results from reaction of fluids and Neoproterozoic strata.Negative correlation between Cl and Cu indicates that Cl might act as an important catalyst during Cu mineralization process.Biotite from Dexing has similar halogen compositions to other porphyry Cu-/Mo deposits in the world.Chlorine contents of hydrothermal fluid may be critical for Cu transportation and enrichment,while consumption of Cl would promote Cu deposition.
基金supported by NSFCs (41306199)the Dean Research Funds for CAS Hefei Institute (YZJJ201304)
文摘The reactive halogens play key roles in the destruction of boundary layer ozone by catalytic reactions and provide a fast pathway to the sedimentation of elemental gaseous mercury.The presence of bromine oxides in the
基金the National Natural Science Foundation of China(Grant Nos.51701180,51871201,U1802254)。
文摘The three halogen solids(Cl_(2),Br_(2),and I_(2))have the isostructural diatomic molecular phaseⅠwith a space group of Cmca at ambient pressure.At high pressure,they all go through an intermediate phaseⅤwith incommensurate structures before eventually dissociating into the monatomic phaseⅡ.However,a new structural transition between phaseⅠandⅤwith anomalous bond-length behavior was observed in bromine under pressure,which,so far,has not been confirmed in iodine and chlorine.Here,we perform first-principles calculations for iodine and chlorine.The new structural transition was predicted to be common to all three halogens under pressure.The transition pressures might be systematically underestimated by the imperfect van der Waals correction method,but they follow the order Cl_(2)>Br_(2)>I_(2),which is consistent with other pressure-induced structural transitions such as metallization and the molecular-to-monatomic transition.
基金supported by the Fundamental Research Funds for the Central Universities(FRF-TP-18-080A1)the National Natural Science Foundation of China(Grant Nos.42002076,41930427,41725009,U1603244)the Science and Technology Planning of Guangdong Province,China(2020B1212060055)。
文摘To constrain the ore-fluid source(s)of the Laoshankou Fe-Cu-Au deposit(Junggar orogen,NW China),we analyzed the fluid inclusion(FI)noble gas(Ar,Kr and Xe)and halogen(Cl,Br and I)compositions in the hydrothermal epidote and quartz.Four hypogene alteration/mineralization stages,including(I)pre-ore Ca-silicate,(II)early-ore amphibole-epidote-magnetite,(III)late-ore pyrite-chalcopyrite,and(IV)post-ore hydrothermal veining,have been identified at Laoshankou.Stage II FIs have salinity of 15.7 wt.%(NaCl eq.),I/Cl molar ratios of 75×10^(−6)-135×10^(−6),and Br/Cl molar ratios of 1.4×10^(−3)-2.1×10^(−3).The moderately-high seawatercorrected Br*/I ratios(0.5-1.5)and low 40ArE/Cl slope(-10−5)indicate the presence of sedimentary marine pore fluid,which was modified by seawater reacting with the Beitashan Fm.volcanic rocks.Stage III fluid is more saline than their stage II and IV counterparts,reaching up to 23.3 wt.%(NaCl+CaCl2 eq.)close to halite saturation(-26 wt.%).The fluid has I/Cl ratios of 75×10^(−6)-90×10^(−6) and Br/Cl ratios of 1.5×10^(−3)-1.8×10^(−3).Considering the increasing 40ArE/Cl trend toward bittern brine and the higher 36Ar content than air-saturated water(ASW),a bittern fluid source is inferred from seawater evaporation,which was modified by interaction with organic-rich marine sedimentary rocks.Stage IV FIs have lower temperature(110-228°C)and Br/Cl(0.90×10^(−3)-1.2×10^(−3)),but higher 36Ar content than ASW,indicative of dissolved evaporite or halite input.Considering also the lowδDfluid(−114‰to−144‰)andδ18Ofluid(2.1‰-3.5‰)values,meteoric water(with minor dissolved evaporites)likely dominated the stage IV fluid.The evaporites may have formed through continuous evaporation of the stage III surface-derived bittern.Involvement of non-magmatic fluids and different ore-fluid origins in stages II and III suggest that the ore-forming process was different from a typical magmatichydrothermal fluid-dominated skarn mineralization,which was previously proposed for Laoshankou.Our noble gas and halogen study at Laoshankou provide new insights on the fluid sources for the Paleozoic Fe−Cu(−Au)deposits in the Central Asian Orogenic Belt(CAOB),and our non-magmatic fluid source interpretation is consistent with the basin inversion setting for the mineralization.
文摘HALOGENS, as mineralizer elements, have been attracting ever increasing attention of geological workers inpetrogenetically experimental and ore-forming fluid geochemical studies. However, little research workhas been done on the contents, variation characteristics and significance of halogens in solid ores(rocks). It is found in the study of the Danzhai Hg-Au deposit that (i) variations in the contents ofhalogens and their distribution regularities in solid rocks and ores can shed light on the formation of thedeposit; and (ii) halogens can serve the function of indicator elements in search of buried orebodies. 1 Main characteristics of the ore
文摘Ensuring the health and safety of drinking water is crucial for both nations and their citizens.Since the 20th century,the disinfection of drinking water,effectively controlling pathogens in water sources,has become one of the significant advances in public health.However,the disinfectants used in the process,such as chlorine and chlorine dioxide,react with natural organic matter in the water to produce disinfection by-products(DBPs).Most of these DBPs contain chlorine,and if the source water contains bromine or iodine,brominated or iodinated DBPs,collectively referred to as Halogenated disinfection byproducts(X-DBPs),are formed.Numerous studies have found that X-DBPs pose potential risks to human health and the environment,leading to widespread concern.Mass spectrometry has become an important means of discovering new types of X-DBPs.This paper focuses on the study of methods for analyzing X-DBPs in drinking water using mass spectrometry.
基金the National Key R&D Program of China(Grant No.2020YFA0908100)the National Nature Science Foundation(Grant Nos.12274356,82070931,and 82271045)+1 种基金Fundamental Research Funds for the Central Universities(20720220022)the 111 Project(B16029)。
文摘Metal–organic frameworks(MOFs)have attracted significant research interest in biomimetic catalysis.However,the modulation of the activity of MOFs by precisely tuning the coordination of metal nodes is still a significant challenge.Inspired by metalloenzymes with well-defined coordination structures,a series of MOFs containing halogen-coordinated copper nodes(Cu-X MOFs,X=Cl,Br,I)are employed to elucidate their structure–activity relationship.Intriguingly,experimental and theoretical results strongly support that precisely tuning the coordination of halogen atoms directly regulates the enzyme-like activities of Cu-X MOFs by influencing the spatial configuration and electronic structure of the Cu active center.The optimal Cu–Cl MOF exhibits excellent superoxide dismutase-like activity with a specific activity one order of magnitude higher than the reported Cu-based nanozymes.More importantly,by performing enzyme-mimicking catalysis,the Cu–Cl MOF nanozyme can significantly scavenge reactive oxygen species and alleviate oxidative stress,thus effectively relieving ocular chemical burns.Mechanistically,the antioxidant and antiapoptotic properties of Cu–Cl MOF are achieved by regulating the NRF2 and JNK or P38 MAPK pathways.Our work provides a novel way to refine MOF nanozymes by directly engineering the coordination microenvironment and,more significantly,demonstrating their potential therapeutic effect in ophthalmic disease.
基金The authors acknowledge financial support from the National Key R&D Program of China(Nos.2020YFB1506400 and 2021YFB3800068)the National Natural Science Foundation of China(Nos.11834011,12074245,U21A20171 and 52102281)+1 种基金Shanghai Sailing Program(No.21YF1421600)Young Elite Scientists Sponsorship Program by China Association for Science and Technology(No.2021QNRC001).
文摘Perovskite solar cells(PSCs)are taking steps to commercialization.However,the halogen-reactive anode with high cost becomes a stumbling block.Here,the halogen migration in PSCs is utilized to in situ generate a uniform tunneling layer between the hole transport materials and anodes,which enriches the options of anodes by breaking the Schottky barrier,enabling the regular PSCs with both high efficiency and stability.Specifically,the regular PSC that uses silver iodide as the tunneling layer and copper as the anode obtains a champion power conversion efficiency of 23.24%(certified 22.74%)with an aperture area of 1.04 cm^(2).The devices are stable,maintaining 98.6%of the initial effi-ciency after 500 h of operation at the maximum power point with continuous 1 sun illumination.PSCs with different tunneling layers and anodes are fabricated,which confirm the generality of the strategy.
文摘The AOX (adsorbable organic halogens) problem in wool shrinkproofing effluents has attracted more attention in recent years. The probable origins and structures of AOX compounds were proved by the reaction of DCCA with the model substances of different amino acid residues. The GC-MS results indicated that available chlorine could chlorinate the side chain of tyrosine, histidine and trypotophan and generate AOX load in the effluent.
文摘Chlorination occurred simultaneously with oxidationwhen wool was treated by chlorine-containing reagents.The adsorbable organic halogens(AOX) compounds were produced by the chlorination of amino acid residues,especially tyrosine residue. The factors that might influence the reaction of dichloroisocyanuric acid (DCCA) with tyrosine residue were discussed. Higher temperature, appropriate pH value and lower concentration of chloride ion are favorable to decrease the percentage of chlorination. Determination of optimum process conditions would be helpful to control AOX compounds formation during wool chlorine pretreatment.
文摘Organic halogens generated in the chlorlnatlon treatment of wool are proven to be acutely toxic to human beings. Legislation on environmental pollution has become more and more stringent in recent years. So the chlorlnation treatment is faced with disuse. Alkaline hydrolysis is adopted to reduce the AOX (Absorbable Organic Halogen) concentrations in the effluents from the chlorlnatlontreatment under 40℃ and pH values 9, 10, 11 and 12. After treatment the reduction of AOX appears approximately 65%.
基金This work was supported by the National Natural Science Foundation of China (No. 20502022) and the Ph.D. Fund of Ningbo ( No. 2004A610010)
文摘Halogenated methyl-phenyl ethers (anisoles) are ubiquitous organic compounds in the environment. In the present study, geometrical optimization and electrostatic potential calcu- lations have been performed for 42 halogenated anisoles at the HF/6-31G* level. A number of sta- tistically based parameters have been obtained. By multiple regression method, linear relationships between the gas-chromatographic relative retention time (RRT) and structural descriptors have been established for the training set of 32 halogenated anisoles. The result showed that the parameters derived from electrostatic potentials (ESPs) together with the molecular volume (Vmc) could be well used to express the quantitative structure-RRT relationships of halogenated anisoles. The best two-variable regression model gives a correlation coefficient of 0.980 and a standard deviation of 0.07, and the leave-one-out cross-validated correlation coefficient is 0.975. The goodness of the model has been further validated through exploring the predictive power for the testing set of 10 halogenated anisoles.
文摘Noninvasive gluoose monitoring development is critical for diabetic patient continuous moni-toring.However,almost all the available devices are invasive and painful.Noninvasive methods such as using spectroscopy have shown some good results.Unfortunately,the drawback was that the tungsten halogen lamps 1usage that is impractical if applied on human skin.This paper compared the light emitting diode(LED)to traditional tungsten halogen lamps as light source for glucose detection where the type of light source plays an important role in achieving a good spectrum quality.Glucose concentration measurement has been developed as part of noninvasive technique using optical spectroscopy.Small change and overlapping in tungsten halogen results need to replace it with a more convenient light source such as LED.Based on the result obtained,the performance of LED for absorbance spectrum gives a signifcantly different and is directly proportional to the glucose concentration.The result shows a linear trend and scucssully detects lowest at 60 to 160 mg/dL glucose concentration.
基金financially supported by the Australian Research Council (Discovery Early Career Researcher Award No. DE190100005)the support of the Australian Research Council (Grant No. FT160100207)the ontinued support from the Queensland University of Technology (QUT) through the centre for Materials Science。
文摘The oxygen evolution reaction(OER) plays a crucial role in many electrochemical energy technologies,and creating multiple beneficial factors for OER catalysis is desirable for achieving high catalytic efficiency.Here,we highlight a new halogen-chlorine(Cl)-anion doping strategy to boost the OER activity of perovskite oxides.As a proof-of-concept,proper Cl doping at the oxygen site of LaFeO3(LFO) perovskite can induce multiple favorable characteristics for catalyzing the OER,including rich oxygen vacancies,increased electrical conductivity and enhanced Fe-O covalency.Benefiting from these factors,the LaFeO2.9-δCl0.1(LFOCl) perovskite displays significant intrinsic activity enhancement by a factor of around three relative to its parent LFO.This work uncovers the effect of Cl-anion doping in perovskites on promoting OER performance and paves a new way to design highly efficient electrocatalysts.
基金supported by the National Natural Science Foundation of China(Nos.2177060378,21627813,and 21521005)the Program for Changjiang Scholars,Innovative Research Teams in Universities(No.IRT1205)the Fundamental Research Funds for the Central Universities(Nos.12060093063 and XK1803-05).
文摘Coordination tuning electronic structure of host materials is a quite effective strategy for activating and improving the intrinsic properties.Herein,halogen anion(X-)-incorporated β-FeOOH(β-FeOOH(X),X=F-,Cl-,and Br-) was investigated with a spontaneous adsorption process,which realized a great improvement of supercapacitor performances by adjusting the coordination geometry.Experiments coupled with theoretical calculations demonstrated that the change of Fe-O bond length and structural distortion of β-FeOOH,which is rooted in halogen ions embedment,led to the relatively narrow band gap.Because of the strong electronegativity of X-,the Fe element in β-FeOOH(X)s presented the unexpected high valence state(3+δ),which is facilitating to adsorb S032-species.Consequently,the designed β-FeOOH(X)s exhibited the good electric conductivity and enhanced the contact between electrode and electrolyte.When used as a negative electrode,the β-FeOOH(F) showed the excellent specific capacity of 391.9 F g-1 at 1 A g-1 current density,almost tenfold improvement compared with initial β-FeOOH,with the superior rate capacity and cyclic stability.This combinational design principle of electronic structure and electrochemical performances provides a promising way to develop advanced electrode materials for supercapacitor.
基金supported by the Qinglan Project of Jiangsu Province of Chinathe Priority Academic Program Development of Jiangsu Higher Education Institutions[PAPD].
文摘The ever-increasing demand for rechargeable batteries with high energy density,abundant resources,and high safety has pushed the development of various battery technologies based on cation,anion,or dual-ion transfer.The use of halogen storage electrode materials has led to new concept battery systems such as halide-ion batteries(HIB)and dual-ion batteries(DIB).This review highlights the recent progress on these electrode materials,including metal(oxy)halides,layered double hydroxides,MXenes,graphite-based materials,and organic materials with carbon or nitrogen redox centers.The reversible electrochemical halogen storage of halide ions(e.g.,F^(−),Cl^(−),and Br^(−)),dual halogen(e.g.,Br_(m)Cl_(n) and [ICl_(2)]^(−)),or binary halide anions(e.g.,PF_(6)^(−),AlCl_(4)^(−),[ZnCl_(x)]^(2−x),and [MgCl_(x)]^(2−x)) in the electrodes is covered.The challenges and mechanisms of halogen storage in various electrode materials in HIBs and DIBs are summarized and analyzed,providing insights into the development of high-performance halogen storage electrode materials for rechargeable batteries.
基金Project supported by the National Natural Science Foundation of China (Grant No. 21263006), the Science Research Foundation of Educational Commission of Yunnan Province, China (Grant No. 2012Y542), and the Introduced Talents Foundation of Kunming University of Science and Technology, China.
文摘In order to construct p-n homojunction of Cu20-based thin film solar cells that may increase its conversion efficiency, to synthesize n-type Cu20 with high conductivity is extremely crucial, and considered as a challenge in the near future. The doping effects of halogen on electronic structure of Cu20 have been investigated by density function theory calculations in the present work. Halogen dopants form donor levels below the bottom of conduction band through gaining or losing electrons, suggesting that halogen doping could make Cu20 have n-type conductivity. The lattice distortion, the impurity formation energy, the position, and the band width of donor level of Cu201-xHx (H = F, C1, Br, I) increase with the halogen atomic number. Based on the calculated results, chlorine doping is an effective n-type dopant for Cu20, owing to the lower impurity formation energy and suitable donor level.
文摘In this paper . the reductive dehalogenation potency of haloarenes in mathanogenic sedirnent - watersystems was divided into two classes according to the length of acclimation period and degradation rate con-stants during acclimation time. Based on the rn