Using 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran(TCF)as a near-infrared fluorescent chromophore,we designed and synthesized a TCF-based fluorescent probe TCF-NS by introducing 2,4-dinitrophenyl ether ...Using 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran(TCF)as a near-infrared fluorescent chromophore,we designed and synthesized a TCF-based fluorescent probe TCF-NS by introducing 2,4-dinitrophenyl ether as the recognized site for H_(2)S.The probe TCF-NS displayed a rapid-response fluorescent against H_(2)S with high sensitivity and selection but had no significant fluorescence response to other biothiols.Furthermore,TCF-NS was applied to sense H_(2)S in living cells successfully with minimized cytotoxicity and a large Stokes shift.展开更多
The use of lithium-sulfur(Li-S)batteries is limited by sulfur redox reactions involving multi-phase transformations,especially at low-temperatures.To address this issue,we report a material(FCNS@NCFs)consisting of nit...The use of lithium-sulfur(Li-S)batteries is limited by sulfur redox reactions involving multi-phase transformations,especially at low-temperatures.To address this issue,we report a material(FCNS@NCFs)consisting of nitrogen-doped carbon fibers loaded with a ternary metal sulf-ide((Fe,Co,Ni)_(9)S_(8))for use as the sulfur host in Li-S batteries.This materi-al was prepared using transfer blot filter paper as the carbon precursor,thiourea as the source of nitrogen and sulfur,and FeCl_(3)·6H_(2)O,CoCl_(2)·6H_(2)O and NiCl_(2)·6H_(2)O as the metal ion sources.It was synthesized by an impreg-nation method followed by calcination.The nitrogen doping significantly in-creased the conductivity of the host,and the metal sulfides have excellent catalytic activities.Theoretical calculations,and adsorption and deposition experiments show that active sites on the surface of FCNS@NCFs selectively adsorb polysulfides,facilitate rapid adsorption and conversion,prevent cathode passivation and inhib-it the polysulfide shuttling.The FCNS@NCFs used as the sulfur host has excellent electrochemical properties.Its initial dis-charge capacity is 1639.0 mAh g^(−1) at 0.2 C and room temperature,and it remains a capacity of 1255.1 mAh g^(−1) after 100 cycles.At−20~C,it has an initial discharge capacity of 1578.5 mAh g^(−1) at 0.2 C,with a capacity of 867.5 mAh g^(−1) after 100 cycles.Its excellent performance at both ambient and low temperatures suggests a new way to produce high-performance low-temper-ature Li-S batteries.展开更多
Traditional pyrometallurgical and hydrometallurgical methods to extract bismuth from sulfide ores face problems such as high cost,low-concentration SO_(2)generation,and long process time.In this study,the cyclone tech...Traditional pyrometallurgical and hydrometallurgical methods to extract bismuth from sulfide ores face problems such as high cost,low-concentration SO_(2)generation,and long process time.In this study,the cyclone technology and slurry electrolysis method were combined.The bismuth sulfide ore was dissolved directly at the anode,while the high purity bismuth was deposited efficiently at the cathode under the advantages of the two methods.The short process and high-efficiency extraction of bismuth sulfide ore were realized,and the pollution of low-concentration SO_(2)was avoided.Then,the effects of several crucial experimental conditions(current density,reaction time,temperature,pH,liquid-solid ratio,and circulation flow rate)on the leaching efficiency and recovery efficiency of bismuth were investigated.The leaching and electrowinning mechanisms during the recovery process were also analyzed according to the research results of this paper to better understand the cyclone slurry electrolysis process.The experimental results showed that 95.19%bismuth was leached into the acid solution in the anode area under optimal conditions,and the recovery efficiency and purity of bismuth on the cathode reached 91.13%and 99.26%,respectively,which were better than those by the traditional hydrometallurgy recovery process.展开更多
Zinc leaching residue(ZLR) contains high content of valuable metals such as zinc and iron. However, zinc and iron mainly exist in the form of zinc ferrite, which are difficult to separate and recover. This study propo...Zinc leaching residue(ZLR) contains high content of valuable metals such as zinc and iron. However, zinc and iron mainly exist in the form of zinc ferrite, which are difficult to separate and recover. This study proposed a new process involving sulfidation roasting, magnetic separation and flotation to recover zinc and iron in ZLR. Through sulfidation roasting of ZLR with pyrite, zinc and iron were converted into ZnS and Fe3 O4. The effects of pyrite dosage, roasting temperature and roasting time on the sulfidation of zinc in ZLR were investigated. The results showed that the sulfidation percentage of zinc reached 91.8% under the optimum condition. Besides, it was found that ball-milling was favorable for the separation and recovery of zinc and iron in sulfidation products. After ball-milling pretreatment, iron and zinc were enriched from sulfidation products by magnetic separation and flotation. The grade of iron in magnetic concentrates was 52.3% and the grade of zinc in flotation concentrates was 31.7%, which realized the recovery of resources.展开更多
In this paper,sulfidation mechanism of cerussite in the presence of sulphur at high temperatures was investigated based on micro-flotation,X-ray powder diffractometry(XRD),electron probe microanalysis(EPMA)and X-ray p...In this paper,sulfidation mechanism of cerussite in the presence of sulphur at high temperatures was investigated based on micro-flotation,X-ray powder diffractometry(XRD),electron probe microanalysis(EPMA)and X-ray photoelectron spectroscopy(XPS).The micro-flotation test results showed that flotation recovery of the treated cerussite increased to above 80%under a suitable flotation condition.It was found that the S/PbCO3 mole ratio and pH obviously affected flotation recovery.XRD analysis results confirmed that the cerussite was decomposed into massicot and then was transformed into mainly PbS and PbO·PbSO4 after sulfidation roasting.EPMA analysis results demonstrated that surface of the obtained massicot was smooth,but surface of the artificial galena was rough and even porous.Content of oxygen decreased,whereas content of sulphur increased with an increase in the S/PbCO3 mole ratio.XPS analysis results revealed that various lead-bearing species,including mainly PbS,PbSO4 and PbO·PbSO4,were generated at the surface.Formation of PbS was advantageous to flotation of the treated cerussite.Based on these results,a reaction model of the cerussite sulfurized with sulphur was proposed.展开更多
To recover Zn, Pb, Fe and Si from a low-grade mining ore in the Lanping basin, Yunnan Province, China, a novel technology using the roasting with pyrite and carbon followed by beneficiation and hydrochloric acid leach...To recover Zn, Pb, Fe and Si from a low-grade mining ore in the Lanping basin, Yunnan Province, China, a novel technology using the roasting with pyrite and carbon followed by beneficiation and hydrochloric acid leaching was proposed. Firstly, several factors such as pyrite dosage, roasting temperature, carbon powder dosage, holding time and particle size affecting on the flotation performance of Zn(Pb) and magnetic separation performance of Fe were simultaneously examined and the optimum process parameters were determined. A flotation concentrate, containing 17.46% Zn and 3.93% Pb, was obtained, and the Zn and Pb recoveries were 86.04% and 69.08%, respectively. The obtained flotation tailing was concentrated by a low-intensity magnetic separator. The grade of iron increased from 5.45% to 43.45% and the recovery of iron reached 64.87%. Hydrochloric acid leaching was then carried out for the magnetic separation tailing and a raw quartz concentrate containing 81.05% SiO2 was obtained. To further interpret the sulfidation mechanism of smithsonite, surface morphology and component of the sample before and after reactions were characterized by XRD and EPMA-EDS. The aim was to achieve the comprehensive utilization of the low-grade mining ore.展开更多
Sulfide solid electrolytes(S-SEs)are widely preferred for their high ionic conductivity and processability.However,the further development of S-SEs is hindered by the excessive price of its critical raw materials of L...Sulfide solid electrolytes(S-SEs)are widely preferred for their high ionic conductivity and processability.However,the further development of S-SEs is hindered by the excessive price of its critical raw materials of Li_(2)S.Herein,a low-cost and environmentally friendly method is proposed to synthesize Li_(2)S by the carbothermal reduction reaction of Li_(2)SO_(4)in one step,and the effects of various factors are also discussed.As a result,a purity of 99.67%is obtained over the self-prepared Li_(2)S.More importantly,the cost of the self-prepared Li_(2)S is only about 50$/kg,which is significantly lower than that of the commercial counterpart(10000−15000 dollar/kg).Moreover,the ionic conductivity of Li_(5.5)PS_(4.5)Cl_(1.5)prepared using self-prepared Li_(2)S as raw materials is 4.19 mS/cm at room temperature,which is a little higher than that of Li_(5.5)PS_(4.5)Cl_(1.5)using commercial Li_(2)S(4.05 mS/cm).And the all-solid-state lithium batteries(ASSLBs)with the as-prepared electrolytes could maintain a discharge capacity of 109.9 mA·h/g with an average coulombic efficiency(CE)of 98%after 100 cycles at 0.2 C,which is equivalent to that using commercial Li_(2)S,demonstrating that the preparation strategy of Li_(2)S proposed in this work is feasible.展开更多
This paper is aimed to present a clean,inexpensive and sustainable method to synthesize high purity lithium sulfide(Li_(2)S)powder through hydrogen reduction of lithium sulfate(Li_(2)SO_(4)).A three-step reduction pro...This paper is aimed to present a clean,inexpensive and sustainable method to synthesize high purity lithium sulfide(Li_(2)S)powder through hydrogen reduction of lithium sulfate(Li_(2)SO_(4)).A three-step reduction process has been successfully developed to synthesize well-crystallized and single-phase Li_(2)S powder by investigating the melting,sintering and reduction behavior of the mixtures of Li_(2)SO_(4)-Li_(2)S.High purity alumina was found to be the most suitable crucible material for producing high purity Li_(2)S,because it was not attacked by the Li_(2)SO_(4)-Li_(2)S melt during heating,as compared with other materials,such as carbon,mullite,quartz,boron nitride and stainless steel.The use of synthesized LizS resulted in higher purity and substantially higher room temperature ionic conductivity(2.77 mS·cm^(-1))for the argyrodite sulfide electrolyte Li_(6)PS_(5)Cl than commercial Li_(2)S(1.12 mS·cm^(-1)).This novel method offers a great opportunity to produce battery grade Li_(2)S for sulfide solid electrolyte applications.展开更多
基金financially supported by the Natural Science Foundation of Jiangsu Province(Grant No.BK20241181)the State Key Laboratory of AnalyticalChemistry for Life Science,School of Chemistry and Chemical Engineering,Nanjing University(Grant No.SKLACLS2419)。
文摘Using 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran(TCF)as a near-infrared fluorescent chromophore,we designed and synthesized a TCF-based fluorescent probe TCF-NS by introducing 2,4-dinitrophenyl ether as the recognized site for H_(2)S.The probe TCF-NS displayed a rapid-response fluorescent against H_(2)S with high sensitivity and selection but had no significant fluorescence response to other biothiols.Furthermore,TCF-NS was applied to sense H_(2)S in living cells successfully with minimized cytotoxicity and a large Stokes shift.
基金partially supported by National Natural Science Foundation of China(52172250)Institute of Process Engineering(IPE)Project for Frontier Basic Research(QYJC-2023-06)。
文摘The use of lithium-sulfur(Li-S)batteries is limited by sulfur redox reactions involving multi-phase transformations,especially at low-temperatures.To address this issue,we report a material(FCNS@NCFs)consisting of nitrogen-doped carbon fibers loaded with a ternary metal sulf-ide((Fe,Co,Ni)_(9)S_(8))for use as the sulfur host in Li-S batteries.This materi-al was prepared using transfer blot filter paper as the carbon precursor,thiourea as the source of nitrogen and sulfur,and FeCl_(3)·6H_(2)O,CoCl_(2)·6H_(2)O and NiCl_(2)·6H_(2)O as the metal ion sources.It was synthesized by an impreg-nation method followed by calcination.The nitrogen doping significantly in-creased the conductivity of the host,and the metal sulfides have excellent catalytic activities.Theoretical calculations,and adsorption and deposition experiments show that active sites on the surface of FCNS@NCFs selectively adsorb polysulfides,facilitate rapid adsorption and conversion,prevent cathode passivation and inhib-it the polysulfide shuttling.The FCNS@NCFs used as the sulfur host has excellent electrochemical properties.Its initial dis-charge capacity is 1639.0 mAh g^(−1) at 0.2 C and room temperature,and it remains a capacity of 1255.1 mAh g^(−1) after 100 cycles.At−20~C,it has an initial discharge capacity of 1578.5 mAh g^(−1) at 0.2 C,with a capacity of 867.5 mAh g^(−1) after 100 cycles.Its excellent performance at both ambient and low temperatures suggests a new way to produce high-performance low-temper-ature Li-S batteries.
基金Projects(52104355,52074363,52374364)supported by the National Natural Science Foundation of ChinaProject(2023YFC2907904)supported by the National Key R&D Program of China。
文摘Traditional pyrometallurgical and hydrometallurgical methods to extract bismuth from sulfide ores face problems such as high cost,low-concentration SO_(2)generation,and long process time.In this study,the cyclone technology and slurry electrolysis method were combined.The bismuth sulfide ore was dissolved directly at the anode,while the high purity bismuth was deposited efficiently at the cathode under the advantages of the two methods.The short process and high-efficiency extraction of bismuth sulfide ore were realized,and the pollution of low-concentration SO_(2)was avoided.Then,the effects of several crucial experimental conditions(current density,reaction time,temperature,pH,liquid-solid ratio,and circulation flow rate)on the leaching efficiency and recovery efficiency of bismuth were investigated.The leaching and electrowinning mechanisms during the recovery process were also analyzed according to the research results of this paper to better understand the cyclone slurry electrolysis process.The experimental results showed that 95.19%bismuth was leached into the acid solution in the anode area under optimal conditions,and the recovery efficiency and purity of bismuth on the cathode reached 91.13%and 99.26%,respectively,which were better than those by the traditional hydrometallurgy recovery process.
基金Project(2018YFC1900305)supported by the National Key R&D Program of ChinaProject(51825403)supported by the National Science Foundation for Distinguished Young Scholars,China+1 种基金Projects(51634010,51474247,51904354)supported by the National Natural Science Foundation of ChinaProject(2019SK2291)supported by the Key Research and Development Program of Hunan Province,China。
文摘Zinc leaching residue(ZLR) contains high content of valuable metals such as zinc and iron. However, zinc and iron mainly exist in the form of zinc ferrite, which are difficult to separate and recover. This study proposed a new process involving sulfidation roasting, magnetic separation and flotation to recover zinc and iron in ZLR. Through sulfidation roasting of ZLR with pyrite, zinc and iron were converted into ZnS and Fe3 O4. The effects of pyrite dosage, roasting temperature and roasting time on the sulfidation of zinc in ZLR were investigated. The results showed that the sulfidation percentage of zinc reached 91.8% under the optimum condition. Besides, it was found that ball-milling was favorable for the separation and recovery of zinc and iron in sulfidation products. After ball-milling pretreatment, iron and zinc were enriched from sulfidation products by magnetic separation and flotation. The grade of iron in magnetic concentrates was 52.3% and the grade of zinc in flotation concentrates was 31.7%, which realized the recovery of resources.
基金Project(51964027)supported by the National Natural Science Foundation of ChinaProject(2017FB084)supported by the Yunnan Province Applied Basic Research Project,ChinaProject(2019J0037)supported by the Education Department of Yunnan Province,China。
文摘In this paper,sulfidation mechanism of cerussite in the presence of sulphur at high temperatures was investigated based on micro-flotation,X-ray powder diffractometry(XRD),electron probe microanalysis(EPMA)and X-ray photoelectron spectroscopy(XPS).The micro-flotation test results showed that flotation recovery of the treated cerussite increased to above 80%under a suitable flotation condition.It was found that the S/PbCO3 mole ratio and pH obviously affected flotation recovery.XRD analysis results confirmed that the cerussite was decomposed into massicot and then was transformed into mainly PbS and PbO·PbSO4 after sulfidation roasting.EPMA analysis results demonstrated that surface of the obtained massicot was smooth,but surface of the artificial galena was rough and even porous.Content of oxygen decreased,whereas content of sulphur increased with an increase in the S/PbCO3 mole ratio.XPS analysis results revealed that various lead-bearing species,including mainly PbS,PbSO4 and PbO·PbSO4,were generated at the surface.Formation of PbS was advantageous to flotation of the treated cerussite.Based on these results,a reaction model of the cerussite sulfurized with sulphur was proposed.
基金Project(51604131)supported by the National Natural Science Foundation of ChinaProject(2017FB084)supported by the Yunnan Province Applied Basic Research Project,ChinaProject(2018T20150055)supported by the Testing and Analyzing Funds of Kunming University of Science and Technology,China
文摘To recover Zn, Pb, Fe and Si from a low-grade mining ore in the Lanping basin, Yunnan Province, China, a novel technology using the roasting with pyrite and carbon followed by beneficiation and hydrochloric acid leaching was proposed. Firstly, several factors such as pyrite dosage, roasting temperature, carbon powder dosage, holding time and particle size affecting on the flotation performance of Zn(Pb) and magnetic separation performance of Fe were simultaneously examined and the optimum process parameters were determined. A flotation concentrate, containing 17.46% Zn and 3.93% Pb, was obtained, and the Zn and Pb recoveries were 86.04% and 69.08%, respectively. The obtained flotation tailing was concentrated by a low-intensity magnetic separator. The grade of iron increased from 5.45% to 43.45% and the recovery of iron reached 64.87%. Hydrochloric acid leaching was then carried out for the magnetic separation tailing and a raw quartz concentrate containing 81.05% SiO2 was obtained. To further interpret the sulfidation mechanism of smithsonite, surface morphology and component of the sample before and after reactions were characterized by XRD and EPMA-EDS. The aim was to achieve the comprehensive utilization of the low-grade mining ore.
基金Project(52374407)supported by the National Natural Science Foundation of China。
文摘Sulfide solid electrolytes(S-SEs)are widely preferred for their high ionic conductivity and processability.However,the further development of S-SEs is hindered by the excessive price of its critical raw materials of Li_(2)S.Herein,a low-cost and environmentally friendly method is proposed to synthesize Li_(2)S by the carbothermal reduction reaction of Li_(2)SO_(4)in one step,and the effects of various factors are also discussed.As a result,a purity of 99.67%is obtained over the self-prepared Li_(2)S.More importantly,the cost of the self-prepared Li_(2)S is only about 50$/kg,which is significantly lower than that of the commercial counterpart(10000−15000 dollar/kg).Moreover,the ionic conductivity of Li_(5.5)PS_(4.5)Cl_(1.5)prepared using self-prepared Li_(2)S as raw materials is 4.19 mS/cm at room temperature,which is a little higher than that of Li_(5.5)PS_(4.5)Cl_(1.5)using commercial Li_(2)S(4.05 mS/cm).And the all-solid-state lithium batteries(ASSLBs)with the as-prepared electrolytes could maintain a discharge capacity of 109.9 mA·h/g with an average coulombic efficiency(CE)of 98%after 100 cycles at 0.2 C,which is equivalent to that using commercial Li_(2)S,demonstrating that the preparation strategy of Li_(2)S proposed in this work is feasible.
基金Fiscal Year 2023-2024 High-Level and Growth Research and Development Subsidy for supporting the research and development activities for small and medium-size enterprise(SMEs),which is administered by Chiba Industry Advancement Center(Grant No.2066 and 2027)。
文摘This paper is aimed to present a clean,inexpensive and sustainable method to synthesize high purity lithium sulfide(Li_(2)S)powder through hydrogen reduction of lithium sulfate(Li_(2)SO_(4)).A three-step reduction process has been successfully developed to synthesize well-crystallized and single-phase Li_(2)S powder by investigating the melting,sintering and reduction behavior of the mixtures of Li_(2)SO_(4)-Li_(2)S.High purity alumina was found to be the most suitable crucible material for producing high purity Li_(2)S,because it was not attacked by the Li_(2)SO_(4)-Li_(2)S melt during heating,as compared with other materials,such as carbon,mullite,quartz,boron nitride and stainless steel.The use of synthesized LizS resulted in higher purity and substantially higher room temperature ionic conductivity(2.77 mS·cm^(-1))for the argyrodite sulfide electrolyte Li_(6)PS_(5)Cl than commercial Li_(2)S(1.12 mS·cm^(-1)).This novel method offers a great opportunity to produce battery grade Li_(2)S for sulfide solid electrolyte applications.
