Within the framework of carbon neutrality,lithium-ion batteries(LIBs)are progressively booming along with the growing utilization of green and clean energy.However,the extensive application of LIBs with limited lifesp...Within the framework of carbon neutrality,lithium-ion batteries(LIBs)are progressively booming along with the growing utilization of green and clean energy.However,the extensive application of LIBs with limited lifespan has brought about a significant recycling dilemma.The traditional hydrometallurgical or pyrometallurgical strategies are not capable to maximize the output value of spent LIBs and minimize the potential environmental hazards.Herein,to alternate the tedious and polluting treatment processes,we propose a high-temperature molten-salt strategy to directly regenerate spent cathodes of LIBs,which can also overcome the barrier of the incomplete defects'restoration with previous low-temperature molten salts.The high-energy and stable medium environment ensures a more thorough and efficient relithiation reaction,and simultaneously provides sufficient driving force for atomic rearrangement and grains secondary growth.In consequence,the regenerated ternary cathode(R-NCM)exhibits significantly enhanced structural stability that effectively suppresses the occurrence of cracks and harmful side reactions.The R-NCM delivers excellent cycling stability,retaining 81.2%of its capacity after 200 cycles at 1 C.This technique further optimizes the traditional eutectic molten-salt approach,broadening its applicability and improving regenerated cathode performance across a wider range of conditions.展开更多
Low-valent sulfur oxy-acid salts(LVSOs)represent a category of oxygen-containing salts characterized by their potent reducing capabilities.Notably,sulfite,dithionite,and thiosulfate are prevalent reducing agents that ...Low-valent sulfur oxy-acid salts(LVSOs)represent a category of oxygen-containing salts characterized by their potent reducing capabilities.Notably,sulfite,dithionite,and thiosulfate are prevalent reducing agents that are readily available,cost-effective,and exhibit minimal ecological toxicity.These LVSOs have the ability to generate or promote the generation of strong oxidants or reductants,which makes them widely used in advanced oxidation processes(AOPs)and advanced reduction processes(ARPs).This article provides a comprehensive review of the recent advancements in AOPs and ARPs involving LVSOs,alongside an examination of the fundamental principles governing the generation of active species within these processes.LVSOs fulfill three primary functions in AOPs:Serving as sources of reactive oxygen species(ROS),auxiliary agents,and activators.Particular attention is devoted to elucidating the reaction mechanisms through which LVSOs,in conjunction with metal ions,metal oxides,ultraviolet light(UV),and ozone,produce potent oxidizing agents in both homogeneous and heterogeneous systems.Regarding ARPs,this review delineates the mechanisms by which LVSOs generate strong reducing agents,including hydrated electrons,hydrogen radicals,and sulfite radicals,under UV irradiation,while also exploring the interactions between these reductants and pollutants.The review identifies existing gaps within the current framework and proposes future research avenues to address these challenges.展开更多
Single crystalline nickel rich Li[Ni_(x)Co_(y)Mn_(1-x–y)]O_(2)(SCNCM)layered oxide cathodes show higher ionic conductivity and better structure integrity than polycrystalline NCM(PCNCM)cathodes by eliminating grain b...Single crystalline nickel rich Li[Ni_(x)Co_(y)Mn_(1-x–y)]O_(2)(SCNCM)layered oxide cathodes show higher ionic conductivity and better structure integrity than polycrystalline NCM(PCNCM)cathodes by eliminating grain boundaries.However,it remains challenges in the controlled synthesis process and restricted cycling stability of SCNCM.Herein,take single crystalline nickel rich Li[Ni_(0.8)Co_(0.1)Mn_(0.1)]O_(2)(SC811)as an example,a dual molten salts(LiOH and Li_(2)SO_(4))assisted secondary calcination method is proposed,for which LiOH salt improves primary crystal size and Li_(2)SO_(4)prevents the aggravation of NCM nanocrystals.To further reduce the interfacial side reactions,Mg-doping and B-coating surface modification was carried out,which effectively suppress anisotropic lattice changes and Li/Ni disorder.In addition,a thin and uniform H_(3)BO_(3)coating effectively prevents direct contact between the electrode and electrolyte,thus reducing harmful parasitic reactions.The single crystal structure engineering and surface modification strategy of oxide layered cathodes significantly improve the cycling stability of the modified SC811 cathode.For example,during a long-term cycling of 470 cycles,a high-capacity retention of 74.2%obtained at 1C rate.Our work provides a new strategy for engineering high energy nickel rich layered oxide NCM cathodes.展开更多
Visible light photocatalytic redox catalysis has become a powerful tool for organic synthesis, and has opened up new avenues for the formation of challenging structural skeletons and chemical bonds. In this respect, d...Visible light photocatalytic redox catalysis has become a powerful tool for organic synthesis, and has opened up new avenues for the formation of challenging structural skeletons and chemical bonds. In this respect, diverse photocatalysts, including ruthenium(II), iridium(Ⅲ), and organic dyes, have been most commonly applied.展开更多
Herein, the electrochemical behaviors of Sr on inert W electrode and reactive Zn/Al electrodes were systematically investig-ated in LiCl–KCl–SrCl2molten salts at 773 K using various electrochemical methods. The chem...Herein, the electrochemical behaviors of Sr on inert W electrode and reactive Zn/Al electrodes were systematically investig-ated in LiCl–KCl–SrCl2molten salts at 773 K using various electrochemical methods. The chemical reaction potentials of Li and Sr on re-active Zn/Al electrodes were determined. We observed that Sr could be extracted by decreasing the activity of the deposited metal Sr onthe reactive electrode, although the standard reduction potential of Sr(II)/Sr was more negative than that of Li(I)/Li. The electrochemicalextraction products of Sr on reactive Zn and Al electrodes were Zn13Sr and Al4Sr, respectively, with no codeposition of Li observed.Based on the density functional theory calculations, both Zn13Sr and Al4Sr were identified as stable intermetallic compounds with Zn-/Al-rich phases. In LiCl–KCl molten salt containing 3wt% SrCl2, the coulombic efficiency of Sr in the Zn electrode was ~54%. The depolar-ization values for Sr on Zn and Al electrodes were 0.864 and 0.485 V, respectively, exhibiting a stronger chemical interaction between Znand Sr than between Al and Sr. This study suggests that using reactive electrodes can facilitate extraction of Sr accumulated while elec-trorefining molten salts, thereby enabling the purification and reuse of the salt and decreasing the volume of the nuclear waste.展开更多
In this investigation,we examined the high-temperature corrosion behavior of three nickel-based single-crystal superalloys subjected to a mixed molten salt environment of Na_(2)SO_(4)and NaCl at 700℃,leading to a pre...In this investigation,we examined the high-temperature corrosion behavior of three nickel-based single-crystal superalloys subjected to a mixed molten salt environment of Na_(2)SO_(4)and NaCl at 700℃,leading to a preliminary elucidation of their molten salt corrosion mechanisms.By further comparing the corrosion degree of the three nickel-based single-crystal superalloys combined with the Gibbs free energy calculation of the corrosion products,the influence of alloying elements on the corrosion performance of nickel-based single-crystal superalloys was analyzed.It was established that the corrosion mechanism of these nickel-based single-crystal superalloys predominantly involves a cyclic process of oxide layer formation and decomposition,ultimately resulting in the establishment of a protective layer principally composed of NiO,with a constantly regenerating Al2O3 barrier,impeding further alloy degradation.Furthermore,the inclusion of elements such as Cr,Al,Ta,and notably Re has been found to markedly improve the thermal corrosion resistance of the superalloys.These insights not only enhance our comprehension of the corrosion mechanisms pertinent to nickel-based superalloys,but also provide strategic directions for alloy composition refinement aimed at bolstering their corrosion resilience.展开更多
Recent advancements have led to the synthesis of various new metal-containing explosives,particularly energetic metal-organic frameworks(EMOFs),which feature high-energy ligands within well-ordered crystalline structu...Recent advancements have led to the synthesis of various new metal-containing explosives,particularly energetic metal-organic frameworks(EMOFs),which feature high-energy ligands within well-ordered crystalline structures.These explosives exhibit significant advantages over traditional compounds,including higher density,greater heats of detonation,improved mechanical hardness,and excellent thermal stability.To effectively evaluate their detonation performance,it is crucial to have a reliable method for predicting detonation heat,velocity,and pressure.This study leverages experimental data and outputs from the leading commercial computer code to identify suitable decomposition pathways for different metal oxides,facilitating straightforward calculations for the detonation performance of alkali metal salts,and metal coordination compounds,along with EMOFs.The new model enhances predictive reliability for detonation velocities,aligning more closely with experimental results,as evi-denced by a root mean square error(RMSE)of 0.68 km/s compared to 1.12 km/s for existing methods.Furthermore,it accommodates a broader range of compounds,including those containing Sr,Cd,and Ag,and provides predictions for EMOFs that are more consistent with computer code outputs than previous predictive models.展开更多
In order to increase the solubility of pyrroloquinoline quinone disodium salt(PQQ-NA_(2))in water,PQQ-NA_(2)ionic salts formed by PQQ-NA_(2)with amine compounds had been developed.Amine compounds specifically refered ...In order to increase the solubility of pyrroloquinoline quinone disodium salt(PQQ-NA_(2))in water,PQQ-NA_(2)ionic salts formed by PQQ-NA_(2)with amine compounds had been developed.Amine compounds specifically refered to aminomethyl propanol,tromethamine,and matrine.The PQQ-NA_(2)ionic salts solubility test result showed an increase as high as 24-fold compared to dissolving PQQ-NA_(2)alone.The antioxidant test indicated that the ionic salts exhibited significant antioxidant property.Two PQQ-NA_(2)gel formulations were prepared containing the ionic salts,and the stability test and PQQ-NA_(2)content test indicated that the formulations were stable and the loss rate of PQQ was below 10%.展开更多
In this study,the mechanism of the reduction-diffusion reaction in a Sm-Fe binary system at low temperature was studied to investigate the possibility of synthesis of a Fe-rich TbCu_(7)-type SmFe_(x)(x>9)by the low...In this study,the mechanism of the reduction-diffusion reaction in a Sm-Fe binary system at low temperature was studied to investigate the possibility of synthesis of a Fe-rich TbCu_(7)-type SmFe_(x)(x>9)by the low-temperature diffusion-reduction(LTRD)process using LiCl-KCl eutectic molten salts.Firstly,the Sm-Fe phase transformation depending on the Sm-Fe composition,the LTRD temperature,and time was investigated,and it is found that the obtained metastable phase is only TbCu_(7)-type SmFe_(~8.5),which is not a Fe-rich phase.This Fe content does not change even after an expended LTRD process,and the metastable TbCu_(7)-type SmFe_(~8.5)tends to transform to the stable Sm_(2)Fe_(17)phase.In addition,it is found that the Sm-Fe phase starts to synthesize from the Sm-rich phase in the order of SmFe_(2),SmFe_(3),and SmFe_(8.5)as the LTRD temperature increases(when the time was 10 h)or the LTRD time increases(when the temperature was 550℃).Core-shell-like particles are observed in the case of a short LTRD time,and the core and the shell are Fe and the Sm-rich Sm-Fe phase,respectively,indicating that the Sm-rich phase begins to produce on the surface of the Fe particles.It is difficult to synthesize a Fe-rich TbCu_(7)-type SmFe_(x)(x>9)phase with the Sm-Fe binary system,suggesting that a different approach,such as addition of other elements,will be necessary.展开更多
A charge transfer complex(CTC)-enabled photoreduction of ether phosphonium salts for the generation of oxyalkyl radicals was described.The photoreduction provides a convenient method to achieve selective oxyalkylation...A charge transfer complex(CTC)-enabled photoreduction of ether phosphonium salts for the generation of oxyalkyl radicals was described.The photoreduction provides a convenient method to achieve selective oxyalkylation of enamides with broad substrate scope.The method features operational simplicity,mild and inherent green conditions.展开更多
The dynamic kinetic asymmetric transformation of racemic propargylic ammonium salts with prochiral aldimine esters through a stereodivergent propargylation is catalyzed by dual nickel and copper catalysis.Thus,a diver...The dynamic kinetic asymmetric transformation of racemic propargylic ammonium salts with prochiral aldimine esters through a stereodivergent propargylation is catalyzed by dual nickel and copper catalysis.Thus,a diverse range of optically activeα-quaternary amino esters were produced via C-N bond cleavage with high reaction efficiency and stereoselectivity(up to>99%ee).By selection of the appropriate pair-wise combination of catalyst configurational isomers,all four possible stereoisomers of the corresponding propargylation products are obtained in high yields with excellent regio-,diastereo-,and enantioselectiv-ities.展开更多
A new 1,4-amidocyanation of 1,3-enynes with N-amidopyridin-1-ium salts and TMSCN using a copper and photoredox synergetic catalysis for producingα-amido allenyl nitriles is developed.Employing N-amidopyridin-1-ium sa...A new 1,4-amidocyanation of 1,3-enynes with N-amidopyridin-1-ium salts and TMSCN using a copper and photoredox synergetic catalysis for producingα-amido allenyl nitriles is developed.Employing N-amidopyridin-1-ium salts as the amidyl radical precursors,the reaction enables the formation of two new bonds,one C(sp^(3))-N bond and one C(sp^(2))-C(sp)bond,in a single reaction step.This reaction represents a mild,general route to the construction of theα-amido allenyl nitrile architectures,which characterizes a broad scope,a good functional group compatibility and an excellent selectivity.展开更多
Considering the widespread presence of the dithiocarbamate skeleton in pharmaceuticals and bioactive molecules,the development of novel and convenient methods for the synthesis of these useful sulfur-containing compou...Considering the widespread presence of the dithiocarbamate skeleton in pharmaceuticals and bioactive molecules,the development of novel and convenient methods for the synthesis of these useful sulfur-containing compounds is of significant interest.Traditionally,S-aryl dithiocarbamates are constructed through the reaction of amines with thiophenols and thiophosgene[1].Recently,transition-metal-catalyzed Ullmann-type coupling between aryl boronic acids or iodoarenes with tetraalkylthiuram disulfides or sodium dialkyldithiocarbamates has been reported[2].展开更多
Developing applicable methods to forge linkages between sp^(3)and sp^(2)-hydridized carbons is of great significance in drug discovery.We show here a new,Ni-catalyzed reductive cross-coupling reaction that forms Csp^(...Developing applicable methods to forge linkages between sp^(3)and sp^(2)-hydridized carbons is of great significance in drug discovery.We show here a new,Ni-catalyzed reductive cross-coupling reaction that forms Csp^(3)-Csp^(2)bonds from aryl iodides and cyclic sulfonium salts.Notably,Csp^(3)-Csp^(2)bonds can be forged selectively at the iodine-bearing carbon of bromo(iodo)arenes which is usually recognized as a huge challenge under the catalytic reductive cross-coupling(CRCC)conditions.Experimental and computational mechanistic studies support LNi~IAr as an active species,while the untraditional anti-Markovnikov selective alkylation of asymmetric sulfonium salts is determined by the oxidative S-substitution of sulfonium salts with LNi~IAr.This protocol further expands the range of alkyl electrophiles under the CRCC conditions and provides a new strategy for the construction of Csp^(3)-Csp^(2)bonds.展开更多
Conditioning-free electrolytes with high reversibility of Mg plating/stripping are of vital importance for the commercialization of the superior rechargeable magnesium batteries(RMBs).In the present work,a non-nucleop...Conditioning-free electrolytes with high reversibility of Mg plating/stripping are of vital importance for the commercialization of the superior rechargeable magnesium batteries(RMBs).In the present work,a non-nucleophilic electrolyte(denoted as MLCH)based on all-inorganic salts of MgCl_(2),LiCl and CrCl_(3) for RMBs is prepared by a straightforward one-step reaction.As a result,the MLCH electrolyte shows the noticeable performance of high ionic conductivity(3.40 mS cm^(−1)),low overpotential(∼46 mV vs Mg/Mg^(2+)),high Coulombic efficiency(∼93%),high anodic stability(SS,∼2.56 V vs Mg/Mg^(2+))and long-term(more than 500 h)cycling stability,especially the conditioning-free characteristic.The main equilibrium species in the MLCH electrolyte are confirmed to be the tetracoordinated anions of[LiCl2(THF)2]−and solvated dimers of[Mg_(2)(μ-Cl)3(THF)6]+.The addition of LiCl can assist the dissolution of MgCl_(2) and activation of the electrode/electrolyte interface,resulting in a superior Mg plating/stripping efficiency.The synergistic effect of LiCl,CrCl_(3),a small amount of HpMS and the absence of polymerization THF enable the conditioning-free characteristic of the MLCH electrolyte.Moreover,the MLCH electrolyte exhibits decent compatibility with the cathodic materials of CuS.The Mg/CuS full cell using the MLCH electrolyte presents a discharge specific capacity of 215 mAh g^(−1)at 0.1 C and the capacity can retain∼72%after 40 cycles.Notably,the MLCH electrolyte has other superiorities such as the broad sources of materials,low-cost and easy-preparation,leading to the potential prospect of commercial application.展开更多
Calcium salt is an important contributing factor for calcium-based biomineralization.To study the effect of calcium salt on soil biomineralization using crude soybean urease,the calcium salts,including the calcium chl...Calcium salt is an important contributing factor for calcium-based biomineralization.To study the effect of calcium salt on soil biomineralization using crude soybean urease,the calcium salts,including the calcium chloride (CaCl_(2)),calcium acetate ((CH_(3)COO)_(2)Ca) and calcium nitrate (Ca(NO_(3))_(2)),were used to prepare the biotreatment solution to carry out the biomineralization tests in this paper.Two series of biomineralization tests in solution and sand column,respectively,were conducted.Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were performed to determine the microscopic characteristics of the precipitated calcium carbonate (CaCO_(3)) crystals.The experimental results indicate that the biomineralization effect is the best for the CaCl2 case,followed by (CH_(3)COO)_(2)Ca,and worst for Ca(NO_(3))_(2) under the test conditions of this study (i.e.1 mol/L of calcium salt-urea).The mechanism for the effect of the calcium salt on the biomineralization of crude soybean urease mainly involves: (1) inhibition of urease activity,and (2) influence on the crystal size and morphology of CaCO_(3).Besides Ca^(2+) ,the anions in solution can inhibit the activity of crude soybean urease,and NO_(3)− has a stronger inhibitory effect on the urease activity compared with both CH_(3)COO^(−) and Cl^(−) .The co-inhibition of Ca^(2+) and NO_(3)− on the activity of urease is the key reason for the worst biomineralization of the Ca(NO_(3))_(2) case in this study.The difference in biomineralization between the CaCl_(2) and (CH_(3)COO)_(2) Ca cases is strongly correlated with the crystal morphology of the precipitated CaCO_(3).展开更多
Thermal energy storage(TES)systems based on molten salt are widely used in concentrating solar power(CSP)plants.The investigation of the corrosion behavior of alloy materials in molten salt is crucial for the correct ...Thermal energy storage(TES)systems based on molten salt are widely used in concentrating solar power(CSP)plants.The investigation of the corrosion behavior of alloy materials in molten salt is crucial for the correct selection of alloy materials and the design of TES systems.In this study,the corrosion behavior of 304,310S,316,and In625 alloys in molten chloride salts(27 mol%NaCl-22 mol%KCl-51 mol%MgCl,)was investigated.The evolution of mass loss of the alloy samples with corrosion time and temperature and the analysis of the experimental results by scanning electron microscopy(SEM),energy dispersive spectrometer(EDS),and X-ray diffraction(XRD)revealed the corrosion mechanism of the alloy samples in molten chloride salts.The main factors affecting the corrosion of the alloy samples were further analyzed.It was found that the loose multi-layer corrosion was formed on the surface of the corroded alloy samples with the increase in corrosion degree.Moreover,the experimental results.showed that Mo played a positive role in improving the corrosion resistance of the alloy samples because the presence of Mo could inhibit the outward diffusion of alloying element Cr.This work enriches the molten salt corrosion database and provides a reference for the selection of alloy materials for TES systems with potential application in CSP plants.展开更多
The hydrophilic ZSM-5 zeolite membranes are applied to separate the inorganic acid solutions and inorganic acid/inorganic salt mixtures by pervaporation,and the membrane presents good stability,dehydration,and desalin...The hydrophilic ZSM-5 zeolite membranes are applied to separate the inorganic acid solutions and inorganic acid/inorganic salt mixtures by pervaporation,and the membrane presents good stability,dehydration,and desalination performance.Influences of inorganic acid type(H_(2)SO_(4),H_(3)PO_(4),HNO_(3),and HCl),H_(2)SO_(4)concentration(1-6 mol·L^(-1)),test temperature(60-90℃)and inorganic acid/inorganic salt type(2 mol·L^(-1)H_(2)SO_(4)and sulfate,2 mol·L^(-1)H3PO4 and phosphate)on the pervaporation performance are investigated in this work.Either for concentrating 3%(mass)H_(2)SO_(4)solution or consecutive dehydrating 20%(mass)H_(2)SO_(4)solution,the hydrophilic ZSM-5 zeolite membrane has a good dehydration performance and stability.Even though the H_(2)SO_(4)concentration and test temperature are increased to 6 M and 90℃,only H_(2)O molecules could pass through the membrane and pH value of the permeation is kept neutral.Besides,the membrane has good dehydration and desalination performance for H_(2)SO_(4)/sulfates and H_(3)PO_(4)/phosphate mixtures,and the rejection of natrium salt,molysite,and magnesium is almost 100%.展开更多
Metastable molybdenum carbide(α-MoC),as a catalyst and an excellent support for metal catalysts,has been widely used in thermo/electro-catalytic reactions.However,the selective synthesis ofα-MoC remains a great chal...Metastable molybdenum carbide(α-MoC),as a catalyst and an excellent support for metal catalysts,has been widely used in thermo/electro-catalytic reactions.However,the selective synthesis ofα-MoC remains a great challenge.Herein,a simple one-pot synthetic strategy for the selective preparation of metastableα-MoC is proposed by electrochemical co-reduction of CO_(2)and MoO_(3)in a low-temperature eutectic molten carbonate.The synthesizedα-MoC shows a reed flower-like morphology.By controlling the electrolysis time and monitoring the phase and morphology of the obtained products,the growth process ofα-MoC is revealed,where the carbon matrix is deposited first followed by the growth ofα-MoC from the carbon matrix.Moreover,by analyzing the composition of the electrolytic products,the formation mechanism forα-MoC is proposed.In addition,through this one-pot synthetic strategy,S-dopedα-MoC is successfully synthesized.Density functional theory(DFT)calculations reveal that S doping enhanced the HER performance ofα-MoC by facilitating water absorption and dissociation and weakening the bond energy of Mo-H to accelerate H desorption.The present work not only highlights the valuable utilization of CO_(2) but also offers a new perspective on the design and controllable synthesis of metal carbides and their derivatives.展开更多
Cesium carbonate was used as a base to achieve the desulfurization reaction of alkenyl sulfonium salts and phosphine oxides at room temperature,forming C(sp2)—P bonds.This method features simple operation,mild reacti...Cesium carbonate was used as a base to achieve the desulfurization reaction of alkenyl sulfonium salts and phosphine oxides at room temperature,forming C(sp2)—P bonds.This method features simple operation,mild reaction conditions,and good functional group compatibility,offering a straightforward and efficient preparation route for terminal vinyl phosphine oxides.展开更多
基金support by National Natural Science Foundation of China(22379166)Natural Science Foundation for Distinguished Young Scholars of Hunan Province(2022JJ10089)Central South University Innovation-Driven Research Programme(2023CXQD034).
文摘Within the framework of carbon neutrality,lithium-ion batteries(LIBs)are progressively booming along with the growing utilization of green and clean energy.However,the extensive application of LIBs with limited lifespan has brought about a significant recycling dilemma.The traditional hydrometallurgical or pyrometallurgical strategies are not capable to maximize the output value of spent LIBs and minimize the potential environmental hazards.Herein,to alternate the tedious and polluting treatment processes,we propose a high-temperature molten-salt strategy to directly regenerate spent cathodes of LIBs,which can also overcome the barrier of the incomplete defects'restoration with previous low-temperature molten salts.The high-energy and stable medium environment ensures a more thorough and efficient relithiation reaction,and simultaneously provides sufficient driving force for atomic rearrangement and grains secondary growth.In consequence,the regenerated ternary cathode(R-NCM)exhibits significantly enhanced structural stability that effectively suppresses the occurrence of cracks and harmful side reactions.The R-NCM delivers excellent cycling stability,retaining 81.2%of its capacity after 200 cycles at 1 C.This technique further optimizes the traditional eutectic molten-salt approach,broadening its applicability and improving regenerated cathode performance across a wider range of conditions.
基金supported by Natural Science Foundation of China(Nos.52070133,42107073,42477075)Natural Science Foundation of Sichuan Province(No.2024NSFSC0130)+2 种基金the Sichuan Science and Technology Program(No.2024NSFTD0014)Key Laboratory of Jiangxi Province for Persistent Pollutants Prevention Control and Resource Reuse(No.2023SSY02061)Key R&D Program of Heilongjiang Province(No.2023ZX02C01)。
文摘Low-valent sulfur oxy-acid salts(LVSOs)represent a category of oxygen-containing salts characterized by their potent reducing capabilities.Notably,sulfite,dithionite,and thiosulfate are prevalent reducing agents that are readily available,cost-effective,and exhibit minimal ecological toxicity.These LVSOs have the ability to generate or promote the generation of strong oxidants or reductants,which makes them widely used in advanced oxidation processes(AOPs)and advanced reduction processes(ARPs).This article provides a comprehensive review of the recent advancements in AOPs and ARPs involving LVSOs,alongside an examination of the fundamental principles governing the generation of active species within these processes.LVSOs fulfill three primary functions in AOPs:Serving as sources of reactive oxygen species(ROS),auxiliary agents,and activators.Particular attention is devoted to elucidating the reaction mechanisms through which LVSOs,in conjunction with metal ions,metal oxides,ultraviolet light(UV),and ozone,produce potent oxidizing agents in both homogeneous and heterogeneous systems.Regarding ARPs,this review delineates the mechanisms by which LVSOs generate strong reducing agents,including hydrated electrons,hydrogen radicals,and sulfite radicals,under UV irradiation,while also exploring the interactions between these reductants and pollutants.The review identifies existing gaps within the current framework and proposes future research avenues to address these challenges.
基金financially supported by the National Natural Science Foundation of China under the Grant No.22209075。
文摘Single crystalline nickel rich Li[Ni_(x)Co_(y)Mn_(1-x–y)]O_(2)(SCNCM)layered oxide cathodes show higher ionic conductivity and better structure integrity than polycrystalline NCM(PCNCM)cathodes by eliminating grain boundaries.However,it remains challenges in the controlled synthesis process and restricted cycling stability of SCNCM.Herein,take single crystalline nickel rich Li[Ni_(0.8)Co_(0.1)Mn_(0.1)]O_(2)(SC811)as an example,a dual molten salts(LiOH and Li_(2)SO_(4))assisted secondary calcination method is proposed,for which LiOH salt improves primary crystal size and Li_(2)SO_(4)prevents the aggravation of NCM nanocrystals.To further reduce the interfacial side reactions,Mg-doping and B-coating surface modification was carried out,which effectively suppress anisotropic lattice changes and Li/Ni disorder.In addition,a thin and uniform H_(3)BO_(3)coating effectively prevents direct contact between the electrode and electrolyte,thus reducing harmful parasitic reactions.The single crystal structure engineering and surface modification strategy of oxide layered cathodes significantly improve the cycling stability of the modified SC811 cathode.For example,during a long-term cycling of 470 cycles,a high-capacity retention of 74.2%obtained at 1C rate.Our work provides a new strategy for engineering high energy nickel rich layered oxide NCM cathodes.
文摘Visible light photocatalytic redox catalysis has become a powerful tool for organic synthesis, and has opened up new avenues for the formation of challenging structural skeletons and chemical bonds. In this respect, diverse photocatalysts, including ruthenium(II), iridium(Ⅲ), and organic dyes, have been most commonly applied.
基金financially supported by the National Postdoctoral Program for Innovative Talents, China (No. BX2021327)the National Natural Science Foundation of China (Nos. 22206194 and U2267222)+1 种基金the Ningbo Natural Science Foundation of China (No. 2023J337)the Yongjiang Talent Introduction Programme, China (No. 2 021A-161-G)。
文摘Herein, the electrochemical behaviors of Sr on inert W electrode and reactive Zn/Al electrodes were systematically investig-ated in LiCl–KCl–SrCl2molten salts at 773 K using various electrochemical methods. The chemical reaction potentials of Li and Sr on re-active Zn/Al electrodes were determined. We observed that Sr could be extracted by decreasing the activity of the deposited metal Sr onthe reactive electrode, although the standard reduction potential of Sr(II)/Sr was more negative than that of Li(I)/Li. The electrochemicalextraction products of Sr on reactive Zn and Al electrodes were Zn13Sr and Al4Sr, respectively, with no codeposition of Li observed.Based on the density functional theory calculations, both Zn13Sr and Al4Sr were identified as stable intermetallic compounds with Zn-/Al-rich phases. In LiCl–KCl molten salt containing 3wt% SrCl2, the coulombic efficiency of Sr in the Zn electrode was ~54%. The depolar-ization values for Sr on Zn and Al electrodes were 0.864 and 0.485 V, respectively, exhibiting a stronger chemical interaction between Znand Sr than between Al and Sr. This study suggests that using reactive electrodes can facilitate extraction of Sr accumulated while elec-trorefining molten salts, thereby enabling the purification and reuse of the salt and decreasing the volume of the nuclear waste.
基金Project(2022QNRC001) supported by the Young Elite Scientists Sponsorship Program by China Association for Science and TechnologyProject supported by the State Key Laboratory of Powder Metallurgy,China。
文摘In this investigation,we examined the high-temperature corrosion behavior of three nickel-based single-crystal superalloys subjected to a mixed molten salt environment of Na_(2)SO_(4)and NaCl at 700℃,leading to a preliminary elucidation of their molten salt corrosion mechanisms.By further comparing the corrosion degree of the three nickel-based single-crystal superalloys combined with the Gibbs free energy calculation of the corrosion products,the influence of alloying elements on the corrosion performance of nickel-based single-crystal superalloys was analyzed.It was established that the corrosion mechanism of these nickel-based single-crystal superalloys predominantly involves a cyclic process of oxide layer formation and decomposition,ultimately resulting in the establishment of a protective layer principally composed of NiO,with a constantly regenerating Al2O3 barrier,impeding further alloy degradation.Furthermore,the inclusion of elements such as Cr,Al,Ta,and notably Re has been found to markedly improve the thermal corrosion resistance of the superalloys.These insights not only enhance our comprehension of the corrosion mechanisms pertinent to nickel-based superalloys,but also provide strategic directions for alloy composition refinement aimed at bolstering their corrosion resilience.
基金the research committee at Malek Ashtar University of Technology (MUT) for their invaluable support of this project
文摘Recent advancements have led to the synthesis of various new metal-containing explosives,particularly energetic metal-organic frameworks(EMOFs),which feature high-energy ligands within well-ordered crystalline structures.These explosives exhibit significant advantages over traditional compounds,including higher density,greater heats of detonation,improved mechanical hardness,and excellent thermal stability.To effectively evaluate their detonation performance,it is crucial to have a reliable method for predicting detonation heat,velocity,and pressure.This study leverages experimental data and outputs from the leading commercial computer code to identify suitable decomposition pathways for different metal oxides,facilitating straightforward calculations for the detonation performance of alkali metal salts,and metal coordination compounds,along with EMOFs.The new model enhances predictive reliability for detonation velocities,aligning more closely with experimental results,as evi-denced by a root mean square error(RMSE)of 0.68 km/s compared to 1.12 km/s for existing methods.Furthermore,it accommodates a broader range of compounds,including those containing Sr,Cd,and Ag,and provides predictions for EMOFs that are more consistent with computer code outputs than previous predictive models.
文摘In order to increase the solubility of pyrroloquinoline quinone disodium salt(PQQ-NA_(2))in water,PQQ-NA_(2)ionic salts formed by PQQ-NA_(2)with amine compounds had been developed.Amine compounds specifically refered to aminomethyl propanol,tromethamine,and matrine.The PQQ-NA_(2)ionic salts solubility test result showed an increase as high as 24-fold compared to dissolving PQQ-NA_(2)alone.The antioxidant test indicated that the ionic salts exhibited significant antioxidant property.Two PQQ-NA_(2)gel formulations were prepared containing the ionic salts,and the stability test and PQQ-NA_(2)content test indicated that the formulations were stable and the loss rate of PQQ was below 10%.
文摘In this study,the mechanism of the reduction-diffusion reaction in a Sm-Fe binary system at low temperature was studied to investigate the possibility of synthesis of a Fe-rich TbCu_(7)-type SmFe_(x)(x>9)by the low-temperature diffusion-reduction(LTRD)process using LiCl-KCl eutectic molten salts.Firstly,the Sm-Fe phase transformation depending on the Sm-Fe composition,the LTRD temperature,and time was investigated,and it is found that the obtained metastable phase is only TbCu_(7)-type SmFe_(~8.5),which is not a Fe-rich phase.This Fe content does not change even after an expended LTRD process,and the metastable TbCu_(7)-type SmFe_(~8.5)tends to transform to the stable Sm_(2)Fe_(17)phase.In addition,it is found that the Sm-Fe phase starts to synthesize from the Sm-rich phase in the order of SmFe_(2),SmFe_(3),and SmFe_(8.5)as the LTRD temperature increases(when the time was 10 h)or the LTRD time increases(when the temperature was 550℃).Core-shell-like particles are observed in the case of a short LTRD time,and the core and the shell are Fe and the Sm-rich Sm-Fe phase,respectively,indicating that the Sm-rich phase begins to produce on the surface of the Fe particles.It is difficult to synthesize a Fe-rich TbCu_(7)-type SmFe_(x)(x>9)phase with the Sm-Fe binary system,suggesting that a different approach,such as addition of other elements,will be necessary.
基金supported by the National Natural Science Foundation of China(No.22001248)the Fundamental Research Funds for the Central Universities and University of Chinese Academy of Sciences.
文摘A charge transfer complex(CTC)-enabled photoreduction of ether phosphonium salts for the generation of oxyalkyl radicals was described.The photoreduction provides a convenient method to achieve selective oxyalkylation of enamides with broad substrate scope.The method features operational simplicity,mild and inherent green conditions.
基金support from the National Natural Science Foundation of China(Nos.21702198,21971227)the Anhui Provincial Natural Science Foundation(No.1808085MB30)the Fundamental Research Funds for the Central Universities(No.WK2340000090).
文摘The dynamic kinetic asymmetric transformation of racemic propargylic ammonium salts with prochiral aldimine esters through a stereodivergent propargylation is catalyzed by dual nickel and copper catalysis.Thus,a diverse range of optically activeα-quaternary amino esters were produced via C-N bond cleavage with high reaction efficiency and stereoselectivity(up to>99%ee).By selection of the appropriate pair-wise combination of catalyst configurational isomers,all four possible stereoisomers of the corresponding propargylation products are obtained in high yields with excellent regio-,diastereo-,and enantioselectiv-ities.
基金the National Natural Science Foundation of China(No.22271245)for the financial supportthe Yantai“Double Hundred Plan”the Talent Induction Program for Youth Innovation Teams in Colleges and Universities of Shan-dong Province。
文摘A new 1,4-amidocyanation of 1,3-enynes with N-amidopyridin-1-ium salts and TMSCN using a copper and photoredox synergetic catalysis for producingα-amido allenyl nitriles is developed.Employing N-amidopyridin-1-ium salts as the amidyl radical precursors,the reaction enables the formation of two new bonds,one C(sp^(3))-N bond and one C(sp^(2))-C(sp)bond,in a single reaction step.This reaction represents a mild,general route to the construction of theα-amido allenyl nitrile architectures,which characterizes a broad scope,a good functional group compatibility and an excellent selectivity.
文摘Considering the widespread presence of the dithiocarbamate skeleton in pharmaceuticals and bioactive molecules,the development of novel and convenient methods for the synthesis of these useful sulfur-containing compounds is of significant interest.Traditionally,S-aryl dithiocarbamates are constructed through the reaction of amines with thiophenols and thiophosgene[1].Recently,transition-metal-catalyzed Ullmann-type coupling between aryl boronic acids or iodoarenes with tetraalkylthiuram disulfides or sodium dialkyldithiocarbamates has been reported[2].
基金supported by the National Natural Science Foundation of China(No.22271170)the Scientific Research Foundation of Qingdao University of Science and Technology。
文摘Developing applicable methods to forge linkages between sp^(3)and sp^(2)-hydridized carbons is of great significance in drug discovery.We show here a new,Ni-catalyzed reductive cross-coupling reaction that forms Csp^(3)-Csp^(2)bonds from aryl iodides and cyclic sulfonium salts.Notably,Csp^(3)-Csp^(2)bonds can be forged selectively at the iodine-bearing carbon of bromo(iodo)arenes which is usually recognized as a huge challenge under the catalytic reductive cross-coupling(CRCC)conditions.Experimental and computational mechanistic studies support LNi~IAr as an active species,while the untraditional anti-Markovnikov selective alkylation of asymmetric sulfonium salts is determined by the oxidative S-substitution of sulfonium salts with LNi~IAr.This protocol further expands the range of alkyl electrophiles under the CRCC conditions and provides a new strategy for the construction of Csp^(3)-Csp^(2)bonds.
基金supported by the Science and Technology Research Program of Chongqing Municipal Education Commission(Grant No.KJQN 202103202)the Doctoral Research Foundation of Chongqing Industry Polytechnic College(Grant No.2022GZYBSZK2-11).
文摘Conditioning-free electrolytes with high reversibility of Mg plating/stripping are of vital importance for the commercialization of the superior rechargeable magnesium batteries(RMBs).In the present work,a non-nucleophilic electrolyte(denoted as MLCH)based on all-inorganic salts of MgCl_(2),LiCl and CrCl_(3) for RMBs is prepared by a straightforward one-step reaction.As a result,the MLCH electrolyte shows the noticeable performance of high ionic conductivity(3.40 mS cm^(−1)),low overpotential(∼46 mV vs Mg/Mg^(2+)),high Coulombic efficiency(∼93%),high anodic stability(SS,∼2.56 V vs Mg/Mg^(2+))and long-term(more than 500 h)cycling stability,especially the conditioning-free characteristic.The main equilibrium species in the MLCH electrolyte are confirmed to be the tetracoordinated anions of[LiCl2(THF)2]−and solvated dimers of[Mg_(2)(μ-Cl)3(THF)6]+.The addition of LiCl can assist the dissolution of MgCl_(2) and activation of the electrode/electrolyte interface,resulting in a superior Mg plating/stripping efficiency.The synergistic effect of LiCl,CrCl_(3),a small amount of HpMS and the absence of polymerization THF enable the conditioning-free characteristic of the MLCH electrolyte.Moreover,the MLCH electrolyte exhibits decent compatibility with the cathodic materials of CuS.The Mg/CuS full cell using the MLCH electrolyte presents a discharge specific capacity of 215 mAh g^(−1)at 0.1 C and the capacity can retain∼72%after 40 cycles.Notably,the MLCH electrolyte has other superiorities such as the broad sources of materials,low-cost and easy-preparation,leading to the potential prospect of commercial application.
基金the financial support by the National Natural Science Foundation of China(NSFC)(Grant Nos.52178319 and 52108307)the Natural Science Foundation of Fujian Province,China(Grant No.2022J05127).
文摘Calcium salt is an important contributing factor for calcium-based biomineralization.To study the effect of calcium salt on soil biomineralization using crude soybean urease,the calcium salts,including the calcium chloride (CaCl_(2)),calcium acetate ((CH_(3)COO)_(2)Ca) and calcium nitrate (Ca(NO_(3))_(2)),were used to prepare the biotreatment solution to carry out the biomineralization tests in this paper.Two series of biomineralization tests in solution and sand column,respectively,were conducted.Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were performed to determine the microscopic characteristics of the precipitated calcium carbonate (CaCO_(3)) crystals.The experimental results indicate that the biomineralization effect is the best for the CaCl2 case,followed by (CH_(3)COO)_(2)Ca,and worst for Ca(NO_(3))_(2) under the test conditions of this study (i.e.1 mol/L of calcium salt-urea).The mechanism for the effect of the calcium salt on the biomineralization of crude soybean urease mainly involves: (1) inhibition of urease activity,and (2) influence on the crystal size and morphology of CaCO_(3).Besides Ca^(2+) ,the anions in solution can inhibit the activity of crude soybean urease,and NO_(3)− has a stronger inhibitory effect on the urease activity compared with both CH_(3)COO^(−) and Cl^(−) .The co-inhibition of Ca^(2+) and NO_(3)− on the activity of urease is the key reason for the worst biomineralization of the Ca(NO_(3))_(2) case in this study.The difference in biomineralization between the CaCl_(2) and (CH_(3)COO)_(2) Ca cases is strongly correlated with the crystal morphology of the precipitated CaCO_(3).
基金financially supported by the China National Key Research and Development Plan Project(No.2018YFA0702300)the National Natural Science Foundation of China(Nos.52227813 and 51950410590)。
文摘Thermal energy storage(TES)systems based on molten salt are widely used in concentrating solar power(CSP)plants.The investigation of the corrosion behavior of alloy materials in molten salt is crucial for the correct selection of alloy materials and the design of TES systems.In this study,the corrosion behavior of 304,310S,316,and In625 alloys in molten chloride salts(27 mol%NaCl-22 mol%KCl-51 mol%MgCl,)was investigated.The evolution of mass loss of the alloy samples with corrosion time and temperature and the analysis of the experimental results by scanning electron microscopy(SEM),energy dispersive spectrometer(EDS),and X-ray diffraction(XRD)revealed the corrosion mechanism of the alloy samples in molten chloride salts.The main factors affecting the corrosion of the alloy samples were further analyzed.It was found that the loose multi-layer corrosion was formed on the surface of the corroded alloy samples with the increase in corrosion degree.Moreover,the experimental results.showed that Mo played a positive role in improving the corrosion resistance of the alloy samples because the presence of Mo could inhibit the outward diffusion of alloying element Cr.This work enriches the molten salt corrosion database and provides a reference for the selection of alloy materials for TES systems with potential application in CSP plants.
基金supported by the National Natural Science Foundation of China(21868012 and 22368025)Jiangxi Provincial Department of Science and Technology(20171BCB24005 and 20202BAB203011).
文摘The hydrophilic ZSM-5 zeolite membranes are applied to separate the inorganic acid solutions and inorganic acid/inorganic salt mixtures by pervaporation,and the membrane presents good stability,dehydration,and desalination performance.Influences of inorganic acid type(H_(2)SO_(4),H_(3)PO_(4),HNO_(3),and HCl),H_(2)SO_(4)concentration(1-6 mol·L^(-1)),test temperature(60-90℃)and inorganic acid/inorganic salt type(2 mol·L^(-1)H_(2)SO_(4)and sulfate,2 mol·L^(-1)H3PO4 and phosphate)on the pervaporation performance are investigated in this work.Either for concentrating 3%(mass)H_(2)SO_(4)solution or consecutive dehydrating 20%(mass)H_(2)SO_(4)solution,the hydrophilic ZSM-5 zeolite membrane has a good dehydration performance and stability.Even though the H_(2)SO_(4)concentration and test temperature are increased to 6 M and 90℃,only H_(2)O molecules could pass through the membrane and pH value of the permeation is kept neutral.Besides,the membrane has good dehydration and desalination performance for H_(2)SO_(4)/sulfates and H_(3)PO_(4)/phosphate mixtures,and the rejection of natrium salt,molysite,and magnesium is almost 100%.
基金the financial support from National Natural Science Foundation of China(Nos.22071070,21971077).
文摘Metastable molybdenum carbide(α-MoC),as a catalyst and an excellent support for metal catalysts,has been widely used in thermo/electro-catalytic reactions.However,the selective synthesis ofα-MoC remains a great challenge.Herein,a simple one-pot synthetic strategy for the selective preparation of metastableα-MoC is proposed by electrochemical co-reduction of CO_(2)and MoO_(3)in a low-temperature eutectic molten carbonate.The synthesizedα-MoC shows a reed flower-like morphology.By controlling the electrolysis time and monitoring the phase and morphology of the obtained products,the growth process ofα-MoC is revealed,where the carbon matrix is deposited first followed by the growth ofα-MoC from the carbon matrix.Moreover,by analyzing the composition of the electrolytic products,the formation mechanism forα-MoC is proposed.In addition,through this one-pot synthetic strategy,S-dopedα-MoC is successfully synthesized.Density functional theory(DFT)calculations reveal that S doping enhanced the HER performance ofα-MoC by facilitating water absorption and dissociation and weakening the bond energy of Mo-H to accelerate H desorption.The present work not only highlights the valuable utilization of CO_(2) but also offers a new perspective on the design and controllable synthesis of metal carbides and their derivatives.
文摘Cesium carbonate was used as a base to achieve the desulfurization reaction of alkenyl sulfonium salts and phosphine oxides at room temperature,forming C(sp2)—P bonds.This method features simple operation,mild reaction conditions,and good functional group compatibility,offering a straightforward and efficient preparation route for terminal vinyl phosphine oxides.
