Industrial waste salts are commonly used to make value-added snow-melting agents to ensure traffic safety in northern China during winter and spring after snowfall.However,heavy metals in industrial waste salts may po...Industrial waste salts are commonly used to make value-added snow-melting agents to ensure traffic safety in northern China during winter and spring after snowfall.However,heavy metals in industrial waste salts may pose certain environmental risks.Snow-melting agents and snow samples were collected and analyzed from highways,arterial roads,footbridges,and other locations in Beijing after the snowstorm in December 2023.It was found that the main component of snow-melting agents was sodium chloride with high concentrations of Cu,Mn,and Zn,which are not regulated in the current policies,despite the recent promotion of environmentally friendly snow-melting agents.The Pb,Zn and Cr contents of some snow samples exceeded the limitation value of surface water quality standards,potentially affecting the soil and water environment near roadsides,although the snow-melting agents comply with relevant standards,which indicates the policy gap in the management of recycled industrial salts.We reviewed and analyzed the relevant standards for snow-melting agents and industrial waste salts proposed nationally and internationally over the past 30 years.Through comparative analysis,we proposed relevant policy recommendations to the existing quality standards of snow-melting agents and the management regulations of industrial waste salts,and the formulation of corresponding usage strategies,aimed at reducing the potential environmental release of heavy metals from the use of snow-melting agents,thereby promoting more sustainable green urban development and environmentally sound waste management.展开更多
A synthetic method for heteroatom-bridged cyclic diaryliodonium salts by using ortho-substituted functionalized diaryliodonium salts is presented.Coumarin skeleton was also incorporated into cyclic diaryliodonium salt...A synthetic method for heteroatom-bridged cyclic diaryliodonium salts by using ortho-substituted functionalized diaryliodonium salts is presented.Coumarin skeleton was also incorporated into cyclic diaryliodonium salts.UV-Visible absorption of these cyclic diaryliodonium salts was performed to demonstrate their potential applications in photo-chemistry.展开更多
In order to find the optimal anions and cations for designing energetic salts with excellent detonation properties,the properties of 140 salts formed from the anions(A–G)of 3,3′-dinitroamino-4,4′-azoxyfurazan(DAAF)...In order to find the optimal anions and cations for designing energetic salts with excellent detonation properties,the properties of 140 salts formed from the anions(A–G)of 3,3′-dinitroamino-4,4′-azoxyfurazan(DAAF)derivatives substituted with the—NH_(2),—N_(3) or—NO_(2) group and the cations(1–20)of guanidine,triazole,or tetrazole derivatives were investigated by means of density-functional theory.The predicted densities,heats of formation,detonation velocities(D),and detonation pressures(P)of 140 salts were 11.72 to 2.06 g·cm ^(−3),570.2 to 2333.4 kJ·mol^(−1),8.29 to 10.02 km·s^(−1) and 30.16 to 47.57 GPa,respectively.Most of the salts had better detonation properties than the widely used hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX).Salts containing—NO_(2) group anions(C and F)have better detonation properties(D is 8.88 to 10.02 km·s^(−1) and P is 35.75 to 47.75 GPa)than other salts.Salts containing the cations NH_(4)^(+)(1),NH_(3)OH^(+)(2)and CH_(2)N_(4)NO_(2)^(+)(20)had good detonation properties(D is 9.38 to 10.02 km·s^(−1) and P is 40.72 to 47.75 GPa).Depending on the detonation properties,anions(C and F)and cations(1,2 and 20)are the recommended ions for the generation of energetic salts.展开更多
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
Oxalic acid salts(oxalate)were recently developed as C1 synthon,potent single-electron-transfer(SET)reductant,and hole scavengers via generation of CO_(2) and CO_(2) radical anion(CO_(2)·^(-))under mild photochem...Oxalic acid salts(oxalate)were recently developed as C1 synthon,potent single-electron-transfer(SET)reductant,and hole scavengers via generation of CO_(2) and CO_(2) radical anion(CO_(2)·^(-))under mild photochemical conditions.A series of challenging reductive transformations were realized with oxalic dianion under catalytic photoredox conditions or through an electron-donor-acceptor(EDA)complex formation process.As a chemical intermediate for carbon capture and utilization(also a cheap and readily available reagent),oxalate salts could release one electron easily(E_(ox)=+0.06 V vs.SCE)via visible-light irradiation to give CO_(2) and CO_(2)·^(-) and therefore opened a new arena for reductive carboxylation reactions with highly expanded reaction diversity and chemical space to realize challenging C-X bond activation,alkenes cross coupling,and reductive carboxylation of unsaturated chemical bonds in a more sustainable and efficient way.This review features the recently developed aspects with oxalate salts and also an outlook for its further application in organic radical transformations.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
To achieve good performance for LiFePO4-based batteries operated at a wide temperature range,mixed salts of LiBF4 LiBOB（lithium bis（oxalato）borate） and LiTFSI（lithium bis（trifluoromethanesulfonyl）imide）-LiBOB ...To achieve good performance for LiFePO4-based batteries operated at a wide temperature range,mixed salts of LiBF4 LiBOB（lithium bis（oxalato）borate） and LiTFSI（lithium bis（trifluoromethanesulfonyl）imide）-LiBOB were investigated as alternative lithium salts to LiPF6 in non-aqueous electrolytes.LiFePO4/Li half cells using LiPF6,LiBF4-LiBOB and LiTFSI-LiBOB slats as lithium salts were investigated by galvanostatic cycling,cyclic voltammetry,thermogravimetric analysis.The results show that LiBF4-LiBOB and LiTFSI-LiBOB mixed salts are much more thermally stable than LiPF6.Corrosion of Al foil in the LiTFSI-based electrolytes can be suppressed successfully by the addition of LiBOB as a co-salt.The electrochemical performance of LiBF4-LiBOB and LiTFSI-LiBOB mixed salts based cells are both better than that of LiPF6-based cell.LiTFSI-LiBOB mixed salt based electrolyte is considered to be a very promising electrolyte candidate for Li-ion batteries that will be used in wide-temperature applications.展开更多
By using cyclic and linear sweep voltammetry,the electrochemical deposition behaviors of Mg^2＋ and B^3＋ in fluorides molten salts of KF-MgF2 and KF-KBF4 at 880℃ were investigated,respectively.The results show that ...By using cyclic and linear sweep voltammetry,the electrochemical deposition behaviors of Mg^2＋ and B^3＋ in fluorides molten salts of KF-MgF2 and KF-KBF4 at 880℃ were investigated,respectively.The results show that the electrochemical reduction of Mg^2＋ is a one-step reaction as Mg^2＋＋2e-→Mg in KF-1%MgF2 molten salt,and the electrochemical reduction of B^3＋ is also a one-step reaction as B^3＋＋3e-→B in KF-KBF4 （1%,2% KBF4） molten salts.Both the cathodic reduction reactions of Mg^2＋ and B^3＋ are controlled by diffusion process.The diffusion coefficients of Mg^2＋ in KF-MgF2 molten salts and B^3＋ in KF-KBF4 molten salts are 6.8×10^-7 cm^2/s and 7.85×10^-7 cm^2/s,respectively.Moreover,the electrochemical synthesis of MgB2 by co-deposition of Mg and B was carried out in the KF-MgF2-KBF4 （molar ratio of 6：1：2） molten salt at 750℃.The X-ray diffraction analysis indicates that MgB2 can be deposited on graphite cathode in the KF-MgF2-KBF4 molten salt at 750℃.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
Carbon-based materials have been widely applied for pollutant removal relying on their rich pore structure,functional groups,chemical stability,and expandability.However,the traditional manufacturing process of carbon...Carbon-based materials have been widely applied for pollutant removal relying on their rich pore structure,functional groups,chemical stability,and expandability.However,the traditional manufacturing process of carbon materials based on organic compounds pyrolysis is high energy-consuming and high-emission,which is not conducive to addressing the climate crisis and achieving the goal of carbon neutrality.Molten salt electrolysis technology enables the direct capture and reduction of CO_(2)to produce solid carbon,resulting in significant environmental benefits while achieving carbon emissions reduction.The molten salt also has a purification function,enabling the production of high-purity carbon materials.The kinetics of the electrochemical reduction process can be easily controlled,and the co-reduction of multiple elements provides convenience for the in-situ optimization of carbon material structure and the expansion of its applications.Therefore,this review focuses on the thermodynamics&kinetics processes of molten salt capture and electrochemical reduction of CO_(2)to prepare carbon materials.It further reviews the recent research progress on the preparation of carbon materials for pollutant removal based on molten salt electrochemical processes for the first time.Finally,we analyze the advantages and challenges of the current molten salt electrochemical processes and offers prospects for future research directions.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 order to better understand the leaching process of rare earth （RE） and aluminum （Al） from the weathered crust elutiondepositedRE ore, the mass transfer of RE and Al in column leaching was investigated using the...In order to better understand the leaching process of rare earth （RE） and aluminum （Al） from the weathered crust elutiondepositedRE ore, the mass transfer of RE and Al in column leaching was investigated using the chromatographic plate theory. Theresults show that a higher initial ammonium concentration in a certain range can enhance the mass transfer process. pH of leachingagent in the range of 2 to 8 almost has no effect on the mass transfer efficiency of RE, but plays a positive role in the mass transferefficiency of Al under strong acidic condition （pH〈4）. There is an optimum flow rate that makes the highest mass transfer efficiency.The optimum leaching condition of RE is the leaching agent pH of 4？8, ammonium concentration of 0.4 mol/L and flow rate of0.5 mL/min. The mass transfer efficiencies of RE and Al both follow the order： （NH4）2SO4〈NH4Cl〈NH4NO3, implying thecomplexing ability of anion.展开更多
Electrochemical studies on silicon deposition were performed in molten salt electrolytes. Purification of metallurgical grade silicon by electrorefining was carried out in molten Si-chloride salts at temperatures from...Electrochemical studies on silicon deposition were performed in molten salt electrolytes. Purification of metallurgical grade silicon by electrorefining was carried out in molten Si-chloride salts at temperatures from 973 K to 1223 K. It was found that the use of a liquid alloy anode of silicon and copper was beneficial in molten CaCl2 with NaCl, CaO and dissolved Si. ICP-AES analysis results showed efficient removal of metal impurities, such as titanium, aluminum and iron, which are present in significant quantities in the feedstock. The contents of boron and phosphorus in the silicon after electrorefining were reduced from 36×10-6 and 25×10-6 to 4.6×10-6 and 2.8 ×10-6, respectively. The energy consumption of electrorefining was estimated to be about 9.3 kW?h/kg.展开更多
The electrical conductivity of NaF-AlF3-CaF2-Al2O3-ZrO2 system was studied by a tube-type cell with fixed cell constant. The results show that the electrical conductivity of NaF-AlF3-3%Al2O3-3%CaF2-ZrO2 molten salt sy...The electrical conductivity of NaF-AlF3-CaF2-Al2O3-ZrO2 system was studied by a tube-type cell with fixed cell constant. The results show that the electrical conductivity of NaF-AlF3-3%Al2O3-3%CaF2-ZrO2 molten salt system decreases with increase of ZrO2 content in an interval of 0-5%. The increase of 1%ZrO2 results in a corresponding electrical conductivity decrease of 0.02 S/cm, and the equivalent conductivity increases with the increase of molar ratio of NaF to AlF3. When the temperature increases by 1 °C, the electrical conductivity increases by 0.004 S/cm. At last, the regression equations of electrical conductivity relative to temperature and ZrO2 are obtained by quadratic regression analysis.展开更多
In order to reveal the permeability rule of leaching agent solution and the effects of anions in the leaching process of weathered crust elution-deposited rare earth（RE） ores, the effects of ammonium concentration, ...In order to reveal the permeability rule of leaching agent solution and the effects of anions in the leaching process of weathered crust elution-deposited rare earth（RE） ores, the effects of ammonium concentration, temperature, particle size and porosity on the permeability were discussed in detail with（NH4）2SO4, NH4Cl and NH4NO3 as the leaching agent. It was found that the permeation velocity of ammonium salts increased linearly with the increase of hydraulic gradient. The seepage of ammonium salts solution in the RE ores followed Darcy’s law and displayed a laminar flow. The properties of the leaching agent solution and RE ores were the main factors that affect the permeability of RE ores. With the decrease of ammonium concentration and increase of temperature, the viscosity of solution decreased and the permeability coefficients of RE ores increased. And the effects of temperature on the viscosity and permeability were larger than ammonium concentration. The permeability of RE ores became worse with the decrease of particle size and porosity, and the particle size played a more important role compared with porosity. The permeability coefficient of RE ores increased and the viscosity of ammonium salts solution decreased in the order of（NH4）2SO4, NH4Cl and NH4NO3, implying that the penetrating power of anions increased in the order of SO42-, Cl- and NO3-. The results may play a vital role in improving the permeability of weathered crust elution-deposited RE ores.展开更多
Rare earth（RE） metals and their alloys have attracted considerable practical interests due to their functional properties. Because of their negative deposition potentials, RE metals cannot be electrochemically depos...Rare earth（RE） metals and their alloys have attracted considerable practical interests due to their functional properties. Because of their negative deposition potentials, RE metals cannot be electrochemically deposited from aqueous media. Using molten salt as medium provides a unique opportunity for the electrowinning and electrorefining of high-purity RE metals, as well as for the electrochemical formation of their alloys and intermetallic compounds. Certainly, the electrochemical behaviors of RE metals and their alloys have been investigated in a number of different molten salts comprising all-fiuorides,all-chlorides and mixed chloride-fiuoride media. Based on the results, RE and their alloys were produced by molten salt electrolysis. In this paper, the developments of preparation of RE metals and their alloys by electrolysis in molten salts in recent years were systematically summarized on both the local and international levels. Attention was paid mainly to the electrodeposition of RE metals and their alloys, including RE-Mg, RE-Al, RE-Ni, RE-Co,RE-Cu, RE-Fe and RE-Zn alloys.展开更多
基金supported by the National Natural Science Foundation of China(No.22176200)the Industrial Innovation Entrepreneurial Team Project of Ordos 2021.
文摘Industrial waste salts are commonly used to make value-added snow-melting agents to ensure traffic safety in northern China during winter and spring after snowfall.However,heavy metals in industrial waste salts may pose certain environmental risks.Snow-melting agents and snow samples were collected and analyzed from highways,arterial roads,footbridges,and other locations in Beijing after the snowstorm in December 2023.It was found that the main component of snow-melting agents was sodium chloride with high concentrations of Cu,Mn,and Zn,which are not regulated in the current policies,despite the recent promotion of environmentally friendly snow-melting agents.The Pb,Zn and Cr contents of some snow samples exceeded the limitation value of surface water quality standards,potentially affecting the soil and water environment near roadsides,although the snow-melting agents comply with relevant standards,which indicates the policy gap in the management of recycled industrial salts.We reviewed and analyzed the relevant standards for snow-melting agents and industrial waste salts proposed nationally and internationally over the past 30 years.Through comparative analysis,we proposed relevant policy recommendations to the existing quality standards of snow-melting agents and the management regulations of industrial waste salts,and the formulation of corresponding usage strategies,aimed at reducing the potential environmental release of heavy metals from the use of snow-melting agents,thereby promoting more sustainable green urban development and environmentally sound waste management.
基金Project supported by the National Natural Science Foundation of China(No.22478117)。
文摘A synthetic method for heteroatom-bridged cyclic diaryliodonium salts by using ortho-substituted functionalized diaryliodonium salts is presented.Coumarin skeleton was also incorporated into cyclic diaryliodonium salts.UV-Visible absorption of these cyclic diaryliodonium salts was performed to demonstrate their potential applications in photo-chemistry.
文摘In order to find the optimal anions and cations for designing energetic salts with excellent detonation properties,the properties of 140 salts formed from the anions(A–G)of 3,3′-dinitroamino-4,4′-azoxyfurazan(DAAF)derivatives substituted with the—NH_(2),—N_(3) or—NO_(2) group and the cations(1–20)of guanidine,triazole,or tetrazole derivatives were investigated by means of density-functional theory.The predicted densities,heats of formation,detonation velocities(D),and detonation pressures(P)of 140 salts were 11.72 to 2.06 g·cm ^(−3),570.2 to 2333.4 kJ·mol^(−1),8.29 to 10.02 km·s^(−1) and 30.16 to 47.57 GPa,respectively.Most of the salts had better detonation properties than the widely used hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX).Salts containing—NO_(2) group anions(C and F)have better detonation properties(D is 8.88 to 10.02 km·s^(−1) and P is 35.75 to 47.75 GPa)than other salts.Salts containing the cations NH_(4)^(+)(1),NH_(3)OH^(+)(2)and CH_(2)N_(4)NO_(2)^(+)(20)had good detonation properties(D is 9.38 to 10.02 km·s^(−1) and P is 40.72 to 47.75 GPa).Depending on the detonation properties,anions(C and F)and cations(1,2 and 20)are the recommended ions for the generation of energetic salts.
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financially supported by the Jiangsu Province Shuangchuang Ph.D.award(No.JSSCBS20211267,Pei Xu)the Natural Science Research Project of Jiangsu Universities(No.23KJB150037,Pei Xu)+2 种基金sponsored by the Jiangsu Specially-Appointed Professor Program(Xu Zhu)the Start-up Funding provided by Xuzhou Medical UniversityThe Public Experimental Research Center of Xuzhou Medical University is also acknowledged。
文摘Oxalic acid salts(oxalate)were recently developed as C1 synthon,potent single-electron-transfer(SET)reductant,and hole scavengers via generation of CO_(2) and CO_(2) radical anion(CO_(2)·^(-))under mild photochemical conditions.A series of challenging reductive transformations were realized with oxalic dianion under catalytic photoredox conditions or through an electron-donor-acceptor(EDA)complex formation process.As a chemical intermediate for carbon capture and utilization(also a cheap and readily available reagent),oxalate salts could release one electron easily(E_(ox)=+0.06 V vs.SCE)via visible-light irradiation to give CO_(2) and CO_(2)·^(-) and therefore opened a new arena for reductive carboxylation reactions with highly expanded reaction diversity and chemical space to realize challenging C-X bond activation,alkenes cross coupling,and reductive carboxylation of unsaturated chemical bonds in a more sustainable and efficient way.This review features the recently developed aspects with oxalate salts and also an outlook for its further application in organic radical transformations.
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Project(2013JSJJ027)supported by the Teacher Research Fund of Central South University,China
文摘To achieve good performance for LiFePO4-based batteries operated at a wide temperature range,mixed salts of LiBF4 LiBOB（lithium bis（oxalato）borate） and LiTFSI（lithium bis（trifluoromethanesulfonyl）imide）-LiBOB were investigated as alternative lithium salts to LiPF6 in non-aqueous electrolytes.LiFePO4/Li half cells using LiPF6,LiBF4-LiBOB and LiTFSI-LiBOB slats as lithium salts were investigated by galvanostatic cycling,cyclic voltammetry,thermogravimetric analysis.The results show that LiBF4-LiBOB and LiTFSI-LiBOB mixed salts are much more thermally stable than LiPF6.Corrosion of Al foil in the LiTFSI-based electrolytes can be suppressed successfully by the addition of LiBOB as a co-salt.The electrochemical performance of LiBF4-LiBOB and LiTFSI-LiBOB mixed salts based cells are both better than that of LiPF6-based cell.LiTFSI-LiBOB mixed salt based electrolyte is considered to be a very promising electrolyte candidate for Li-ion batteries that will be used in wide-temperature applications.
基金Project(50804010) supported by the National Natural Science Foundation of ChinaProject(2007CB210305) supported by the National Basic Research Program of China
文摘By using cyclic and linear sweep voltammetry,the electrochemical deposition behaviors of Mg^2＋ and B^3＋ in fluorides molten salts of KF-MgF2 and KF-KBF4 at 880℃ were investigated,respectively.The results show that the electrochemical reduction of Mg^2＋ is a one-step reaction as Mg^2＋＋2e-→Mg in KF-1%MgF2 molten salt,and the electrochemical reduction of B^3＋ is also a one-step reaction as B^3＋＋3e-→B in KF-KBF4 （1%,2% KBF4） molten salts.Both the cathodic reduction reactions of Mg^2＋ and B^3＋ are controlled by diffusion process.The diffusion coefficients of Mg^2＋ in KF-MgF2 molten salts and B^3＋ in KF-KBF4 molten salts are 6.8×10^-7 cm^2/s and 7.85×10^-7 cm^2/s,respectively.Moreover,the electrochemical synthesis of MgB2 by co-deposition of Mg and B was carried out in the KF-MgF2-KBF4 （molar ratio of 6：1：2） molten salt at 750℃.The X-ray diffraction analysis indicates that MgB2 can be deposited on graphite cathode in the KF-MgF2-KBF4 molten salt at 750℃.
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supported by the National Natural Science Foundation of China(Nos.52200143,51979011 and 52276208)the Natural Science Foundation of Hubei Province(No.2024AFB546)the Fundamental Research Funds for Central Public Welfare Research Institutes(Nos.CKSF2023302/CL and CKSF2023314/CL).
文摘Carbon-based materials have been widely applied for pollutant removal relying on their rich pore structure,functional groups,chemical stability,and expandability.However,the traditional manufacturing process of carbon materials based on organic compounds pyrolysis is high energy-consuming and high-emission,which is not conducive to addressing the climate crisis and achieving the goal of carbon neutrality.Molten salt electrolysis technology enables the direct capture and reduction of CO_(2)to produce solid carbon,resulting in significant environmental benefits while achieving carbon emissions reduction.The molten salt also has a purification function,enabling the production of high-purity carbon materials.The kinetics of the electrochemical reduction process can be easily controlled,and the co-reduction of multiple elements provides convenience for the in-situ optimization of carbon material structure and the expansion of its applications.Therefore,this review focuses on the thermodynamics&kinetics processes of molten salt capture and electrochemical reduction of CO_(2)to prepare carbon materials.It further reviews the recent research progress on the preparation of carbon materials for pollutant removal based on molten salt electrochemical processes for the first time.Finally,we analyze the advantages and challenges of the current molten salt electrochemical processes and offers prospects for future research directions.
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%.
基金Projects(51274152,41472071)supported by the National Natural Science Foundation of ChinaProject(T201506)supported by the Program for Excellent Young Scientific and Technological Innovation Team of Hubei Provincial Department of Education,China
文摘In order to better understand the leaching process of rare earth （RE） and aluminum （Al） from the weathered crust elutiondepositedRE ore, the mass transfer of RE and Al in column leaching was investigated using the chromatographic plate theory. Theresults show that a higher initial ammonium concentration in a certain range can enhance the mass transfer process. pH of leachingagent in the range of 2 to 8 almost has no effect on the mass transfer efficiency of RE, but plays a positive role in the mass transferefficiency of Al under strong acidic condition （pH〈4）. There is an optimum flow rate that makes the highest mass transfer efficiency.The optimum leaching condition of RE is the leaching agent pH of 4？8, ammonium concentration of 0.4 mol/L and flow rate of0.5 mL/min. The mass transfer efficiencies of RE and Al both follow the order： （NH4）2SO4〈NH4Cl〈NH4NO3, implying thecomplexing ability of anion.
基金Project (2007J0012) supported by the Natural Science Foundation of Fujian Province, ChinaProject (019811) supported by Foxy in the 6th Framework Program, European Commission
文摘Electrochemical studies on silicon deposition were performed in molten salt electrolytes. Purification of metallurgical grade silicon by electrorefining was carried out in molten Si-chloride salts at temperatures from 973 K to 1223 K. It was found that the use of a liquid alloy anode of silicon and copper was beneficial in molten CaCl2 with NaCl, CaO and dissolved Si. ICP-AES analysis results showed efficient removal of metal impurities, such as titanium, aluminum and iron, which are present in significant quantities in the feedstock. The contents of boron and phosphorus in the silicon after electrorefining were reduced from 36×10-6 and 25×10-6 to 4.6×10-6 and 2.8 ×10-6, respectively. The energy consumption of electrorefining was estimated to be about 9.3 kW?h/kg.
基金Project (2007CB210305) supported by the National Basic Research Program of ChinaProject (51074045) supported by the National Natural Science Foundation of China
文摘The electrical conductivity of NaF-AlF3-CaF2-Al2O3-ZrO2 system was studied by a tube-type cell with fixed cell constant. The results show that the electrical conductivity of NaF-AlF3-3%Al2O3-3%CaF2-ZrO2 molten salt system decreases with increase of ZrO2 content in an interval of 0-5%. The increase of 1%ZrO2 results in a corresponding electrical conductivity decrease of 0.02 S/cm, and the equivalent conductivity increases with the increase of molar ratio of NaF to AlF3. When the temperature increases by 1 °C, the electrical conductivity increases by 0.004 S/cm. At last, the regression equations of electrical conductivity relative to temperature and ZrO2 are obtained by quadratic regression analysis.
基金supported by the National Natural Science Foundation of China(51274152,41472071)the Fundamental Research Funds for the Central Universities,South-Central University for Nationalities(CZQ17011,CZP17070)the Scientific Research Foundation of South-Central University for Nationalities(YZZ16002)
文摘In order to reveal the permeability rule of leaching agent solution and the effects of anions in the leaching process of weathered crust elution-deposited rare earth（RE） ores, the effects of ammonium concentration, temperature, particle size and porosity on the permeability were discussed in detail with（NH4）2SO4, NH4Cl and NH4NO3 as the leaching agent. It was found that the permeation velocity of ammonium salts increased linearly with the increase of hydraulic gradient. The seepage of ammonium salts solution in the RE ores followed Darcy’s law and displayed a laminar flow. The properties of the leaching agent solution and RE ores were the main factors that affect the permeability of RE ores. With the decrease of ammonium concentration and increase of temperature, the viscosity of solution decreased and the permeability coefficients of RE ores increased. And the effects of temperature on the viscosity and permeability were larger than ammonium concentration. The permeability of RE ores became worse with the decrease of particle size and porosity, and the particle size played a more important role compared with porosity. The permeability coefficient of RE ores increased and the viscosity of ammonium salts solution decreased in the order of（NH4）2SO4, NH4Cl and NH4NO3, implying that the penetrating power of anions increased in the order of SO42-, Cl- and NO3-. The results may play a vital role in improving the permeability of weathered crust elution-deposited RE ores.
基金financially supported by Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, the National Natural Science foundation of China (Nos. 11675044, 21271054, 11575047 and 21173060)the Major Research Plan of the National Natural Science Foundation of China (Nos. 91326113 and 91226201)the Fundamental Research Funds for the Central Universities (No. HEUCF2016012)
文摘Rare earth（RE） metals and their alloys have attracted considerable practical interests due to their functional properties. Because of their negative deposition potentials, RE metals cannot be electrochemically deposited from aqueous media. Using molten salt as medium provides a unique opportunity for the electrowinning and electrorefining of high-purity RE metals, as well as for the electrochemical formation of their alloys and intermetallic compounds. Certainly, the electrochemical behaviors of RE metals and their alloys have been investigated in a number of different molten salts comprising all-fiuorides,all-chlorides and mixed chloride-fiuoride media. Based on the results, RE and their alloys were produced by molten salt electrolysis. In this paper, the developments of preparation of RE metals and their alloys by electrolysis in molten salts in recent years were systematically summarized on both the local and international levels. Attention was paid mainly to the electrodeposition of RE metals and their alloys, including RE-Mg, RE-Al, RE-Ni, RE-Co,RE-Cu, RE-Fe and RE-Zn alloys.
