Sulfur and selenium have been paid more and more attention in energy storage systems because of their high theoretical specific gravimetric and volumetric capacities.With the increasing scarcity of lithium resources,s...Sulfur and selenium have been paid more and more attention in energy storage systems because of their high theoretical specific gravimetric and volumetric capacities.With the increasing scarcity of lithium resources,secondary batteries made of sulfur and selenium coupled with other alkali metal/alkaline earth metals(e.g.Na,K,Mg)are expected to play a vital role in future production and human life.Due to the volume expansion,poor conductivity and shuttle effect,the structure design of cathode,as one of the important roles in metal-S/Se batteries,has always been a hot and difficult point.In the review,various host materials of S and Se are clarified and discussed.Typically,carbonaceous materials are the most widely used hosts,while polar materials are becoming more and more popular in metal-S/Se batteries.Through a comprehensive overview,it is hoped that previous research experiences can provide further reference and guidance for the sustainable development of metal-S/Se batteries.展开更多
Herein,3‑aminopropyltriethoxysilane(APTES)was used to modify F‑containing silica slag(SS)by simple grafting and served as a multifunctional barrier layer.The amino group(—NH2)in the amino‑modified SS(NH2‑SS)forms lig...Herein,3‑aminopropyltriethoxysilane(APTES)was used to modify F‑containing silica slag(SS)by simple grafting and served as a multifunctional barrier layer.The amino group(—NH2)in the amino‑modified SS(NH2‑SS)forms ligand bonds or hydrogen bonds with sulfur ions in lithium polysulfides(LiPSs),thus inhibiting the shuttle effect.Electrochemical analyses demonstrated that lithium‑sulfur(Li‑S)batteries employing the NH2‑SS interlayer exhibited discharge specific capacities of 1048 and 789 mAh·g^(-1) at 0.2C and 2C,respectively,and even at 4C,the initial discharge specific capacity remained at 590 mAh·g^(-1),outperforming the Li‑S battery with unmodified SS as the interlayer.展开更多
The practical application of lithium-sulfur(Li-S)batteries is still impeded by the severe shuttle effect of lithium polysulfides(LiPSs)and sluggish reaction kinetics of active sulfur.Designing catalytic carriers with ...The practical application of lithium-sulfur(Li-S)batteries is still impeded by the severe shuttle effect of lithium polysulfides(LiPSs)and sluggish reaction kinetics of active sulfur.Designing catalytic carriers with abundant active sites and strong chemisorption capability for LiPSs,is regarded as effective strategy to address these issues.Herein,Se-doping is introduced into the nitrogen-doped carbon coated CoP composite(Se-CoP@NC)to generate structural defects,which effectively enlarges the lattice spacing of CoP and reduces the conversion reaction energy barriers of LiPSs.Meanwhile,Se-doping sites bridges the interface of CoP and nitrogen-doped carbon,accelerating the charge transfer behavior and conversion reaction kinetics of LiPSs.Benefiting from the structural advantages,the assembled Li-S batteries with S/Se-CoP@NC as cathode exhibit high reversible capacity of 779.6 mAh/g at 0.5 C after 500 cycles,and high specific capacity of 805.9 mAh/g at 2 C.Even under extreme conditions(high sulfur-loading content of 6.9 mg/cm^(2);lean electrolyte dosage of 7μL/mg),the corresponding Li-S batteries also keep high reversible areal capacity of 4.5 mAh/cm^(2) after 100 cycles at 0.1 C.This work will inspire the design of metal compounds-based catalysts from atomic level to facilitate the practicability of Li-S batteries.展开更多
The implementation of multifunctional application scenarios for mobile terminal devices has increased the energy density requirements of batteries.Increasing the charging voltage can rapidly increase the specific capa...The implementation of multifunctional application scenarios for mobile terminal devices has increased the energy density requirements of batteries.Increasing the charging voltage can rapidly increase the specific capacity of layered transition metal oxides;however,it also exacerbates the release of lattice oxygen and the contraction of the unit cell.Ternary materials are designed in a secondary particle state to meet the requirements of power battery applications.Therefore,to create ternary materials that can operate under ultrahigh voltages,attention should be given to both surface modification and particle integrity maintenance.By utilizing elemental selenium(Se)with a low melting point,easy sublimation,and multiple variable valence states,deep grain boundary modification was implemented inside the particles.The performance of the cathode material was evaluated through pouch cells,and the improvement mechanism was explored through molecular dynamics simulation calculations.Under the protection of a three-dimensional Se-rich modified layer,LiNi_(1/3)Co_(1/3)Mn_(1/3)O_(2)achieved stable operation at ultrahigh voltages(4.6 V vs.Li/Li^(+));a sacrificial protection mechanism based on the chronic decomposition of the Se-rich layer was proposed to explain the efficacy of Se modification in stabilizing ternary materials.This deep grain boundary modification based on elemental Se provides a new solution for the ultrahigh-voltage operation of transition metal oxides and provides a scientific basis and technical support for solving the interface contact problem of all-solid-state batteries.展开更多
Hard carbon(HC)in sodium-ion batteries is searched by numerous investigations,which can offer the excellent performance of reversible Na^(+)insertion and extraction.The covalent heteroatom doping in HC is recently wor...Hard carbon(HC)in sodium-ion batteries is searched by numerous investigations,which can offer the excellent performance of reversible Na^(+)insertion and extraction.The covalent heteroatom doping in HC is recently worth concentrating,which can dilate the interlayer spacing of graphite to adjust the electrochemical storage performance in carbon anodes.However,the reported doping strategies of the modified HC have only resulted in limited improvement,especially unobvious effects on tuning porous structure.In this study,tannin extract and K_(2)SO_(4) are respectively utilized as carbon source and sulfur source for the fabrication of HC,in which K_(2)SO_(4) can contribute to the heteroatom doping,and the pore forming as well.The tannin-derived sulfur-doped carbon anode shows the excellent cycle stability,achieving a high reversible capacity of 520.5 mAh/g at a current density of 100 mA/g.Even after 500 cycles at a current density of 3 A/g,a high specific capacity of 236.7 mAh/g and a capacity retention rate of 92.6%can be reserved.Compared with the initial carbon,the adsorption energy of Na^(+)is multifold times higher,whereas Na^(+)diffusion energy barriers manyfold decrease.Moreover,the full battery assembled with Na_(3)V_(2)(PO_(4))_(3)/tannin-based HC demonstrates a stable cycling performance.This work can manifest the potentiality of the tannin-based electrode as anode for a high-performance sodium-ion batteries(SIBs),which could especially offer an explanation of Na^(+)storage and solid-electrolyte interface(SEI)stability to the electrochemical performance.展开更多
Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systemat...Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties.In this work,we propose an autogenously transformed CoWO_(4)/WO_(2) heterojunction catalyst,integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity.CoWO_(4) effectively captures polysulfides,while the CoWO_(4)/WO_(2) interface facilitates their S-S bond activation on heterogenous catalytic sites.Benefiting from its directional intercalation channels,CoWO_(4) not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport.Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite.As a result,the CoWO_(4)/WO_(2) heterostructure demonstrates significantly enhanced catalytic performance,delivering a high capacity of 1262 mAh g^(−1) at 0.1 C.Furthermore,its rate capability and high sulfur loading performance are markedly improved,surpassing the limitations of its single-component counterparts.This study provides new insights into the catalytic mechanisms governing Li-S chemistry and offers a promising strategy for the rational design of high-performance Li-S battery catalysts.展开更多
Ferroptosis has exhibited great potential in therapies and intracellular reducing agents of sulfur species(RSSs) in the thiol-dependent redox systems are crucial in ferroptosis.This makes the simultaneous detection of...Ferroptosis has exhibited great potential in therapies and intracellular reducing agents of sulfur species(RSSs) in the thiol-dependent redox systems are crucial in ferroptosis.This makes the simultaneous detection of multiple RSSs significant for evaluating ferroptosis therapy.However,the traditional techniques,including fluorescent(FL) imaging and electrospray ionization-based mass spectrometry(MS) detection,cannot achieve the discrimination of different RSSs.Herein,simultaneous MS detection of multiple RSSs,including cysteine(Cys),homocysteine(Hcy),glutathione(GSH) and hydrogen sulfide(H_(2)S),was obtained upon enhancing ionization efficiency by a fluorescent probe(NBD-O-1).Based on the interaction between NBD-O-1 and RSSs,the complex of RSSs with a fragment of NBD-O-1 can be generated,which can be easily ionized for MS detection in the negative mode.Therefore,the intracellular RSSs can be well detected upon the incubation of He La cells with the probe of NBD-O-1,exhibiting the total RSS levels by the FL imaging and further providing expression of each RSS by enhanced MS detection.Furthermore,the RSSs during ferroptosis in He La cells have been evaluated using the present strategy,demonstrating the potential for ferroptosis examinations.This work has made an unconventional application of a fluorescent probe to enhance the detection of multiple RSSs by MS,providing significant molecular information for addressing the ferroptosis mechanism.展开更多
The development of catalytic multicomponent reactions for constructing complex organic scaffolds from readily accessible commodity chemicals is a key pursuit in contemporary synthetic chemistry.Current methods for syn...The development of catalytic multicomponent reactions for constructing complex organic scaffolds from readily accessible commodity chemicals is a key pursuit in contemporary synthetic chemistry.Current methods for synthesizing thioesters primarily rely on the acylation of thiols,which produces substantial waste and requires malodorous,unstable sulfur sources.In this work,we introduce a photocatalyzed hydrogen transfer strategy that enables a three-component synthesis of thioesters using abundant primary alcohols,easily available alkenes and elemental sulfur under mild conditions.This protocol demonstrates broad applicability and high chemo-and regioselectivity for both primary alcohols and alkenes,highlighting the advantage and potential of photo-mediated hydrogen transfer in facilitating multicomponent reactions using primary alcohol and elemental sulfur feedstocks.展开更多
Photo-assisted lithium–sulfur batteries(PALSBs)offer an eco-friendly solution to address the issue of sluggish reaction kinetics of conventional LSBs.However,designing an efficient photoelectrode for practical implem...Photo-assisted lithium–sulfur batteries(PALSBs)offer an eco-friendly solution to address the issue of sluggish reaction kinetics of conventional LSBs.However,designing an efficient photoelectrode for practical implementation remains a significant challenge.Herein,we construct a free-standing polymer–inorganic hybrid photoelectrode with a direct Z-scheme heterostructure to develop high-efficiency PALSBs.Specifically,polypyrrole(PPy)is in situ vapor-phase polymerized on the surface of N-doped TiO_(2) nanorods supported on carbon cloth(N-TiO_(2)/CC),thereby forming a well-defined p–n heterojunction.This architecture efficiently facilitates the carrier separation of photo-generated electron–hole pairs and significantly enhances carrier transport by creating a built-in electric field.Thus,the PPy@N-TiO_(2)/CC can simultaneously act as a photocatalyst and an electrocatalyst to accelerate the reduction and evolution of sulfur,enabling ultrafast sulfur redox dynamics,as convincingly validated by both theoretical simulations and experimental results.Consequently,the PPy@N-TiO_(2)/CC PALSB achieves a high discharge capacity of 1653 mAh g^(−1),reaching 98.7%of the theoretical value.Furthermore,5 h of photo-charging without external voltage enables the PALSB to deliver a discharge capacity of 333 mAh g^(−1),achieving dual-mode energy harvesting capabilities.This work successfully integrates solar energy conversion and storage within a rechargeable battery system,providing a promising strategy for sustainable energy storage technologies.展开更多
The rapid recombination of photogenerated charge carriers and the poor stability of metal sulfides remain bottlenecks limiting their practical applications. In this study, sulfur vacancies were introduced into an S-sc...The rapid recombination of photogenerated charge carriers and the poor stability of metal sulfides remain bottlenecks limiting their practical applications. In this study, sulfur vacancies were introduced into an S-scheme AgIn_(5)S_(8)/Bi_(2)S_(3) heterojunction via an in situ hydrothermal method. The sulfur vacancies induced charge density redistribution within the heterojunction and generated efficient active sites for electrons, thereby creating a localized electron-rich environment. The synergistic effects of the sulfur vacancies, internal electric field, and defect energy levels accelerated the separation and transfer of photogenerated charge carriers via the S-scheme pathway, thereby enhancing the visible-light photocatalytic performance, by achieving a Cr(Ⅵ) reduction efficiency of 99.6%. More importantly, the long-term stability and excellent anti-interference capability of the S-scheme AgIn_(5)S_(8)/Bi_(2)S_(3) heterojunction demonstrate its practical application potential, achieving 98.9% Cr(Ⅵ) removal from real electroplating wastewater and meeting discharge standards. This work provides a theoretical basis for constructing highly-catalytic S-scheme heterojunctions and serves as a promising solution for Cr(VI)-containing electroplating wastewater treatment.展开更多
Fifteen samples from three study areas （the Bancun diabase dykes, the Bali hornblende gabbro dykes, the Linzifen gabbro-diabase dykes） were collected and analyzed for selenium （Se）, sulfur （S）, copper （Cu）, ma...Fifteen samples from three study areas （the Bancun diabase dykes, the Bali hornblende gabbro dykes, the Linzifen gabbro-diabase dykes） were collected and analyzed for selenium （Se）, sulfur （S）, copper （Cu）, major and trace elements. In general, Se, S and Cu do positively correlate to each other. The concentration of S and Se and the S/Se ratio are higher than the corresponding value of primitive mantle （PM）, and the Cu/S ratio falls in a narrow range （0.04-0.29）, which is consistent with that of primitive mantle （0.05-0.20）. The Bancun diabase dykes and the Bali hornblende gabbro dykes were located in an intraplate environment during the Late Mesozoic. Oceanic subduction was closely related to magmatic activities. The magmatic activities play an important role in the transportation mechanism of Se and S. Because those two groups were closer to fault zones, which may affect the distribution of S and Se and other elements. In the two groups, no crustal contamination was observed, indicating that all analyzed elements may come from enriched mantle metasomtism associated with slab subduction. However, the Linzifen gabbro-diabase dykes were located in an intraplate rift environment, and its invading age is older than the other two groups, the primitive magma comes from mantle, and there is an anomalous relation between S, Se and Al2O3, （La/Sm）N, and all these factors could result in higher S and Se concentration.展开更多
A hydroponic study was conducted to determine the effects of selenium(Se:0,3,6μmol L^-1)on senescence-related oxidative stress in garlic plants grown under two sulfur(S)levels.We evaluated the yields of plants harves...A hydroponic study was conducted to determine the effects of selenium(Se:0,3,6μmol L^-1)on senescence-related oxidative stress in garlic plants grown under two sulfur(S)levels.We evaluated the yields of plants harvested at 160 and 200 days after sowing.Plants grown under a low Se dose(0.3μmol L^-1)at low S level showed higher yields(12.0%increase in fresh weight yield,13.7%increase in dry weight yield)than the controls,despite a decrease in chlorophyll concentration.Compared with control plants,the Se-treated plants showed lower levels of lipid peroxidation.The Se-treated plants also showed higher activities of glut athione peroxidase and catalase,but lower superoxide dismutase activities.Changes in Fv/Fm values and proline contents were affected more strongly by S than by Se.On the basis of our results,we can conclude that Se plays a key role in the antioxidant systems in garlic seedlings.It delays senescence by alleviating the peroxide stress,but it can be toxic at high levels.A high S level may increase tolerance to high Se concentrations through reducing Se accumulation in plants.展开更多
Flue gas from coal combustion contains significant amounts of volatile selenium （Se）. The capture of Se in the flue gas desulfurization （FGD） scrubber unit has resulted in a generation of metal-laden residues. It ...Flue gas from coal combustion contains significant amounts of volatile selenium （Se）. The capture of Se in the flue gas desulfurization （FGD） scrubber unit has resulted in a generation of metal-laden residues. It is important to determine Se speciation to understand the environmental impact of its disposal. A simple method has been developed for selective inorganic Se（IV）, Se（VI） and organic Se determination in the liquid-phase FGD residues by hydride generation atomic fluorescence spectrometry （AFS）. It has been determined that Se（IV）, Se（VI） and organic Se can be accurately determined with detection limits （DL） of 0.05, 0.06 and 0.06 μg/L, respectively. The accuracy of the proposed method was evaluated by analyzing the certified reference material, NIST CRM 1632c, and also by analyzing spiked tap-water samples. Analysis indicates that the concentration of Se is high in FGD liquid residues and primarily exists in a reduced state as selenite （Se（IV））. The toxicity of Se（IV） is the strongest of all Se species. Flue gas desulfurization residues pose a serious environmental risk.展开更多
The leaching kinetics of selenium from copper anode slimes was studied in a nitric acid?sulfuric acid mixture.The effects of main parameters on selenium leaching showed that the leaching rate of selenium was practical...The leaching kinetics of selenium from copper anode slimes was studied in a nitric acid?sulfuric acid mixture.The effects of main parameters on selenium leaching showed that the leaching rate of selenium was practically independent of stirring speed,while dependent on temperature and the concentrations of HNO3and H2SO4.The leaching of selenium includes two stages.The activation energy in the first stage is103.5kJ/mol,and the chemical reaction is the rate controlling step.It was almost independent of H2SO4concentration and dependent on HNO3concentration since the empirical reaction order with respect to HNO3concentration is0.5613.In the second stage,the activation energy is30.6kJ/mol,and the process is controlled by a mixture of diffusion and chemical reaction.The leaching of selenium was almost independent of HNO3concentration.展开更多
Accelerating the(NH_4)_(2)SO_(3) oxidation gives rise to the reclaiming of byproduct, while there are secondary environmental risks from reduction of the coexisted selenium species by sulfite. In this study, a bi-func...Accelerating the(NH_4)_(2)SO_(3) oxidation gives rise to the reclaiming of byproduct, while there are secondary environmental risks from reduction of the coexisted selenium species by sulfite. In this study, a bi-functional Co-SBA-15-SH, were synthesized through Co impregnation and sulfhydryl(-SH) decoration, which can simultaneously uptake Se and accelerate sulfite oxidation efficiently. Meanwhile, the adsorption kinetics and migration mechanism of Se species were revealed through characterization and density functional calculations, with maximum adsorption capacity of 223 mg/g. The inhibition of Se~0 re-emission and poisonous effect of Se on sulfite oxidation was also investigated. Using the findings of this study, the ammonia desulfurization can be improved by enabling purification of the byproduct and lowering the toxicity of effluent by removing toxic pollutants.展开更多
A simple and general method for the synthesis of bi(acyl)disulfides is reported.Sulfur is allowed to react with sodium hydroxide to give sodium disulfide at 65℃ under PTC,which can react with acyl halides to afford b...A simple and general method for the synthesis of bi(acyl)disulfides is reported.Sulfur is allowed to react with sodium hydroxide to give sodium disulfide at 65℃ under PTC,which can react with acyl halides to afford bi(acyl)disulfides in good to excellent isolated yields.The effects of solvents and phase transfer catalysts are discussed.展开更多
The increasing demand of the green energy storage system encourages us to develop a higher energy storage system to take the place of the present lithium-ion batteries with limited energy/power densities[1,2].Among th...The increasing demand of the green energy storage system encourages us to develop a higher energy storage system to take the place of the present lithium-ion batteries with limited energy/power densities[1,2].Among the diverse candidates。展开更多
基金support from National Natural Science Foundation of China(No.21772188,No.22179109)Chongqing Natural Science Foundation(cstc2021ycjh-bgzxm0164,cstc2020jcyj-zdxmX0010)。
文摘Sulfur and selenium have been paid more and more attention in energy storage systems because of their high theoretical specific gravimetric and volumetric capacities.With the increasing scarcity of lithium resources,secondary batteries made of sulfur and selenium coupled with other alkali metal/alkaline earth metals(e.g.Na,K,Mg)are expected to play a vital role in future production and human life.Due to the volume expansion,poor conductivity and shuttle effect,the structure design of cathode,as one of the important roles in metal-S/Se batteries,has always been a hot and difficult point.In the review,various host materials of S and Se are clarified and discussed.Typically,carbonaceous materials are the most widely used hosts,while polar materials are becoming more and more popular in metal-S/Se batteries.Through a comprehensive overview,it is hoped that previous research experiences can provide further reference and guidance for the sustainable development of metal-S/Se batteries.
文摘Herein,3‑aminopropyltriethoxysilane(APTES)was used to modify F‑containing silica slag(SS)by simple grafting and served as a multifunctional barrier layer.The amino group(—NH2)in the amino‑modified SS(NH2‑SS)forms ligand bonds or hydrogen bonds with sulfur ions in lithium polysulfides(LiPSs),thus inhibiting the shuttle effect.Electrochemical analyses demonstrated that lithium‑sulfur(Li‑S)batteries employing the NH2‑SS interlayer exhibited discharge specific capacities of 1048 and 789 mAh·g^(-1) at 0.2C and 2C,respectively,and even at 4C,the initial discharge specific capacity remained at 590 mAh·g^(-1),outperforming the Li‑S battery with unmodified SS as the interlayer.
基金the financial support from the National Natural Science Foundation of China(No.52101250)the S&T program of Hebei(Nos.215A4401D and 225A4404D)+5 种基金the Collaborative Innovation Center of Marine Science and Technology of Hainan University(No.XTCX2022HYC14)the Fundamental Research Funds for the Hebei University(No.2021YWF11)the Science Research Project of Hebei Education Department(No.QN2024087)the Xingtai City Natural Science Foundation(No.2023ZZ027)the Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),College of Chemistry,Nankai Universitypartially supported by the Pico Election Microscopy Center of Hainan University。
文摘The practical application of lithium-sulfur(Li-S)batteries is still impeded by the severe shuttle effect of lithium polysulfides(LiPSs)and sluggish reaction kinetics of active sulfur.Designing catalytic carriers with abundant active sites and strong chemisorption capability for LiPSs,is regarded as effective strategy to address these issues.Herein,Se-doping is introduced into the nitrogen-doped carbon coated CoP composite(Se-CoP@NC)to generate structural defects,which effectively enlarges the lattice spacing of CoP and reduces the conversion reaction energy barriers of LiPSs.Meanwhile,Se-doping sites bridges the interface of CoP and nitrogen-doped carbon,accelerating the charge transfer behavior and conversion reaction kinetics of LiPSs.Benefiting from the structural advantages,the assembled Li-S batteries with S/Se-CoP@NC as cathode exhibit high reversible capacity of 779.6 mAh/g at 0.5 C after 500 cycles,and high specific capacity of 805.9 mAh/g at 2 C.Even under extreme conditions(high sulfur-loading content of 6.9 mg/cm^(2);lean electrolyte dosage of 7μL/mg),the corresponding Li-S batteries also keep high reversible areal capacity of 4.5 mAh/cm^(2) after 100 cycles at 0.1 C.This work will inspire the design of metal compounds-based catalysts from atomic level to facilitate the practicability of Li-S batteries.
基金supported by the National Natural Science Foundation of China (52302259)the China Postdoctoral Science Foundation (CPSF) under Grant Number 2023M741479+4 种基金the Postdoctoral Fellowship Program of CPSF under Grant Number GZB20240280the Jiangxi Provincial Natural Science Foundation (20224ACB218006)the financial support from High-level Talent Research Special Funds of Jiangxi University of Science and Technology (Grant No. 205200100670)the Jiangxi Provincial Key Laboratory of Power Energy Storage Batteries and Materials (2024SSY10011)the Major Scientific and Technological Research R&D Special Project of Jiangxi Province(20244AFI92002)
文摘The implementation of multifunctional application scenarios for mobile terminal devices has increased the energy density requirements of batteries.Increasing the charging voltage can rapidly increase the specific capacity of layered transition metal oxides;however,it also exacerbates the release of lattice oxygen and the contraction of the unit cell.Ternary materials are designed in a secondary particle state to meet the requirements of power battery applications.Therefore,to create ternary materials that can operate under ultrahigh voltages,attention should be given to both surface modification and particle integrity maintenance.By utilizing elemental selenium(Se)with a low melting point,easy sublimation,and multiple variable valence states,deep grain boundary modification was implemented inside the particles.The performance of the cathode material was evaluated through pouch cells,and the improvement mechanism was explored through molecular dynamics simulation calculations.Under the protection of a three-dimensional Se-rich modified layer,LiNi_(1/3)Co_(1/3)Mn_(1/3)O_(2)achieved stable operation at ultrahigh voltages(4.6 V vs.Li/Li^(+));a sacrificial protection mechanism based on the chronic decomposition of the Se-rich layer was proposed to explain the efficacy of Se modification in stabilizing ternary materials.This deep grain boundary modification based on elemental Se provides a new solution for the ultrahigh-voltage operation of transition metal oxides and provides a scientific basis and technical support for solving the interface contact problem of all-solid-state batteries.
基金supported by National Natural Science Foundation of China(Nos.32271791,32171709 and 22475053)Hunan Provincial Natural Science Foundation of China(No.2024JJ7643)Natural Science Foundation of Shanghai(No.22ZR1404100).
文摘Hard carbon(HC)in sodium-ion batteries is searched by numerous investigations,which can offer the excellent performance of reversible Na^(+)insertion and extraction.The covalent heteroatom doping in HC is recently worth concentrating,which can dilate the interlayer spacing of graphite to adjust the electrochemical storage performance in carbon anodes.However,the reported doping strategies of the modified HC have only resulted in limited improvement,especially unobvious effects on tuning porous structure.In this study,tannin extract and K_(2)SO_(4) are respectively utilized as carbon source and sulfur source for the fabrication of HC,in which K_(2)SO_(4) can contribute to the heteroatom doping,and the pore forming as well.The tannin-derived sulfur-doped carbon anode shows the excellent cycle stability,achieving a high reversible capacity of 520.5 mAh/g at a current density of 100 mA/g.Even after 500 cycles at a current density of 3 A/g,a high specific capacity of 236.7 mAh/g and a capacity retention rate of 92.6%can be reserved.Compared with the initial carbon,the adsorption energy of Na^(+)is multifold times higher,whereas Na^(+)diffusion energy barriers manyfold decrease.Moreover,the full battery assembled with Na_(3)V_(2)(PO_(4))_(3)/tannin-based HC demonstrates a stable cycling performance.This work can manifest the potentiality of the tannin-based electrode as anode for a high-performance sodium-ion batteries(SIBs),which could especially offer an explanation of Na^(+)storage and solid-electrolyte interface(SEI)stability to the electrochemical performance.
基金support of the National Natural Science Foundation of China(22075131 and 22078265)the Shaanxi Fundamental Science Research Project for Mathematics and Physics under Grants(No.22JSZ005)the State-Key Laboratory of Multiphase Complex Systems(No.MPCS-2021-A).
文摘Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties.In this work,we propose an autogenously transformed CoWO_(4)/WO_(2) heterojunction catalyst,integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity.CoWO_(4) effectively captures polysulfides,while the CoWO_(4)/WO_(2) interface facilitates their S-S bond activation on heterogenous catalytic sites.Benefiting from its directional intercalation channels,CoWO_(4) not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport.Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite.As a result,the CoWO_(4)/WO_(2) heterostructure demonstrates significantly enhanced catalytic performance,delivering a high capacity of 1262 mAh g^(−1) at 0.1 C.Furthermore,its rate capability and high sulfur loading performance are markedly improved,surpassing the limitations of its single-component counterparts.This study provides new insights into the catalytic mechanisms governing Li-S chemistry and offers a promising strategy for the rational design of high-performance Li-S battery catalysts.
基金supported by the National Key Research and Development Program of China (No.2024YFA1509600)National Natural Science Foundation of China (Nos.22474010 and 22274012)the Fundamental Research Funds for the Central Universities (No.2233300007)。
文摘Ferroptosis has exhibited great potential in therapies and intracellular reducing agents of sulfur species(RSSs) in the thiol-dependent redox systems are crucial in ferroptosis.This makes the simultaneous detection of multiple RSSs significant for evaluating ferroptosis therapy.However,the traditional techniques,including fluorescent(FL) imaging and electrospray ionization-based mass spectrometry(MS) detection,cannot achieve the discrimination of different RSSs.Herein,simultaneous MS detection of multiple RSSs,including cysteine(Cys),homocysteine(Hcy),glutathione(GSH) and hydrogen sulfide(H_(2)S),was obtained upon enhancing ionization efficiency by a fluorescent probe(NBD-O-1).Based on the interaction between NBD-O-1 and RSSs,the complex of RSSs with a fragment of NBD-O-1 can be generated,which can be easily ionized for MS detection in the negative mode.Therefore,the intracellular RSSs can be well detected upon the incubation of He La cells with the probe of NBD-O-1,exhibiting the total RSS levels by the FL imaging and further providing expression of each RSS by enhanced MS detection.Furthermore,the RSSs during ferroptosis in He La cells have been evaluated using the present strategy,demonstrating the potential for ferroptosis examinations.This work has made an unconventional application of a fluorescent probe to enhance the detection of multiple RSSs by MS,providing significant molecular information for addressing the ferroptosis mechanism.
基金National Natural Science Foundation of China (Nos.22071185 and 22271224)the Fundamental Research Funds for the Central Universities (No.2042019kf0008)Wuhan University startup funding for financial support。
文摘The development of catalytic multicomponent reactions for constructing complex organic scaffolds from readily accessible commodity chemicals is a key pursuit in contemporary synthetic chemistry.Current methods for synthesizing thioesters primarily rely on the acylation of thiols,which produces substantial waste and requires malodorous,unstable sulfur sources.In this work,we introduce a photocatalyzed hydrogen transfer strategy that enables a three-component synthesis of thioesters using abundant primary alcohols,easily available alkenes and elemental sulfur under mild conditions.This protocol demonstrates broad applicability and high chemo-and regioselectivity for both primary alcohols and alkenes,highlighting the advantage and potential of photo-mediated hydrogen transfer in facilitating multicomponent reactions using primary alcohol and elemental sulfur feedstocks.
基金the financial support from the National Natural Science Foundation of China (22109127)the Chinese Postdoctoral Science Foundation (2021M702666)+2 种基金the Research Fund of the State Key Laboratory of Solidification Processing (NPU),China (Grant No.2023-TS-02)The financial support from the Youth Project of"Shaanxi High-level Talents Introduction Plan"the Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) are also sincerely appreciated
文摘Photo-assisted lithium–sulfur batteries(PALSBs)offer an eco-friendly solution to address the issue of sluggish reaction kinetics of conventional LSBs.However,designing an efficient photoelectrode for practical implementation remains a significant challenge.Herein,we construct a free-standing polymer–inorganic hybrid photoelectrode with a direct Z-scheme heterostructure to develop high-efficiency PALSBs.Specifically,polypyrrole(PPy)is in situ vapor-phase polymerized on the surface of N-doped TiO_(2) nanorods supported on carbon cloth(N-TiO_(2)/CC),thereby forming a well-defined p–n heterojunction.This architecture efficiently facilitates the carrier separation of photo-generated electron–hole pairs and significantly enhances carrier transport by creating a built-in electric field.Thus,the PPy@N-TiO_(2)/CC can simultaneously act as a photocatalyst and an electrocatalyst to accelerate the reduction and evolution of sulfur,enabling ultrafast sulfur redox dynamics,as convincingly validated by both theoretical simulations and experimental results.Consequently,the PPy@N-TiO_(2)/CC PALSB achieves a high discharge capacity of 1653 mAh g^(−1),reaching 98.7%of the theoretical value.Furthermore,5 h of photo-charging without external voltage enables the PALSB to deliver a discharge capacity of 333 mAh g^(−1),achieving dual-mode energy harvesting capabilities.This work successfully integrates solar energy conversion and storage within a rechargeable battery system,providing a promising strategy for sustainable energy storage technologies.
基金supported by the National Natural Science Foundation of China (Grant No.52470078)the Natural Science Foundation of Jiangxi Province (Grant No.20252BAC250042)the Key Laboratory of Jiangxi Province for Persistent Pollutants Prevention Control and Resource Reuse (Grant No.2023SSY02061)。
文摘The rapid recombination of photogenerated charge carriers and the poor stability of metal sulfides remain bottlenecks limiting their practical applications. In this study, sulfur vacancies were introduced into an S-scheme AgIn_(5)S_(8)/Bi_(2)S_(3) heterojunction via an in situ hydrothermal method. The sulfur vacancies induced charge density redistribution within the heterojunction and generated efficient active sites for electrons, thereby creating a localized electron-rich environment. The synergistic effects of the sulfur vacancies, internal electric field, and defect energy levels accelerated the separation and transfer of photogenerated charge carriers via the S-scheme pathway, thereby enhancing the visible-light photocatalytic performance, by achieving a Cr(Ⅵ) reduction efficiency of 99.6%. More importantly, the long-term stability and excellent anti-interference capability of the S-scheme AgIn_(5)S_(8)/Bi_(2)S_(3) heterojunction demonstrate its practical application potential, achieving 98.9% Cr(Ⅵ) removal from real electroplating wastewater and meeting discharge standards. This work provides a theoretical basis for constructing highly-catalytic S-scheme heterojunctions and serves as a promising solution for Cr(VI)-containing electroplating wastewater treatment.
基金This project was funded by the ＂National Basic Research Program of China＂ （2007CB411402）；Natural Science Foundation of China （40773034）； ＂West Light＂ of the Chinese Academy of Sciences；the Guizhou Natural Science Foundation （J（2007）2170）.
文摘Fifteen samples from three study areas （the Bancun diabase dykes, the Bali hornblende gabbro dykes, the Linzifen gabbro-diabase dykes） were collected and analyzed for selenium （Se）, sulfur （S）, copper （Cu）, major and trace elements. In general, Se, S and Cu do positively correlate to each other. The concentration of S and Se and the S/Se ratio are higher than the corresponding value of primitive mantle （PM）, and the Cu/S ratio falls in a narrow range （0.04-0.29）, which is consistent with that of primitive mantle （0.05-0.20）. The Bancun diabase dykes and the Bali hornblende gabbro dykes were located in an intraplate environment during the Late Mesozoic. Oceanic subduction was closely related to magmatic activities. The magmatic activities play an important role in the transportation mechanism of Se and S. Because those two groups were closer to fault zones, which may affect the distribution of S and Se and other elements. In the two groups, no crustal contamination was observed, indicating that all analyzed elements may come from enriched mantle metasomtism associated with slab subduction. However, the Linzifen gabbro-diabase dykes were located in an intraplate rift environment, and its invading age is older than the other two groups, the primitive magma comes from mantle, and there is an anomalous relation between S, Se and Al2O3, （La/Sm）N, and all these factors could result in higher S and Se concentration.
基金funded by the Agricultural Research Special Funds for Public Welfare Projects from the Ministry of Agriculture of the People’s Republic of China(200903018)
文摘A hydroponic study was conducted to determine the effects of selenium(Se:0,3,6μmol L^-1)on senescence-related oxidative stress in garlic plants grown under two sulfur(S)levels.We evaluated the yields of plants harvested at 160 and 200 days after sowing.Plants grown under a low Se dose(0.3μmol L^-1)at low S level showed higher yields(12.0%increase in fresh weight yield,13.7%increase in dry weight yield)than the controls,despite a decrease in chlorophyll concentration.Compared with control plants,the Se-treated plants showed lower levels of lipid peroxidation.The Se-treated plants also showed higher activities of glut athione peroxidase and catalase,but lower superoxide dismutase activities.Changes in Fv/Fm values and proline contents were affected more strongly by S than by Se.On the basis of our results,we can conclude that Se plays a key role in the antioxidant systems in garlic seedlings.It delays senescence by alleviating the peroxide stress,but it can be toxic at high levels.A high S level may increase tolerance to high Se concentrations through reducing Se accumulation in plants.
基金supported by the National Natural Science Foundation of China (No.90410018)the Shanxi Nature Science Foundation (No.20051017)+1 种基金the Shanxi Returned Scholar Research Project (No.2005-21)the Programfor Changjiang Scholars and Innovative Research Team at University in MOE,China (No.IRT0517)
文摘Flue gas from coal combustion contains significant amounts of volatile selenium （Se）. The capture of Se in the flue gas desulfurization （FGD） scrubber unit has resulted in a generation of metal-laden residues. It is important to determine Se speciation to understand the environmental impact of its disposal. A simple method has been developed for selective inorganic Se（IV）, Se（VI） and organic Se determination in the liquid-phase FGD residues by hydride generation atomic fluorescence spectrometry （AFS）. It has been determined that Se（IV）, Se（VI） and organic Se can be accurately determined with detection limits （DL） of 0.05, 0.06 and 0.06 μg/L, respectively. The accuracy of the proposed method was evaluated by analyzing the certified reference material, NIST CRM 1632c, and also by analyzing spiked tap-water samples. Analysis indicates that the concentration of Se is high in FGD liquid residues and primarily exists in a reduced state as selenite （Se（IV））. The toxicity of Se（IV） is the strongest of all Se species. Flue gas desulfurization residues pose a serious environmental risk.
基金Projects(51374066,U1608254) supported by the National Natural Science Foundation of ChinaProject(2014BAC03B07) supported by the National Key Technology R&D Program of ChinaProjects(2012223002,2014020037) supported by Industrial Research Projects in Liaoning Province,China
文摘The leaching kinetics of selenium from copper anode slimes was studied in a nitric acid?sulfuric acid mixture.The effects of main parameters on selenium leaching showed that the leaching rate of selenium was practically independent of stirring speed,while dependent on temperature and the concentrations of HNO3and H2SO4.The leaching of selenium includes two stages.The activation energy in the first stage is103.5kJ/mol,and the chemical reaction is the rate controlling step.It was almost independent of H2SO4concentration and dependent on HNO3concentration since the empirical reaction order with respect to HNO3concentration is0.5613.In the second stage,the activation energy is30.6kJ/mol,and the process is controlled by a mixture of diffusion and chemical reaction.The leaching of selenium was almost independent of HNO3concentration.
文摘Accelerating the(NH_4)_(2)SO_(3) oxidation gives rise to the reclaiming of byproduct, while there are secondary environmental risks from reduction of the coexisted selenium species by sulfite. In this study, a bi-functional Co-SBA-15-SH, were synthesized through Co impregnation and sulfhydryl(-SH) decoration, which can simultaneously uptake Se and accelerate sulfite oxidation efficiently. Meanwhile, the adsorption kinetics and migration mechanism of Se species were revealed through characterization and density functional calculations, with maximum adsorption capacity of 223 mg/g. The inhibition of Se~0 re-emission and poisonous effect of Se on sulfite oxidation was also investigated. Using the findings of this study, the ammonia desulfurization can be improved by enabling purification of the byproduct and lowering the toxicity of effluent by removing toxic pollutants.
文摘A simple and general method for the synthesis of bi(acyl)disulfides is reported.Sulfur is allowed to react with sodium hydroxide to give sodium disulfide at 65℃ under PTC,which can react with acyl halides to afford bi(acyl)disulfides in good to excellent isolated yields.The effects of solvents and phase transfer catalysts are discussed.
文摘The increasing demand of the green energy storage system encourages us to develop a higher energy storage system to take the place of the present lithium-ion batteries with limited energy/power densities[1,2].Among the diverse candidates。
