Pyrite is one of the common authigenic minerals in marine sediments.Previous studies have shown that the morphological and isotopic characteristics of pyrite are closely related to the geochemical environment where it...Pyrite is one of the common authigenic minerals in marine sediments.Previous studies have shown that the morphological and isotopic characteristics of pyrite are closely related to the geochemical environment where it is formed.To better understand the for-mation mechanism of authigenic pyrite,we analyzed the isotopic composition,morphology,and distribution of pyrite in the sediment at 500m below the seafloor from Xisha Trough,South China Sea.Mineral morphologies were observed by scanning electron micros-copy and Raman spectrography.X-Ray computed tomography was applied to measure the particle size of pyrite.The size of pyrite crystals in the matrix sediment mainly ranged between 25 and 65µm(av.ca.40µm),although crystals were larger(av.ca.50μm)in the veins.The pyrites had a fine-grained truncated octahedral shape with occasionally well-developed growth steps,which implies the low growth rate and weak anaerobic oxidation of methane-sulfate reduction when pyrite was formed.Theδ^(34)S values of pyrites ranged from+20.8‰Vienna-defined Canyon Diablo Troilite(V-CDT)to+33.2‰V-CDT and from+44.8‰V-CDT to+48.9‰,which suggest two growth stages.In the first stage,with the continuous low methane flux,the pyrite possibly formed in an environment with good access to seawater.In the second stage,the pyrites mainly developed in sediment fractures and appeared in veins,probably due to the limited availability of sulfate.The less exposure of pyrite to the environment in the second stage was probably caused by sediment accumulation or perturbation.In this study,an episodic pyritization process was identified,and the paleoenvironment was reconstructed for the sediment investigated.展开更多
Glucosinolates(GSLs) are a group of nitrogen-and sulfur-containing secondary metabolites, synthesized primarily in members of the Brassicaceae family, that play an important role in food flavor, plant antimicrobial ac...Glucosinolates(GSLs) are a group of nitrogen-and sulfur-containing secondary metabolites, synthesized primarily in members of the Brassicaceae family, that play an important role in food flavor, plant antimicrobial activity, resistance to insect attack, stress tolerance, and human anti-cancer effects. As a sulfur-containing compound, glutathione has a strong connection with GSLs biosynthesis as a sulfur donor or redox system, and exists in reduced(glutathione;GSH) and oxidized(glutathione disulfide;GSSG) forms. However, the mechanism of GSH regulating GSLs biosynthesis remainds unclear. Hence, the exogenous therapy to pakchoi under normal growth condition and sulfur deficiency condition were conducted in this work to explore the relevant mechanism. The results showed that exogenous application of buthionine sulfoximine, an inhibitor of GSH synthesis, decreased the transcript levels of GSLs synthesis-related genes and transcription factors, as well as sulfur assimilation-related genes under the normal growth condition. Application of exogenous GSH inhibited the expression of GSLs synthesis-and sulfur assimilation-related genes under the normal condition, while the GSLs biosynthesis and the sulfur assimilation pathway were activated by exogenous application of GSH when the content of GSH in vivo of plants decreased owing to sulfur deficiency. Moreover,exogenous application of GSSG increased the transcript levels of GSLs synthesis-and sulfur assimilation-related genes under the normal growth condition and under sulfur deficiency. The present work provides new insights into the molecular mechanisms of GSLs biosynthesis underlying glutathione regulation.展开更多
Traditional hydrometallurgical methods for recovering spent lithium-ion batteries(LIBs)involve acid leaching to simultaneously extract all valuable metals into the leachate.These methods usually are followed by a seri...Traditional hydrometallurgical methods for recovering spent lithium-ion batteries(LIBs)involve acid leaching to simultaneously extract all valuable metals into the leachate.These methods usually are followed by a series of separation steps such as precipitation,extraction,and stripping to separate the individual valuable metals.In this study,we present a process for selectively leaching lithium through the synergistic effect of sulfuric and oxalic acids.Under optimal leaching conditions(leaching time of 1.5 h,leaching temperature of 70°C,liquid-solid ratio of 4 mL/g,oxalic acid ratio of 1.3,and sulfuric acid ratio of 1.3),the lithium leaching efficiency reached89.6%,and the leaching efficiencies of Ni,Co,and Mn were 12.8%,6.5%,and 21.7%.X-ray diffraction(XRD)and inductively coupled plasma optical emission spectrometer(ICP-OES)analyses showed that most of the Ni,Co,and Mn in the raw material remained as solid residue oxides and oxalates.This study offers a new approach to enriching the relevant theory for selectively recovering lithium from spent LIBs.展开更多
The state-selective cross section data are useful for understanding and modeling the x-ray emission in celestial observations.In the present work,using the cold target recoil ion momentum spectroscopy,for the first ti...The state-selective cross section data are useful for understanding and modeling the x-ray emission in celestial observations.In the present work,using the cold target recoil ion momentum spectroscopy,for the first time we investigated the state-selective single electron capture processes for S^(q+)–He and H_(2)(q=11–15)collision systems at an impact energy of q×20 keV and obtained the relative state-selective cross sections.The results indicate that only a few principal quantum states of the projectile energy level are populated in a single electron capture process.In particular,the increase of the projectile charge state leads to the population of the states with higher principal quantum numbers.It is also shown that the experimental averaged n-shell populations are reproduced well by the over-barrier model.The database is openly available in Science Data Bank at 10.57760/sciencedb.j00113.00091.展开更多
Lithium-sulfur(Li-S) batteries have attracted considerable attention as one of the most appealing energy storage systems.Strenuous efforts have been devoted to tackling the tremendous challenges,mainly pertaining to t...Lithium-sulfur(Li-S) batteries have attracted considerable attention as one of the most appealing energy storage systems.Strenuous efforts have been devoted to tackling the tremendous challenges,mainly pertaining to the severe shuttle effect,sluggish redox kinetics and lithium dendritic growth.Single-atomic mediators as promising candidates exhibit impressive performance in addressing these intractable issues.Related research often utilizes a trial-and-error approach,proposing solutions to fabricate single-atomic materials with diversified features.However,comprehensive review articles especially targeting demand-driven preparation are still in a nascent stage.Inspired by these considerations,this review summarizes the design of single-atomic mediators based on the application case-studies in LiS batteries and other metal-sulfur systems.Emerging preparation routes represented by chemical vapor deposition technology are introduced in a demand-oriented classification.Finally,future research directions are proposed to foster the advancement of single-atomic mediators in Li-S realm.展开更多
There have been several studies on sulfur depletion in dense cores like TMC-1(Taurus Molecular Cloud 1),employing updated reaction networks for sulfur species to explain the missing sulfur in the gas within dense clou...There have been several studies on sulfur depletion in dense cores like TMC-1(Taurus Molecular Cloud 1),employing updated reaction networks for sulfur species to explain the missing sulfur in the gas within dense clouds.Most of these studies used a C/O ratio of 0.7 or lower.We present NSRT(NanShan 26m Radio Telescope)observations of TMC-1 alongside results from time-dependent chemical simulations using an updated chemical network.Our findings highlight the impact of the C/O ratio on the gas-phase evolution of C2S and C3S.The simulation results show that the C/O ratio is an important parameter,playing a fundamental role in determining the gas-phase abundances of sulfur species in dense cores.展开更多
Objective:To investigate the relationship between ambient sulfur dioxide(SO2)exposure and semen quality parameters.Methods:A systematic literature search was conducted to identify relevant studies investigating the as...Objective:To investigate the relationship between ambient sulfur dioxide(SO2)exposure and semen quality parameters.Methods:A systematic literature search was conducted to identify relevant studies investigating the association between SO2 exposure and semen quality parameters.This search encompassed the timeframe from January 2000 to May 2023 and included electronic databases such as Web of Science,Google Scholar,PubMed,Cochrane,and Scopus.Pooled effect estimates with 95%confidence intervals(CI)were calculated using percent changes(PC).The meta-analysis included seven studies with 6711 participants and 15087 semen samples.Results:The results revealed a significant negative association between ambient SO2 exposure and certain semen quality parameters.In particular,SO2 exposure was associated with a significant decrease in progressive motility(PC=0.032;95%CI:-0.063 to-0.001;P=0.044)and sperm concentration(PC=-0.020;95%CI:-0.036 to-0.005;P=0.012).However,no statistically significant associations were observed for total sperm count(PC=-0.038;95%CI:-0.079 to 0.003;P=0.070),seminal fluid volume(PC=-0.009;95%CI:-0.048 to-0.030;P=0.662)and sperm motility(PC=-0.17;95%CI:-0.363 to 0.022;P=0.830).In addition,the results of the subgroup analysis revealed specific variables that were associated with the decrease in relevant sperm parameters.Conclusions:This systematic review and meta-analysis provides compelling evidence supporting a consistent negative association between exposure to ambient SO2 and semen quality parameters.展开更多
The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high in...The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high interfacial impedances existing between the SSEs and the electrodes(both lithium anodes and sulfur cathodes)hinder the charge transfer and intensify the uneven deposition of lithium,which ultimately result in insufficient capacity utilization and poor cycling stability.Hence,the reduction of interfacial resistance between SSEs and electrodes is of paramount importance in the pursuit of efficacious solid-state batteries.In this review,we focus on the experimental strategies employed to enhance the interfacial contact between SSEs and electrodes,and summarize recent progresses of their applications in solidstate Li–S batteries.Moreover,the challenges and perspectives of rational interfacial design in practical solid-state Li–S batteries are outlined as well.We expect that this review will provide new insights into the further technique development and practical applications of solid-state lithium batteries.展开更多
Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review f...Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.展开更多
Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of ...Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.展开更多
The practical application of lithium-sulfur(Li-S)batteries is greatly hindered by soluble polysulfides shuttling and sluggish sulfur redox kinetics.Rational design of multifunctional hybrid materials with superior ele...The practical application of lithium-sulfur(Li-S)batteries is greatly hindered by soluble polysulfides shuttling and sluggish sulfur redox kinetics.Rational design of multifunctional hybrid materials with superior electronic conductivity and high electrocatalytic activity,e.g.,heterostructures,is a promising strategy to solve the above obstacles.Herein,a binary metal sulfide MnS-MoS_(2) heterojunction electrocatalyst is first designed for the construction of high-sulfur-loaded and durable Li-S batteries.The MnS-MoS_(2) p-n heterojunction shows a unique structure of MoS_(2) nanosheets decorated with ample MnS nanodots,which contributes to the formation of a strong built-in electric field at the two-phase interface.The MnS-MoS_(2) hybrid host shows strong soluble polysulfide affinity,enhanced electronic conductivity,and exceptional catalytic effect on sulfur reduction.Benefiting from the synergistic effect,the as-derived S/MnS-MoS_(2) cathode delivers a superb rate capability(643 m A h g^(-1)at 6 C)and a durable cyclability(0.048%decay per cycle over 1000 cycles).More impressively,an areal capacity of 9.9 m A h cm^(-2)can be achieved even under an extremely high sulfur loading of 14.7 mg cm^(-2)and a low electrolyte to sulfur ratio of 2.9μL mg^(-1).This work provides an in-depth understanding of the interfacial catalytic effect of binary metal compound heterojunctions on sulfur reaction kinetics.展开更多
Hydrogen sulfide(H_(2)S)is an industrial exhausted gas that is highly toxic to humans and the environment.Combining desulfurization and fabrication of cathode materials for lithium-sulfur batteries(LSBs)can solve this...Hydrogen sulfide(H_(2)S)is an industrial exhausted gas that is highly toxic to humans and the environment.Combining desulfurization and fabrication of cathode materials for lithium-sulfur batteries(LSBs)can solve this issue with a double benefit.Herein,the amino-functionalized lotus root-like carbon nanofibers(NH_(2)-PLCNFs)are prepared by the amination of electrospinning carbon nanofibers under dielectric barrier discharge plasma.Selective catalytic oxidation of H_(2)S to elemental sulfur(S)is achieved over the metalfree NH_(2)-PLCNFs catalyst,and the obtained composite S@NH_(2)-PLCNFs is further used as cathode in LSBs.NH_(2)-PLCNFs enable efficient desulfurization(removal capacity as high as 3.46 g H_(2)S g^(−1) catalyst)and strongly covalent stabilization of S on modified carbon nanofibers.LSBs equipped with S@NH_(2)-PLCNFs deliver a high specific capacity of 705.8 mA h g^(−1) at 1 C after 1000 cycles based on the spatial confinement and the covalent stabilization of electroactive materials on amino-functionalized porous carbon matrix.It is revealed that S@NH_(2)-PLCNFs obtained by this kind of chemical vapor deposition leads to a more homogeneous S distribution and superior electrochemical performance to the sample S/NH_(2)-PLCNF-M prepared by the traditional molten infusion.This work opens a new avenue for the combination of environment protection and energy storage.展开更多
Lithium sulfur batteries(LSBs)are recognized as promising devices for developing next-generation energy storage systems.In addition,they are attractive rechargeable battery systems for replacing lithium-ion batteries(...Lithium sulfur batteries(LSBs)are recognized as promising devices for developing next-generation energy storage systems.In addition,they are attractive rechargeable battery systems for replacing lithium-ion batteries(LIBs)for commercial use owing to their higher theoretical energy density and lower cost compared to those of LIBs.However,LSBs are still beset with some persistent issues that prevent them from being used industrially,such as the unavoidable dissolution of lithium polysulfide intermediates during electrochemical reactions and large volume expansion(up to 80%)upon the formation of Li_(2)S,resulting in serious battery life and safety limitations.In the process of solving these problems,it is necessary to maintain a high sulfur content in the cathode materials to ensure that the LSBs have high energy densities and excellent cycle performance.In this review,the novel preparation methods and cathode materials used for preparing LSBs in recent years are reviewed considering the sulfur content and cycle performance.In addition,the problems and difficulties in practically applying cathode materials are described,and the development trend is discussed.展开更多
Lithium-sulfur batteries with liquid electrolytes have been obstructed by severe shuttle effects and intrinsic safety concerns.Introducing inorganic solid-state electrolytes into lithium-sulfur systems is believed as ...Lithium-sulfur batteries with liquid electrolytes have been obstructed by severe shuttle effects and intrinsic safety concerns.Introducing inorganic solid-state electrolytes into lithium-sulfur systems is believed as an effective approach to eliminate these issues without sacrificing the high-energy density,which determines sulfidebased all-solid-state lithium-sulfur batteries.However,the lack of design principles for high-performance composite sulfur cathodes limits their further application.The sulfur cathode regulation should take several factors including the intrinsic insulation of sulfur,well-designed conductive networks,integrated sulfur-electrolyte interfaces,and porous structure for volume expansion,and the correlation between these factors into account.Here,we summarize the challenges of regulating composite sulfur cathodes with respect to ionic/electronic diffusions and put forward the corresponding solutions for obtaining stable positive electrodes.In the last section,we also outlook the future research pathways of architecture sulfur cathode to guide the develop high-performance all-solid-state lithium-sulfur batteries.展开更多
High-energy lithium-sulfur batteries(LSBs)have experienced relentless development over the past decade with discernible improvements in electrochemical performance.However,a scrutinization of the cell operation condit...High-energy lithium-sulfur batteries(LSBs)have experienced relentless development over the past decade with discernible improvements in electrochemical performance.However,a scrutinization of the cell operation conditions reveals a huge gap between the demands for practical batteries and those in the literature.Low sulfur loading,a high electrolyte/sulfur(E/S)ratio and excess anodes for lab-scale LSBs significantly offset their high-energy merit.To approach practical LSBs,high loading and lean electrolyte parameters are needed,which involve budding challenges of slow charge transfer,polysulfide precipitation and severe shuttle effects.To track these obstacles,the exploration of electrocatalysts to immobilize polysulfides and accelerate Li-S redox kinetics has been widely reported.Herein,this review aims to survey state-of-the-art catalytic materials for practical LSBs with emphasis on elucidating the correlation among catalyst design strategies,material structures and electrochemical performance.We also statistically evaluate the state-of-the-art catalyst-modified LSBs to identify the remaining discrepancy between the current advancements and the real-world requirements.In closing,we put forward our proposal for a catalytic material study to help realize practical LSBs.展开更多
Sulfur element possesses an ultrahigh theoretical specific capacity,while the utilization of sulfur in the whole cathode is lower obviously owing to the sluggish kinetics of sulfur and discharged products,limiting the...Sulfur element possesses an ultrahigh theoretical specific capacity,while the utilization of sulfur in the whole cathode is lower obviously owing to the sluggish kinetics of sulfur and discharged products,limiting the enhancement on energy density of lithium-sulfur batteries.Herein,for the first time,Fe_(0.24)Co_(0.26)Ni_(0.10)Cu_(0.15)Mn_(0.25)high-entropy alloy is introduced as the core catalytic host to activate the electrochemical performance of the sulfur cathode for lithium-sulfur batteries.It is manifested that Fe_(0.24)Co_(0.26)Ni_(0.10)Cu_(0.15)Mn_(0.25)high-entropy alloy nanocrystallites distributed on nitrogen-doped carbon exhibit high electrocatalytic activity toward the conversion of solid sulfur to solid discharged products across soluble intermediate lithium polysulfides.In particular,benefiting from the accelerated kinetics by high-entropy alloy nanocrystallites and synergistic adsorption by nitrogen-doped carbon,the cathode exhibits high reversible capacity of 1079.5 mAh g_(-cathode)^(-1)(high utilization of 89.4%)with the whole cathode as active material,instead of sulfur element.Moreover,under both lean electrolyte(3μmg^(-1))and ultrahigh sulfur loading(27.0 mg cm^(-2))condition,the high discharge capacity of 868.2 mAh g_(-cathode)^(-1)can be still achieved for the sulfur cathode.This strategy opens up a new path to explore catalytic host materials for enhancing the utilization of sulfur in the whole cathode for lithium-sulfur batteries.展开更多
Microbial communities,sulfur isotope of sulfides(δ^(34)S_(AVS)and δ^(34)S_(CRS)),and sulfur and oxygen isotopes of sulfate(δ^(34)S_(SO_(4))and δ^(18)O_(SO_(4)))in sediments were analyzed to reveal the biogeochemic...Microbial communities,sulfur isotope of sulfides(δ^(34)S_(AVS)and δ^(34)S_(CRS)),and sulfur and oxygen isotopes of sulfate(δ^(34)S_(SO_(4))and δ^(18)O_(SO_(4)))in sediments were analyzed to reveal the biogeochemical transformations of sulfur in a seabird-affected lake Y2 and a se abird-free YO from Fildes Peninsula,Antarctic Peninsula.The microbial communities in Y2 were mainly associated with penguin activities,while those in YO were limited by nutrients.The much enriched δ^(34)S_(SO_(4))recorded at depth of 30,41,and 52 cm in Y2indicates very strong sulfate reduction therein.The sulfur-degrading bacteria Pseudomonas in 0-23 cm of Y2 was 3.5 time s as abundant as that of sulfur oxidizing bacteria(SOB),indicating remarkable remineralization of organic sulfur.The abundant SOB and ^(34)S-depleted sulfate indicate considerable sulfur oxidation in 34-56-cm layer in Y2.In YO sediments,the highest abundance of Desulfotalea and the most enriched δ^(34)S_(SO_(4))(35.2‰)and δ^(34)S_(CRS)(2.5‰)indicate the strongest sulfate reduction in 28-cm layer.High abundance of Pseudomonas indicates active remineralization of organic sulfur in 3-5-cm layer in YO.The medium δ^(34)S_(SO_(4))and considerable abundance of SOB and sulfate-reducing bacteria(SRB)indicate concurrence of sulfur oxidation and sulfate reduction in other layers in YO.Therefore,a high level of organic matter input from penguin populations supported the diverse microbial community and transformations of sulfur in aquatic ecosystems in Antarctica.展开更多
Lithium-sulfur(Li-S)batteries have attracted wide attention for their high theoretical energy density,low cost,and environmental friendliness.However,the shuttle effect of polysulfides and the insulation of active mat...Lithium-sulfur(Li-S)batteries have attracted wide attention for their high theoretical energy density,low cost,and environmental friendliness.However,the shuttle effect of polysulfides and the insulation of active materials severely restrict the development of Li-S batteries.Constructing conductive sulfur scaffolds with catalytic conversion capability for cathodes is an efficient approach to solving above issues.Vanadium-based compounds and their heterostructures have recently emerged as functional sulfur catalysts supported on conductive scaffolds.These compounds interact with polysulfides via different mechanisms to alleviate the shuttle effect and accelerate the redox kinetics,leading to higher Coulombic efficiency and enhanced sulfur utilization.Reports on vanadium-based nanomaterials in Li-S batteries have been steadily increasing over the past several years.In this review,first,we provide an overview of the synthesis of vanadium-based compounds and heterostructures.Then,we discuss the interactions and constitutive relationships between vanadium-based catalysts and polysulfides formed at sulfur cathodes.We summarize the mechanisms that contribute to the enhancement of electrochemical performance for various types of vanadium-based catalysts,thus providing insights for the rational design of sulfur catalysts.Finally,we offer a perspective on the future directions for the research and development of vanadium-based sulfur catalysts.展开更多
As well known in the petroleum industry and academia,Ni/ZnO catalysts have excellent desulfurization performance.However,the sulfur transfer mechanism of reactive adsorption desulfurization(RADS)that occurs on Ni/ZnO ...As well known in the petroleum industry and academia,Ni/ZnO catalysts have excellent desulfurization performance.However,the sulfur transfer mechanism of reactive adsorption desulfurization(RADS)that occurs on Ni/ZnO catalysts remains controversial.Herein,a periodic Ni nanorod supported on ZnO slab was built to represent the Ni/ZnO system,and density functional theory calculations were performed to study the sulfur transfer process and the role of H_(2)within the process.The results elucidate that the direct solid-state diffusion of S from Ni to interfacial oxygen vacancies(Ov)is more favorable than the hydrogenation of S to SH/H_(2)S on Ni and the subsequent H_(2)S desorption,and accordingly,H_(2)O is produced on Ni rather than on ZnO.Ab initio thermodynamics analysis shows that the hydrogen atmosphere applied in preparing Ni/ZnO catalysts greatly promotes the O_(v)formation on ZnO surface,which accounts for the presence of interfacial O_(v)in freshly prepared catalysts.Under RADS condition,hydrogenation of interfacial O atoms to form O-H groups facilitates the reverse spillover of these lattice O atoms from ZnO to Ni,accompanied with the interfacial O_(v)generation.In contrast to the classic S transfer mechanism via H_(2)S,the present work clearly demonstrates that the interfacial S transfer is a feasible reaction pathway in the RADS mechanism.More importantly,the existence of interfacial O_(v)is an essential prerequisite for this interfacial S diffusion,and H_(2)plays a key role in facilitating the O_(v)formation.展开更多
With the high theoretical specific capacity and energy density,lithium-sulfur batteries(LSBs)have been intensively studied as promising candidates for energy storage devices.However,LSBs are largely hindered by inferi...With the high theoretical specific capacity and energy density,lithium-sulfur batteries(LSBs)have been intensively studied as promising candidates for energy storage devices.However,LSBs are largely hindered by inferior sulfur utilization and uncontrollable dendritic growth.Herein,a hierarchical functionalization strategy of stepwise catalytic-adsorption-conversion for sulfur species via the synergetic of the efficiently catalytic host cathode and light multifunctional interlayer has been proposed to concurrently address the issues arising on the dual sides of the LSBs.The multi-layer SnS_(2) micro-flowers embedded into the natural three-dimensional(3D)interconnected carbonized bacterial cellulose(CBC)nanofibers are fabricated as the sulfur host that provides numerous catalytic sites for the rapid catalytic conversion of sulfur species.Moreover,the distinctive CBC-based SnO_(2)-SnS_(2) heterostructure network accompanied high conductive carbon nanofibers as the multifunctional interlayer promotes the rapid anchoringdiffusion-conversion of lithium polysulfides,Li^(+)flux redistribution,and uniform Li deposition.LSBs equipped with our strategy exhibit a high reversible capacity of 1361.5 m A h g^(-1)at 0.2 C and superior cycling stability with an ultra-low capacity fading of 0.031%per cycle in 1000 cycles at 1.5 C and 0.046%at 3 C.A favorable specific capacity of 859.5 m A h g^(-1)at 0.3 C is achieved with a high sulfur mass loading of 5.2 mg cm^(-2),highlighting the potential of practical application.The rational design in this work can provide a feasible solution for high-performance LSBs and promote the development of advanced energy storage devices.展开更多
基金supported by the Guangdong Major Project of Basic and Applied Basic Research(No.2020B0301030003).
文摘Pyrite is one of the common authigenic minerals in marine sediments.Previous studies have shown that the morphological and isotopic characteristics of pyrite are closely related to the geochemical environment where it is formed.To better understand the for-mation mechanism of authigenic pyrite,we analyzed the isotopic composition,morphology,and distribution of pyrite in the sediment at 500m below the seafloor from Xisha Trough,South China Sea.Mineral morphologies were observed by scanning electron micros-copy and Raman spectrography.X-Ray computed tomography was applied to measure the particle size of pyrite.The size of pyrite crystals in the matrix sediment mainly ranged between 25 and 65µm(av.ca.40µm),although crystals were larger(av.ca.50μm)in the veins.The pyrites had a fine-grained truncated octahedral shape with occasionally well-developed growth steps,which implies the low growth rate and weak anaerobic oxidation of methane-sulfate reduction when pyrite was formed.Theδ^(34)S values of pyrites ranged from+20.8‰Vienna-defined Canyon Diablo Troilite(V-CDT)to+33.2‰V-CDT and from+44.8‰V-CDT to+48.9‰,which suggest two growth stages.In the first stage,with the continuous low methane flux,the pyrite possibly formed in an environment with good access to seawater.In the second stage,the pyrites mainly developed in sediment fractures and appeared in veins,probably due to the limited availability of sulfate.The less exposure of pyrite to the environment in the second stage was probably caused by sediment accumulation or perturbation.In this study,an episodic pyritization process was identified,and the paleoenvironment was reconstructed for the sediment investigated.
基金funded by the National Natural Science Foundation of China (Grant Nos.31972394 and 31501748)。
文摘Glucosinolates(GSLs) are a group of nitrogen-and sulfur-containing secondary metabolites, synthesized primarily in members of the Brassicaceae family, that play an important role in food flavor, plant antimicrobial activity, resistance to insect attack, stress tolerance, and human anti-cancer effects. As a sulfur-containing compound, glutathione has a strong connection with GSLs biosynthesis as a sulfur donor or redox system, and exists in reduced(glutathione;GSH) and oxidized(glutathione disulfide;GSSG) forms. However, the mechanism of GSH regulating GSLs biosynthesis remainds unclear. Hence, the exogenous therapy to pakchoi under normal growth condition and sulfur deficiency condition were conducted in this work to explore the relevant mechanism. The results showed that exogenous application of buthionine sulfoximine, an inhibitor of GSH synthesis, decreased the transcript levels of GSLs synthesis-related genes and transcription factors, as well as sulfur assimilation-related genes under the normal growth condition. Application of exogenous GSH inhibited the expression of GSLs synthesis-and sulfur assimilation-related genes under the normal condition, while the GSLs biosynthesis and the sulfur assimilation pathway were activated by exogenous application of GSH when the content of GSH in vivo of plants decreased owing to sulfur deficiency. Moreover,exogenous application of GSSG increased the transcript levels of GSLs synthesis-and sulfur assimilation-related genes under the normal growth condition and under sulfur deficiency. The present work provides new insights into the molecular mechanisms of GSLs biosynthesis underlying glutathione regulation.
基金financially supported by the Young Scientists Fund of the National Natural Science Foundation of China(Nos.52104395 and 52304365)the Science and Technology Planning Project of Guangzhou,China(Nos.202102021080 and 2024A04J10006)+1 种基金the National Key R&D Program of China(No.2021YFC2902605)the Natural Science Foundation of Guangdong Province,China(Nos.2023A1515030145 and 2023A1515011847)。
文摘Traditional hydrometallurgical methods for recovering spent lithium-ion batteries(LIBs)involve acid leaching to simultaneously extract all valuable metals into the leachate.These methods usually are followed by a series of separation steps such as precipitation,extraction,and stripping to separate the individual valuable metals.In this study,we present a process for selectively leaching lithium through the synergistic effect of sulfuric and oxalic acids.Under optimal leaching conditions(leaching time of 1.5 h,leaching temperature of 70°C,liquid-solid ratio of 4 mL/g,oxalic acid ratio of 1.3,and sulfuric acid ratio of 1.3),the lithium leaching efficiency reached89.6%,and the leaching efficiencies of Ni,Co,and Mn were 12.8%,6.5%,and 21.7%.X-ray diffraction(XRD)and inductively coupled plasma optical emission spectrometer(ICP-OES)analyses showed that most of the Ni,Co,and Mn in the raw material remained as solid residue oxides and oxalates.This study offers a new approach to enriching the relevant theory for selectively recovering lithium from spent LIBs.
基金Project supported by the National Key Research and Development Program of China(Grant No.2017YFA0402400)the National Natural Science Foundation of China(Grant Nos.11974358 and 11934004)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB34020000)the Heavy Ion Research Facility in Lanzhou(HIRFL).
文摘The state-selective cross section data are useful for understanding and modeling the x-ray emission in celestial observations.In the present work,using the cold target recoil ion momentum spectroscopy,for the first time we investigated the state-selective single electron capture processes for S^(q+)–He and H_(2)(q=11–15)collision systems at an impact energy of q×20 keV and obtained the relative state-selective cross sections.The results indicate that only a few principal quantum states of the projectile energy level are populated in a single electron capture process.In particular,the increase of the projectile charge state leads to the population of the states with higher principal quantum numbers.It is also shown that the experimental averaged n-shell populations are reproduced well by the over-barrier model.The database is openly available in Science Data Bank at 10.57760/sciencedb.j00113.00091.
基金supported by the National Natural Science Foundation of China(22179089)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX23_3245)support from Suzhou Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies,Suzhou,China。
文摘Lithium-sulfur(Li-S) batteries have attracted considerable attention as one of the most appealing energy storage systems.Strenuous efforts have been devoted to tackling the tremendous challenges,mainly pertaining to the severe shuttle effect,sluggish redox kinetics and lithium dendritic growth.Single-atomic mediators as promising candidates exhibit impressive performance in addressing these intractable issues.Related research often utilizes a trial-and-error approach,proposing solutions to fabricate single-atomic materials with diversified features.However,comprehensive review articles especially targeting demand-driven preparation are still in a nascent stage.Inspired by these considerations,this review summarizes the design of single-atomic mediators based on the application case-studies in LiS batteries and other metal-sulfur systems.Emerging preparation routes represented by chemical vapor deposition technology are introduced in a demand-oriented classification.Finally,future research directions are proposed to foster the advancement of single-atomic mediators in Li-S realm.
基金supported by the Natural Science Foundation of Xinjiang Uygur Autonomous Region (Grant No. 2022D01B221)he Xinjiang Tianchi Talent Program (2023)+4 种基金the NSRT operators for their assistance during the observationspartly supported by the OperationMaintenance and Upgrading Fund for Astronomical Telescopes and Facility Instrumentsbudgeted from the Ministry of Finance of China and administrated by the Chinese Academy of Sciencesthe Urumqi Nanshan Astronomy and Deep Space Exploration Observation and Research Station of Xinjiang (Grant No. XJYWZ2303)
文摘There have been several studies on sulfur depletion in dense cores like TMC-1(Taurus Molecular Cloud 1),employing updated reaction networks for sulfur species to explain the missing sulfur in the gas within dense clouds.Most of these studies used a C/O ratio of 0.7 or lower.We present NSRT(NanShan 26m Radio Telescope)observations of TMC-1 alongside results from time-dependent chemical simulations using an updated chemical network.Our findings highlight the impact of the C/O ratio on the gas-phase evolution of C2S and C3S.The simulation results show that the C/O ratio is an important parameter,playing a fundamental role in determining the gas-phase abundances of sulfur species in dense cores.
文摘Objective:To investigate the relationship between ambient sulfur dioxide(SO2)exposure and semen quality parameters.Methods:A systematic literature search was conducted to identify relevant studies investigating the association between SO2 exposure and semen quality parameters.This search encompassed the timeframe from January 2000 to May 2023 and included electronic databases such as Web of Science,Google Scholar,PubMed,Cochrane,and Scopus.Pooled effect estimates with 95%confidence intervals(CI)were calculated using percent changes(PC).The meta-analysis included seven studies with 6711 participants and 15087 semen samples.Results:The results revealed a significant negative association between ambient SO2 exposure and certain semen quality parameters.In particular,SO2 exposure was associated with a significant decrease in progressive motility(PC=0.032;95%CI:-0.063 to-0.001;P=0.044)and sperm concentration(PC=-0.020;95%CI:-0.036 to-0.005;P=0.012).However,no statistically significant associations were observed for total sperm count(PC=-0.038;95%CI:-0.079 to 0.003;P=0.070),seminal fluid volume(PC=-0.009;95%CI:-0.048 to-0.030;P=0.662)and sperm motility(PC=-0.17;95%CI:-0.363 to 0.022;P=0.830).In addition,the results of the subgroup analysis revealed specific variables that were associated with the decrease in relevant sperm parameters.Conclusions:This systematic review and meta-analysis provides compelling evidence supporting a consistent negative association between exposure to ambient SO2 and semen quality parameters.
基金the funding support from the National Natural Science Foundation of China(22222902,22209062)the Natural Science Foundation of Jiangsu Province(BK20200047)+2 种基金the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(22KJB150004)the Youth Talent Promotion Project of Jiangsu Association for Science and Technology of China(JSTJ-2022-023)Undergraduate Innovation and Entrepreneurship Training Program(202310320066Z)。
文摘The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high interfacial impedances existing between the SSEs and the electrodes(both lithium anodes and sulfur cathodes)hinder the charge transfer and intensify the uneven deposition of lithium,which ultimately result in insufficient capacity utilization and poor cycling stability.Hence,the reduction of interfacial resistance between SSEs and electrodes is of paramount importance in the pursuit of efficacious solid-state batteries.In this review,we focus on the experimental strategies employed to enhance the interfacial contact between SSEs and electrodes,and summarize recent progresses of their applications in solidstate Li–S batteries.Moreover,the challenges and perspectives of rational interfacial design in practical solid-state Li–S batteries are outlined as well.We expect that this review will provide new insights into the further technique development and practical applications of solid-state lithium batteries.
基金The authors acknowledge funding from National Natural Science Foundation of China(52302307)Shaanxi Province(2023-ZDLGY-24,2023-JC-QN-0473)+2 种基金project funded by China Postdoctoral Science Foundation(2023MD734210)the Open Foundation of State Key Laboratory for Advanced Metals and Materials(2022-Z01)Shaanxi Provincial Department of Education industrialization project(21JC018).
文摘Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.
基金supported by Thailand Science Research and Innovation Fund Chulalongkorn University,Thailand(IND66210014)。
文摘Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.
基金financial support from the National Natural Science Foundation of China (NSFC,21875155,22032004)the support of the National Key Research and Development Program of China (2021YFA1201502)the support of the Nanqiang Young Top-notch Talent Fellowship in Xiamen University。
文摘The practical application of lithium-sulfur(Li-S)batteries is greatly hindered by soluble polysulfides shuttling and sluggish sulfur redox kinetics.Rational design of multifunctional hybrid materials with superior electronic conductivity and high electrocatalytic activity,e.g.,heterostructures,is a promising strategy to solve the above obstacles.Herein,a binary metal sulfide MnS-MoS_(2) heterojunction electrocatalyst is first designed for the construction of high-sulfur-loaded and durable Li-S batteries.The MnS-MoS_(2) p-n heterojunction shows a unique structure of MoS_(2) nanosheets decorated with ample MnS nanodots,which contributes to the formation of a strong built-in electric field at the two-phase interface.The MnS-MoS_(2) hybrid host shows strong soluble polysulfide affinity,enhanced electronic conductivity,and exceptional catalytic effect on sulfur reduction.Benefiting from the synergistic effect,the as-derived S/MnS-MoS_(2) cathode delivers a superb rate capability(643 m A h g^(-1)at 6 C)and a durable cyclability(0.048%decay per cycle over 1000 cycles).More impressively,an areal capacity of 9.9 m A h cm^(-2)can be achieved even under an extremely high sulfur loading of 14.7 mg cm^(-2)and a low electrolyte to sulfur ratio of 2.9μL mg^(-1).This work provides an in-depth understanding of the interfacial catalytic effect of binary metal compound heterojunctions on sulfur reaction kinetics.
基金financial support from projects funded by the National Natural Science Foundation of China(22179017,52172038).
文摘Hydrogen sulfide(H_(2)S)is an industrial exhausted gas that is highly toxic to humans and the environment.Combining desulfurization and fabrication of cathode materials for lithium-sulfur batteries(LSBs)can solve this issue with a double benefit.Herein,the amino-functionalized lotus root-like carbon nanofibers(NH_(2)-PLCNFs)are prepared by the amination of electrospinning carbon nanofibers under dielectric barrier discharge plasma.Selective catalytic oxidation of H_(2)S to elemental sulfur(S)is achieved over the metalfree NH_(2)-PLCNFs catalyst,and the obtained composite S@NH_(2)-PLCNFs is further used as cathode in LSBs.NH_(2)-PLCNFs enable efficient desulfurization(removal capacity as high as 3.46 g H_(2)S g^(−1) catalyst)and strongly covalent stabilization of S on modified carbon nanofibers.LSBs equipped with S@NH_(2)-PLCNFs deliver a high specific capacity of 705.8 mA h g^(−1) at 1 C after 1000 cycles based on the spatial confinement and the covalent stabilization of electroactive materials on amino-functionalized porous carbon matrix.It is revealed that S@NH_(2)-PLCNFs obtained by this kind of chemical vapor deposition leads to a more homogeneous S distribution and superior electrochemical performance to the sample S/NH_(2)-PLCNF-M prepared by the traditional molten infusion.This work opens a new avenue for the combination of environment protection and energy storage.
基金the National Natural Science Foundation of China(52103093)the Young Elite Scientists Sponsorship Program by China Association for Science and Technology(2021QNRC001)+2 种基金the Jiangxi Provincial Natural Science Foundation(20212BAB214048)Science and Technology Support Project of Shangrao(2020L009,2021J006)Science and Technological Project of Education Department of Jiangxi(GJJ211704)for funding their contributions to this paper。
文摘Lithium sulfur batteries(LSBs)are recognized as promising devices for developing next-generation energy storage systems.In addition,they are attractive rechargeable battery systems for replacing lithium-ion batteries(LIBs)for commercial use owing to their higher theoretical energy density and lower cost compared to those of LIBs.However,LSBs are still beset with some persistent issues that prevent them from being used industrially,such as the unavoidable dissolution of lithium polysulfide intermediates during electrochemical reactions and large volume expansion(up to 80%)upon the formation of Li_(2)S,resulting in serious battery life and safety limitations.In the process of solving these problems,it is necessary to maintain a high sulfur content in the cathode materials to ensure that the LSBs have high energy densities and excellent cycle performance.In this review,the novel preparation methods and cathode materials used for preparing LSBs in recent years are reviewed considering the sulfur content and cycle performance.In addition,the problems and difficulties in practically applying cathode materials are described,and the development trend is discussed.
基金supported by the National Natural Science Foundation of China(No.52272241)the start-up funding from Zhejiang University。
文摘Lithium-sulfur batteries with liquid electrolytes have been obstructed by severe shuttle effects and intrinsic safety concerns.Introducing inorganic solid-state electrolytes into lithium-sulfur systems is believed as an effective approach to eliminate these issues without sacrificing the high-energy density,which determines sulfidebased all-solid-state lithium-sulfur batteries.However,the lack of design principles for high-performance composite sulfur cathodes limits their further application.The sulfur cathode regulation should take several factors including the intrinsic insulation of sulfur,well-designed conductive networks,integrated sulfur-electrolyte interfaces,and porous structure for volume expansion,and the correlation between these factors into account.Here,we summarize the challenges of regulating composite sulfur cathodes with respect to ionic/electronic diffusions and put forward the corresponding solutions for obtaining stable positive electrodes.In the last section,we also outlook the future research pathways of architecture sulfur cathode to guide the develop high-performance all-solid-state lithium-sulfur batteries.
基金supported by grants from the Research Grants Council of the Hong Kong Special Administrative Region,China(Poly U25216121,Poly U15303219)the National Natural Science Foundation of China for Young Scholar(52102310)the Research Committee of the Hong Kong Polytechnic University(A-PB1 M,1-BBXK,1-CD4 M,and G-UAMV)。
文摘High-energy lithium-sulfur batteries(LSBs)have experienced relentless development over the past decade with discernible improvements in electrochemical performance.However,a scrutinization of the cell operation conditions reveals a huge gap between the demands for practical batteries and those in the literature.Low sulfur loading,a high electrolyte/sulfur(E/S)ratio and excess anodes for lab-scale LSBs significantly offset their high-energy merit.To approach practical LSBs,high loading and lean electrolyte parameters are needed,which involve budding challenges of slow charge transfer,polysulfide precipitation and severe shuttle effects.To track these obstacles,the exploration of electrocatalysts to immobilize polysulfides and accelerate Li-S redox kinetics has been widely reported.Herein,this review aims to survey state-of-the-art catalytic materials for practical LSBs with emphasis on elucidating the correlation among catalyst design strategies,material structures and electrochemical performance.We also statistically evaluate the state-of-the-art catalyst-modified LSBs to identify the remaining discrepancy between the current advancements and the real-world requirements.In closing,we put forward our proposal for a catalytic material study to help realize practical LSBs.
基金Financial support from National Natural Science Foundation of China(21935006)is gratefully acknowledged。
文摘Sulfur element possesses an ultrahigh theoretical specific capacity,while the utilization of sulfur in the whole cathode is lower obviously owing to the sluggish kinetics of sulfur and discharged products,limiting the enhancement on energy density of lithium-sulfur batteries.Herein,for the first time,Fe_(0.24)Co_(0.26)Ni_(0.10)Cu_(0.15)Mn_(0.25)high-entropy alloy is introduced as the core catalytic host to activate the electrochemical performance of the sulfur cathode for lithium-sulfur batteries.It is manifested that Fe_(0.24)Co_(0.26)Ni_(0.10)Cu_(0.15)Mn_(0.25)high-entropy alloy nanocrystallites distributed on nitrogen-doped carbon exhibit high electrocatalytic activity toward the conversion of solid sulfur to solid discharged products across soluble intermediate lithium polysulfides.In particular,benefiting from the accelerated kinetics by high-entropy alloy nanocrystallites and synergistic adsorption by nitrogen-doped carbon,the cathode exhibits high reversible capacity of 1079.5 mAh g_(-cathode)^(-1)(high utilization of 89.4%)with the whole cathode as active material,instead of sulfur element.Moreover,under both lean electrolyte(3μmg^(-1))and ultrahigh sulfur loading(27.0 mg cm^(-2))condition,the high discharge capacity of 868.2 mAh g_(-cathode)^(-1)can be still achieved for the sulfur cathode.This strategy opens up a new path to explore catalytic host materials for enhancing the utilization of sulfur in the whole cathode for lithium-sulfur batteries.
基金Supported by the National Natural Science Foundation of China(No.41476165)the University Natural Science Research Project of Anhui Province(No.KJ2019A0042)。
文摘Microbial communities,sulfur isotope of sulfides(δ^(34)S_(AVS)and δ^(34)S_(CRS)),and sulfur and oxygen isotopes of sulfate(δ^(34)S_(SO_(4))and δ^(18)O_(SO_(4)))in sediments were analyzed to reveal the biogeochemical transformations of sulfur in a seabird-affected lake Y2 and a se abird-free YO from Fildes Peninsula,Antarctic Peninsula.The microbial communities in Y2 were mainly associated with penguin activities,while those in YO were limited by nutrients.The much enriched δ^(34)S_(SO_(4))recorded at depth of 30,41,and 52 cm in Y2indicates very strong sulfate reduction therein.The sulfur-degrading bacteria Pseudomonas in 0-23 cm of Y2 was 3.5 time s as abundant as that of sulfur oxidizing bacteria(SOB),indicating remarkable remineralization of organic sulfur.The abundant SOB and ^(34)S-depleted sulfate indicate considerable sulfur oxidation in 34-56-cm layer in Y2.In YO sediments,the highest abundance of Desulfotalea and the most enriched δ^(34)S_(SO_(4))(35.2‰)and δ^(34)S_(CRS)(2.5‰)indicate the strongest sulfate reduction in 28-cm layer.High abundance of Pseudomonas indicates active remineralization of organic sulfur in 3-5-cm layer in YO.The medium δ^(34)S_(SO_(4))and considerable abundance of SOB and sulfate-reducing bacteria(SRB)indicate concurrence of sulfur oxidation and sulfate reduction in other layers in YO.Therefore,a high level of organic matter input from penguin populations supported the diverse microbial community and transformations of sulfur in aquatic ecosystems in Antarctica.
基金supported by the National Natural Science Foundation of China(51962002)the Natural Science Foundation of Guangxi(2022GXNSFAA035463)the National Key R&D Program of China(2022YFB2404402)。
文摘Lithium-sulfur(Li-S)batteries have attracted wide attention for their high theoretical energy density,low cost,and environmental friendliness.However,the shuttle effect of polysulfides and the insulation of active materials severely restrict the development of Li-S batteries.Constructing conductive sulfur scaffolds with catalytic conversion capability for cathodes is an efficient approach to solving above issues.Vanadium-based compounds and their heterostructures have recently emerged as functional sulfur catalysts supported on conductive scaffolds.These compounds interact with polysulfides via different mechanisms to alleviate the shuttle effect and accelerate the redox kinetics,leading to higher Coulombic efficiency and enhanced sulfur utilization.Reports on vanadium-based nanomaterials in Li-S batteries have been steadily increasing over the past several years.In this review,first,we provide an overview of the synthesis of vanadium-based compounds and heterostructures.Then,we discuss the interactions and constitutive relationships between vanadium-based catalysts and polysulfides formed at sulfur cathodes.We summarize the mechanisms that contribute to the enhancement of electrochemical performance for various types of vanadium-based catalysts,thus providing insights for the rational design of sulfur catalysts.Finally,we offer a perspective on the future directions for the research and development of vanadium-based sulfur catalysts.
基金supported by the National Natural Science Foundation of China(22178388,21776315)the Taishan Scholars Program of Shandong Province(tsqn201909065)the Fundamental Research Funds for the Central Universities(19CX05001A).
文摘As well known in the petroleum industry and academia,Ni/ZnO catalysts have excellent desulfurization performance.However,the sulfur transfer mechanism of reactive adsorption desulfurization(RADS)that occurs on Ni/ZnO catalysts remains controversial.Herein,a periodic Ni nanorod supported on ZnO slab was built to represent the Ni/ZnO system,and density functional theory calculations were performed to study the sulfur transfer process and the role of H_(2)within the process.The results elucidate that the direct solid-state diffusion of S from Ni to interfacial oxygen vacancies(Ov)is more favorable than the hydrogenation of S to SH/H_(2)S on Ni and the subsequent H_(2)S desorption,and accordingly,H_(2)O is produced on Ni rather than on ZnO.Ab initio thermodynamics analysis shows that the hydrogen atmosphere applied in preparing Ni/ZnO catalysts greatly promotes the O_(v)formation on ZnO surface,which accounts for the presence of interfacial O_(v)in freshly prepared catalysts.Under RADS condition,hydrogenation of interfacial O atoms to form O-H groups facilitates the reverse spillover of these lattice O atoms from ZnO to Ni,accompanied with the interfacial O_(v)generation.In contrast to the classic S transfer mechanism via H_(2)S,the present work clearly demonstrates that the interfacial S transfer is a feasible reaction pathway in the RADS mechanism.More importantly,the existence of interfacial O_(v)is an essential prerequisite for this interfacial S diffusion,and H_(2)plays a key role in facilitating the O_(v)formation.
基金financially supported by the National Natural Science Foundation of China (52073212,52272303)。
文摘With the high theoretical specific capacity and energy density,lithium-sulfur batteries(LSBs)have been intensively studied as promising candidates for energy storage devices.However,LSBs are largely hindered by inferior sulfur utilization and uncontrollable dendritic growth.Herein,a hierarchical functionalization strategy of stepwise catalytic-adsorption-conversion for sulfur species via the synergetic of the efficiently catalytic host cathode and light multifunctional interlayer has been proposed to concurrently address the issues arising on the dual sides of the LSBs.The multi-layer SnS_(2) micro-flowers embedded into the natural three-dimensional(3D)interconnected carbonized bacterial cellulose(CBC)nanofibers are fabricated as the sulfur host that provides numerous catalytic sites for the rapid catalytic conversion of sulfur species.Moreover,the distinctive CBC-based SnO_(2)-SnS_(2) heterostructure network accompanied high conductive carbon nanofibers as the multifunctional interlayer promotes the rapid anchoringdiffusion-conversion of lithium polysulfides,Li^(+)flux redistribution,and uniform Li deposition.LSBs equipped with our strategy exhibit a high reversible capacity of 1361.5 m A h g^(-1)at 0.2 C and superior cycling stability with an ultra-low capacity fading of 0.031%per cycle in 1000 cycles at 1.5 C and 0.046%at 3 C.A favorable specific capacity of 859.5 m A h g^(-1)at 0.3 C is achieved with a high sulfur mass loading of 5.2 mg cm^(-2),highlighting the potential of practical application.The rational design in this work can provide a feasible solution for high-performance LSBs and promote the development of advanced energy storage devices.
