Three small-molecule donors based on dithieno [2,3-d:2’,3 ’-d’]-benzo[1,2-b:4,5-b’] dithiophene(DTBDT)unit were designed and synthesized by side chain regulation with chlorinated or/and sulfurated substitutions(na...Three small-molecule donors based on dithieno [2,3-d:2’,3 ’-d’]-benzo[1,2-b:4,5-b’] dithiophene(DTBDT)unit were designed and synthesized by side chain regulation with chlorinated or/and sulfurated substitutions(namely ZR1,ZR1-Cl,and ZR1-S-Cl respectively),along with a crystalline non-fullerene acceptor IDIC-4 Cl with a chlorinated 1,1-dicyanomethylene-3-indanone(IC) end group.Energy levels,molar extinction coefficients and crystallinities of three donor molecules can be effectively altered by combining chlorination and sulfuration strategies.Especially,the ZR1-S-Cl exhibited the best absorption ability,lowest higher occupied molecular orbital(HOMO) energy level and highest crystallinity among three donors,resulting in the corresponding all-small-molecule organic solar cells to produce a high power conversion efficiency(PCE) of 12.05% with IDIC-4 Cl as an acceptor.展开更多
The thermal dissolved sulfuration technology is brought forward and performed based on the characteristic of low grade lead-zinc oxide ore in lanpin. Using sulfur as the sulphidizing agent in the experiment, the oxide...The thermal dissolved sulfuration technology is brought forward and performed based on the characteristic of low grade lead-zinc oxide ore in lanpin. Using sulfur as the sulphidizing agent in the experiment, the oxides in the sandstone and ignimbrite are changed into sulfides. The disproportionation reaction of sulfur in a solution is confirmed as 4S＋3H2O=2S^2-＋S2O3^2--＋6H^＋. The dynamics process is studied and the first-order reaction rate equation -1n（1-a）=ktt is obtained. The effects of the reactive products, stirring speed, dosage of sulfuration agent, value of pH and sulphidizing temperature on the sulfuration of oxide ore are investigated. The results indicate that the reactive apparent activation energy is 100.8 kJ/mol and the sulfuration ratio of lead-zinc oxide ore reaches 60% under the conditions of pH 5.9-7.5, the sulfuration temperature of 130 ℃, sulfuration time of 180 min and the stirring speed of 800 r/min.展开更多
An efficient C-3 sulfuration of oxindoles has been developed.Using disulfide as the sulfurating agent,a wide range of sulfurated oxindoles have been synthesized under t-BuOK/N,N-dimethylformamide(DMF)promoted conditio...An efficient C-3 sulfuration of oxindoles has been developed.Using disulfide as the sulfurating agent,a wide range of sulfurated oxindoles have been synthesized under t-BuOK/N,N-dimethylformamide(DMF)promoted conditions.The present method is highly atom economic,environmentally friendly and tolerated a broad scope of substrates.展开更多
Two-dimensional transition-metal dichalcogenides （WS2 and SnS2） have recently joined the family of energy storage materials （for lithium-ion batteries and supercapacitors） as a result of their favorable ion interc...Two-dimensional transition-metal dichalcogenides （WS2 and SnS2） have recently joined the family of energy storage materials （for lithium-ion batteries and supercapacitors） as a result of their favorable ion intercalation. So far, challenges in the synthesis of phase-pure WS2, restacking between WS2 nanosheets, low electronic conductivity, and the brittle nature of WS2, severely limit its use Li-ion battery application. Herein, we develop a facile low temperature solution sulfuration process to improve battery performance dramatically. The sulfuration process is demonstrated to be effective in converting WO3 impurities to WS2, and in repairing the sulfur vacancies, to improve cyclability and rate capability. Lithium-ion battery measurements demonstrate that the stable capacity of the WS2 anode could be enhanced by 48.4% via sulfuration reprocessing, i.e., from 381.7 to 566.8 rnAh/g at a relatively high current density of 0.8 A/g after 50 cycles. We further show that the sulfuration process can be readily extended to other dichalcogenides, and may provide a class of versatile electrode materials for lithium-ion batteries with improved electrochemical characteristics.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
It is crucial to develop arsenic removal adsorbents with strong sulfur resistance under middle-low-temperature flue gas conditions(<400℃).In this work,five Fe-Ce-La oxides were prepared by co-precipitation method,...It is crucial to develop arsenic removal adsorbents with strong sulfur resistance under middle-low-temperature flue gas conditions(<400℃).In this work,five Fe-Ce-La oxides were prepared by co-precipitation method,and FeCeLaO/SiO_(2)-Al_(2)O_(3) composite adsorbents were prepared by coupling fly ash-based Si-Al carriers.The active components Fe-Ce-La oxides and Si-Al carriers were characterized by TPD,TG,XRF,BET and XPS,respectively.The effects of temperature,Si/Al ratio and FeCeLaO loading rate on the sulfur resistance were investigated.Results show that the SO_(2) promotes the arsenic removal of Fe_(2)O_(3),CeLaO and FeCeLaO.At 400℃,the arsenic removal efficiencies of the three oxides increase from 45.3%,72.5% and 81.3% without SO_(2) to 62.6%,80.5%and 91.0%,respectively.The SO_(2) inhibits the arsenic removal of La_(2)O_(2)CO_(3) and FeLaO,and the inhibition effect is pronounced at high temperatures.The sulfur poisoning resistance of Si-Al carriers increases with the increase of Si/Al ratio.When the Si/Al ratio is increased to 9.74,the arsenic removal efficiency in the SO_(2) environment is 13.9% higher than that in the absence of SO_(2).Introducing FeCeLaO active components is beneficial for enhancing the SO_(2) poisoning resistance of Si-Al carriers.The strong sulfur resistance of the FeCeLaO/SiO_(2)-Al_(2)O_(3) composite adsorbent results from multiple factors:protective effects of Ce on Fe,La and Al;sulfation-induced generation of Ce^(3+)and surface-adsorbed oxygen;and strong surface acidity of SiO_(2).展开更多
A reaction between steroidal sapogenins and hydrogen sulfide promoted by BF3•Et2O is described.The thio-diosgenin and thiotigogenin comprising a sulfur atom on the F ring can be easily afforded in one step under this ...A reaction between steroidal sapogenins and hydrogen sulfide promoted by BF3•Et2O is described.The thio-diosgenin and thiotigogenin comprising a sulfur atom on the F ring can be easily afforded in one step under this mild reaction condition.Furthermore,a hypothetical mechanism is also shown.展开更多
Sulfur is closely associated with various types of ore deposits,particularly orogenic gold(Au)systems,where sulfur-bearing melts and fluids play a critical role in transporting oreforming elements essential for ore fo...Sulfur is closely associated with various types of ore deposits,particularly orogenic gold(Au)systems,where sulfur-bearing melts and fluids play a critical role in transporting oreforming elements essential for ore formation.The widely accepted metamorphic devolatilization model suggests that compositionally fertile sedimentary rocks serve as potential gold sources.Therefore,understanding sulfur behavior during prograde metamorphism is essential for elucidating the mechanisms underlying metal activation and mobility.In this study,we conducted in-situ sulfur isotope(δ^(34)S)analyses using secondary ion mass spectrometry(SIMS)on samples from the Hongshankou area,a representative Barrovian-type metamorphic sequence characterized by intermediate pressure-temperature(P-T)conditions.This sequence comprises the biotite,garnet,staurolite,and kyanite zones.Our results show a systematic increase in δ^(34)S values(from 3.1‰ to 5.5‰)coupled with a progressive decrease in total sulfur content(from 320 ppm to 165 ppm)as metamorphic grade increases.The most pronounced sulfur mobilization occurs between the garnet and staurolite zones.In all analyzed samples,Au or Au-bearing minerals predominantly occur along the edges or within pyrite grains,highlighting the critical role of pyrite breakdown in controlling gold mobility.Thus,sulfur isotope fractionation provides robust constraints for quantitatively assessing sulfur mobility during metamorphism.These findings reinforce the concept that metasedimentary rocks and their metamorphic fluids represent fertile sources of Au and other metals enriched in orogenic gold deposits.展开更多
Sluggish kinetics coupled with parasitic shuttling reactions are pivotal challenges hindering the performance of lithium-sulfur(Li-S)batteries.Improving areal capacity and cyclability of Li-S batteries can be achieved...Sluggish kinetics coupled with parasitic shuttling reactions are pivotal challenges hindering the performance of lithium-sulfur(Li-S)batteries.Improving areal capacity and cyclability of Li-S batteries can be achieved by addressing these challenges.A composite sulfur host material is synthesized herein by in situ anchoring ultrafine cobalt-iron phosphide nanoparticles(5-7 nm)onto a hollow mesoporous carbon sphere(HMCS)framework.This strategy achieved exceptional spatial restriction and a high density of catalytically active sites through the encapsulation of sulfur within a hollow-structured framework.Specifically,HMCS expedites rapid Li_(2)S nucleation kinetics,while CoFeP facilitates robust Li_(2)S dissolution kinetics by mitigating decomposition barriers.This synergistic integration equips CoFeP@HMCS with robust bi-directional catalytic activity,significantly promoting interracial charge-transfer,facilitate sulfu r multistep catalytic conversion,and inhibiting shuttling.Consequently,the battery exhibits excellent rate performance(991 mA h g^(-1) at 5.0 C)and retains a high areal capacity of 6.06 mA h cm^(-2) after 200 cycles under a high areal sulfur loading of 8.2 mg cm^(-2) but a low electrolyte/sulfur ratio of 4.8μL mg^(-1).This work contributes to enhancing the practical specific capacity of lithium-sulfur batteries and deepens the understanding of catalysts enabling bidirectional electrocatalytic sulfur conversion.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
A novel method for the synthesis of 2,4-disubstituted thiophenes via the reactions of N,N-disubstituted enaminones and elemental sulfur is developed.By simply heating the substrates in pure water in the presence of Na...A novel method for the synthesis of 2,4-disubstituted thiophenes via the reactions of N,N-disubstituted enaminones and elemental sulfur is developed.By simply heating the substrates in pure water in the presence of NaOH,the thiophene annulation practically takes place via the generation of one C-C and two C-S bonds via cascade dual C-H functionalization and C-N bond thiolation without using any transition metal reagent.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
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
The rate capability and cycling stability of sodium metal batteries taking FeS_(2) or sulfur as cathode are limited due to their low reaction kinetics and severe shuttle effect.Herein,we rationally design a novel sing...The rate capability and cycling stability of sodium metal batteries taking FeS_(2) or sulfur as cathode are limited due to their low reaction kinetics and severe shuttle effect.Herein,we rationally design a novel single-atom-dispersed S_(2)-FeNC/FeS_(2) nanocluster heterojunction embedded in carbon spheres(SFNC/FeS_(2)) for the electrode material of sodium metal batteries.Interestingly,during the discharging process,the Na^(+) is inserted into FeS_(2) to generate Na_(2)S,as well as the unique electrochemical reaction between S_(2)-FeNC and Na^(+) to form Na_(2)S.Meanwhile,the FeNC can adsorb Na_(2)S and catalyze the conversion from Na_(2)S and Fe to FeS_(2) or from Na_(2)S and FeNC to S_(2)-FeNC for suppressing the shuttle effect and promoting the distinct hybrid reversible electrochemical behavior,which improves performance tremendously.Notably,the SFNC/FeS_(2) electrode delivers a specific capacity of 338.7 mAh g^(-1) after superlong 2000 cycles at a current density of 5.0 A g^(-1) and achieves a high energy density of 430.1 Wh Kg^(-1) at a current density of 0.05 A g^(-1).This work presents a novel approach to studying sodium metal batteries with hybrid behavior for excellent high energy density and cycling stability.展开更多
Renewable electricity-driven production of value-added sulfur and H_(2)via electrocatalytic H_(2)S decomposition represents a sustainable route to conventional thermocatalysis.Both the electrocatalyst and electrolyte ...Renewable electricity-driven production of value-added sulfur and H_(2)via electrocatalytic H_(2)S decomposition represents a sustainable route to conventional thermocatalysis.Both the electrocatalyst and electrolyte solution strongly impact the H_(2)S decomposition performance.Despite significant progress in developing sophisticated electrocatalysts,a well-designed electrolyte solution in conjunction with industrial catalysts is an attractive strategy to advance the industrialization process of electrocatalytic H_(2)S decomposition,but remains unexplored.Here,for the first time,we design a solid-liquid-gas three-phase indirect electrolysis system based on a kind of CS_(2)-N electrolyte solution and Ni-Mo_(2)C that can efficiently enable H_(2)S decomposition into valuable H_(2)and sulfur.Specifically,the solid-phase Ni-Mo_(2)C as a heterogeneous redox mediator presents excellent electrocatalytic efficiency for the H_(2)S removal efficiency of up to 99%,and the formation of liquid-phase sulfur product(CS_(2)-N electrolyte solution dissolves sulfur,yield up to 95%)with the generation of gas-phase H_(2)product(~1.32 mL min^(-1)),resulting in an interesting three-phase indirect electrolysis system.Remarkably,it enables the scale-up production(~6 g in a batch experiment)of sulfur with continuous operation for 120 h without attenuation.This work may inaugurate a new electrocatalytic H_(2)S decomposition avenue to explore porous metal materials and electrolyte systems in simultaneous production of value-added sulfur and H_(2).展开更多
In this work,ofloxacin(OFL),a kind of frequently detected antibiotic in groundwater,was selected to explore its impact(at ng/L-μg/L-level)on denitrification performance in an autotrophic denitrification system driven...In this work,ofloxacin(OFL),a kind of frequently detected antibiotic in groundwater,was selected to explore its impact(at ng/L-μg/L-level)on denitrification performance in an autotrophic denitrification system driven by pyrite/sulfur(FeS2/S0).Results showed that OFL restrained nitrate removal efficiency,and the inhibition degree was positively related to the concentration of OFL.After being exposed to increased OFL(200 ng/L-100μg/L)for 69 days,higher inhibition of electron transport activity(ETSA),enzyme activities of nitrate reductase(NAR),and nitrite reductase(NIR)were acquired.Meanwhile,the extracellular protein(PN)content of sludge samples was remarkably stimulated by OFL to resist the augmented toxicity.OFL contributed to increased microbial diversity and sulfur/sulfide oxidation functional genes in ng/L-level bioreactors,whereas led to a decline inμg/L level experiments.With OFL at concentrations of 200 ng/L and 100μg/L,the whole expression of 10 key denitrification functional genes was depressed,and the higher the OFL concentration,the lower the expression level.However,no significant proliferation of antibiotic resistance genes(ARGs)either in 200 ng/L-OFL or 100μg/L-OFL groups was observed.Two-factor correlation analysis results indicated that Thiobacillus,Anaerolineae,Anaerolineales,and Nitrospirae might be the main hosts of existing ARGs in this system.展开更多
Designing cathode possessing crystalline@amorphous core-shell structure with both active core and shell is a meaningful work for resolving the low specific capacity,unstable cycling performance and sluggish reaction ki...Designing cathode possessing crystalline@amorphous core-shell structure with both active core and shell is a meaningful work for resolving the low specific capacity,unstable cycling performance and sluggish reaction kinetics issues of rechargeable magnesium batteries(RMBs)by providing more active sites as well as releasing inner stress during cycling.Herein,WO_(3)@WO_(3-x)S_(x) owning crystalline@amorphous core-shell structure containing both active core and active shell is constructed successfully by introducing S into metastable WO3 structure under temperaturefield applying.In such structure,amorphous shell would provide continuous Mg^(2+)diffusion channels due to its isotropy property for most Mg^(2+)migrating rapidly to interface and then adsorb at ions reservoir formed by interfacial electricfield for increasing specific capacity.It also makes security for stable structure of WO_(3)@WO_(3-x)S_(x) by alleviating volume expansion of crystalline core WO_(3) during cycling to prolong cycling life.Additionally,“softer”ions S^(2-)would weaken interaction between hard acid Mg^(2+) and ionic lattice to enhance Mg^(2+)storage kinetics.Therefore,WO_(3)@WO_(3-x)S_(x) delivers the superior cycling performance(1000 cycles with 83.3%),rate capability(88.5 mAh g^(-1) at 1000 mA g^(-1))and specific capacity(about 150 mAh g^(-1) at 50 mA g^(-1)),which is near 2 times higher than that of WO3.It is believed that the crystalline@amorphous core-shell structure with both active core and shell designing via doping strategy is enlightening for the development of high-performance RMBs,and such design can be extended to other energy storage devices for better electrochemical performance.展开更多
Lithium-sulfur (Li-S) batteries have gained great attention due to the high theoretical energy density and low cost,yet their further commercialization has been obstructed by the notorious shuttle effect and sluggish ...Lithium-sulfur (Li-S) batteries have gained great attention due to the high theoretical energy density and low cost,yet their further commercialization has been obstructed by the notorious shuttle effect and sluggish redox dynamics.Herein,we supply a strategy to optimize the electron structure of Ni_(2)P by concurrently introducing B-doped atoms and P vacancies in Ni_(2)P (Vp-B-Ni_(2)P),thereby enhancing the bidirectional sulfur conversion.The study indicates that the simultaneous introduction of B-doped atoms and P vacancies in Ni_(2)P causes the redistribution of electron around Ni atoms,bringing about the upward shift of d-band center of Ni atoms and effective d-p orbital hybridization between Ni atoms and sulfur species,thus strengthening the chemical anchoring for lithium polysulfides (LiPSs) as well as expediting the bidirectional conversion kinetics of sulfur species.Meanwhile,theoretical calculations reveal that the incorporation of B-doped atoms and P vacancies in Ni_(2)P selectively promotes Li2S dissolution and nucleation processes.Thus,the Li-S batteries with Vp-B-Ni_(2)P-separators present outstanding rate ability of 777 m A h g^(-1)at 5 C and high areal capacity of 8.03 mA h cm^(-2)under E/S of 5μL mg^(-1)and sulfur loading of 7.20 mg cm^(-2).This work elucidates that introducing heteroatom and vacancy in metal phosphide collaboratively regulates the electron structure to accelerate bidirectional sulfur conversion.展开更多
基金the financial support from the National Natural Science Foundation of China (Grant Nos. 21822503, 51973043, 21534003, 21721002, 51863002 and 51973042)the Ministry of Science and Technology of China (Grant No. 2016YFA0200700)+2 种基金Youth Innovation Promotion AssociationK. C. Wong Education Foundationthe Chinese Academy of Sciences。
文摘Three small-molecule donors based on dithieno [2,3-d:2’,3 ’-d’]-benzo[1,2-b:4,5-b’] dithiophene(DTBDT)unit were designed and synthesized by side chain regulation with chlorinated or/and sulfurated substitutions(namely ZR1,ZR1-Cl,and ZR1-S-Cl respectively),along with a crystalline non-fullerene acceptor IDIC-4 Cl with a chlorinated 1,1-dicyanomethylene-3-indanone(IC) end group.Energy levels,molar extinction coefficients and crystallinities of three donor molecules can be effectively altered by combining chlorination and sulfuration strategies.Especially,the ZR1-S-Cl exhibited the best absorption ability,lowest higher occupied molecular orbital(HOMO) energy level and highest crystallinity among three donors,resulting in the corresponding all-small-molecule organic solar cells to produce a high power conversion efficiency(PCE) of 12.05% with IDIC-4 Cl as an acceptor.
基金supported by Cooperated Project of Academy and College Yunnan province(2003CBALA02P023)
文摘The thermal dissolved sulfuration technology is brought forward and performed based on the characteristic of low grade lead-zinc oxide ore in lanpin. Using sulfur as the sulphidizing agent in the experiment, the oxides in the sandstone and ignimbrite are changed into sulfides. The disproportionation reaction of sulfur in a solution is confirmed as 4S＋3H2O=2S^2-＋S2O3^2--＋6H^＋. The dynamics process is studied and the first-order reaction rate equation -1n（1-a）=ktt is obtained. The effects of the reactive products, stirring speed, dosage of sulfuration agent, value of pH and sulphidizing temperature on the sulfuration of oxide ore are investigated. The results indicate that the reactive apparent activation energy is 100.8 kJ/mol and the sulfuration ratio of lead-zinc oxide ore reaches 60% under the conditions of pH 5.9-7.5, the sulfuration temperature of 130 ℃, sulfuration time of 180 min and the stirring speed of 800 r/min.
文摘An efficient C-3 sulfuration of oxindoles has been developed.Using disulfide as the sulfurating agent,a wide range of sulfurated oxindoles have been synthesized under t-BuOK/N,N-dimethylformamide(DMF)promoted conditions.The present method is highly atom economic,environmentally friendly and tolerated a broad scope of substrates.
基金This work was financially supported by the National Basic Research Program of China （No. 2013CB932903）, the National Natural Science Foundation of China （Nos. 61205057 and 61203289）, China Postdoctoral Science special Foundation （No. 2012T50488）, Qing Lan Pro- ject, by the ＂1311 Talent Plan＂ Foundation of Nanjing University of Posts and Telecommunications.
文摘Two-dimensional transition-metal dichalcogenides （WS2 and SnS2） have recently joined the family of energy storage materials （for lithium-ion batteries and supercapacitors） as a result of their favorable ion intercalation. So far, challenges in the synthesis of phase-pure WS2, restacking between WS2 nanosheets, low electronic conductivity, and the brittle nature of WS2, severely limit its use Li-ion battery application. Herein, we develop a facile low temperature solution sulfuration process to improve battery performance dramatically. The sulfuration process is demonstrated to be effective in converting WO3 impurities to WS2, and in repairing the sulfur vacancies, to improve cyclability and rate capability. Lithium-ion battery measurements demonstrate that the stable capacity of the WS2 anode could be enhanced by 48.4% via sulfuration reprocessing, i.e., from 381.7 to 566.8 rnAh/g at a relatively high current density of 0.8 A/g after 50 cycles. We further show that the sulfuration process can be readily extended to other dichalcogenides, and may provide a class of versatile electrode materials for lithium-ion batteries with improved electrochemical characteristics.
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.
文摘It is crucial to develop arsenic removal adsorbents with strong sulfur resistance under middle-low-temperature flue gas conditions(<400℃).In this work,five Fe-Ce-La oxides were prepared by co-precipitation method,and FeCeLaO/SiO_(2)-Al_(2)O_(3) composite adsorbents were prepared by coupling fly ash-based Si-Al carriers.The active components Fe-Ce-La oxides and Si-Al carriers were characterized by TPD,TG,XRF,BET and XPS,respectively.The effects of temperature,Si/Al ratio and FeCeLaO loading rate on the sulfur resistance were investigated.Results show that the SO_(2) promotes the arsenic removal of Fe_(2)O_(3),CeLaO and FeCeLaO.At 400℃,the arsenic removal efficiencies of the three oxides increase from 45.3%,72.5% and 81.3% without SO_(2) to 62.6%,80.5%and 91.0%,respectively.The SO_(2) inhibits the arsenic removal of La_(2)O_(2)CO_(3) and FeLaO,and the inhibition effect is pronounced at high temperatures.The sulfur poisoning resistance of Si-Al carriers increases with the increase of Si/Al ratio.When the Si/Al ratio is increased to 9.74,the arsenic removal efficiency in the SO_(2) environment is 13.9% higher than that in the absence of SO_(2).Introducing FeCeLaO active components is beneficial for enhancing the SO_(2) poisoning resistance of Si-Al carriers.The strong sulfur resistance of the FeCeLaO/SiO_(2)-Al_(2)O_(3) composite adsorbent results from multiple factors:protective effects of Ce on Fe,La and Al;sulfation-induced generation of Ce^(3+)and surface-adsorbed oxygen;and strong surface acidity of SiO_(2).
基金support from the Natural Science Foundation of China(Nos.29070070,29372077).
文摘A reaction between steroidal sapogenins and hydrogen sulfide promoted by BF3•Et2O is described.The thio-diosgenin and thiotigogenin comprising a sulfur atom on the F ring can be easily afforded in one step under this mild reaction condition.Furthermore,a hypothetical mechanism is also shown.
基金supported by the National Natural Science Foundation of China(Nos.42225301 and 42330304)。
文摘Sulfur is closely associated with various types of ore deposits,particularly orogenic gold(Au)systems,where sulfur-bearing melts and fluids play a critical role in transporting oreforming elements essential for ore formation.The widely accepted metamorphic devolatilization model suggests that compositionally fertile sedimentary rocks serve as potential gold sources.Therefore,understanding sulfur behavior during prograde metamorphism is essential for elucidating the mechanisms underlying metal activation and mobility.In this study,we conducted in-situ sulfur isotope(δ^(34)S)analyses using secondary ion mass spectrometry(SIMS)on samples from the Hongshankou area,a representative Barrovian-type metamorphic sequence characterized by intermediate pressure-temperature(P-T)conditions.This sequence comprises the biotite,garnet,staurolite,and kyanite zones.Our results show a systematic increase in δ^(34)S values(from 3.1‰ to 5.5‰)coupled with a progressive decrease in total sulfur content(from 320 ppm to 165 ppm)as metamorphic grade increases.The most pronounced sulfur mobilization occurs between the garnet and staurolite zones.In all analyzed samples,Au or Au-bearing minerals predominantly occur along the edges or within pyrite grains,highlighting the critical role of pyrite breakdown in controlling gold mobility.Thus,sulfur isotope fractionation provides robust constraints for quantitatively assessing sulfur mobility during metamorphism.These findings reinforce the concept that metasedimentary rocks and their metamorphic fluids represent fertile sources of Au and other metals enriched in orogenic gold deposits.
基金financially supported by the Nation Key R&D Program China(2018YFA0703200)the Key Research and Development Program of Hubei Province(2022BAA026)+1 种基金the National Natural Science Foundation of China(51772110)the Open Research Fund(2024JYBKF01)of Key Laboratory of Material Chemistry for Energy Conversion and Storage(HUST),Ministry of Education。
文摘Sluggish kinetics coupled with parasitic shuttling reactions are pivotal challenges hindering the performance of lithium-sulfur(Li-S)batteries.Improving areal capacity and cyclability of Li-S batteries can be achieved by addressing these challenges.A composite sulfur host material is synthesized herein by in situ anchoring ultrafine cobalt-iron phosphide nanoparticles(5-7 nm)onto a hollow mesoporous carbon sphere(HMCS)framework.This strategy achieved exceptional spatial restriction and a high density of catalytically active sites through the encapsulation of sulfur within a hollow-structured framework.Specifically,HMCS expedites rapid Li_(2)S nucleation kinetics,while CoFeP facilitates robust Li_(2)S dissolution kinetics by mitigating decomposition barriers.This synergistic integration equips CoFeP@HMCS with robust bi-directional catalytic activity,significantly promoting interracial charge-transfer,facilitate sulfu r multistep catalytic conversion,and inhibiting shuttling.Consequently,the battery exhibits excellent rate performance(991 mA h g^(-1) at 5.0 C)and retains a high areal capacity of 6.06 mA h cm^(-2) after 200 cycles under a high areal sulfur loading of 8.2 mg cm^(-2) but a low electrolyte/sulfur ratio of 4.8μL mg^(-1).This work contributes to enhancing the practical specific capacity of lithium-sulfur batteries and deepens the understanding of catalysts enabling bidirectional electrocatalytic sulfur conversion.
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supported by the National Natural Science Foundation of China(No.22261026).
文摘A novel method for the synthesis of 2,4-disubstituted thiophenes via the reactions of N,N-disubstituted enaminones and elemental sulfur is developed.By simply heating the substrates in pure water in the presence of NaOH,the thiophene annulation practically takes place via the generation of one C-C and two C-S bonds via cascade dual C-H functionalization and C-N bond thiolation without using any transition metal reagent.
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financially supported by the National Natural Science Foundation of China (No. 22579095)the Beijing-Tianjin-Hebei Basic Research Cooperation Special Project (B2024204027)+2 种基金the Youth Top-notch Talent Foundation of Hebei Provincial Universities (BJK2022023)the Natural Science Foundation of Hebei Province (B2023204006)the talent training project of Hebei province (No. B20231004)。
文摘The rate capability and cycling stability of sodium metal batteries taking FeS_(2) or sulfur as cathode are limited due to their low reaction kinetics and severe shuttle effect.Herein,we rationally design a novel single-atom-dispersed S_(2)-FeNC/FeS_(2) nanocluster heterojunction embedded in carbon spheres(SFNC/FeS_(2)) for the electrode material of sodium metal batteries.Interestingly,during the discharging process,the Na^(+) is inserted into FeS_(2) to generate Na_(2)S,as well as the unique electrochemical reaction between S_(2)-FeNC and Na^(+) to form Na_(2)S.Meanwhile,the FeNC can adsorb Na_(2)S and catalyze the conversion from Na_(2)S and Fe to FeS_(2) or from Na_(2)S and FeNC to S_(2)-FeNC for suppressing the shuttle effect and promoting the distinct hybrid reversible electrochemical behavior,which improves performance tremendously.Notably,the SFNC/FeS_(2) electrode delivers a specific capacity of 338.7 mAh g^(-1) after superlong 2000 cycles at a current density of 5.0 A g^(-1) and achieves a high energy density of 430.1 Wh Kg^(-1) at a current density of 0.05 A g^(-1).This work presents a novel approach to studying sodium metal batteries with hybrid behavior for excellent high energy density and cycling stability.
基金supported by the National Natural Science Foundation of China(No.22278439 and 21776313).
文摘Renewable electricity-driven production of value-added sulfur and H_(2)via electrocatalytic H_(2)S decomposition represents a sustainable route to conventional thermocatalysis.Both the electrocatalyst and electrolyte solution strongly impact the H_(2)S decomposition performance.Despite significant progress in developing sophisticated electrocatalysts,a well-designed electrolyte solution in conjunction with industrial catalysts is an attractive strategy to advance the industrialization process of electrocatalytic H_(2)S decomposition,but remains unexplored.Here,for the first time,we design a solid-liquid-gas three-phase indirect electrolysis system based on a kind of CS_(2)-N electrolyte solution and Ni-Mo_(2)C that can efficiently enable H_(2)S decomposition into valuable H_(2)and sulfur.Specifically,the solid-phase Ni-Mo_(2)C as a heterogeneous redox mediator presents excellent electrocatalytic efficiency for the H_(2)S removal efficiency of up to 99%,and the formation of liquid-phase sulfur product(CS_(2)-N electrolyte solution dissolves sulfur,yield up to 95%)with the generation of gas-phase H_(2)product(~1.32 mL min^(-1)),resulting in an interesting three-phase indirect electrolysis system.Remarkably,it enables the scale-up production(~6 g in a batch experiment)of sulfur with continuous operation for 120 h without attenuation.This work may inaugurate a new electrocatalytic H_(2)S decomposition avenue to explore porous metal materials and electrolyte systems in simultaneous production of value-added sulfur and H_(2).
基金supported by the National Natural Science Foundation of China(No.42377083)the Natural Science Foundation of Sichuan Province,China(No.2025 ZNSFSC0433).
文摘In this work,ofloxacin(OFL),a kind of frequently detected antibiotic in groundwater,was selected to explore its impact(at ng/L-μg/L-level)on denitrification performance in an autotrophic denitrification system driven by pyrite/sulfur(FeS2/S0).Results showed that OFL restrained nitrate removal efficiency,and the inhibition degree was positively related to the concentration of OFL.After being exposed to increased OFL(200 ng/L-100μg/L)for 69 days,higher inhibition of electron transport activity(ETSA),enzyme activities of nitrate reductase(NAR),and nitrite reductase(NIR)were acquired.Meanwhile,the extracellular protein(PN)content of sludge samples was remarkably stimulated by OFL to resist the augmented toxicity.OFL contributed to increased microbial diversity and sulfur/sulfide oxidation functional genes in ng/L-level bioreactors,whereas led to a decline inμg/L level experiments.With OFL at concentrations of 200 ng/L and 100μg/L,the whole expression of 10 key denitrification functional genes was depressed,and the higher the OFL concentration,the lower the expression level.However,no significant proliferation of antibiotic resistance genes(ARGs)either in 200 ng/L-OFL or 100μg/L-OFL groups was observed.Two-factor correlation analysis results indicated that Thiobacillus,Anaerolineae,Anaerolineales,and Nitrospirae might be the main hosts of existing ARGs in this system.
基金supported by the National Natural Science Foundation of China under Grant No.52072196,52002200,52102106,52202262,22379081,22379080,Major Basic Research Program of Natural Science Foundation of Shandong Province under Grant No.ZR2020ZD09the Natural Science Foundation of Shandong Province under Grant No.ZR2020QE063,ZR202108180009,ZR2023QE059the Postdoctoral Program in Qingdao under No.QDBSH20220202019.
文摘Designing cathode possessing crystalline@amorphous core-shell structure with both active core and shell is a meaningful work for resolving the low specific capacity,unstable cycling performance and sluggish reaction kinetics issues of rechargeable magnesium batteries(RMBs)by providing more active sites as well as releasing inner stress during cycling.Herein,WO_(3)@WO_(3-x)S_(x) owning crystalline@amorphous core-shell structure containing both active core and active shell is constructed successfully by introducing S into metastable WO3 structure under temperaturefield applying.In such structure,amorphous shell would provide continuous Mg^(2+)diffusion channels due to its isotropy property for most Mg^(2+)migrating rapidly to interface and then adsorb at ions reservoir formed by interfacial electricfield for increasing specific capacity.It also makes security for stable structure of WO_(3)@WO_(3-x)S_(x) by alleviating volume expansion of crystalline core WO_(3) during cycling to prolong cycling life.Additionally,“softer”ions S^(2-)would weaken interaction between hard acid Mg^(2+) and ionic lattice to enhance Mg^(2+)storage kinetics.Therefore,WO_(3)@WO_(3-x)S_(x) delivers the superior cycling performance(1000 cycles with 83.3%),rate capability(88.5 mAh g^(-1) at 1000 mA g^(-1))and specific capacity(about 150 mAh g^(-1) at 50 mA g^(-1)),which is near 2 times higher than that of WO3.It is believed that the crystalline@amorphous core-shell structure with both active core and shell designing via doping strategy is enlightening for the development of high-performance RMBs,and such design can be extended to other energy storage devices for better electrochemical performance.
基金Institute of Technology Research Fund Program for Young Scholars21C Innovation Laboratory Contemporary Amperex Technology Co.,Limited,Ninde, 352100, China (21C–OP-202314)。
文摘Lithium-sulfur (Li-S) batteries have gained great attention due to the high theoretical energy density and low cost,yet their further commercialization has been obstructed by the notorious shuttle effect and sluggish redox dynamics.Herein,we supply a strategy to optimize the electron structure of Ni_(2)P by concurrently introducing B-doped atoms and P vacancies in Ni_(2)P (Vp-B-Ni_(2)P),thereby enhancing the bidirectional sulfur conversion.The study indicates that the simultaneous introduction of B-doped atoms and P vacancies in Ni_(2)P causes the redistribution of electron around Ni atoms,bringing about the upward shift of d-band center of Ni atoms and effective d-p orbital hybridization between Ni atoms and sulfur species,thus strengthening the chemical anchoring for lithium polysulfides (LiPSs) as well as expediting the bidirectional conversion kinetics of sulfur species.Meanwhile,theoretical calculations reveal that the incorporation of B-doped atoms and P vacancies in Ni_(2)P selectively promotes Li2S dissolution and nucleation processes.Thus,the Li-S batteries with Vp-B-Ni_(2)P-separators present outstanding rate ability of 777 m A h g^(-1)at 5 C and high areal capacity of 8.03 mA h cm^(-2)under E/S of 5μL mg^(-1)and sulfur loading of 7.20 mg cm^(-2).This work elucidates that introducing heteroatom and vacancy in metal phosphide collaboratively regulates the electron structure to accelerate bidirectional sulfur conversion.
