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
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
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
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
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
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
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
Titanium-bearing blast furnace slag(Ti-BFS)is an industrial solid waste rich in titanium,magnesium and aluminum.However,it is difficult to utilize Ti,Mg and Al from Ti-BFS for the strong stability and poor reaction ac...Titanium-bearing blast furnace slag(Ti-BFS)is an industrial solid waste rich in titanium,magnesium and aluminum.However,it is difficult to utilize Ti,Mg and Al from Ti-BFS for the strong stability and poor reaction activity of Ti-BFS.A comprehensive utilization route of Ti,Mg and Al from Ti-BFS was proposed.Ti-BFS was firstly roasted with H_(2)SO_(4)to realizes the conversion of Ti,Mg and Al to their corresponding sulphates.The sulphates were leached by dilute H_(2)SO_(4)solution to extraction Ti,Mg and Al from roasted Ti-BFS.The roasting conditions were optimized as follows,sulfuric acid concentration of 85%(mass),temperature of 200℃,acid-slag ratio of 5.5,particle size of Ti-BFS<75μm,and reaction time of 1 h.The extraction rates of titanium,aluminum,and magnesium reached 82.42%,88.78%and 90.53%,respectively.The leachate was hydrolyzed at 102℃for 5 h with a titanium hydrolysis ratio of 96%.After filtration and calcination,TiO_(2)with a purity of 97%(mass)was obtained.Al in the leachate was converted to NH_(4)Al(SO_(4))_(2)·12H_(2)O by the neutralization of ammonia water at pH=4.5.Al_(2)O_(3) was obtained by the calcination of NH_(4)Al(SO_(4))_(2)·12H_(2)O.The residual solution can be used to prepare products of magnesium sulfate.In the proposed process,Ti,Mg and Al were extracted from Ti-BFS and utilized comprehensively to prepare valuable products.The leaching behavior of roasted Ti-BFS with water was also studied.It followed the unreacted shrinking core model.The apparent activation energy was 26.07 kJ·mol^(-1).This research not only provides a viable method for recovering valuable metals in Ti-BFS,but also provides a strategy to comprehensive utilize the valuable elements in Ti-BFS.展开更多
Potassium hydroxide(KOH)was introduced into the molybdenite roasting process to convert molybdenum(Mo)and sulfur(S)into water-soluble potassium molybdate(K_(2)MoO_(4))and potassium sulfate(K_(2)SO_(4)).Roasting with a...Potassium hydroxide(KOH)was introduced into the molybdenite roasting process to convert molybdenum(Mo)and sulfur(S)into water-soluble potassium molybdate(K_(2)MoO_(4))and potassium sulfate(K_(2)SO_(4)).Roasting with a 1.8-fold excess of KOH at 400℃ for 3 h enabled the leaching of over 99%of Mo from the molybdenum calcine using water.A precipitation method involving potassium–magnesium(K-Mg)salts was proposed for impurity removal.Under the conditions of pH 11,30℃,excess coefficient of 1.7 for Mg salts,and a duration of 1 h,98.37%of phosphorus(P)was removed from the K_(2)MoO_(4) solution.With post-purification,over 99%of Mo crystallized upon adjustment of pH to 1.Subsequently,S and K were recovered as K_(2)SO_(4) fertilizer from the crystalline mother liquor.An environmentally sustainable approach was proposed to conduct molybdenite production and ensure the efficient recovery of both Mo and S.展开更多
The use of lithium-sulfur(Li-S)batteries is limited by sulfur redox reactions involving multi-phase transformations,especially at low-temperatures.To address this issue,we report a material(FCNS@NCFs)consisting of nit...The use of lithium-sulfur(Li-S)batteries is limited by sulfur redox reactions involving multi-phase transformations,especially at low-temperatures.To address this issue,we report a material(FCNS@NCFs)consisting of nitrogen-doped carbon fibers loaded with a ternary metal sulf-ide((Fe,Co,Ni)_(9)S_(8))for use as the sulfur host in Li-S batteries.This materi-al was prepared using transfer blot filter paper as the carbon precursor,thiourea as the source of nitrogen and sulfur,and FeCl_(3)·6H_(2)O,CoCl_(2)·6H_(2)O and NiCl_(2)·6H_(2)O as the metal ion sources.It was synthesized by an impreg-nation method followed by calcination.The nitrogen doping significantly in-creased the conductivity of the host,and the metal sulfides have excellent catalytic activities.Theoretical calculations,and adsorption and deposition experiments show that active sites on the surface of FCNS@NCFs selectively adsorb polysulfides,facilitate rapid adsorption and conversion,prevent cathode passivation and inhib-it the polysulfide shuttling.The FCNS@NCFs used as the sulfur host has excellent electrochemical properties.Its initial dis-charge capacity is 1639.0 mAh g^(−1) at 0.2 C and room temperature,and it remains a capacity of 1255.1 mAh g^(−1) after 100 cycles.At−20~C,it has an initial discharge capacity of 1578.5 mAh g^(−1) at 0.2 C,with a capacity of 867.5 mAh g^(−1) after 100 cycles.Its excellent performance at both ambient and low temperatures suggests a new way to produce high-performance low-temper-ature Li-S batteries.展开更多
A transformative beryllium metallurgy theory and method was proposed based on the low-temperature dissociation of hydrofluoric acid and purification by exploiting the large difference of fluoride solubility.Hydrofluor...A transformative beryllium metallurgy theory and method was proposed based on the low-temperature dissociation of hydrofluoric acid and purification by exploiting the large difference of fluoride solubility.Hydrofluoric acid can quickly dissociate berylum ore powder directly at low or room temperature with more than 99%dissociation rate.The solubility of AlF_(3),FeF_(3) CrF_(3) and MgF_(2),is low.Coupled with common ion effect,99.9%-purity beryllium products can be prepared without chemical purification.For high-purity beryllium products of grade 4N or higher,they can be prepared through the superior property that the pH intervals of iron,chromium,and other hydroxide precipitates are distinctly different from those corresponding to Be(OH)_(2),precipitates.This new method can be used to prepare most of the beryllium products that are prepared by modern beryllium metallurgy.展开更多
Lithium metal batteries(LMBs)have attracted great intention due to the high energy density[1].Among various battery technologies,lithium-sulfur(Li-S)batteries are also very unique but important due to its high energy ...Lithium metal batteries(LMBs)have attracted great intention due to the high energy density[1].Among various battery technologies,lithium-sulfur(Li-S)batteries are also very unique but important due to its high energy density,low cost and available sources[2].Although Li-s batteries exhibit high energy density,the cycling life is poor,especially for large-capacity pouch cells[3].The cycling performance of Li-s batteries is crucially determined by 16-electron complex sulfur reduction reaction(SRR)from S_(8)molecules to Li_(2)S,solid,which involves the multiple potential interwoven branches among lithium polysulfide intermediates(LiPS,e.g.,S_(8),Li_(2)S_(8),Li_(2)S_(6),Li_(2)S_(4)and Li_(2)S)[4].The obvious shuttle for soluble Lips across the cathode and anode leads to the battery capacity fading.Thus,it is necessary to decrease the accumulation of soluble Lips in the electrolyte through catalysts fastening the key conversion step from high-order polysulfides to insoluble Li_(2)S_(2)/Li_(2)S.Although some effort has been devoted to catalyze SRR,the complex mechanism remains unclear.To address this issue,Duan et al.tried to solve it based on nitrogen,sulfur,dualdoped holey graphene framework(N,S-HGF)electrocatalyst in Nature[5].展开更多
Sulfur was typically regarded as a poison to precious metal complex catalysts in hydroformylation of olefins.However,the combination of sulfur and phosphine may present an intriguing interaction with heterogeneous mon...Sulfur was typically regarded as a poison to precious metal complex catalysts in hydroformylation of olefins.However,the combination of sulfur and phosphine may present an intriguing interaction with heterogeneous mononuclear complex due to the difference of their electronegativities,and coordination capabilities.Herein,we report a novel sulfur-phosphine co-coordinated heterogeneous Rh mononuclear complex catalyst(Rh_(1)/POPs-PPh_(3)&S),which exhibits an unexpected 1.5–2.0 times catalytic activity for hydroformylation of olefins(C_(3)=,C_(5)=–C_(8)=),in comparison with the solely phosphine-coordinated Rh mononuclear complex catalyst(Rh_(1)/POPs-PPh_(3)).In contrast,sulfur coordination alone leads to severe sulfur poisoning with significantly inhibited catalytic performance.Experimental and theoretical analyses reveal that phosphine coordination promotes catalytic activity via its strong electron-donating ability,while sulfur occupies a coordination site and reduces the electronic density of Rh ions.The synergistical coordination of sulfur and phosphine optimizes the electronic density of active Rh ions and decreases the energy barrier of the rate-determining step of olefin insertion,thus enhancing the hydroformylation activity,regioselectivity and stability of Rh_(1)/POPs-PPh_(3)&S.展开更多
In this work,a new process for achieving the recovery of elemental sulfur by utilizing a fluidized catalytic cracking(FCC) riser reactor for SOxtreatment(FCC-DeSOx) is proposed.The process leverages the high temperatu...In this work,a new process for achieving the recovery of elemental sulfur by utilizing a fluidized catalytic cracking(FCC) riser reactor for SOxtreatment(FCC-DeSOx) is proposed.The process leverages the high temperatures and hydrocarbon concentrations in the FCC riser reactor to convert SOxinto H_(2)S.Subsequently,H_(2)S,along with the cracked gas,is processed downstream to produce sulfur.Thermodynamic analysis of the key reduction reactions in the FCC-DeSOxprocess revealed that complete conversion of SOxto H_(2)S is feasible in the dry gas(hydrogen-rich) prelift zone,as well as the upper and lower zones of the riser,upon achieving thermodynamic equilibrium.Experimental studies were conducted to replicate the conditions of these reaction zones using a low concentration of hydrogen gas as the reducing agent.Through process optimization,investigation of the minimum reaction time,and kinetic studies,the potential of this method for the complete reduction of SOxwas further confirmed.展开更多
High-entropy oxides(HEOs)have sparked scientific interest recently as a potential material technology for lithium-sulfur(Li–S)batteries.This interest stems from their simultaneous roles as sulfur hosts and electrocat...High-entropy oxides(HEOs)have sparked scientific interest recently as a potential material technology for lithium-sulfur(Li–S)batteries.This interest stems from their simultaneous roles as sulfur hosts and electrocatalysts,which provide enhancements to the performance of sulfur cathode composites.Nonetheless,their incorporation into the active material blend results in compromised energy density,particularly when their gravimetric proportion is substantial(≥10 wt.%,in the sulfur-based cathode).展开更多
Despite significant progress has been achieved regarding the shuttle-effect of lithium polysulfides,the suppressed specific capacity and retarded redox kinetics under high sulfur loading still threat the actual energy...Despite significant progress has been achieved regarding the shuttle-effect of lithium polysulfides,the suppressed specific capacity and retarded redox kinetics under high sulfur loading still threat the actual energy density and power density of lithium-sulfur batteries.In this study,a graham condenser-inspired carbon@WS_(2)host with coil-in-tube structure was designed and synthesized using anodic aluminum oxide(AAO)membrane with vertically aligned nanopores as template.The vertical array of carbon nanotubes with internal carbon coils not only leads to efficient charge transfer across through the thickness of the cathode,but also provides significant confinement to polysulfide diffusion towards both the lateral and longitudinal directions.Few-layer WS_(2)in the carbon coils perform a synergistic role in suppressing the shuttle-effect as well as boosting the cathodic kinetics.As a result,high specific capacity(1180 m Ah/g at 0.1 C)and long-cycling stability at 0.5 C for 500 cycles has been achieved at 3 mgS/cm^(2).Impressive areal capacity of 7.4 m Ah/cm^(2)has been demonstrated when the sulfur loading reaches 8.4 mg/cm^(2).The unique coil-in-tube structure developed in this work provides a new solution for high sulfur loading cathode towards practical lithium-sulfur batteries.展开更多
Many catalysts have shown excellent activity for the sulfur reduction reaction(SRR),but sluggish electrochemistry kinetics have hindered the development of lithium-sulfur batteries.It has been found that the activity ...Many catalysts have shown excellent activity for the sulfur reduction reaction(SRR),but sluggish electrochemistry kinetics have hindered the development of lithium-sulfur batteries.It has been found that the activity of catalysts for the sulfur evolution reaction(SER)plays a crucial role in determining the overall reaction kinetics.To address this issue,the rational design of catalysts is crucial.Here,we proposed a popular rule to accelerate SER by using chip-like high-entropy perovskite oxide La_(0.7)Sr_(0.3)(Fe_(0.2)Co_(0.2)Ni_(0.2)Zn_(0.2)Mn_(0.2))O_(3-δ)(LMO-HEO)as advanced electrocatalysts.The strong interaction between the adjacent metal atoms in different metals of LMO-HEO electrocatalysts could lead to a"cocktail effect",which not only greatly improved the catalytic capacity toward sulfur species,but also accelerated the oxidation reaction kinetics of Li_2S.As a result,the S/La_(0.7)Sr_(0.3)(Fe_(0.2)Co_(0.2)Ni_(0.2)Zn_(0.2))Mn_(0.2)O_(3-δ)cathodes delivered excellent cyclic stability with a capacity decay of only 0.025%after 1200 cycles at 2 C.This work has provided a rational design idea for new multifunctional electrocatalysts with high catalytic capacity.展开更多
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 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the financial support from the National Natural Science Foundation of China (22109127)the Chinese Postdoctoral Science Foundation (2021M702666)+2 种基金the Research Fund of the State Key Laboratory of Solidification Processing (NPU),China (Grant No.2023-TS-02)The financial support from the Youth Project of"Shaanxi High-level Talents Introduction Plan"the Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) are also sincerely appreciated
文摘Photo-assisted lithium–sulfur batteries(PALSBs)offer an eco-friendly solution to address the issue of sluggish reaction kinetics of conventional LSBs.However,designing an efficient photoelectrode for practical implementation remains a significant challenge.Herein,we construct a free-standing polymer–inorganic hybrid photoelectrode with a direct Z-scheme heterostructure to develop high-efficiency PALSBs.Specifically,polypyrrole(PPy)is in situ vapor-phase polymerized on the surface of N-doped TiO_(2) nanorods supported on carbon cloth(N-TiO_(2)/CC),thereby forming a well-defined p–n heterojunction.This architecture efficiently facilitates the carrier separation of photo-generated electron–hole pairs and significantly enhances carrier transport by creating a built-in electric field.Thus,the PPy@N-TiO_(2)/CC can simultaneously act as a photocatalyst and an electrocatalyst to accelerate the reduction and evolution of sulfur,enabling ultrafast sulfur redox dynamics,as convincingly validated by both theoretical simulations and experimental results.Consequently,the PPy@N-TiO_(2)/CC PALSB achieves a high discharge capacity of 1653 mAh g^(−1),reaching 98.7%of the theoretical value.Furthermore,5 h of photo-charging without external voltage enables the PALSB to deliver a discharge capacity of 333 mAh g^(−1),achieving dual-mode energy harvesting capabilities.This work successfully integrates solar energy conversion and storage within a rechargeable battery system,providing a promising strategy for sustainable energy storage technologies.
基金supported by the National Natural Science Foundation of China(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.
基金the Pangang Group Company Limited for its financial supportthe support from the Fundamental Research Funds for the Central Universities(SCU2024D009)。
文摘Titanium-bearing blast furnace slag(Ti-BFS)is an industrial solid waste rich in titanium,magnesium and aluminum.However,it is difficult to utilize Ti,Mg and Al from Ti-BFS for the strong stability and poor reaction activity of Ti-BFS.A comprehensive utilization route of Ti,Mg and Al from Ti-BFS was proposed.Ti-BFS was firstly roasted with H_(2)SO_(4)to realizes the conversion of Ti,Mg and Al to their corresponding sulphates.The sulphates were leached by dilute H_(2)SO_(4)solution to extraction Ti,Mg and Al from roasted Ti-BFS.The roasting conditions were optimized as follows,sulfuric acid concentration of 85%(mass),temperature of 200℃,acid-slag ratio of 5.5,particle size of Ti-BFS<75μm,and reaction time of 1 h.The extraction rates of titanium,aluminum,and magnesium reached 82.42%,88.78%and 90.53%,respectively.The leachate was hydrolyzed at 102℃for 5 h with a titanium hydrolysis ratio of 96%.After filtration and calcination,TiO_(2)with a purity of 97%(mass)was obtained.Al in the leachate was converted to NH_(4)Al(SO_(4))_(2)·12H_(2)O by the neutralization of ammonia water at pH=4.5.Al_(2)O_(3) was obtained by the calcination of NH_(4)Al(SO_(4))_(2)·12H_(2)O.The residual solution can be used to prepare products of magnesium sulfate.In the proposed process,Ti,Mg and Al were extracted from Ti-BFS and utilized comprehensively to prepare valuable products.The leaching behavior of roasted Ti-BFS with water was also studied.It followed the unreacted shrinking core model.The apparent activation energy was 26.07 kJ·mol^(-1).This research not only provides a viable method for recovering valuable metals in Ti-BFS,but also provides a strategy to comprehensive utilize the valuable elements in Ti-BFS.
基金financially supported by the National Natural Science Foundation of China(No.52174340)the National Key Research and Development Project of China(No.2022YFC2904505)the Hunan FURONG Scholars Project and the Basic Science Centre of the National Natural Science Foundation of China(No.72088101)。
文摘Potassium hydroxide(KOH)was introduced into the molybdenite roasting process to convert molybdenum(Mo)and sulfur(S)into water-soluble potassium molybdate(K_(2)MoO_(4))and potassium sulfate(K_(2)SO_(4)).Roasting with a 1.8-fold excess of KOH at 400℃ for 3 h enabled the leaching of over 99%of Mo from the molybdenum calcine using water.A precipitation method involving potassium–magnesium(K-Mg)salts was proposed for impurity removal.Under the conditions of pH 11,30℃,excess coefficient of 1.7 for Mg salts,and a duration of 1 h,98.37%of phosphorus(P)was removed from the K_(2)MoO_(4) solution.With post-purification,over 99%of Mo crystallized upon adjustment of pH to 1.Subsequently,S and K were recovered as K_(2)SO_(4) fertilizer from the crystalline mother liquor.An environmentally sustainable approach was proposed to conduct molybdenite production and ensure the efficient recovery of both Mo and S.
基金partially supported by National Natural Science Foundation of China(52172250)Institute of Process Engineering(IPE)Project for Frontier Basic Research(QYJC-2023-06)。
文摘The use of lithium-sulfur(Li-S)batteries is limited by sulfur redox reactions involving multi-phase transformations,especially at low-temperatures.To address this issue,we report a material(FCNS@NCFs)consisting of nitrogen-doped carbon fibers loaded with a ternary metal sulf-ide((Fe,Co,Ni)_(9)S_(8))for use as the sulfur host in Li-S batteries.This materi-al was prepared using transfer blot filter paper as the carbon precursor,thiourea as the source of nitrogen and sulfur,and FeCl_(3)·6H_(2)O,CoCl_(2)·6H_(2)O and NiCl_(2)·6H_(2)O as the metal ion sources.It was synthesized by an impreg-nation method followed by calcination.The nitrogen doping significantly in-creased the conductivity of the host,and the metal sulfides have excellent catalytic activities.Theoretical calculations,and adsorption and deposition experiments show that active sites on the surface of FCNS@NCFs selectively adsorb polysulfides,facilitate rapid adsorption and conversion,prevent cathode passivation and inhib-it the polysulfide shuttling.The FCNS@NCFs used as the sulfur host has excellent electrochemical properties.Its initial dis-charge capacity is 1639.0 mAh g^(−1) at 0.2 C and room temperature,and it remains a capacity of 1255.1 mAh g^(−1) after 100 cycles.At−20~C,it has an initial discharge capacity of 1578.5 mAh g^(−1) at 0.2 C,with a capacity of 867.5 mAh g^(−1) after 100 cycles.Its excellent performance at both ambient and low temperatures suggests a new way to produce high-performance low-temper-ature Li-S batteries.
基金National Key Research and Development Program of China(2021YFC2902301,2021YFC2902302)。
文摘A transformative beryllium metallurgy theory and method was proposed based on the low-temperature dissociation of hydrofluoric acid and purification by exploiting the large difference of fluoride solubility.Hydrofluoric acid can quickly dissociate berylum ore powder directly at low or room temperature with more than 99%dissociation rate.The solubility of AlF_(3),FeF_(3) CrF_(3) and MgF_(2),is low.Coupled with common ion effect,99.9%-purity beryllium products can be prepared without chemical purification.For high-purity beryllium products of grade 4N or higher,they can be prepared through the superior property that the pH intervals of iron,chromium,and other hydroxide precipitates are distinctly different from those corresponding to Be(OH)_(2),precipitates.This new method can be used to prepare most of the beryllium products that are prepared by modern beryllium metallurgy.
文摘Lithium metal batteries(LMBs)have attracted great intention due to the high energy density[1].Among various battery technologies,lithium-sulfur(Li-S)batteries are also very unique but important due to its high energy density,low cost and available sources[2].Although Li-s batteries exhibit high energy density,the cycling life is poor,especially for large-capacity pouch cells[3].The cycling performance of Li-s batteries is crucially determined by 16-electron complex sulfur reduction reaction(SRR)from S_(8)molecules to Li_(2)S,solid,which involves the multiple potential interwoven branches among lithium polysulfide intermediates(LiPS,e.g.,S_(8),Li_(2)S_(8),Li_(2)S_(6),Li_(2)S_(4)and Li_(2)S)[4].The obvious shuttle for soluble Lips across the cathode and anode leads to the battery capacity fading.Thus,it is necessary to decrease the accumulation of soluble Lips in the electrolyte through catalysts fastening the key conversion step from high-order polysulfides to insoluble Li_(2)S_(2)/Li_(2)S.Although some effort has been devoted to catalyze SRR,the complex mechanism remains unclear.To address this issue,Duan et al.tried to solve it based on nitrogen,sulfur,dualdoped holey graphene framework(N,S-HGF)electrocatalyst in Nature[5].
文摘Sulfur was typically regarded as a poison to precious metal complex catalysts in hydroformylation of olefins.However,the combination of sulfur and phosphine may present an intriguing interaction with heterogeneous mononuclear complex due to the difference of their electronegativities,and coordination capabilities.Herein,we report a novel sulfur-phosphine co-coordinated heterogeneous Rh mononuclear complex catalyst(Rh_(1)/POPs-PPh_(3)&S),which exhibits an unexpected 1.5–2.0 times catalytic activity for hydroformylation of olefins(C_(3)=,C_(5)=–C_(8)=),in comparison with the solely phosphine-coordinated Rh mononuclear complex catalyst(Rh_(1)/POPs-PPh_(3)).In contrast,sulfur coordination alone leads to severe sulfur poisoning with significantly inhibited catalytic performance.Experimental and theoretical analyses reveal that phosphine coordination promotes catalytic activity via its strong electron-donating ability,while sulfur occupies a coordination site and reduces the electronic density of Rh ions.The synergistical coordination of sulfur and phosphine optimizes the electronic density of active Rh ions and decreases the energy barrier of the rate-determining step of olefin insertion,thus enhancing the hydroformylation activity,regioselectivity and stability of Rh_(1)/POPs-PPh_(3)&S.
基金supported by General Program of National Natural Science Foundation of China (22178385)。
文摘In this work,a new process for achieving the recovery of elemental sulfur by utilizing a fluidized catalytic cracking(FCC) riser reactor for SOxtreatment(FCC-DeSOx) is proposed.The process leverages the high temperatures and hydrocarbon concentrations in the FCC riser reactor to convert SOxinto H_(2)S.Subsequently,H_(2)S,along with the cracked gas,is processed downstream to produce sulfur.Thermodynamic analysis of the key reduction reactions in the FCC-DeSOxprocess revealed that complete conversion of SOxto H_(2)S is feasible in the dry gas(hydrogen-rich) prelift zone,as well as the upper and lower zones of the riser,upon achieving thermodynamic equilibrium.Experimental studies were conducted to replicate the conditions of these reaction zones using a low concentration of hydrogen gas as the reducing agent.Through process optimization,investigation of the minimum reaction time,and kinetic studies,the potential of this method for the complete reduction of SOxwas further confirmed.
基金financially supported by the National Natural Science Foundation of China(52372289 and 52102368)Guangdong Special Fund for Key Areas(20237DZX3042)+2 种基金State Key Laboratory of New Ceramic Materials Tsinghua University(No.KF202415)Shenzhen Stable Support Projectsupported by the Centre for Advances in Reliability and Safety(CAiRS)admitted under AIR@Inno HK Research Cluster and HK Poly U Postdoc Matching Fund Scheme(1-W28H)。
文摘High-entropy oxides(HEOs)have sparked scientific interest recently as a potential material technology for lithium-sulfur(Li–S)batteries.This interest stems from their simultaneous roles as sulfur hosts and electrocatalysts,which provide enhancements to the performance of sulfur cathode composites.Nonetheless,their incorporation into the active material blend results in compromised energy density,particularly when their gravimetric proportion is substantial(≥10 wt.%,in the sulfur-based cathode).
基金the National Natural Science Foundation of China(Nos.22075027,52003030)Starting Grant from Beijing Institute of Technology and financial support from the State Key Laboratory of Explosion Science and Safety Protection(Nos.YBKT2106,YBKT23-05)Beijing Institute of Technology Research Fund Program for Young Scholars。
文摘Despite significant progress has been achieved regarding the shuttle-effect of lithium polysulfides,the suppressed specific capacity and retarded redox kinetics under high sulfur loading still threat the actual energy density and power density of lithium-sulfur batteries.In this study,a graham condenser-inspired carbon@WS_(2)host with coil-in-tube structure was designed and synthesized using anodic aluminum oxide(AAO)membrane with vertically aligned nanopores as template.The vertical array of carbon nanotubes with internal carbon coils not only leads to efficient charge transfer across through the thickness of the cathode,but also provides significant confinement to polysulfide diffusion towards both the lateral and longitudinal directions.Few-layer WS_(2)in the carbon coils perform a synergistic role in suppressing the shuttle-effect as well as boosting the cathodic kinetics.As a result,high specific capacity(1180 m Ah/g at 0.1 C)and long-cycling stability at 0.5 C for 500 cycles has been achieved at 3 mgS/cm^(2).Impressive areal capacity of 7.4 m Ah/cm^(2)has been demonstrated when the sulfur loading reaches 8.4 mg/cm^(2).The unique coil-in-tube structure developed in this work provides a new solution for high sulfur loading cathode towards practical lithium-sulfur batteries.
基金partially supported by grants from the National Natural Science Foundation of China(No.52072099)Team program of the Natural Science Foundation of Heilongjiang Province,China(No.TD2021E005)Joint Guidance Project of the Natural Science Foundation of Heilongjiang Province,China(No.LH2022E093)。
文摘Many catalysts have shown excellent activity for the sulfur reduction reaction(SRR),but sluggish electrochemistry kinetics have hindered the development of lithium-sulfur batteries.It has been found that the activity of catalysts for the sulfur evolution reaction(SER)plays a crucial role in determining the overall reaction kinetics.To address this issue,the rational design of catalysts is crucial.Here,we proposed a popular rule to accelerate SER by using chip-like high-entropy perovskite oxide La_(0.7)Sr_(0.3)(Fe_(0.2)Co_(0.2)Ni_(0.2)Zn_(0.2)Mn_(0.2))O_(3-δ)(LMO-HEO)as advanced electrocatalysts.The strong interaction between the adjacent metal atoms in different metals of LMO-HEO electrocatalysts could lead to a"cocktail effect",which not only greatly improved the catalytic capacity toward sulfur species,but also accelerated the oxidation reaction kinetics of Li_2S.As a result,the S/La_(0.7)Sr_(0.3)(Fe_(0.2)Co_(0.2)Ni_(0.2)Zn_(0.2))Mn_(0.2)O_(3-δ)cathodes delivered excellent cyclic stability with a capacity decay of only 0.025%after 1200 cycles at 2 C.This work has provided a rational design idea for new multifunctional electrocatalysts with high catalytic capacity.
