Developing highly efficient,durable,and non-noble electrocatalysts for the sluggish anodic oxygen evolution reaction(OER)is the pivotal for meeting the practical demand in water splitting.However,the current transitio...Developing highly efficient,durable,and non-noble electrocatalysts for the sluggish anodic oxygen evolution reaction(OER)is the pivotal for meeting the practical demand in water splitting.However,the current transition-metal electrocatalysts still suffer from low activity and durability on account of poor interfacial reaction kinetics.In this work,a facile solid-state synthesis strategy is developed to construct transition-metal sulfides heterostructures(denoted as MS_(2)/NiS_(2),M=Mo or W)for boosting OER electrocatalysis.As a result,MoS2/NiS2 and WS2/NiS2 show lower overpotentials of 300 mV and 320 mV to achieve the current density of 10 mA·cm^(-2),and smaller Tafel slopes of 60 mV.dec^(-1) and 83 mV.dec^(-1)in 1 mol·L^(-1) KOH,respectively,in comparison with the single MoS2,WS2,NiS2,as well as even the benchmark RuO2.The experiments reveal that the designed heterostructures have strong electronic interactions and spontaneously develop a built-in electric field at the heterointerface with uneven charge distribution based on the difference of band structures,which promote interfacial charge transfer,improve absorptivity of OH-,and modulate the energy level more comparable to the OER.Thus,the designed transition-metal sulfides heterostructures exhibit a remarkably high electrocatalytic activity for OER.This study provides a simple strategy to manipulate the heterostructure interface via an energy level engineering method for OER and can be extended to fabricate other heterostructures for various energy-related applications.展开更多
Hydrogen sulfide(H_(2)S)is a toxic,essential gas used in various biological and physical processes and has been the subject of many targeted studies on its role as a new gas transmitter.These studies have mainly focus...Hydrogen sulfide(H_(2)S)is a toxic,essential gas used in various biological and physical processes and has been the subject of many targeted studies on its role as a new gas transmitter.These studies have mainly focused on the production and pharmacological side effects caused by H_(2)S.Therefore,effective strategies to remove H_(2)S has become a key research topic.Furthermore,the development of novel nanoplatforms has provided new tools for the targeted removal of H_(2)S.This paper was performed to review the association between H_(2)S anddisease,relatedH_(2)S inhibitory drugs,aswell as H_(2)S responsive nanoplatforms(HRNs).This review first analyzed the role of H_(2)S in multiple tissues and conditions.Second,common drugs used to eliminate H_(2)S,as well as their potential for combination with anticancer agents,were summarized.Not only the existing studies on HRNs,but also the inhibition H_(2)S combined with different therapeutic methods were both sorted out in this review.Furthermore,this review provided in-depth analysis of the potential of HRNs about treatment or detection in detail.Finally,potential challenges of HRNs were proposed.This study demonstrates the excellent potential of HRNs for biomedical applications.展开更多
The production of toxic sulfides is a common environmental problem in mariculture.Therefore,the effective inhibition of sulfidogens is the key to prevent sulfides production.In this study,the possibility and mechanism...The production of toxic sulfides is a common environmental problem in mariculture.Therefore,the effective inhibition of sulfidogens is the key to prevent sulfides production.In this study,the possibility and mechanism of nitrate(NO_(3)^(−))inhibiting the activity of the sulfate-reducing microbiota(SRM)from mariculture sediments was investigated.The results showed that 1,3,and 5 mmol L^(−1)NO_(3)^(−)continuously inhibited sulfide production for 1-3 d.As NO_(3)^(−) dosage increased to 7 mmol L^(−1),the duration of inhibition increased to 6 days.Denitrifying product NO_(2)^(−)heavily inhibited the activity of dissimilar sulfate reductase gene(dsrB)by 3 orders,which was the main reason that the sulfate-reducing activity was inhibited.The SRM structure changed significantly with the dosage of NO_(3)^(−),while the abundance of sulfidogens Desulfovibrio species increased due to their capability of detoxifying nitrite through nitrite reductase.Hence,sulfidogens Desulfovibrio species are more adaptable to a high nitrate/nitrite environment,and the traditional control strategies by dosing nitrate/nitrite should be paid more attention to.The findings will serve as helpful guidelines for sulfate-reducing microbiota in the habitat of mariculture to reduce their generation of poisonous sulfide.展开更多
The solubility of H_(2)S was measured in solutions of N-butyl-N-methylmorpholine acetate([Bmmorp][Ac])containing 20%-40%(mass)water at experimental temperatures ranged from 298.15 to 328.15 K and pressures up to 320 k...The solubility of H_(2)S was measured in solutions of N-butyl-N-methylmorpholine acetate([Bmmorp][Ac])containing 20%-40%(mass)water at experimental temperatures ranged from 298.15 to 328.15 K and pressures up to 320 k Pa.The total solubility of H_(2)S increased with higher temperatures,lower pressures,and reduced water content.The reaction equilibrium thermodynamic model was used to correlate the solubility data.The results indicate that the chemical reaction equilibrium constant decrease with increasing water content and temperature,whereas Henry constant increase with increasing water content and temperature.Compared with other ionic liquids,H_(2)S exhibits a higher physical absorption enthalpy and a lower chemical absorption enthalpy in[Bmmorp][Ac]aqueous solution.This suggests that[Bmmorp][Ac]has a strong physical affinity for H_(2)S and low energy requirement for desorption.Quantum chemical methods were used to investigate the molecular mechanism of H_(2)S absorption in ionic liquids.The interaction energy analysis revealed that the binding of H_(2)S with the ionic liquid in a1:2 ratio is more stable.Detailed analyses by the methods of the interaction region indicator and the atoms in molecules were conducted to the interactions between H_(2)S and the ionic liquid.展开更多
The flotation separation of Cu–Fe sulfide minerals at low alkalinity can be achieved using selective depressants.In the flotation system of Cu–Fe sulfide minerals,depressants usually preferentially interact with the...The flotation separation of Cu–Fe sulfide minerals at low alkalinity can be achieved using selective depressants.In the flotation system of Cu–Fe sulfide minerals,depressants usually preferentially interact with the pyrite surface to render the mineral surface hydrophilic and hinder the adsorption of the collector.This review summarizes the advances in depressants for the flotation separation of Cu–Fe sulfide minerals at low alkalinity.These advances include use of inorganic depressants (oxidants and sulfur–oxygen compounds),natural polysaccharides (starch,dextrin,konjac glucomannan,and galactomannan),modified polymers (carboxymethyl cellulose,polyacrylamide,lignosulfonate,and tricarboxylate sodium starch),organic acids (polyglutamic acid,sodium humate,tannic acid,pyrogallic acid,salicylic acid,and lactic acid),sodium dimethyl dithiocarbamate,and diethylenetriamine.The potential application of specific inorganic and organic depressants in the flotation separation of Cu–Fe sulfide minerals at low alkalinity is reviewed.The advances in the use of organic depressants with respect to the flotation separation of Cu–Fe sulfide minerals are comprehensively detailed.Additionally,the depression performances and mechanisms of different types of organic depressants on mineral surfaces are summarized.Finally,several perspectives on depressants vis-à-vis flotation separation of Cu–Fe sulfide minerals at low alkalinity are proposed.展开更多
Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au...Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au nanoparticles(NPs)(denoted as HP-Au@CoxSy@ZIF-67)hybrid is synthesized by low-temperature sulfuration treatment.The well-defined macroporous-mesoporous-microporous structure is obtained based on the combination of polystyrene spheres,as-formed CoxSy nanosheets,and ZIF-67 frameworks.This novel three-dimensional hierarchical structure significantly enlarges the three-phase interfaces,accelerating the mass transfer and exposing the active centers for oxygen evolution reaction.The electronic structure of Co is modulated by Au through charge transfer,and a series of experiments,together with theoretical analysis,is performed to ascertain the electronic modulation of Co by Au.Meanwhile,HP-Au@CoxSy@ZIF-67 catalysts with different amounts of Au were synthesized,wherein Au and NaBH4 reductant result in an interesting“competition effect”to regulate the relative ratio of Co^(2+)/Co^(3+),and moderate Au assists the electrochemical performance to reach the highest value.Consequently,the optimized HP-Au@CoxSy@ZIF-67 exhibits a low overpotential of 340 mV at 10 mA cm^(-2)and a Tafel slope of 42 mV dec-1 for OER in 0.1 M aqueous KOH,enabling efficient water splitting and Zn-air battery performance.The work here highlights the pivotal roles of both microstructural and electronic modulation in enhancing electrocatalytic activity and presents a feasible strategy for designing and optimizing advanced electrocatalysts.展开更多
We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed ...We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed laser ablation of Co,Fe,Ti,and Mo metals in acetone.The interaction between carbon s-p-orbitals and metal d-orbitals causes a redistribution of valence structure through charge transfer,leading to the formation of surface defects as observed by X-ray photoelectron spectroscopy.These defects influence the evolved TMCs,making them effective for hydrogen and oxygen evolution reactions(HER and OER)in an alkaline medium.Co_(3)C with more oxygen affinity promoted CoO(OH)intermediates,and the electrochemical surface oxidation to Co_(3)O_(4)was captured via in situ/operando electrochemical Raman probes,increasing the number of active sites for OER activity.MoC with more d-vacancies exhibits strong hydrogen binding,promoting HER kinetics,whereas Fe_(3)C and TiC with more defect states to trap charge carriers may hinder both OER and HER activities.The results show that the assembled membrane-less electrolyzer with Co_(3)C∥Co_(3)C and MoC∥MoC electrodes requires~2.01 and 1.99 V,respectively,to deliver a 10 mA cm−2 with excellent electrochemical and structural stability.In addition,the ascertained pulsed laser synthesis mechanism and unit-cell packing relations will open up sustainable pathways for obtaining highly stable electrocatalysts for electrolyzers.展开更多
Although the internal electric field(IEF)of photocatalysts is acknowledged as a potent driving force for photocharge separation,modulating the IEF intensity to achieve enhanced photocatalytic performances remains a ch...Although the internal electric field(IEF)of photocatalysts is acknowledged as a potent driving force for photocharge separation,modulating the IEF intensity to achieve enhanced photocatalytic performances remains a challenge.Herein,cuprous sulfide nanosheets with different Cu vacancy concentration were employed to study IEF modulation and corresponding direct charge transfer.Among the samples,Cu_(1.8)S nanosheets possessed intensified IEF intensity compared with those of Cu_(2)S and Cu_(1.95)S nanosheets,suggesting that an enhanced IEF intensity could be achieved by introducing more Cu vacancies.This intensified IEF of Cu_(1.8)S nanosheets induced numerous photogenerated electrons to migrate to its surface,and the dissociative electrons were then captured by Cu vacancies,resulting in efficient charge separation spatially.In addition,the Cu vacancies on Cu_(1.8)S nanosheets accumulated electrons as active sites to lower the energy barrier of rate-determining step of CO_(2)photoreduction,leading to the selective conversion of CO_(2)to CO.Herein,the manipulation of IEF intensity through Cu vacancy concentration regulation of cuprous sulfide photocatalysts for efficient charge separation has been discussed,providing a scientific strategy to rationally improve photocata lytic performances for solar energy conversion.展开更多
The pathophysiology of Huntington's disease involves high levels of the neurotoxin quinolinic acid. Quinolinic acid accumulation results in oxidative stress, which leads to neurotoxicity. However, the molecular an...The pathophysiology of Huntington's disease involves high levels of the neurotoxin quinolinic acid. Quinolinic acid accumulation results in oxidative stress, which leads to neurotoxicity. However, the molecular and cellular mechanisms by which quinolinic acid contributes to Huntington's disease pathology remain unknown. In this study, we established in vitro and in vivo models of Huntington's disease by administering quinolinic acid to the PC12 neuronal cell line and the striatum of mice, respectively. We observed a decrease in the levels of hydrogen sulfide in both PC12 cells and mouse serum, which was accompanied by down-regulation of cystathionine β-synthase, an enzyme responsible for hydrogen sulfide production. However, treatment with NaHS(a hydrogen sulfide donor) increased hydrogen sulfide levels in the neurons and in mouse serum, as well as cystathionine β-synthase expression in the neurons and the mouse striatum, while also improving oxidative imbalance and mitochondrial dysfunction in PC12 cells and the mouse striatum. These beneficial effects correlated with upregulation of nuclear factor erythroid 2-related factor 2 expression. Finally, treatment with the nuclear factor erythroid 2-related factor 2inhibitor ML385 reversed the beneficial impact of exogenous hydrogen sulfide on quinolinic acid-induced oxidative stress. Taken together, our findings show that hydrogen sulfide reduces oxidative stress in Huntington's disease by activating nuclear factor erythroid 2-related factor 2,suggesting that hydrogen sulfide is a novel neuroprotective drug candidate for treating patients with Huntington's disease.展开更多
Lithium-sulfur(Li-S)batteries are considered as one of the most promising candidates for next-generation energy storage systems with high energy density and reliable performance.However,the commercial applications of ...Lithium-sulfur(Li-S)batteries are considered as one of the most promising candidates for next-generation energy storage systems with high energy density and reliable performance.However,the commercial applications of lithium-sulfur batteries is hindered by several shortcomings like the poor conductivity of sulfur and its reaction products,and the loss of active materials owing to the diffusion of lithium polysulfides(LiPSs)into the electrolyte.Hence,the effective restraining of the LiPSs and the promotion of the sluggish conversion are highly demanded to fulfill the potential of lithium-sulfur batteries.Here,we summarize the applications of transition-metal sulfides(TMSs)in the cathodes over recent years and demonstrate the unique advantages they possess to realize reliable long-life lithium-sulfur batteries.展开更多
Nitrogen-doped carbon-coated transition-metal sulfides(TMS@NCs)have been considered as efficient anodes for sodium-ion batteries.However,the uncontrollable morphology and weak core-shell binding forces significantly l...Nitrogen-doped carbon-coated transition-metal sulfides(TMS@NCs)have been considered as efficient anodes for sodium-ion batteries.However,the uncontrollable morphology and weak core-shell binding forces significantly limit the sodium storage performance and life.Herein,based on the reversible ring-opening reaction of the epoxy group of the tertiary amino group-rich epoxide cationic polyacrylamide(ECP)at the beginning of hydrothermal process(acidic environment)and the irreversible ring-opening(cross-linking reactions)at the late hydrothermal period(alkaline environment),47 nm-sized ZnS@NCs were prepared via a one-pot hydrothermal process.During this process,the covalent bonds formed between the ZnS core and elastic carbon shell significantly improved the mechanical and chemical stabilities of ZnS@NC.Benefiting from the nanosize,fast ion/electron transfer,and high stability,ZnS@NC exhibited a high reversible capacity of 421.9 mAh g^(−1) at a current density of 0.1 A g^(−1) after 1000 cycles and a superior rate capability of 273.8 mAh g^(−1) at a current density of 5 A g^(−1).Moreover,via this universal synthesis strategy,a series of TMS@NCs,such as MoS_(2)@NC,NiS@NC,and CuS@NC were developed with excellent capacity and cyclability.展开更多
In order to better understand the thermodynamic properties of magnesium oxysulfate(MOS)cement,pure reagent was analyzed to prepare magnesium sulfide cement,non-isothermal kinetics calculation of the main hydration pro...In order to better understand the thermodynamic properties of magnesium oxysulfate(MOS)cement,pure reagent was analyzed to prepare magnesium sulfide cement,non-isothermal kinetics calculation of the main hydration products was also carried out,and the conversion process of magnesium sulfide cement 517 phase at different temperatures was investigated.Composition of magnesium sulfide cement prepared was measured by XRD technique,and decomposed by a comprehensive thermal analyzer,and DSC curves of magnesium sulfide cement under different temperature rising rates were processed by Kinssinger method and Dolye-Ozawa method.According to the TG-DSC curves of magnesium sulfide cement,the thermal decomposition reaction process can be divided into five stages under normal conditions.The DSC curve was processed by Kinssinger method and Dolye-Ozawa method,and the kinetic analysis was carried out to calculate the 517 phase activation energy of magnesium sulfide cement.The three stages correspond to different activation energies.Therefore,flame retardant mechanism and thermal decomposition mechanism of magnesium sulfide cement based materials are deduced.展开更多
A copper-based non-aqueous-phase desulfurization agent is prepared by adding CuCl_(2) to the solvent N,Ndimethylformamide(DMF).Static desulfurization experiments show that the agent has high efficiency.However,the des...A copper-based non-aqueous-phase desulfurization agent is prepared by adding CuCl_(2) to the solvent N,Ndimethylformamide(DMF).Static desulfurization experiments show that the agent has high efficiency.However,the desulfurization reaction leads to the formation of a copper sulfide precipitate.It is found that the addition of chloride ions in the form of hydrochloric acid or potassium chloride prevents the formation of copper sulfide,and elemental sulfur is precipitated instead.The efficient absorption of H2S by the Cu/HCl–DMF agent relies on the rapid coordination of Cu^(2+)with DMF,Cl^(−),and H2S molecules to form a[Cu(DMF)_(n−p)(HS−)_(p)(Cl−)_(m)]_((2−p−m))+complex.The desulfurization agent has a sulfur capacity of up to 9.81 g/L when used in static bubble desulfurization at atmospheric pressure.The system has low viscosity and good chemical and thermal stability.It can be rapidly regenerated through continuous oxidation.After five repetitions of the regeneration procedure,the sulfur capacity reaches more than 91%of the initial capacity,indicating the potential of the system for commercial applications.展开更多
Water electrolysis is a promising technology to produce hydrogen but it was severely restricted by the slow oxygen evolution reaction(OER).Herein,we firstly reported an advanced electrocatalyst of MOF-derived hollow Z...Water electrolysis is a promising technology to produce hydrogen but it was severely restricted by the slow oxygen evolution reaction(OER).Herein,we firstly reported an advanced electrocatalyst of MOF-derived hollow Zn-Co-Ni sulfides(ZnS@Co_(9)S_(8)@Ni_(3)S_(2)-1/2,abbreviated as ZCNS-1/2)nanosword arrays(NSAs)with remarkable hydrogen evolution reaction(HER),OER and corresponding water electrolysis performance.To reach a current density of 10 mA cm^(-2),the cell voltage of assembled ZCNS-1/2//ZCNS-1/2 for urea electrolysis(1.314 V)is 208 mV lower than that for water electrolysis(1.522 V)and stably catalyzed for over 15 h,substantially outperforming the most reported water and urea electrolysis electrocatalysts.Density functional theory calculations and experimental result clearly reveal that the properties of large electrochemical active surface area(ECSA)caused by hollow NSAs and fast charge transfer resulted from the Co_(9)S_(8)@Ni_(3)S_(2) heterostructure endow the ZCNS-1/2 electrode with an enhanced electrocatalytic performance.展开更多
Sulfide solid electrolytes are promising for high energy density and safety in all-solid-state batteries due to their high ionic conductivity and good mechanical properties.However,the application of sulfide solid ele...Sulfide solid electrolytes are promising for high energy density and safety in all-solid-state batteries due to their high ionic conductivity and good mechanical properties.However,the application of sulfide solid electrolytes in all-solid-state batteries with lithium anode is restricted by the side reactions at lithium/electrolytes interfaces and the growth of lithium dendrite caused by nonuniform lithium deposition.Herein,a homogeneous LiF-Li_(3)N composite protective layer is in situ formed via a manipulated reaction of pentafluorobenzamide with Li metal.The LiF-Li_(3)N layer with both high interfacial energy and interfacial adhesion energy can synergistically suppress side reactions and inhibit the growth of lithium dendrite,achieving uniform deposition of lithium.The critical current densities of Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl are increased to 3.25 and 1.25 mA cm^(-2)with Li@LiF-Li_(3)N layer,which are almost triple and twice as those of Li-symmetric cells in the absence of protection layer,respectively.Moreover,the Li@LiF-Li_(3)N/Li10GeP2S12/Li@LiF-Li_(3)N cell can stably cycle for 9000 h at 0.1 mA cm^(-2)under 0.1 mA h cm^(-2),and Li@LiF-Li_(3)N/Li_(6)PS_(5)Cl/Li@LiF-Li_(3)N cell achieves stable Li plating/stripping for 8000 h at 0.1 mA cm^(-2)under10 m A h cm^(-2).The improved dynamic stability of lithium plating/stripping in Li@LiF-Li_(3)N/Li_(10)GeP_(2)S_(12)or Li_(6)PS_(5)Cl interfaces is proved by three-electrode cells.As a result,LiCoO_(2)/electrolytes/Li@LiF-Li_(3)N batteries with Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl exhibit remarkable cycling stability of 500 cycles with capacity retentions of 93.5%and 89.2%at 1 C,respectively.展开更多
High energy density Li-CO_(2)batteries have attracted much attention owing to the"two birds with one stone"feature in fixing greenhouse gas CO_(2)and providing renewable energy.However,poor reversibility of ...High energy density Li-CO_(2)batteries have attracted much attention owing to the"two birds with one stone"feature in fixing greenhouse gas CO_(2)and providing renewable energy.However,poor reversibility of the discharge product Li_(2)CO_(3)is one of the main problems that limit its application,resulting in poor cycling stability and severe polarization.Herein,copper indium sulfide(CIS),a semiconducting non-precious metal sulfide,is fabricated as cathode catalysts for high-performance Li-CO_(2)batteries.Combined with the synergistic effect of bimetallic valence bonding and coordinated electron transfer,Li-CO_(2)batteries using CIS cathodes exhibit high full specific discharge capacity,excellent rate capability and cycle stability,namely it delivers a high specific full discharge capacity of 8878μAh cm^(-2),runs steadily from 10 to 100μA cm^(-2),and performs a stable long-term cycling behavior(>1050 h)under a high energy efficiency of 84%and a low charge voltage of approximately 3.4 V at 20μA cm^(-2)within 100μAh cm^(-2).In addition,a flexible Li-CO_(2)pouch cell is constructed to reveal the potential of employing CIS to fabricate flexible high energy storage devices in practical applications.This work shows a promising development pathway toward next-generation sustainable energy storage devices.展开更多
BACKGROUND Ferroptosis can induce low retention and engraftment after mesenchymal stem cell(MSC)delivery,which is considered a major challenge to the effectiveness of MSC-based pulmonary arterial hypertension(PAH)ther...BACKGROUND Ferroptosis can induce low retention and engraftment after mesenchymal stem cell(MSC)delivery,which is considered a major challenge to the effectiveness of MSC-based pulmonary arterial hypertension(PAH)therapy.Interestingly,the cystathionineγ-lyase(CSE)/hydrogen sulfide(H_(2)S)pathway may contribute to mediating ferroptosis.However,the influence of the CSE/H_(2)S pathway on ferroptosis in human umbilical cord MSCs(HUCMSCs)remains unclear.AIM To clarify whether the effect of HUCMSCs on vascular remodelling in PAH mice is affected by CSE/H_(2)S pathway-mediated ferroptosis,and to investigate the functions of the CSE/H_(2)S pathway in ferroptosis in HUCMSCs and the underlying mechanisms.METHODS Erastin and ferrostatin-1(Fer-1)were used to induce and inhibit ferroptosis,respectively.HUCMSCs were transfected with a vector to overexpress or inhibit expression of CSE.A PAH mouse model was established using 4-wk-old male BALB/c nude mice under hypoxic conditions,and pulmonary pressure and vascular remodelling were measured.The survival of HUCMSCs after delivery was observed by in vivo bioluminescence imaging.Cell viability,iron accumulation,reactive oxygen species production,cystine uptake,and lipid peroxidation in HUCMSCs were tested.Ferroptosis-related proteins and S-sulfhydrated Kelchlike ECH-associating protein 1(Keap1)were detected by western blot analysis.RESULTS In vivo,CSE overexpression improved cell survival after erastin-treated HUCMSC delivery in mice with hypoxiainduced PAH.In vitro,CSE overexpression improved H_(2)S production and ferroptosis-related indexes,such as cell viability,iron level,reactive oxygen species production,cystine uptake,lipid peroxidation,mitochondrial membrane density,and ferroptosis-related protein expression,in erastin-treated HUCMSCs.In contrast,in vivo,CSE inhibition decreased cell survival after Fer-1-treated HUCMSC delivery and aggravated vascular remodelling in PAH mice.In vitro,CSE inhibition decreased H_(2)S levels and restored ferroptosis in Fer-1-treated HUCMSCs.Interestingly,upregulation of the CSE/H_(2)S pathway induced Keap1 S-sulfhydration,which contributed to the inhibition of ferroptosis.CONCLUSION Regulation of the CSE/H_(2)S pathway in HUCMSCs contributes to the inhibition of ferroptosis and improves the suppressive effect on vascular remodelling in mice with hypoxia-induced PAH.Moreover,the protective effect of the CSE/H_(2)S pathway against ferroptosis in HUCMSCs is mediated via S-sulfhydrated Keap1/nuclear factor erythroid 2-related factor 2 signalling.The present study may provide a novel therapeutic avenue for improving the protective capacity of transplanted MSCs in PAH.展开更多
Effectively strengthening the surface sulfidation is essential for recovering hemimorphite by froth flotation.In this work,inductively coupled plasma optical emission spectrometer(ICP-OES)measurements,Visual MINTEQ ca...Effectively strengthening the surface sulfidation is essential for recovering hemimorphite by froth flotation.In this work,inductively coupled plasma optical emission spectrometer(ICP-OES)measurements,Visual MINTEQ calculation,X-ray photoelectron spectroscopy(XPS)analysis,time of flight secondary ion mass spectrometry(ToF-SIMS)analysis,and micro-flotation experiments were explored to systematically investigate the effect of ammonium sulfate((NH_(4))_(2)SO_(4))on the formation of zinc sulfide species on hemimorphite surface and its role in sulfidation flotation.The results showed that(NH_(4))_(2)SO_(4)exhibited a positive influence on hemimorphite sulfidation flotation.It was ascribed to the number of zinc components in the form of Zn^(2+)and[Zn(NH_(3))_(i)]^(2+)(i=1–4)increased in the flotation system after hemimorphite treatment with(NH_(4))_(2)SO_(4),which was beneficial to its interaction with sulfur species in solution,resulting in a dense and stable zinc sulfide layer generated on the hemimorphite surface.[Zn(NH_(3))_(i)]^(2+)participated in the sulfidation reaction of hemimorphite as a transition state.In addition the sulfidation reaction of hemimorphite was accelerated by(NH_(4))_(2)SO_(4).Thus,(NH_(4))_(2)SO_(4)presents a vital role in promoting the sulfidation of hemimorphite.展开更多
Sustainable production of H2 through electrochemical water splitting is of great importance in the foreseeable future.Transition-metal metaphosphates(TMMPs)have a three-dimensional(3D)open-framework structure and a hi...Sustainable production of H2 through electrochemical water splitting is of great importance in the foreseeable future.Transition-metal metaphosphates(TMMPs)have a three-dimensional(3D)open-framework structure and a high content of P(which exists as PO3-),and therefore have been recognized as highly efficient catalysts for oxygen evolution reaction(OER)and the bottleneck of electrochemical water splitting.Furthermore,TMMPs can also contribute to hydrogen evolution reaction(HER)in alkaline and neutral media by facilitating water dissociation,and thus,overall water splitting can be achieved using this kind of material.In this timely review,we summarize the recent advances in the synthesis of TMMPs and their applications in OER and HER.We present a brief introduction of the structure and synthetic strategies of TMMPs in the first two parts.Then,we review the latest progress made in research on TMMPs as OER,HER,and overall water-splitting electrocatalysts.In this part,the intrinsic activity of TMMPs as well as the current strategy for improving the catalytic activity will be discussed systematically.Finally,we present the future opportunities and the remaining challenges for the application of TMMPs in the electrocatalysis field.展开更多
基金supported by the National Natural Science Foun-dation of China(21922814,22138012,21961160745,21921005,22178349,22078333,22108281 and 31961133019)Excellent Member in Youth Innovation Promotion Association,Chinese Academy of Sciences(Y202014)Shandong Energy Institute(Grant Number SEI 1202133).
文摘Developing highly efficient,durable,and non-noble electrocatalysts for the sluggish anodic oxygen evolution reaction(OER)is the pivotal for meeting the practical demand in water splitting.However,the current transition-metal electrocatalysts still suffer from low activity and durability on account of poor interfacial reaction kinetics.In this work,a facile solid-state synthesis strategy is developed to construct transition-metal sulfides heterostructures(denoted as MS_(2)/NiS_(2),M=Mo or W)for boosting OER electrocatalysis.As a result,MoS2/NiS2 and WS2/NiS2 show lower overpotentials of 300 mV and 320 mV to achieve the current density of 10 mA·cm^(-2),and smaller Tafel slopes of 60 mV.dec^(-1) and 83 mV.dec^(-1)in 1 mol·L^(-1) KOH,respectively,in comparison with the single MoS2,WS2,NiS2,as well as even the benchmark RuO2.The experiments reveal that the designed heterostructures have strong electronic interactions and spontaneously develop a built-in electric field at the heterointerface with uneven charge distribution based on the difference of band structures,which promote interfacial charge transfer,improve absorptivity of OH-,and modulate the energy level more comparable to the OER.Thus,the designed transition-metal sulfides heterostructures exhibit a remarkably high electrocatalytic activity for OER.This study provides a simple strategy to manipulate the heterostructure interface via an energy level engineering method for OER and can be extended to fabricate other heterostructures for various energy-related applications.
基金supported by National Key Research and Development Program of China(contract No.2019YFA0904800)National Nature Science Foundation of China(32030065,31722033,92049304 to Y.Z.)+5 种基金Shanghai Sailing Program(contract No.21YF1410300)Science and Technology Commission of Shanghai Municipality(contract No.10DZ2220500)The Shanghai Committee of Science and Technology(grant No.11DZ2260600)Shanghai Frontiers Science Center of Optogenetic Techniques for CellMetabolism(Y.Z.)Research Unit of New Techniques for Live-cell Metabolic Imaging(Chinese Academy of Medical Sciences,2019-I2M-5-013 to Y.Z.)the State Key Laboratory of Bioreactor Engineering,the Fundamental Research Funds for the Central Universities.
文摘Hydrogen sulfide(H_(2)S)is a toxic,essential gas used in various biological and physical processes and has been the subject of many targeted studies on its role as a new gas transmitter.These studies have mainly focused on the production and pharmacological side effects caused by H_(2)S.Therefore,effective strategies to remove H_(2)S has become a key research topic.Furthermore,the development of novel nanoplatforms has provided new tools for the targeted removal of H_(2)S.This paper was performed to review the association between H_(2)S anddisease,relatedH_(2)S inhibitory drugs,aswell as H_(2)S responsive nanoplatforms(HRNs).This review first analyzed the role of H_(2)S in multiple tissues and conditions.Second,common drugs used to eliminate H_(2)S,as well as their potential for combination with anticancer agents,were summarized.Not only the existing studies on HRNs,but also the inhibition H_(2)S combined with different therapeutic methods were both sorted out in this review.Furthermore,this review provided in-depth analysis of the potential of HRNs about treatment or detection in detail.Finally,potential challenges of HRNs were proposed.This study demonstrates the excellent potential of HRNs for biomedical applications.
基金supported by the National Natural Science Foundation of China(No.41977315)the Fundamental Research Funds for the Central Universities of China(No.201964004).
文摘The production of toxic sulfides is a common environmental problem in mariculture.Therefore,the effective inhibition of sulfidogens is the key to prevent sulfides production.In this study,the possibility and mechanism of nitrate(NO_(3)^(−))inhibiting the activity of the sulfate-reducing microbiota(SRM)from mariculture sediments was investigated.The results showed that 1,3,and 5 mmol L^(−1)NO_(3)^(−)continuously inhibited sulfide production for 1-3 d.As NO_(3)^(−) dosage increased to 7 mmol L^(−1),the duration of inhibition increased to 6 days.Denitrifying product NO_(2)^(−)heavily inhibited the activity of dissimilar sulfate reductase gene(dsrB)by 3 orders,which was the main reason that the sulfate-reducing activity was inhibited.The SRM structure changed significantly with the dosage of NO_(3)^(−),while the abundance of sulfidogens Desulfovibrio species increased due to their capability of detoxifying nitrite through nitrite reductase.Hence,sulfidogens Desulfovibrio species are more adaptable to a high nitrate/nitrite environment,and the traditional control strategies by dosing nitrate/nitrite should be paid more attention to.The findings will serve as helpful guidelines for sulfate-reducing microbiota in the habitat of mariculture to reduce their generation of poisonous sulfide.
基金Financial support from the National Natural Science Foundation of China(21775081)Shandong Province Natural Science Foundation(ZR2020MB145)。
文摘The solubility of H_(2)S was measured in solutions of N-butyl-N-methylmorpholine acetate([Bmmorp][Ac])containing 20%-40%(mass)water at experimental temperatures ranged from 298.15 to 328.15 K and pressures up to 320 k Pa.The total solubility of H_(2)S increased with higher temperatures,lower pressures,and reduced water content.The reaction equilibrium thermodynamic model was used to correlate the solubility data.The results indicate that the chemical reaction equilibrium constant decrease with increasing water content and temperature,whereas Henry constant increase with increasing water content and temperature.Compared with other ionic liquids,H_(2)S exhibits a higher physical absorption enthalpy and a lower chemical absorption enthalpy in[Bmmorp][Ac]aqueous solution.This suggests that[Bmmorp][Ac]has a strong physical affinity for H_(2)S and low energy requirement for desorption.Quantum chemical methods were used to investigate the molecular mechanism of H_(2)S absorption in ionic liquids.The interaction energy analysis revealed that the binding of H_(2)S with the ionic liquid in a1:2 ratio is more stable.Detailed analyses by the methods of the interaction region indicator and the atoms in molecules were conducted to the interactions between H_(2)S and the ionic liquid.
基金financially supported by the Yunnan Major Scientific and Technological Projects,China (No.202202AG050015)the National Natural Science Foundation of China (No.51464029)。
文摘The flotation separation of Cu–Fe sulfide minerals at low alkalinity can be achieved using selective depressants.In the flotation system of Cu–Fe sulfide minerals,depressants usually preferentially interact with the pyrite surface to render the mineral surface hydrophilic and hinder the adsorption of the collector.This review summarizes the advances in depressants for the flotation separation of Cu–Fe sulfide minerals at low alkalinity.These advances include use of inorganic depressants (oxidants and sulfur–oxygen compounds),natural polysaccharides (starch,dextrin,konjac glucomannan,and galactomannan),modified polymers (carboxymethyl cellulose,polyacrylamide,lignosulfonate,and tricarboxylate sodium starch),organic acids (polyglutamic acid,sodium humate,tannic acid,pyrogallic acid,salicylic acid,and lactic acid),sodium dimethyl dithiocarbamate,and diethylenetriamine.The potential application of specific inorganic and organic depressants in the flotation separation of Cu–Fe sulfide minerals at low alkalinity is reviewed.The advances in the use of organic depressants with respect to the flotation separation of Cu–Fe sulfide minerals are comprehensively detailed.Additionally,the depression performances and mechanisms of different types of organic depressants on mineral surfaces are summarized.Finally,several perspectives on depressants vis-à-vis flotation separation of Cu–Fe sulfide minerals at low alkalinity are proposed.
基金National Natural Science Foundation of China,Grant/Award Numbers:52102260,52171211,51972220,61903235,U22A20145Shandong Provincial Natural Science Foundation,Grant/Award Numbers:ZR2020QB069,ZR2022ME051+4 种基金National Key Research and Development Program of China,Grant/Award Number:2022YFB4002004Scientific and Technological Innovation Ability Improvement Project of Minor Enterprises in Shandong Province,Grant/Award Number:2022TSGC1021Announce the List and Take Charge Project in Jinan,Grant/Award Number:202214012Major innovation project for integrating science,education and industry of Qilu University of Technology (Shandong Academy of Sciences),Grant/Award Numbers:2022JBZ01-07,2022PY044China Postdoctoral Science Foundation,Grant/Award Number:2022M711545。
文摘Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au nanoparticles(NPs)(denoted as HP-Au@CoxSy@ZIF-67)hybrid is synthesized by low-temperature sulfuration treatment.The well-defined macroporous-mesoporous-microporous structure is obtained based on the combination of polystyrene spheres,as-formed CoxSy nanosheets,and ZIF-67 frameworks.This novel three-dimensional hierarchical structure significantly enlarges the three-phase interfaces,accelerating the mass transfer and exposing the active centers for oxygen evolution reaction.The electronic structure of Co is modulated by Au through charge transfer,and a series of experiments,together with theoretical analysis,is performed to ascertain the electronic modulation of Co by Au.Meanwhile,HP-Au@CoxSy@ZIF-67 catalysts with different amounts of Au were synthesized,wherein Au and NaBH4 reductant result in an interesting“competition effect”to regulate the relative ratio of Co^(2+)/Co^(3+),and moderate Au assists the electrochemical performance to reach the highest value.Consequently,the optimized HP-Au@CoxSy@ZIF-67 exhibits a low overpotential of 340 mV at 10 mA cm^(-2)and a Tafel slope of 42 mV dec-1 for OER in 0.1 M aqueous KOH,enabling efficient water splitting and Zn-air battery performance.The work here highlights the pivotal roles of both microstructural and electronic modulation in enhancing electrocatalytic activity and presents a feasible strategy for designing and optimizing advanced electrocatalysts.
基金National Research Foundation of Korea,Grant/Award Numbers:2019H1D3A1A01071209,2021R1I1A1A01060380,2022R1A2C2010686,2022R1A4A3033528Korea Basic Science Institute,Grant/Award Numbers:2019R1A6C1010042,2021R1A6C103A427。
文摘We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed laser ablation of Co,Fe,Ti,and Mo metals in acetone.The interaction between carbon s-p-orbitals and metal d-orbitals causes a redistribution of valence structure through charge transfer,leading to the formation of surface defects as observed by X-ray photoelectron spectroscopy.These defects influence the evolved TMCs,making them effective for hydrogen and oxygen evolution reactions(HER and OER)in an alkaline medium.Co_(3)C with more oxygen affinity promoted CoO(OH)intermediates,and the electrochemical surface oxidation to Co_(3)O_(4)was captured via in situ/operando electrochemical Raman probes,increasing the number of active sites for OER activity.MoC with more d-vacancies exhibits strong hydrogen binding,promoting HER kinetics,whereas Fe_(3)C and TiC with more defect states to trap charge carriers may hinder both OER and HER activities.The results show that the assembled membrane-less electrolyzer with Co_(3)C∥Co_(3)C and MoC∥MoC electrodes requires~2.01 and 1.99 V,respectively,to deliver a 10 mA cm−2 with excellent electrochemical and structural stability.In addition,the ascertained pulsed laser synthesis mechanism and unit-cell packing relations will open up sustainable pathways for obtaining highly stable electrocatalysts for electrolyzers.
基金supported by the National Natural Science Foundation of China(52200123)the Open Project of Key Laboratory of Green Chemical Engineering Process of Ministry of Education(GCP2022007)the Scientific Research and Innovation Team Program of Sichuan University of Science and Engineering(SUSE652A014)。
文摘Although the internal electric field(IEF)of photocatalysts is acknowledged as a potent driving force for photocharge separation,modulating the IEF intensity to achieve enhanced photocatalytic performances remains a challenge.Herein,cuprous sulfide nanosheets with different Cu vacancy concentration were employed to study IEF modulation and corresponding direct charge transfer.Among the samples,Cu_(1.8)S nanosheets possessed intensified IEF intensity compared with those of Cu_(2)S and Cu_(1.95)S nanosheets,suggesting that an enhanced IEF intensity could be achieved by introducing more Cu vacancies.This intensified IEF of Cu_(1.8)S nanosheets induced numerous photogenerated electrons to migrate to its surface,and the dissociative electrons were then captured by Cu vacancies,resulting in efficient charge separation spatially.In addition,the Cu vacancies on Cu_(1.8)S nanosheets accumulated electrons as active sites to lower the energy barrier of rate-determining step of CO_(2)photoreduction,leading to the selective conversion of CO_(2)to CO.Herein,the manipulation of IEF intensity through Cu vacancy concentration regulation of cuprous sulfide photocatalysts for efficient charge separation has been discussed,providing a scientific strategy to rationally improve photocata lytic performances for solar energy conversion.
基金supported by the National Natural Science Foundation of China,Nos.82271327 (to ZW),82072535 (to ZW),81873768 (to ZW),and 82001253 (to TL)。
文摘The pathophysiology of Huntington's disease involves high levels of the neurotoxin quinolinic acid. Quinolinic acid accumulation results in oxidative stress, which leads to neurotoxicity. However, the molecular and cellular mechanisms by which quinolinic acid contributes to Huntington's disease pathology remain unknown. In this study, we established in vitro and in vivo models of Huntington's disease by administering quinolinic acid to the PC12 neuronal cell line and the striatum of mice, respectively. We observed a decrease in the levels of hydrogen sulfide in both PC12 cells and mouse serum, which was accompanied by down-regulation of cystathionine β-synthase, an enzyme responsible for hydrogen sulfide production. However, treatment with NaHS(a hydrogen sulfide donor) increased hydrogen sulfide levels in the neurons and in mouse serum, as well as cystathionine β-synthase expression in the neurons and the mouse striatum, while also improving oxidative imbalance and mitochondrial dysfunction in PC12 cells and the mouse striatum. These beneficial effects correlated with upregulation of nuclear factor erythroid 2-related factor 2 expression. Finally, treatment with the nuclear factor erythroid 2-related factor 2inhibitor ML385 reversed the beneficial impact of exogenous hydrogen sulfide on quinolinic acid-induced oxidative stress. Taken together, our findings show that hydrogen sulfide reduces oxidative stress in Huntington's disease by activating nuclear factor erythroid 2-related factor 2,suggesting that hydrogen sulfide is a novel neuroprotective drug candidate for treating patients with Huntington's disease.
基金This work was financially supported by the National Natural Science Foundation of China(Grant No.51872012)the National Key R&D Program of China(Grant No.2018YFA900)the Fundamental Research Funds for the Central Universities and the 111 Project(Grant No.B17002).
文摘Lithium-sulfur(Li-S)batteries are considered as one of the most promising candidates for next-generation energy storage systems with high energy density and reliable performance.However,the commercial applications of lithium-sulfur batteries is hindered by several shortcomings like the poor conductivity of sulfur and its reaction products,and the loss of active materials owing to the diffusion of lithium polysulfides(LiPSs)into the electrolyte.Hence,the effective restraining of the LiPSs and the promotion of the sluggish conversion are highly demanded to fulfill the potential of lithium-sulfur batteries.Here,we summarize the applications of transition-metal sulfides(TMSs)in the cathodes over recent years and demonstrate the unique advantages they possess to realize reliable long-life lithium-sulfur batteries.
基金supported by research grants from the National Research Foundation of Korea(Nos.2020R1I1A1A01072996,2021K2A9A2A06044652,and 2019H1D3A1A01069779)KIST Institutional Program(2E331863)funded by the government of the Republic of Korea.
文摘Nitrogen-doped carbon-coated transition-metal sulfides(TMS@NCs)have been considered as efficient anodes for sodium-ion batteries.However,the uncontrollable morphology and weak core-shell binding forces significantly limit the sodium storage performance and life.Herein,based on the reversible ring-opening reaction of the epoxy group of the tertiary amino group-rich epoxide cationic polyacrylamide(ECP)at the beginning of hydrothermal process(acidic environment)and the irreversible ring-opening(cross-linking reactions)at the late hydrothermal period(alkaline environment),47 nm-sized ZnS@NCs were prepared via a one-pot hydrothermal process.During this process,the covalent bonds formed between the ZnS core and elastic carbon shell significantly improved the mechanical and chemical stabilities of ZnS@NC.Benefiting from the nanosize,fast ion/electron transfer,and high stability,ZnS@NC exhibited a high reversible capacity of 421.9 mAh g^(−1) at a current density of 0.1 A g^(−1) after 1000 cycles and a superior rate capability of 273.8 mAh g^(−1) at a current density of 5 A g^(−1).Moreover,via this universal synthesis strategy,a series of TMS@NCs,such as MoS_(2)@NC,NiS@NC,and CuS@NC were developed with excellent capacity and cyclability.
基金Fund by the National Natural Science Foundation of China (No.51778101)the General Program (Key Program,Major Research Plan)of National Natural Science Foundation of China+2 种基金the National Key R&D Program (No.2020YFC1909304)the National Program on Key Basic Research Project of Chinathe Joint Fund Project of National Natural Fund of China (U1908227)。
文摘In order to better understand the thermodynamic properties of magnesium oxysulfate(MOS)cement,pure reagent was analyzed to prepare magnesium sulfide cement,non-isothermal kinetics calculation of the main hydration products was also carried out,and the conversion process of magnesium sulfide cement 517 phase at different temperatures was investigated.Composition of magnesium sulfide cement prepared was measured by XRD technique,and decomposed by a comprehensive thermal analyzer,and DSC curves of magnesium sulfide cement under different temperature rising rates were processed by Kinssinger method and Dolye-Ozawa method.According to the TG-DSC curves of magnesium sulfide cement,the thermal decomposition reaction process can be divided into five stages under normal conditions.The DSC curve was processed by Kinssinger method and Dolye-Ozawa method,and the kinetic analysis was carried out to calculate the 517 phase activation energy of magnesium sulfide cement.The three stages correspond to different activation energies.Therefore,flame retardant mechanism and thermal decomposition mechanism of magnesium sulfide cement based materials are deduced.
基金the China National Science and Technology Major Project(2016ZX05017)the Sinopec Group Corporation 2020 Science and Technology Project“Organic Sulfur Catalytic Hydrolysis Technology Improves Quality Research”(No.120049-1).
文摘A copper-based non-aqueous-phase desulfurization agent is prepared by adding CuCl_(2) to the solvent N,Ndimethylformamide(DMF).Static desulfurization experiments show that the agent has high efficiency.However,the desulfurization reaction leads to the formation of a copper sulfide precipitate.It is found that the addition of chloride ions in the form of hydrochloric acid or potassium chloride prevents the formation of copper sulfide,and elemental sulfur is precipitated instead.The efficient absorption of H2S by the Cu/HCl–DMF agent relies on the rapid coordination of Cu^(2+)with DMF,Cl^(−),and H2S molecules to form a[Cu(DMF)_(n−p)(HS−)_(p)(Cl−)_(m)]_((2−p−m))+complex.The desulfurization agent has a sulfur capacity of up to 9.81 g/L when used in static bubble desulfurization at atmospheric pressure.The system has low viscosity and good chemical and thermal stability.It can be rapidly regenerated through continuous oxidation.After five repetitions of the regeneration procedure,the sulfur capacity reaches more than 91%of the initial capacity,indicating the potential of the system for commercial applications.
基金financially supported by the National Science Foundation of China (Grant No.21802126).
文摘Water electrolysis is a promising technology to produce hydrogen but it was severely restricted by the slow oxygen evolution reaction(OER).Herein,we firstly reported an advanced electrocatalyst of MOF-derived hollow Zn-Co-Ni sulfides(ZnS@Co_(9)S_(8)@Ni_(3)S_(2)-1/2,abbreviated as ZCNS-1/2)nanosword arrays(NSAs)with remarkable hydrogen evolution reaction(HER),OER and corresponding water electrolysis performance.To reach a current density of 10 mA cm^(-2),the cell voltage of assembled ZCNS-1/2//ZCNS-1/2 for urea electrolysis(1.314 V)is 208 mV lower than that for water electrolysis(1.522 V)and stably catalyzed for over 15 h,substantially outperforming the most reported water and urea electrolysis electrocatalysts.Density functional theory calculations and experimental result clearly reveal that the properties of large electrochemical active surface area(ECSA)caused by hollow NSAs and fast charge transfer resulted from the Co_(9)S_(8)@Ni_(3)S_(2) heterostructure endow the ZCNS-1/2 electrode with an enhanced electrocatalytic performance.
基金supported by the National Key R&D Program of China(2022YFB3807700)the National Natural Science Foundation of China(U1964205,51872303,52172253)+3 种基金the Ningbo S&T Innovation 2025 Major Special Programme(2019B10044,2021Z122)the Zhejiang Provincial Key R&D Program of China(2022C01072)the Jiangsu Provincial S&T Innovation Special Programme for carbon peak and carbon neutrality(BE2022007)the Youth Innovation Promotion Association CAS(Y2021080)。
文摘Sulfide solid electrolytes are promising for high energy density and safety in all-solid-state batteries due to their high ionic conductivity and good mechanical properties.However,the application of sulfide solid electrolytes in all-solid-state batteries with lithium anode is restricted by the side reactions at lithium/electrolytes interfaces and the growth of lithium dendrite caused by nonuniform lithium deposition.Herein,a homogeneous LiF-Li_(3)N composite protective layer is in situ formed via a manipulated reaction of pentafluorobenzamide with Li metal.The LiF-Li_(3)N layer with both high interfacial energy and interfacial adhesion energy can synergistically suppress side reactions and inhibit the growth of lithium dendrite,achieving uniform deposition of lithium.The critical current densities of Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl are increased to 3.25 and 1.25 mA cm^(-2)with Li@LiF-Li_(3)N layer,which are almost triple and twice as those of Li-symmetric cells in the absence of protection layer,respectively.Moreover,the Li@LiF-Li_(3)N/Li10GeP2S12/Li@LiF-Li_(3)N cell can stably cycle for 9000 h at 0.1 mA cm^(-2)under 0.1 mA h cm^(-2),and Li@LiF-Li_(3)N/Li_(6)PS_(5)Cl/Li@LiF-Li_(3)N cell achieves stable Li plating/stripping for 8000 h at 0.1 mA cm^(-2)under10 m A h cm^(-2).The improved dynamic stability of lithium plating/stripping in Li@LiF-Li_(3)N/Li_(10)GeP_(2)S_(12)or Li_(6)PS_(5)Cl interfaces is proved by three-electrode cells.As a result,LiCoO_(2)/electrolytes/Li@LiF-Li_(3)N batteries with Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl exhibit remarkable cycling stability of 500 cycles with capacity retentions of 93.5%and 89.2%at 1 C,respectively.
基金supports by the National Natural Science Foundation of China(No.52072352,21875226,U20A2072,52102320)the Foundation for the Youth S&T Innovation Team of Sichuan Province(2020JDTD0035)+1 种基金Tianfu Rencai Plan,the Science Foundation for Distinguished Young Scholars of Sichuan Province(2017JQ0036)the Chengdu Talent plan,Science and Technology Projects for Administration for Market Regulation of Sichuan Province(SCSJ2020016).
文摘High energy density Li-CO_(2)batteries have attracted much attention owing to the"two birds with one stone"feature in fixing greenhouse gas CO_(2)and providing renewable energy.However,poor reversibility of the discharge product Li_(2)CO_(3)is one of the main problems that limit its application,resulting in poor cycling stability and severe polarization.Herein,copper indium sulfide(CIS),a semiconducting non-precious metal sulfide,is fabricated as cathode catalysts for high-performance Li-CO_(2)batteries.Combined with the synergistic effect of bimetallic valence bonding and coordinated electron transfer,Li-CO_(2)batteries using CIS cathodes exhibit high full specific discharge capacity,excellent rate capability and cycle stability,namely it delivers a high specific full discharge capacity of 8878μAh cm^(-2),runs steadily from 10 to 100μA cm^(-2),and performs a stable long-term cycling behavior(>1050 h)under a high energy efficiency of 84%and a low charge voltage of approximately 3.4 V at 20μA cm^(-2)within 100μAh cm^(-2).In addition,a flexible Li-CO_(2)pouch cell is constructed to reveal the potential of employing CIS to fabricate flexible high energy storage devices in practical applications.This work shows a promising development pathway toward next-generation sustainable energy storage devices.
基金the Natural Science Foundation of Shandong Province of China,No.ZR2021QH179 and ZR2020MH014.
文摘BACKGROUND Ferroptosis can induce low retention and engraftment after mesenchymal stem cell(MSC)delivery,which is considered a major challenge to the effectiveness of MSC-based pulmonary arterial hypertension(PAH)therapy.Interestingly,the cystathionineγ-lyase(CSE)/hydrogen sulfide(H_(2)S)pathway may contribute to mediating ferroptosis.However,the influence of the CSE/H_(2)S pathway on ferroptosis in human umbilical cord MSCs(HUCMSCs)remains unclear.AIM To clarify whether the effect of HUCMSCs on vascular remodelling in PAH mice is affected by CSE/H_(2)S pathway-mediated ferroptosis,and to investigate the functions of the CSE/H_(2)S pathway in ferroptosis in HUCMSCs and the underlying mechanisms.METHODS Erastin and ferrostatin-1(Fer-1)were used to induce and inhibit ferroptosis,respectively.HUCMSCs were transfected with a vector to overexpress or inhibit expression of CSE.A PAH mouse model was established using 4-wk-old male BALB/c nude mice under hypoxic conditions,and pulmonary pressure and vascular remodelling were measured.The survival of HUCMSCs after delivery was observed by in vivo bioluminescence imaging.Cell viability,iron accumulation,reactive oxygen species production,cystine uptake,and lipid peroxidation in HUCMSCs were tested.Ferroptosis-related proteins and S-sulfhydrated Kelchlike ECH-associating protein 1(Keap1)were detected by western blot analysis.RESULTS In vivo,CSE overexpression improved cell survival after erastin-treated HUCMSC delivery in mice with hypoxiainduced PAH.In vitro,CSE overexpression improved H_(2)S production and ferroptosis-related indexes,such as cell viability,iron level,reactive oxygen species production,cystine uptake,lipid peroxidation,mitochondrial membrane density,and ferroptosis-related protein expression,in erastin-treated HUCMSCs.In contrast,in vivo,CSE inhibition decreased cell survival after Fer-1-treated HUCMSC delivery and aggravated vascular remodelling in PAH mice.In vitro,CSE inhibition decreased H_(2)S levels and restored ferroptosis in Fer-1-treated HUCMSCs.Interestingly,upregulation of the CSE/H_(2)S pathway induced Keap1 S-sulfhydration,which contributed to the inhibition of ferroptosis.CONCLUSION Regulation of the CSE/H_(2)S pathway in HUCMSCs contributes to the inhibition of ferroptosis and improves the suppressive effect on vascular remodelling in mice with hypoxia-induced PAH.Moreover,the protective effect of the CSE/H_(2)S pathway against ferroptosis in HUCMSCs is mediated via S-sulfhydrated Keap1/nuclear factor erythroid 2-related factor 2 signalling.The present study may provide a novel therapeutic avenue for improving the protective capacity of transplanted MSCs in PAH.
基金Fundamental Research Funds for the Central Universities(No.2023YQTD03,2022JCCX HH09,2022YJSHH01)the Yueqi Outstanding Scholaraward of China University of Mining&Technology(Beijing)+3 种基金the National Natural Science Foundation of China(No.52274283)the National Key R&D Program of China(No.SQ2022YFC2900065)the Ordos Science&Technology Plan(No.202204&2023XM06)the Open Research Fund of State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization(No.CNMRCUKF 2107)。
文摘Effectively strengthening the surface sulfidation is essential for recovering hemimorphite by froth flotation.In this work,inductively coupled plasma optical emission spectrometer(ICP-OES)measurements,Visual MINTEQ calculation,X-ray photoelectron spectroscopy(XPS)analysis,time of flight secondary ion mass spectrometry(ToF-SIMS)analysis,and micro-flotation experiments were explored to systematically investigate the effect of ammonium sulfate((NH_(4))_(2)SO_(4))on the formation of zinc sulfide species on hemimorphite surface and its role in sulfidation flotation.The results showed that(NH_(4))_(2)SO_(4)exhibited a positive influence on hemimorphite sulfidation flotation.It was ascribed to the number of zinc components in the form of Zn^(2+)and[Zn(NH_(3))_(i)]^(2+)(i=1–4)increased in the flotation system after hemimorphite treatment with(NH_(4))_(2)SO_(4),which was beneficial to its interaction with sulfur species in solution,resulting in a dense and stable zinc sulfide layer generated on the hemimorphite surface.[Zn(NH_(3))_(i)]^(2+)participated in the sulfidation reaction of hemimorphite as a transition state.In addition the sulfidation reaction of hemimorphite was accelerated by(NH_(4))_(2)SO_(4).Thus,(NH_(4))_(2)SO_(4)presents a vital role in promoting the sulfidation of hemimorphite.
基金the Natural Science Foundation of China(Grant Nos.21871065,22209129,and 22071038)the Heilongjiang Touyan Team(HITTY-20190033)+3 种基金High-Level Innovation and Entrepreneurship(QCYRCXM-2022-123)the Talent Project of Qinchuangyuan and Interdisciplinary Research Foundation of HIT(IR2021205)Professor Li acknowledges the financial support from the“Young Talent Support Plan”of Xi'an Jiaotong University(HG6J024)the“Young Talent Lift Plan”of Xi'an city(095920221352).
文摘Sustainable production of H2 through electrochemical water splitting is of great importance in the foreseeable future.Transition-metal metaphosphates(TMMPs)have a three-dimensional(3D)open-framework structure and a high content of P(which exists as PO3-),and therefore have been recognized as highly efficient catalysts for oxygen evolution reaction(OER)and the bottleneck of electrochemical water splitting.Furthermore,TMMPs can also contribute to hydrogen evolution reaction(HER)in alkaline and neutral media by facilitating water dissociation,and thus,overall water splitting can be achieved using this kind of material.In this timely review,we summarize the recent advances in the synthesis of TMMPs and their applications in OER and HER.We present a brief introduction of the structure and synthetic strategies of TMMPs in the first two parts.Then,we review the latest progress made in research on TMMPs as OER,HER,and overall water-splitting electrocatalysts.In this part,the intrinsic activity of TMMPs as well as the current strategy for improving the catalytic activity will be discussed systematically.Finally,we present the future opportunities and the remaining challenges for the application of TMMPs in the electrocatalysis field.