A series of leaching and electrochemical experiments were conducted to elucidate the critical role of hydrogen sulfide(H_(2)S)in copper-driven reduction of chalcopyrite.Results demonstrate that in the absence of H_(2)...A series of leaching and electrochemical experiments were conducted to elucidate the critical role of hydrogen sulfide(H_(2)S)in copper-driven reduction of chalcopyrite.Results demonstrate that in the absence of H_(2)S,metallic copper converts chalcopyrite into bornite(Cu_(5)FeS_(4)).However,the introduction of H_(2)S promotes the formation of chalcocite(Cu_(2)S)by altering the oxidation pathway of copper.Electrochemical analysis demonstrates that the presence of H₂S significantly reduces the corrosion potential of copper from 0.251 to−0.223 V(vs SHE),reaching the threshold necessary for the formation of Cu_(2)S.Nevertheless,excessive H_(2)S triggers sulfate reduction via the reaction of 8Cu+H_(2)SO_(4)+3H_(2)S=4Cu_(2)S+4H_(2)O(ΔG=−519.429 kJ/mol at 50℃),leading to inefficient copper utilization.展开更多
High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instab...High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instability between the cathode and electrolyte.Given the surface alkalinity of NCM811,we propose a strategy to construct a solid-polymer-electrolyte(SPE)interphase on NCM811 surface by leveraging the surface alkaline residues to nucleophilically initiate the in-situ ring-opening polymerization of cyclic organic molecules.As a proof-of-concept,this study demonstrates that the ring-opening copolymerization of 1,3-dioxolane and maleic anhydride produces a homogeneous,compact,and conformal SPE layer on NCM811 surface to prevent the cathode from contact and reaction with Li6PS5Cl solid-state electrolyte.Consequently,the SPE-modified-NCM811 in ASSLBs exhibits high capacities of 193.5 mA h g^(-1) at 0.2 C,160.9 mA h g^(-1) at 2.0 C and 112.3 mA h g^(-1) at 10 C,and particularly,excellent long-term cycling stabilities over 11000 cycles with a 71.95%capacity retention at 10 C at 25℃,as well as a remained capacity of 117.9 mA h g^(-1) after 8000 cycles at 30 C at 60℃,showing a great application prospect.This study provides a new route for creating electrochemically and structurally stable solid-solid interfaces for ASSLBs.展开更多
Despite their attractive features of high energy density,low cost,and safety,polysulfide/iodide flow batteries(SIFBs)are hampered by the sluggish kinetics of the iodide redox couple,which restricts overall performance...Despite their attractive features of high energy density,low cost,and safety,polysulfide/iodide flow batteries(SIFBs)are hampered by the sluggish kinetics of the iodide redox couple,which restricts overall performance.Multicomponent sulfides are demonstrated as promising catalysts for accelerating I^(-)/I_(3)^(-) redox reactions.Concurrently,the enhanced configurational entropy arising from multinary compositions drives synergistic effects among constituent elements,establishing a viable pathway to optimize catalytic performance.Building on these foundations,this work introduces a targeted orbital hybridization-optimized electron density strategy to enhance the catalytic activity.Implementing this concept,we developed an in-situ solvothermal synthesis process for an entropy-enhanced AgCuZnSnS_(4) loaded graphite felt(ACZTS/GF)electrode.The engineered electrode demonstrates exceptional electrocatalytic performance with improved bulk conductivity and interfacial charge transfer kinetics within a SIFB.The cell achieves a high energy efficiency of 88.5%at 20 mA·cm^(−2) with 10%state-of-charge.Furthermore,the battery delivers a maximum power density of 119.8 mW·cm^(−2) and exhibits excellent long-term cycling stability.These significant results stem from orbital hybridization-driven electronic state optimization and entropy effect-induced synergistic catalysis.展开更多
High concentration of secondary hydrogen sulfide(sH_(2)S) in thermal recovery reservoirs of Liaohe Oilfield,NE China was concluded to originate from thermochemical sulfate reduction(TSR),and no biotic source of H_(2)S...High concentration of secondary hydrogen sulfide(sH_(2)S) in thermal recovery reservoirs of Liaohe Oilfield,NE China was concluded to originate from thermochemical sulfate reduction(TSR),and no biotic source of H_(2)S under abundant biomass has been reported in these presumed steam sterilized reservoirs ever before.In this study,we propose a new mechanism,biomass thermal decomposition for sulfur compounds(BTDS),to interpret the increasing of sH_(2)S.Sulfur of cells' dry weight took 0.20%-1.92% of the active strains isolated from the in-situ thermal recovery reservoirs of Liaohe Oilfield.When microbial organic sulfur compounds(MOSC) in biomass were exposed to injected steam,it resulted in the BTDS process.The isolated Bacillus subtilis D3(G+) and Pseudomonas aeruginosa XJ14(G-) were chosen to simulate this process.About 36% of sulfur in MOSC emitted as H_(2)S in steam chamber by BTDS.The δ^(34)S of H_(2)S from produced gas ranged from 8.7‰ to 17.0‰,close to the δ^(34)S of H_(2)S 11.2‰ from BTDS simulation experiment.It provides new insight into the contribution and sulfur cycle made by subterranean microorganisms on H_(2)S formation.展开更多
Due to the difference in chemical potential between sulfide solid electrolytes(SSEs)and high-energy nickel-rich layered oxide cathode materials LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811),the space charge layer(SCL)with l...Due to the difference in chemical potential between sulfide solid electrolytes(SSEs)and high-energy nickel-rich layered oxide cathode materials LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811),the space charge layer(SCL)with large impedance is formed at the interface,which severely compromises the electrochemical performance of all-solid-state lithium batteries(ASSLBs).Herein,a gradient sulfide Ti_(3)(PO_(4))_(4)coating for NCM811 was designed and prepared.Due to the highly favorable O-S exchange,a gradient sulfide coating with structural and chemical similarity to Li_(5.3)PS_(4.3)Cl_(1.7)SSE was formed by in situ sulfide Ti_(3)(PO_(4))_(4)on the surface of NCM811 using the sulfur-rich phosphorus sulfide molecule P_(4)S_(16).The increased sulfur content towards the outer surface of the coating reduces the chemical potential difference between the NCM811 cathode and SSEs,thereby reducing the formation of the SCL and ensuring stable and fast Li^(+)transport at the interface.The full cell with gradient sulfide Ti_(3)(PO_(4))_(4)-coated NCM811 cathode(PS-NCM811@TiP)exhibited excellent long-cycle stability,with a capacity retention rate of 95.2% after 100 cycles at 0.057 mA cm^(-2)and 25℃.This work provides a new perspective on the surface modification of cathodes for sulfide-based ASSLBs.展开更多
Lithium-sulfur(Li-S)batteries with high energy density suffer from the soluble lithium polysulfide species,Traditional metal sulfides containing a single metal element used as electrocatalysts for Li-S batteries commo...Lithium-sulfur(Li-S)batteries with high energy density suffer from the soluble lithium polysulfide species,Traditional metal sulfides containing a single metal element used as electrocatalysts for Li-S batteries commonly have limited catalytic abilities to improve battery performance.Herein,based on the Hume-Rothery rule and solvothermal method,the high-entropy sulfide NiCoCuTiVS_(x)derived from Co_(9)S_(8)was designed and synthesized,to realize the combination of small local strain and excellent catalytic performance.With all five metal elements(Ni,Co,Cu,Ti,and V)capable of chemical interactions with soluble polysulfides,NiCoCuTiVS_(x)exhibited strong chemical confinement of polysulfides and promoted fast kinetics for polysulfides conversion.Consequently,the S/NiCoCuTiVS_(x)cathode can maintain a high discharge capacity of 968.9 mA h g^(-1)after 200 cycles at 0.5 C and its capacity retention is 1.3 times higher than that of S/Co_(9)S_(8).The improved cycle stability can be attributed to the synergistic effect originating from the multiple metal elements,coupled with the reduced nucleation and activation barriers of Li_(2)S.The present work opens a path to explore novel electrocatalyst materials based on high entropy materials for the achievement of advanced Li-S batteries.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
Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,how...Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,however,constrain their delicate constructions.Herein,an innovative alternative is proposed:carrageenan-assistant cations-regulated(CACR)strategy,which induces a series of sulfides nanoparticles rooted in situ on the surface of carbon matrix.This unique configuration originates from strategic vacancy formation energy of sulfides and strong sulfides-carbon support interaction,benefiting the delicate construction of defects-rich heterostructures in M_(x)S_(y)/carbon composites(M-CAs).Impressively,these generated sulfur vacancies are firstly found to strengthen electron accumulation/consumption ability at heterointerfaces and,simultaneously,induct local asymmetry of electronic structure to evoke large dipole moment,ultimately leading to polarization coupling,i.e.,defect-type interfacial polarization.Such“Janus effect”(Janus effect means versatility,as in the Greek two-headed Janus)of interfacial sulfur vacancies is intuitively confirmed by both theoretical and experimental investigations for the first time.Consequently,the sulfur vacancies-rich heterostructured Co/Ni-CAs displays broad absorption bandwidth of 6.76 GHz at only 1.8 mm,compared to sulfur vacancies-free CAs without any dielectric response.Harnessing defects-rich heterostructures,this one-pot CACR strategy may steer the design and development of advanced nanomaterials,boosting functionality across diverse application domains beyond electromagnetic response.展开更多
This study shows that sulfide solid-state electrolytes,β-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature&l...This study shows that sulfide solid-state electrolytes,β-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature<300℃.Sulfur vapor is a highly flammable gas,which then auto-ignites to produce a flame.This behavior suggests that an O_(2)-S gas-gas reaction mechanism may contribute to all-solid-state battery thermal runaway.To improve all-solid-state battery safety,current work focuses on eliminating the O_(2)source by changing the cathode active material.The conclusion of this study suggests that all-solidstate battery safety can also be realized by the development of solid-state electrolytes with less susceptibility to sulfur volatilization.展开更多
Adopting high-voltage Ni-rich cathodes in halide and sulfide-based all-solid-state lithium batteries(ASSLBs)holds great promise for breaking through the 400 Wh kg^(-1)bottleneck.However,both cell configurations are co...Adopting high-voltage Ni-rich cathodes in halide and sulfide-based all-solid-state lithium batteries(ASSLBs)holds great promise for breaking through the 400 Wh kg^(-1)bottleneck.However,both cell configurations are confronted with intricate interfacial challenges in high-voltage regines(>4.5 V),resulting in inadequate cathode utilization and premature cell degradation.Moreover,contrary to previous studies,coupled with LiNi_(0.85)Co_(0.1)Mn_(0.05)O_(2)cathodes,typical halide(Li_(2)ZrCl_(6))-based cells at 4.5 V feature unlimited interfacial degradation and poor long cycle stability,while typical sulfide(Li_(6)PS_(5)Cl)-based cells feature self-limited interfacial degradation and poor initial cycle stability.Herein,this work addresses the high-voltage limitations of Li_(2)ZrCl_(6)and Li_(6)PS_(5)Cl catholyte-based cells by manipulating electrode mass fraction and tailoring interfacial composition,thereby effectively improving interfacial charge-transfer kinetics and(electro)chemical stability within cathodes.After appropriate interface design,both optimized cells at 4.5 V demonstrate remarkably increased initial discharge capacities(>195 mA h g^(-1)at0.1 C),improved cycle stabilities(>80%after 600 cycles at 0.5 C),and enhanced rate performances(>115 mA h g^(-1)at 1.0 C).This work deepens our understanding of high-voltage applications for halide/sulfide electrolytes and provides generalized interfacial design strategies for advancing high-voltage ASSLBs.展开更多
The issues of fossil energy shortage and environmental pollution caused by the excessive consumption of conventional fossil fuels necessitates the exploration of renewable and clean energy sources such as hydrogen,whi...The issues of fossil energy shortage and environmental pollution caused by the excessive consumption of conventional fossil fuels necessitates the exploration of renewable and clean energy sources such as hydrogen,which is viable alternative to traditional energy sources in view of its high energy density and nonpolluting nature.In this regard,photocatalytic technology powered by inexhaustible solar energy is an ideal hydrogen production method.The recently developed copper-and zinc-based multinary metal sulfide(MMS)semiconductor photocatalysts exhibit the advantages of suitable bandgap,wide light-harvesting range,and flexible elemental composition,thus possessing great potential for achieving considerable photocatalytic hydrogen evolution(PHE)performance.Despite great progress has been achieved,the current photocatalysts still cannot meet the commercial application demands,which highlights the mechanisms understanding and optimization strategies for efficient PHE.Herein,the basic mechanisms of PHE,and effective optimization strategies are firstly introduced.Afterwards,the research process and the performance of copper-and zinc-based MMS photocatalysts,are thoroughly reviewed.Finally,the unresolved issues,and challenges hindering the achievement of overall water splitting have been discussed.展开更多
Transition metal sulfides are considered promising anode materials for sodium-ion batteries(SIBs)due to their high theoretical capacity and low synthesis cost.However,is-sues such as poor cyclic stability and rate per...Transition metal sulfides are considered promising anode materials for sodium-ion batteries(SIBs)due to their high theoretical capacity and low synthesis cost.However,is-sues such as poor cyclic stability and rate performance,arising from volume expansion and structural degradation,remain sig-nificant challenges.We report a novel FeS_(2)/CoS_(2) heterostruc-ture embedded in a 3D carbon aerogel matrix(FeS_(2)/CoS_(2)@C)synthesized by a cross-linking and vulcanization process.The resulting core-shell structure,with bimetallic FeS_(2)/CoS_(2) nano-particles encapsulated in a conductive carbon shell,effectively reduces the adverse effects of volume changes during sodiation/desodiation cycles.The 3D porous carbon network increases both ion and electron diffusion,while preventing agglomeration of the active material and maintaining interface integrity.The FeS_(2)/CoS_(2)@C composite has an outstanding electrochemical performance,including a high specific capacity of 725 mAh g^(-1)at 0.5 A g^(-1)and an exceptional rate capability of 572 mAh g^(-1)at 10 A g^(-1).It also has remarkable cycling stability with no signific-ant capacity decay over 1000 cycles at 5 A g^(-1).展开更多
CuS-C50,the cathode materials for magnesium ion batteries,was synthesized by adding the surfactant cetyltrimethyl ammonium bromide(CTAB)and adjusting the percentage of ethylene glycol to 50vol%in hydrothermal synthesi...CuS-C50,the cathode materials for magnesium ion batteries,was synthesized by adding the surfactant cetyltrimethyl ammonium bromide(CTAB)and adjusting the percentage of ethylene glycol to 50vol%in hydrothermal synthesis process.Results show that CuS-C50 has the complete nanoflower structure.In aluminum chloride-pentamethylcydopentodiene/tetrahydrofuran(APC/THF)electrolyte,the CuS-C50 exhibits a high specific capacity of 331.19 mAh/g when the current density is 50 mA/g and still keeps a specific capacity of 136.92 mAh/g over 50 cycles when the current density is 200 mA/g.Results of morphology characterizations indicate that the complete nanoflower structure can provide more active sites and reduce the barriers for Mg^(2+)movement,eventually improving the charge and discharge performance of the CuS cathode materials for magnesium ion batteries.展开更多
Using 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran(TCF)as a near-infrared fluorescent chromophore,we designed and synthesized a TCF-based fluorescent probe TCF-NS by introducing 2,4-dinitrophenyl ether ...Using 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran(TCF)as a near-infrared fluorescent chromophore,we designed and synthesized a TCF-based fluorescent probe TCF-NS by introducing 2,4-dinitrophenyl ether as the recognized site for H_(2)S.The probe TCF-NS displayed a rapid-response fluorescent against H_(2)S with high sensitivity and selection but had no significant fluorescence response to other biothiols.Furthermore,TCF-NS was applied to sense H_(2)S in living cells successfully with minimized cytotoxicity and a large Stokes shift.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
Sulfide precipitation is an effective method for treating acidic heavy metal wastewater.However,the process often generates tiny particles with poor settling performance.The factors and mechanisms influencing particle...Sulfide precipitation is an effective method for treating acidic heavy metal wastewater.However,the process often generates tiny particles with poor settling performance.The factors and mechanisms influencing particle size and settling performance remain unclear.In this study,the growth behavior of CuS particles generated by two sulfide precipitation methods,gas-liquid and liquid-liquid sulfidation,was investigated.The effects of acidity,sulfur-to-copper molar ratio,and temperature on particle size were analyzed.The results showed that increasing the temperature had an adverse effect on CuS particle growth.Additionally,we found that acidity and sulfur-to-copper molar ratio had a more significant impact on particle growth in the liquid-liquid sulfidation system than in the gas-liquid sulfidation system.Based on supersaturation calculations and XPS analysis,it is found that particle growth in gas-liquid sulfidation systems is mainly influenced by supersaturation,while particle growth in liquid-liquid sulfidation systems is mainly affected by surface charge.This study provides valuable insights into the factors that influence particle growth in sulfide precipitation and can inform the development of strategies to improve the effective precipitation of sulfide nanoparticles in acidic wastewater.展开更多
The development of efficient catalysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is of great significance for the practical application of water splitting in alkaline electrolytes.Transitio...The development of efficient catalysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is of great significance for the practical application of water splitting in alkaline electrolytes.Transition metal sulfide electrocatalysts have been widely recognized as efficient catalysts for water splitting in alkaline media.In this work,an original and efficient synthesis strategy is proposed for the fabrication of asymmetric anode(N-(Co-Cu)S_(x))and cathode(N-CoS/Cu_(2)S).Impressively,these electrodes exhibit superior performance,benefiting from the construction of three-dimensional(3D)structures and the electronic structure adjustment caused by N-doping with increased active sites,improved mass/charge transport and enhanced evolution and release of gas bubbles.Hence,N-(Co-Cu)S_(x)anode exhibits excellent OER performance with only 217 mV overpotential at 10 mA·cm^(-2),while N-CoS/Cu_(2)S cathode possesses excellent HER performance with only 67 mV overpotential at 10 mA·cm^(-2).N-(Co-Cu)S_(x)||N-CoS/Cu_(2)S electrolyzer presents a low cell voltage of 1.53 V at 10 mA·cm^(-2)toward overall water splitting,which is superior to most recently reported transition metal sulfide-based catalysts.展开更多
By introduction of hydrogen peroxide into the reaction system of ZrOCl_(2)·8H_(2)O and K14[As_(2)W_(19)O_(67)(H_(2)O)],a novel polyoxometalate K_(8)Na_(19.5)H_(0.5)[Zr_(2)(O_(2))_(2)(β-AsVW_(10)O_(38))]4·68...By introduction of hydrogen peroxide into the reaction system of ZrOCl_(2)·8H_(2)O and K14[As_(2)W_(19)O_(67)(H_(2)O)],a novel polyoxometalate K_(8)Na_(19.5)H_(0.5)[Zr_(2)(O_(2))_(2)(β-AsVW_(10)O_(38))]4·68H_(2)O(1)has been successfully obtained via one-pot method and systematically characterized by IR,XPS,solid UV spectra,PXRD pattern,and TGA analysis.The analysis of X-ray crystallography exhibits that compound 1 crystallizes in the triclinic space group P-1 and presents a novel square-shaped Zr-substituted tetrameric polyoxometalate.The catalytic oxidation of sulfides by 1 are carried out,which demonstrate that 1 exhibits a good performance for the catalytic oxidation of sulfides to sulfones with high conversion(100%)and high selectivity(100%).展开更多
The discovery of quantum dots(QDs)stands as one of the paramount technological breakthroughs of the 20th century.Their versatility spans from everyday applications to cutting-edge scientific research,encompassing area...The discovery of quantum dots(QDs)stands as one of the paramount technological breakthroughs of the 20th century.Their versatility spans from everyday applications to cutting-edge scientific research,encompassing areas such as displays,lighting,photocatalysis,bio-imaging,and photonics devices and so on.Among the myriad QDs technologies,industrially relevant CuInS_(2)(CIS)QDs have emerged as promising alternatives to traditional Cd-and Pb-based QDs.Their tunable optoelectronic properties,high absorption coefficient,compositional flexibility,remarkable stability as well as Restriction of Hazardous Substances-compliance,with recent trends revealing a renewed interest in this material for various visible and near-infrared technological applications.This review focuses on recent advancements in CIS QDs as multidisciplinary field from its genesis in the mid-1990 to date with an emphasis on key breakthroughs in their synthesis,surface chemistry,post-synthesis modifications,and various applications.First,the comparation of properties of CIS QDs with relevant knowledge from other classes of QDs and from Ⅰ-Ⅱ-Ⅲ semiconductors as well is summarized.Second,recent advances in the synthesis methods,structure-optoelectronic properties,their defects,and passivation strategies as well as CIS-based heterostructures are discussed.Third,the state-of-the-art applications of CIS QDs ranging from solar cells,luminescence solar concentrations,photocatalysis,light emitting diodes,bioimaging and some emerging applications are summarized.Finally,we discuss open challenges and future perspectives for further advancement in this field.展开更多
Industrial high-current-density oxygen evolution catalyst is the key to accelerating the practical application of hydrogen energy.Herein,Co_(9)S_(8)/CoS heterojunctions were rationally encapsulated in S,N-codoped carb...Industrial high-current-density oxygen evolution catalyst is the key to accelerating the practical application of hydrogen energy.Herein,Co_(9)S_(8)/CoS heterojunctions were rationally encapsulated in S,N-codoped carbon((Co_(9)S_(8)/CoS)@SNC)microleaf arrays,which are rooted on S-doped carbonized wood fibers(SCWF).Benefiting from the synergistic electronic interactions on heterointerfaces and the accelerated mass transfer by array structure,the obtained self-supporting(Co_(9)S_(8)/CoS)@SNC/SCWF electrode exhibits superior performance toward alkaline oxygen evolution reaction(OER)with an ultra-low overpotential of 274 mV at 1000 mA/cm^(2),a small Tafel slope of 48.84 mV/dec,and ultralong stability up to 100 h.Theoretical calculations show that interfacing Co_(9)S_(8)with CoS can upshift the d-band center of the Co atoms and strengthen the interactions with oxygen intermediates,thereby favoring OER performance.Furthermore,the(Co_(9)S_(8)/CoS)@SNC/SCWF electrode shows outstanding rechargeability and stable cycle life in aqueous Zn-air batteries with a peak power density of 201.3 mW/cm^(2),exceeding the commercial RuO_(2)and Pt/C hybrid catalysts.This work presents a promising strategy for the design of high-current-density OER electrocatalysts from sustainable wood fiber resources,thus promoting their practical applications in the field of electrochemical energy storage and conversion.展开更多
基金financially supported by the National Key Research and Development Program of China (No. 2022YFC2105300)。
文摘A series of leaching and electrochemical experiments were conducted to elucidate the critical role of hydrogen sulfide(H_(2)S)in copper-driven reduction of chalcopyrite.Results demonstrate that in the absence of H_(2)S,metallic copper converts chalcopyrite into bornite(Cu_(5)FeS_(4)).However,the introduction of H_(2)S promotes the formation of chalcocite(Cu_(2)S)by altering the oxidation pathway of copper.Electrochemical analysis demonstrates that the presence of H₂S significantly reduces the corrosion potential of copper from 0.251 to−0.223 V(vs SHE),reaching the threshold necessary for the formation of Cu_(2)S.Nevertheless,excessive H_(2)S triggers sulfate reduction via the reaction of 8Cu+H_(2)SO_(4)+3H_(2)S=4Cu_(2)S+4H_(2)O(ΔG=−519.429 kJ/mol at 50℃),leading to inefficient copper utilization.
基金supported by the National Key R&D Program of China(2021YFB3800300).
文摘High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instability between the cathode and electrolyte.Given the surface alkalinity of NCM811,we propose a strategy to construct a solid-polymer-electrolyte(SPE)interphase on NCM811 surface by leveraging the surface alkaline residues to nucleophilically initiate the in-situ ring-opening polymerization of cyclic organic molecules.As a proof-of-concept,this study demonstrates that the ring-opening copolymerization of 1,3-dioxolane and maleic anhydride produces a homogeneous,compact,and conformal SPE layer on NCM811 surface to prevent the cathode from contact and reaction with Li6PS5Cl solid-state electrolyte.Consequently,the SPE-modified-NCM811 in ASSLBs exhibits high capacities of 193.5 mA h g^(-1) at 0.2 C,160.9 mA h g^(-1) at 2.0 C and 112.3 mA h g^(-1) at 10 C,and particularly,excellent long-term cycling stabilities over 11000 cycles with a 71.95%capacity retention at 10 C at 25℃,as well as a remained capacity of 117.9 mA h g^(-1) after 8000 cycles at 30 C at 60℃,showing a great application prospect.This study provides a new route for creating electrochemically and structurally stable solid-solid interfaces for ASSLBs.
基金supported by the National Natural Science Foundation of China(Nos.22171180,22461142137,and 22478242)the Shanghai Municipal Science and Technology Major Project,China.
文摘Despite their attractive features of high energy density,low cost,and safety,polysulfide/iodide flow batteries(SIFBs)are hampered by the sluggish kinetics of the iodide redox couple,which restricts overall performance.Multicomponent sulfides are demonstrated as promising catalysts for accelerating I^(-)/I_(3)^(-) redox reactions.Concurrently,the enhanced configurational entropy arising from multinary compositions drives synergistic effects among constituent elements,establishing a viable pathway to optimize catalytic performance.Building on these foundations,this work introduces a targeted orbital hybridization-optimized electron density strategy to enhance the catalytic activity.Implementing this concept,we developed an in-situ solvothermal synthesis process for an entropy-enhanced AgCuZnSnS_(4) loaded graphite felt(ACZTS/GF)electrode.The engineered electrode demonstrates exceptional electrocatalytic performance with improved bulk conductivity and interfacial charge transfer kinetics within a SIFB.The cell achieves a high energy efficiency of 88.5%at 20 mA·cm^(−2) with 10%state-of-charge.Furthermore,the battery delivers a maximum power density of 119.8 mW·cm^(−2) and exhibits excellent long-term cycling stability.These significant results stem from orbital hybridization-driven electronic state optimization and entropy effect-induced synergistic catalysis.
文摘High concentration of secondary hydrogen sulfide(sH_(2)S) in thermal recovery reservoirs of Liaohe Oilfield,NE China was concluded to originate from thermochemical sulfate reduction(TSR),and no biotic source of H_(2)S under abundant biomass has been reported in these presumed steam sterilized reservoirs ever before.In this study,we propose a new mechanism,biomass thermal decomposition for sulfur compounds(BTDS),to interpret the increasing of sH_(2)S.Sulfur of cells' dry weight took 0.20%-1.92% of the active strains isolated from the in-situ thermal recovery reservoirs of Liaohe Oilfield.When microbial organic sulfur compounds(MOSC) in biomass were exposed to injected steam,it resulted in the BTDS process.The isolated Bacillus subtilis D3(G+) and Pseudomonas aeruginosa XJ14(G-) were chosen to simulate this process.About 36% of sulfur in MOSC emitted as H_(2)S in steam chamber by BTDS.The δ^(34)S of H_(2)S from produced gas ranged from 8.7‰ to 17.0‰,close to the δ^(34)S of H_(2)S 11.2‰ from BTDS simulation experiment.It provides new insight into the contribution and sulfur cycle made by subterranean microorganisms on H_(2)S formation.
基金supported by the National Natural Science Foundation of China(No.52272258)the Beijing Nova Program(No.20220484214)。
文摘Due to the difference in chemical potential between sulfide solid electrolytes(SSEs)and high-energy nickel-rich layered oxide cathode materials LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811),the space charge layer(SCL)with large impedance is formed at the interface,which severely compromises the electrochemical performance of all-solid-state lithium batteries(ASSLBs).Herein,a gradient sulfide Ti_(3)(PO_(4))_(4)coating for NCM811 was designed and prepared.Due to the highly favorable O-S exchange,a gradient sulfide coating with structural and chemical similarity to Li_(5.3)PS_(4.3)Cl_(1.7)SSE was formed by in situ sulfide Ti_(3)(PO_(4))_(4)on the surface of NCM811 using the sulfur-rich phosphorus sulfide molecule P_(4)S_(16).The increased sulfur content towards the outer surface of the coating reduces the chemical potential difference between the NCM811 cathode and SSEs,thereby reducing the formation of the SCL and ensuring stable and fast Li^(+)transport at the interface.The full cell with gradient sulfide Ti_(3)(PO_(4))_(4)-coated NCM811 cathode(PS-NCM811@TiP)exhibited excellent long-cycle stability,with a capacity retention rate of 95.2% after 100 cycles at 0.057 mA cm^(-2)and 25℃.This work provides a new perspective on the surface modification of cathodes for sulfide-based ASSLBs.
基金financially supported by the National Natural Science Foundation of China(U22A20113,52261135543)。
文摘Lithium-sulfur(Li-S)batteries with high energy density suffer from the soluble lithium polysulfide species,Traditional metal sulfides containing a single metal element used as electrocatalysts for Li-S batteries commonly have limited catalytic abilities to improve battery performance.Herein,based on the Hume-Rothery rule and solvothermal method,the high-entropy sulfide NiCoCuTiVS_(x)derived from Co_(9)S_(8)was designed and synthesized,to realize the combination of small local strain and excellent catalytic performance.With all five metal elements(Ni,Co,Cu,Ti,and V)capable of chemical interactions with soluble polysulfides,NiCoCuTiVS_(x)exhibited strong chemical confinement of polysulfides and promoted fast kinetics for polysulfides conversion.Consequently,the S/NiCoCuTiVS_(x)cathode can maintain a high discharge capacity of 968.9 mA h g^(-1)after 200 cycles at 0.5 C and its capacity retention is 1.3 times higher than that of S/Co_(9)S_(8).The improved cycle stability can be attributed to the synergistic effect originating from the multiple metal elements,coupled with the reduced nucleation and activation barriers of Li_(2)S.The present work opens a path to explore novel electrocatalyst materials based on high entropy materials for the achievement of advanced Li-S batteries.
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financially supported by the National Natural Science Foundation of China(Grants nos.62201411,62371378,22205168,52302150 and 62304171)the China Postdoctoral Science Foundation(2022M722500)+1 种基金the Fundamental Research Funds for the Central Universities(Grants nos.ZYTS2308 and 20103237929)Startup Foundation of Xidian University(10251220001).
文摘Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,however,constrain their delicate constructions.Herein,an innovative alternative is proposed:carrageenan-assistant cations-regulated(CACR)strategy,which induces a series of sulfides nanoparticles rooted in situ on the surface of carbon matrix.This unique configuration originates from strategic vacancy formation energy of sulfides and strong sulfides-carbon support interaction,benefiting the delicate construction of defects-rich heterostructures in M_(x)S_(y)/carbon composites(M-CAs).Impressively,these generated sulfur vacancies are firstly found to strengthen electron accumulation/consumption ability at heterointerfaces and,simultaneously,induct local asymmetry of electronic structure to evoke large dipole moment,ultimately leading to polarization coupling,i.e.,defect-type interfacial polarization.Such“Janus effect”(Janus effect means versatility,as in the Greek two-headed Janus)of interfacial sulfur vacancies is intuitively confirmed by both theoretical and experimental investigations for the first time.Consequently,the sulfur vacancies-rich heterostructured Co/Ni-CAs displays broad absorption bandwidth of 6.76 GHz at only 1.8 mm,compared to sulfur vacancies-free CAs without any dielectric response.Harnessing defects-rich heterostructures,this one-pot CACR strategy may steer the design and development of advanced nanomaterials,boosting functionality across diverse application domains beyond electromagnetic response.
文摘This study shows that sulfide solid-state electrolytes,β-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature<300℃.Sulfur vapor is a highly flammable gas,which then auto-ignites to produce a flame.This behavior suggests that an O_(2)-S gas-gas reaction mechanism may contribute to all-solid-state battery thermal runaway.To improve all-solid-state battery safety,current work focuses on eliminating the O_(2)source by changing the cathode active material.The conclusion of this study suggests that all-solidstate battery safety can also be realized by the development of solid-state electrolytes with less susceptibility to sulfur volatilization.
基金supported by the National Key R&D Program of China(2022YFB3803505)National Natural Scientific Foundation of China(U21A2080&22479009)National Related Project and the Fundamental Research Funds for the Central Universities(FRF-TP-22-01C2)。
文摘Adopting high-voltage Ni-rich cathodes in halide and sulfide-based all-solid-state lithium batteries(ASSLBs)holds great promise for breaking through the 400 Wh kg^(-1)bottleneck.However,both cell configurations are confronted with intricate interfacial challenges in high-voltage regines(>4.5 V),resulting in inadequate cathode utilization and premature cell degradation.Moreover,contrary to previous studies,coupled with LiNi_(0.85)Co_(0.1)Mn_(0.05)O_(2)cathodes,typical halide(Li_(2)ZrCl_(6))-based cells at 4.5 V feature unlimited interfacial degradation and poor long cycle stability,while typical sulfide(Li_(6)PS_(5)Cl)-based cells feature self-limited interfacial degradation and poor initial cycle stability.Herein,this work addresses the high-voltage limitations of Li_(2)ZrCl_(6)and Li_(6)PS_(5)Cl catholyte-based cells by manipulating electrode mass fraction and tailoring interfacial composition,thereby effectively improving interfacial charge-transfer kinetics and(electro)chemical stability within cathodes.After appropriate interface design,both optimized cells at 4.5 V demonstrate remarkably increased initial discharge capacities(>195 mA h g^(-1)at0.1 C),improved cycle stabilities(>80%after 600 cycles at 0.5 C),and enhanced rate performances(>115 mA h g^(-1)at 1.0 C).This work deepens our understanding of high-voltage applications for halide/sulfide electrolytes and provides generalized interfacial design strategies for advancing high-voltage ASSLBs.
文摘The issues of fossil energy shortage and environmental pollution caused by the excessive consumption of conventional fossil fuels necessitates the exploration of renewable and clean energy sources such as hydrogen,which is viable alternative to traditional energy sources in view of its high energy density and nonpolluting nature.In this regard,photocatalytic technology powered by inexhaustible solar energy is an ideal hydrogen production method.The recently developed copper-and zinc-based multinary metal sulfide(MMS)semiconductor photocatalysts exhibit the advantages of suitable bandgap,wide light-harvesting range,and flexible elemental composition,thus possessing great potential for achieving considerable photocatalytic hydrogen evolution(PHE)performance.Despite great progress has been achieved,the current photocatalysts still cannot meet the commercial application demands,which highlights the mechanisms understanding and optimization strategies for efficient PHE.Herein,the basic mechanisms of PHE,and effective optimization strategies are firstly introduced.Afterwards,the research process and the performance of copper-and zinc-based MMS photocatalysts,are thoroughly reviewed.Finally,the unresolved issues,and challenges hindering the achievement of overall water splitting have been discussed.
文摘Transition metal sulfides are considered promising anode materials for sodium-ion batteries(SIBs)due to their high theoretical capacity and low synthesis cost.However,is-sues such as poor cyclic stability and rate performance,arising from volume expansion and structural degradation,remain sig-nificant challenges.We report a novel FeS_(2)/CoS_(2) heterostruc-ture embedded in a 3D carbon aerogel matrix(FeS_(2)/CoS_(2)@C)synthesized by a cross-linking and vulcanization process.The resulting core-shell structure,with bimetallic FeS_(2)/CoS_(2) nano-particles encapsulated in a conductive carbon shell,effectively reduces the adverse effects of volume changes during sodiation/desodiation cycles.The 3D porous carbon network increases both ion and electron diffusion,while preventing agglomeration of the active material and maintaining interface integrity.The FeS_(2)/CoS_(2)@C composite has an outstanding electrochemical performance,including a high specific capacity of 725 mAh g^(-1)at 0.5 A g^(-1)and an exceptional rate capability of 572 mAh g^(-1)at 10 A g^(-1).It also has remarkable cycling stability with no signific-ant capacity decay over 1000 cycles at 5 A g^(-1).
基金National Natural Science Foundation of China(52171101)Fundamental Research Funds for the Central Universities(2024IAIS-QN009)National Key R&D Program of China(2021YFB3701100)。
文摘CuS-C50,the cathode materials for magnesium ion batteries,was synthesized by adding the surfactant cetyltrimethyl ammonium bromide(CTAB)and adjusting the percentage of ethylene glycol to 50vol%in hydrothermal synthesis process.Results show that CuS-C50 has the complete nanoflower structure.In aluminum chloride-pentamethylcydopentodiene/tetrahydrofuran(APC/THF)electrolyte,the CuS-C50 exhibits a high specific capacity of 331.19 mAh/g when the current density is 50 mA/g and still keeps a specific capacity of 136.92 mAh/g over 50 cycles when the current density is 200 mA/g.Results of morphology characterizations indicate that the complete nanoflower structure can provide more active sites and reduce the barriers for Mg^(2+)movement,eventually improving the charge and discharge performance of the CuS cathode materials for magnesium ion batteries.
基金financially supported by the Natural Science Foundation of Jiangsu Province(Grant No.BK20241181)the State Key Laboratory of AnalyticalChemistry for Life Science,School of Chemistry and Chemical Engineering,Nanjing University(Grant No.SKLACLS2419)。
文摘Using 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran(TCF)as a near-infrared fluorescent chromophore,we designed and synthesized a TCF-based fluorescent probe TCF-NS by introducing 2,4-dinitrophenyl ether as the recognized site for H_(2)S.The probe TCF-NS displayed a rapid-response fluorescent against H_(2)S with high sensitivity and selection but had no significant fluorescence response to other biothiols.Furthermore,TCF-NS was applied to sense H_(2)S in living cells successfully with minimized cytotoxicity and a large Stokes shift.
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supported by the Foundation for Innovative Research Groups of the National Natural Science Foundation of China(No.52121004)the National Natural Science Foundation of China(No.52274414).
文摘Sulfide precipitation is an effective method for treating acidic heavy metal wastewater.However,the process often generates tiny particles with poor settling performance.The factors and mechanisms influencing particle size and settling performance remain unclear.In this study,the growth behavior of CuS particles generated by two sulfide precipitation methods,gas-liquid and liquid-liquid sulfidation,was investigated.The effects of acidity,sulfur-to-copper molar ratio,and temperature on particle size were analyzed.The results showed that increasing the temperature had an adverse effect on CuS particle growth.Additionally,we found that acidity and sulfur-to-copper molar ratio had a more significant impact on particle growth in the liquid-liquid sulfidation system than in the gas-liquid sulfidation system.Based on supersaturation calculations and XPS analysis,it is found that particle growth in gas-liquid sulfidation systems is mainly influenced by supersaturation,while particle growth in liquid-liquid sulfidation systems is mainly affected by surface charge.This study provides valuable insights into the factors that influence particle growth in sulfide precipitation and can inform the development of strategies to improve the effective precipitation of sulfide nanoparticles in acidic wastewater.
基金supported by the Science and Technology Project of Southwest Petroleum University(No.2021JBGS03)the Local Science and Technology Development Fund Projects Guided by the Central Government of China(No.2021ZYD0060)+2 种基金the National Natural Science Foundation of China(Nos.22209143 and 52371241)Guangdong High-level Innovation Institute Project(Nos.2021B0909050001 and 2021CX02L365)Guangdong Basic and Applied Basic Research Foundation(No.2023B1515120095).
文摘The development of efficient catalysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is of great significance for the practical application of water splitting in alkaline electrolytes.Transition metal sulfide electrocatalysts have been widely recognized as efficient catalysts for water splitting in alkaline media.In this work,an original and efficient synthesis strategy is proposed for the fabrication of asymmetric anode(N-(Co-Cu)S_(x))and cathode(N-CoS/Cu_(2)S).Impressively,these electrodes exhibit superior performance,benefiting from the construction of three-dimensional(3D)structures and the electronic structure adjustment caused by N-doping with increased active sites,improved mass/charge transport and enhanced evolution and release of gas bubbles.Hence,N-(Co-Cu)S_(x)anode exhibits excellent OER performance with only 217 mV overpotential at 10 mA·cm^(-2),while N-CoS/Cu_(2)S cathode possesses excellent HER performance with only 67 mV overpotential at 10 mA·cm^(-2).N-(Co-Cu)S_(x)||N-CoS/Cu_(2)S electrolyzer presents a low cell voltage of 1.53 V at 10 mA·cm^(-2)toward overall water splitting,which is superior to most recently reported transition metal sulfide-based catalysts.
基金financially supported by the National Natural Science Foundation of China(No.22071043).
文摘By introduction of hydrogen peroxide into the reaction system of ZrOCl_(2)·8H_(2)O and K14[As_(2)W_(19)O_(67)(H_(2)O)],a novel polyoxometalate K_(8)Na_(19.5)H_(0.5)[Zr_(2)(O_(2))_(2)(β-AsVW_(10)O_(38))]4·68H_(2)O(1)has been successfully obtained via one-pot method and systematically characterized by IR,XPS,solid UV spectra,PXRD pattern,and TGA analysis.The analysis of X-ray crystallography exhibits that compound 1 crystallizes in the triclinic space group P-1 and presents a novel square-shaped Zr-substituted tetrameric polyoxometalate.The catalytic oxidation of sulfides by 1 are carried out,which demonstrate that 1 exhibits a good performance for the catalytic oxidation of sulfides to sulfones with high conversion(100%)and high selectivity(100%).
基金X.H.acknowledges the financial support by Australian Research Council(ARC)Future Fellowship(FT190100756)M.P.S.gratefully acknowledges the support by the ARC under Discovery Early Career Researcher Award(DECRA)(DE210101565)and Discovery Project(DP230101676).
文摘The discovery of quantum dots(QDs)stands as one of the paramount technological breakthroughs of the 20th century.Their versatility spans from everyday applications to cutting-edge scientific research,encompassing areas such as displays,lighting,photocatalysis,bio-imaging,and photonics devices and so on.Among the myriad QDs technologies,industrially relevant CuInS_(2)(CIS)QDs have emerged as promising alternatives to traditional Cd-and Pb-based QDs.Their tunable optoelectronic properties,high absorption coefficient,compositional flexibility,remarkable stability as well as Restriction of Hazardous Substances-compliance,with recent trends revealing a renewed interest in this material for various visible and near-infrared technological applications.This review focuses on recent advancements in CIS QDs as multidisciplinary field from its genesis in the mid-1990 to date with an emphasis on key breakthroughs in their synthesis,surface chemistry,post-synthesis modifications,and various applications.First,the comparation of properties of CIS QDs with relevant knowledge from other classes of QDs and from Ⅰ-Ⅱ-Ⅲ semiconductors as well is summarized.Second,recent advances in the synthesis methods,structure-optoelectronic properties,their defects,and passivation strategies as well as CIS-based heterostructures are discussed.Third,the state-of-the-art applications of CIS QDs ranging from solar cells,luminescence solar concentrations,photocatalysis,light emitting diodes,bioimaging and some emerging applications are summarized.Finally,we discuss open challenges and future perspectives for further advancement in this field.
基金supported by National Key Research and Development Program of China(No.2023YFD2200503)the Young Elite Scientists Sponsorship Program from National Forestry and Grassland Administration of China(No.2019132614)+1 种基金the Science and Technology Innovation Program of Hunan Province(Nos.2021RC3103 and 2022RC3054)the Scientific Research Project of Hunan Provincial Education Department(Nos.23B0276 and 21B0225).
文摘Industrial high-current-density oxygen evolution catalyst is the key to accelerating the practical application of hydrogen energy.Herein,Co_(9)S_(8)/CoS heterojunctions were rationally encapsulated in S,N-codoped carbon((Co_(9)S_(8)/CoS)@SNC)microleaf arrays,which are rooted on S-doped carbonized wood fibers(SCWF).Benefiting from the synergistic electronic interactions on heterointerfaces and the accelerated mass transfer by array structure,the obtained self-supporting(Co_(9)S_(8)/CoS)@SNC/SCWF electrode exhibits superior performance toward alkaline oxygen evolution reaction(OER)with an ultra-low overpotential of 274 mV at 1000 mA/cm^(2),a small Tafel slope of 48.84 mV/dec,and ultralong stability up to 100 h.Theoretical calculations show that interfacing Co_(9)S_(8)with CoS can upshift the d-band center of the Co atoms and strengthen the interactions with oxygen intermediates,thereby favoring OER performance.Furthermore,the(Co_(9)S_(8)/CoS)@SNC/SCWF electrode shows outstanding rechargeability and stable cycle life in aqueous Zn-air batteries with a peak power density of 201.3 mW/cm^(2),exceeding the commercial RuO_(2)and Pt/C hybrid catalysts.This work presents a promising strategy for the design of high-current-density OER electrocatalysts from sustainable wood fiber resources,thus promoting their practical applications in the field of electrochemical energy storage and conversion.
