Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systemat...Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties.In this work,we propose an autogenously transformed CoWO_(4)/WO_(2) heterojunction catalyst,integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity.CoWO_(4) effectively captures polysulfides,while the CoWO_(4)/WO_(2) interface facilitates their S-S bond activation on heterogenous catalytic sites.Benefiting from its directional intercalation channels,CoWO_(4) not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport.Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite.As a result,the CoWO_(4)/WO_(2) heterostructure demonstrates significantly enhanced catalytic performance,delivering a high capacity of 1262 mAh g^(−1) at 0.1 C.Furthermore,its rate capability and high sulfur loading performance are markedly improved,surpassing the limitations of its single-component counterparts.This study provides new insights into the catalytic mechanisms governing Li-S chemistry and offers a promising strategy for the rational design of high-performance Li-S battery catalysts.展开更多
Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temp...Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.展开更多
This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0...This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.1)Mo_(0.05)O_(3-δ)(B S CNM_(0.05)),Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.05)Mo_(0.1)O_(3-δ)(BSCNM_(0.1)),and Ba_(0.6)Sr_(0.4)Co_(0.85)Mo_(0.15)O_(3-δ)(BSCM)—with Mo doping contents of 5mol%,10mol%,and15mol%,respectively,were successfully prepared using the sol-gel method.The effects of Mo doping on the crystal structure,conductivity,thermal expansion coefficient,oxygen reduction reaction(ORR)activity,and electrochemical performance were systematically evaluated using X-ray diffraction analysis,thermally induced characterization,electrochemical impedance spectroscopy,and single-cell performance tests.The results revealed that Mo doping could improve the conductivity of the materials,suppress their thermal expansion effects,and significantly improve the electrochemical performance.Surface chemical state analysis using X-ray photoelectron spectroscopy revealed that 5mol%Mo doping could facilitate a high adsorbed oxygen concentration leading to enhanced ORR activity in the materials.Density functional theory calculations confirmed that Mo doping promoted the ORR activity in the materials.At an operating temperature of 600℃,the BSCNM_(0.05)cathode material exhibited significantly enhanced electrochemical impedance characteristics,with a reduced area specific resistance of 0.048Ω·cm~2,which was lower than that of the undoped BSCN matrix material by 32.39%.At the same operating temperature,an anode-supported single cell using a BSCNM_(0.05)cathode achieved a peak power density of 1477 mW·cm^(-2),which was 30.71%,56.30%,and 171.50%higher than those of BSCN,BSCNM_(0.1),and B SCM,respectively.The improved ORR activity and electrochemical performance of BSCNM_(0.05)indicate that it can be used as a cathode material in low-temperature solid oxide fuel cells.展开更多
Single-atom catalysts(SACs)have garnered significant attention in lithium-sulfur(Li-S)batteries for their potential to mitigate the severe polysulfide shuttle effect and sluggish redox kinetics.However,the development...Single-atom catalysts(SACs)have garnered significant attention in lithium-sulfur(Li-S)batteries for their potential to mitigate the severe polysulfide shuttle effect and sluggish redox kinetics.However,the development of highly efficient SACs and a comprehensive understanding of their structure-activity relationships remain enormously challenging.Herein,a novel kind of Fe-based SAC featuring an asymmetric FeN_(5)-TeN_(4) coordination structure was precisely designed by introducing Te atom adjacent to the Fe active center to enhance the catalytic activity.Theoretical calculations reveal that the neighboring Te atom modulates the local coordination environment of the central Fe site,elevating the d-band center closer to the Fermi level and strengthening the d-p orbital hybridization between the catalyst and sulfur species,thereby immobilizing polysulfides and improving the bidirectional catalysis of Li-S redox.Consequently,the Fe-Te atom pair catalyst endows Li-S batteries with exceptional rate performance,achieving a high specific capacity of 735 mAh g^(−1) at 5 C,and remarkable cycling stability with a low decay rate of 0.038%per cycle over 1000 cycles at 1 C.This work provides fundamental insights into the electronic structure modulation of SACs and establishes a clear correlation between precisely engineered atomic configurations and their enhanced catalytic performance in Li-S electrochemistry.展开更多
Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent c...Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent catalysis,supramolecular systems can create dynamic and adaptable microenvironments tailored to specific substrates,similar to how enzymes work.This strategy has shown great promise in asymmetric catalysis,cascade reactions,and green chemistry applications.Recent advances focus on leveraging less conventional noncovalent forces to expand the toolbox of supramolecular strategies in catalysis.展开更多
Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-form...Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-forming properties and high dielectric constant.However,the elevated freezing point,high viscosity,and strong solvation energy of EC significantly hinder the transport rate of Li^(+)and the desolvation process at low temperatures.This leads to substantial capacity loss and even lithium plating on graphite anodes.Herein,we have developed an efficient electrolyte system specifically designed for lowtemperature conditions,which consists of 1.0 M lithium bis(fluorosulfonyl)imide(LiFSI)in isoxazole(IZ)with fluorobenzene(FB)as an uncoordinated solvent and fluoroethylene carbonate(FEC)as a filmforming co-solvent.This system effectively lowers the desolvation energy of Li^(+)through dipole-dipole interactions.The weak solvation capability allows more anions to enter the solvation sheath,promoting the formation of contact ion pairs(CIPs)and aggregates(AGGs)that enhance the transport rate of Li^(+)while maintaining high ionic conductivity across a broad temperature range.Moreover,the formation of inorganic-dominant interfacial phases on the graphite anode,induced by fluoroethylene carbonate,significantly enhances the kinetics of Li^(+)transport.At a low temperature of-20℃,this electrolyte system achieves an impressive reversible capacity of 200.9 mAh g^(-1)in graphite half-cell,which is nearly three times that observed with conventional EC-based electrolytes,demonstrating excellent stability throughout its operation.展开更多
To completely recover valuable elements and reduce the amount of waste,the impact of phosphoric acid on the decomposition of rare earth,fluorine and phosphorus during cyclic leaching was studied based on the character...To completely recover valuable elements and reduce the amount of waste,the impact of phosphoric acid on the decomposition of rare earth,fluorine and phosphorus during cyclic leaching was studied based on the characteristics of low-tempe rature sulfuric acid deco mposition.When a single monazite was leached using 75 wt% H_(2)SO_(4) solution with phosphoric acid,the size and number of monazite particles in the washing slag gradually decrease with the increase in phosphoric acid content in the leaching solution.The monazite phase can hardly be found in the slag when the phosphoric acid content reaches 70 g/L,which indicates that phosphoric acid is favorable for monazite decomposition.The mixed rare earth concentrate was leached by 75 wt% H_(2)SO_(4) containing 70 g/L phosphoric acid,the mineral compositions of the washing slag are only gypsum and unwashed rare earth sulfuric acid.After cyclic leaching of75 wt% H_(2)SO_(4),the mineral compositions of the primary leaching washing slag are mainly undecomposed monazite,rare earth sulfate and calcium sulfate.However,monazite is not found in the mineral phase of the second and third leaching washing slag.The leaching rates of rare earth and phosphorus gradually increase with the increase in cyclic leaching times.In addition,the phosphoric acid content in the leaching solution increases with the increase in the number of cyclic leaching time.However,the rising trend decreases when the phosphoric acid content reaches 50 g/L by adsorption and crystallization of phosphoric acid.A small amount of water can be used to clean the leaching residue before washing to recover the more soluble phosphorus acid according to the difference of dissolution between phosphoric acid and rare earth sulfuric acid.展开更多
Researchers have recently developed various surface engineering approaches to modify environmental catalysts and improve their catalytic activity.Defect engineering has proved to be one of the most promising modificat...Researchers have recently developed various surface engineering approaches to modify environmental catalysts and improve their catalytic activity.Defect engineering has proved to be one of the most promising modification methods.Constructing defects on the surface of catalytic materials can effectively modulate the coordination environment of the active sites,affecting and changing the electrons,geometry,and other important properties at the catalytic active sites,thus altering the catalytic activity of the catalysts.However,the conformational relationship between defects and catalytic activity remains to be clarified.This dissertation focuses on an overview of recent advances in defect engineering in environmental catalysis.Based on defining the classification of defects in catalytic materials,defect construction methods,and characterization techniques are summarized and discussed.Focusing on an overview of the characteristics of the role of defects in electrocatalytic,photocatalytic,and thermal catalytic reactions and the mechanism of catalytic reactions.An elaborate link is given between the reaction activity and the structure of catalyst defects.Finally,the existing challenges and possible future directions for the application of defect engineering in environmental catalysis are discussed,which are expected to guide the design and development of efficient environmental catalysts and mechanism studies.展开更多
Lithium-sulfur(Li-S)chemistry reaction opens a new battery era with high energy density;meanwhile,multiple electrons migration leads to the complex phase transition of sulfur species.To manipulate the binding strength...Lithium-sulfur(Li-S)chemistry reaction opens a new battery era with high energy density;meanwhile,multiple electrons migration leads to the complex phase transition of sulfur species.To manipulate the binding strength of multiple key intermediates more efficiently,the bimetallic TiVC MXene is utilized to realize multi-dimensional catalysis.Based on the macroscopic three-dimensional(3D)structure using two-dimensional(2D)MXene architecture,electron conductivity and sulfur utilization are improved.Microscopically,Ti-V catalytic systems regulate multiple reaction intermediates through intermetallic synergies customized surface properties and atomic scale coordination,thereby improving electronic and ionic conductivity.In-situ Raman spectroscopy and electrochemical analysis show that the conversion rate of polysulfides was accelerated during the charge-discharge process.The Ti-V interaction exhibits unique catalytic activity and regulates multiple continuous processes of sulfur species phase transformation,which are essential for the excellent energy performance of Li-S batteries.This study not only clarifies the catalytic mechanism of Ti-V at different dimensions but also proposes a promising strategy for the design of advanced catalytic systems in energy storage technology.展开更多
With the ongoing depletion of fossil fuels,energy and environmental issues have become increasingly critical,necessitating the search for effective solutions.Catalysis,being one of the hallmarks of modern industry,off...With the ongoing depletion of fossil fuels,energy and environmental issues have become increasingly critical,necessitating the search for effective solutions.Catalysis,being one of the hallmarks of modern industry,offers a promising avenue for researchers.However,the question of how to significantly enhance the performance of catalysts has gradually drawn the attention of scholars.Defect engineering,a commonly employed and effective approach to improve catalyst activity,has become a significant research focus in the catalysis field in recent years.Nonmetal vacancies have received extensive attention due to their simple form.Consequently,exploration of metal vacancies has remained stagnant for a considerable period,resulting in a scarcity of comprehensive reviews on this topic.Therefore,based on the latest research findings,this paper summarizes and consolidates the construction strategies for metal vacancies,characterization techniques,and their roles in typical energy and environmental catalytic reactions.Additionally,it outlines potential challenges in the future,aiming to provide valuable references for researchers interested in investigating metal vacancies.展开更多
The dielectric loss of carbon materials is closely related to the microstructure and the degree of crystallization,and the microstructure modulation of electromagnetic wave absorbing carbon materials is the key to enh...The dielectric loss of carbon materials is closely related to the microstructure and the degree of crystallization,and the microstructure modulation of electromagnetic wave absorbing carbon materials is the key to enhancing absorption properties.In this work,a porous elastic Co@CNF-PDMS composite was prepared by freeze-drying and confined catalysis.The graphitization degree and conductivity loss of carbon nanofibers(CNFs)were regulated by heat treatment temperature and Co catalyst content.The construction of a heterointerface between Co and C enhances the interfacial polarization loss.The Co@CNF-PDMS composite with 4.5 mm achieves the minimum reflection loss(RLmin)of-81.0 dB at 9.9 GHz and RL no higher than-12.1 dB in the whole of the X-band.After applying a load of up to 40% strain and 100 cycles to Co@CNF-PDMS,the dielectric properties of the composite remain stable.With the increase of compression strain,the distribution density of the absorbent increases,and the CNF sheet layer extrusion contact forms a conductive path,which leads to the conductive loss increase,finally,the absorption band moves to a high frequency.The absorption band can be bi-directionally regulated by loading and strain with good stability,which provides a new strategy for the development of intelligent electromagnetic wave absorbing materials.展开更多
MgH_(2)is a promising solid-state hydrogen storage material.However,its high thermodynamics and sluggish kinetics hinder its practical application.Catalytic strategy is effective in improving its kinetic performance.N...MgH_(2)is a promising solid-state hydrogen storage material.However,its high thermodynamics and sluggish kinetics hinder its practical application.Catalytic strategy is effective in improving its kinetic performance.Nevertheless,the highly efficient catalysts or additives are normally of low-yield in fabrication with high cost.In this work,a novel structural LaVO_(4)fabricated by a low-cost method of spraying dry followed by a calcination is used as a catalytic additive for the hydrogen storage of MgH_(2).With an optimized addition of LaVO_(4),the overall hydrogen storage performances of MgH_(2)are significantly improved.An onset dehydrogenation temperature of only 183℃is obtained after an initial activation of dehydrogenation and hydrogenation.The system can desorb 5.7 wt%H_(2)at 250℃within 10 min and maintains a dehydrogenation capacity of 5.0 wt%H_(2)after 50 cycles.It is found that LaVO_(4)is transferred to lanthanum hydride and metallic vanadium in the initial dehydrogenation process,the former acts as a highly effective catalyst for the hydrogen storage of MgH_(2)and the latter undergoes reversible hydrogenation and dehydrogenation in the subsequent cycles.The structural design of the catalyst and its scalable fabrication are highly valuable in realizing the practical application of catalytic strategy for the hydrogen storage of MgH_(2).展开更多
The production of renewable methanol(CH_(3)OH)via the photocatalytic hydrogenation of CO_(2) is an ideal method to ameliorate energy shortages and mitigate CO_(2) emissions:however,the highly selective synthesis of me...The production of renewable methanol(CH_(3)OH)via the photocatalytic hydrogenation of CO_(2) is an ideal method to ameliorate energy shortages and mitigate CO_(2) emissions:however,the highly selective synthesis of methanol at atmospheric pressure remains challenging owing to the competing reverse water-gas shift(RWGS)reaction.Herein,we present a novel approach for the synthesis of CH_(3)OH via photocatalytic CO_(2) hydrogenation using a catalyst featuring highly dispersed Au nanoparticles loaded on oxygen vacancy(OV)-rich molybdenum dioxide(MoO_(2)),resulting in a remarkable selectivity of 43.78%.The active sites in the Au/MoO_(2) catalyst are high-density Au-oxygen vacancies,which synergistically promote the tandem methanol synthesis via an initial RWGS reaction and subsequent CO hydrogenation.This work provides comprehensive insights into the design of metal-vacancy synergistic sites for the highly selective photocatalytic hydrogenation of CO_(2) to CH_(3)OH.展开更多
Aqueous zinc metal batteries(ZMBs)which are environmentally benign and cheap can be used for grid-scale energy storage,but have a short cycling life mainly due to the poor reversibility of zinc metal anodes in mild aq...Aqueous zinc metal batteries(ZMBs)which are environmentally benign and cheap can be used for grid-scale energy storage,but have a short cycling life mainly due to the poor reversibility of zinc metal anodes in mild aqueous electrolytes.A zincophilic carbon(ZC)layer was deposited on a Zn metal foil at 450°C by the up-stream pyrolysis of a hydrogen-bonded supramolecular substance framework,as-sembled from melamine(ME)and cyanuric acid(CA).The zincophilic groups(C=O and C=N)in the ZC layer guide uniform zinc plating/stripping and eliminate dendrites and side reactions.so that assembled symmetrical batteries(ZC@Zn//ZC@Zn)have a long-term service life of 2500 h at 1 mA cm^(−2) and 1 mAh cm^(−2),which is much longer than that of bare Zn anodes(180 h).In addition,ZC@Zn//V2O5 full batteries have a higher capacity of 174 mAh g^(−1) after 1200 cycles at 2 A g^(−1) than a Zn//V_(2)O_(5) counterpart(100 mAh g^(−1)).The strategy developed for the low-temperat-ure deposition of the ZC layer is a new way to construct advanced zinc metal anodes for ZMBs.展开更多
Electrochemical metallurgy at low temperature(<473 K)shows promise for the extraction and refinement of metals and alloys in a green and sustainable manner.However,the kinetics of the electrodeposition process is g...Electrochemical metallurgy at low temperature(<473 K)shows promise for the extraction and refinement of metals and alloys in a green and sustainable manner.However,the kinetics of the electrodeposition process is generally slow at low temperature,resulting in large overpotential and low current efficiency.Thus,the application of external physical fields has emerged as an effective strategy for improving the mass and charge transfer processes during electrochemical reactions.This review highlights the challenges associated with low-temperature electrochemical processes and briefly discusses recent achievements in optimizing electrodeposition processes through the use of external physical fields.The regulating effects on the optimization of the electrodeposition process and the strategies for select-ing various external physical fields,including magnetic,supergravity,and ultrasonic fields are summarized from the perspectives of equipment and mechanisms.Finally,advanced methods for in-situ characterization of external physical field-assisted electrodeposition processes are reviewed to gain a deeper understanding of metallic electrodeposition.An in-depth exploration of the mechanism by which external physical fields affect the electrode process is essential for enhancing the efficiency of metal extraction at low temperatures.展开更多
Catalysis is a cornerstone of modern chemistry,enabling the development of sustainable processes and the production of essential chemicals.However,a fundamental challenge in catalysis lies in understanding the nature ...Catalysis is a cornerstone of modern chemistry,enabling the development of sustainable processes and the production of essential chemicals.However,a fundamental challenge in catalysis lies in understanding the nature of the catalytic species and active centers,particularly the key mechanistic understanding of homogeneous and heterogeneous systems.This review describes the concept of“cocktail”-type catalysis,demonstrating that catalytic active species are not static but evolve through the interconversion of molecular complexes,clusters,and nanoparticles.By bridging homogeneous and heterogeneous catalysis,this paradigm challenges conventional mechanistic views and initiates discussions for a universal theory of catalysis.The findings highlight the importance of adaptive catalyst behavior,leading to more efficient,selective,and robust catalytic systems.The impact of the“cocktail”-type approach extends beyond fundamental research,offering practical applications in industrial catalysis,green chemistry,and synthetic methodologies.By embracing catalytic dynamics,new opportunities arise for designing next-generation catalysts that are both versatile and highly effective in diverse transformations.展开更多
Maize(Zea mays L.),a globally significant cereal crop,is produced in vast quantities worldwide.However,its growth is severely constrained by low temperatures,particularly during seed germination,which significantly im...Maize(Zea mays L.),a globally significant cereal crop,is produced in vast quantities worldwide.However,its growth is severely constrained by low temperatures,particularly during seed germination,which significantly impairs seedling emergence.In this study,genetic diversity across six germination-associated phenotypic traits(RGR,RSL,RTL,RRSA,RRV,and RSVI)of 304 inbred lines was analyzed,to evaluate the capacity of these lines for low-temperature tolerance.Genome-wide association study(GWAS)was carried out by combining six germination-associated phenotypic traits and genotypic data from 30-fold resequencing.The gene ZmBARK1 was identified through integrated GWAS and RNA-seq analyses,and its association with low-temperature tolerance during maize germination was validated by quantitative real-time PCR(qRT-PCR).ZmBARK1,encoding BRASSINOSTEROID INSENSITIVE 1-associated receptor kinase 1,was located on the bin 4.09 region of maize chromosome 4.Amino acid comparison and subcellular localization analyses revealed that ZmBARK1 is highly homologous to AtBAK1 and is localized to the plasma membrane of the cell,which may be involved in regulating brassinosteroid(BR)signaling.In addition,we revealed the role of ZmBARK1 in low-temperature tolerance during maize germination.Compared with wild-type(WT),the ethyl methanesulfonate(EMS)mutant zmbark1 was characterized by substantially enhanced low-temperature tolerance.Overall,these findings provide promising candidate genes,improve low-temperature tolerance in maize,and advance the understanding of regulatory mechanisms underlying maize's response to low-temperature stress.展开更多
Magnesium alloys are widely used in aerospace and automotive industries due to their lightweight.However,their poor fatigue performance limits the broader application,especially in dynamic stress environments.This stu...Magnesium alloys are widely used in aerospace and automotive industries due to their lightweight.However,their poor fatigue performance limits the broader application,especially in dynamic stress environments.This study explores novel coupled pretreatments of free-end largeangle pre-torsion and low-temperature aging to improve the fatigue resistance of rolled ZK60 magnesium alloy.STA(pre-torsion followed by low-temperature aging)and SAT(low-temperature aging followed by pre-torsion)samples were prepared to investigate the influences of pretreatment coupling sequences.The results of microstructure characterization reveal that pre-torsion significantly enhances the formation of tensile twins and introduces a gradient microstructure with increased dislocation density from the center to the edges.STA process resulted in the highest twinning area fraction of 35.2% and a kernel average misorientation of 0.94 at the edge.Mechanical testing demonstrated that the coupled pre-treatment obtained a better combination of strength and plasticity,significantly improved the yield strength in the compression stage,and increased the tensile-compressive yield ratio to>0.9.In the low-cycle fatigue test,the STA samples exhibited lower cyclic mean stress,a smaller cyclic hardening trend,and better hysteretic symmetry,leading to an improvement in fatigue life of up to 256%.The findings suggest that the combined pre-torsion and low-temperature aging treatments offer a promising approach to enhance the mechanical properties and fatigue resistance of ZK60 magnesium alloy,making it suitable for structural applications in demanding environments.展开更多
Abscisic acid(ABA)plays a key role in promoting the growth and development of plants,as well as mediating the responses of plants to adverse environmental conditions.Here,we measured the photosynthetic capacity of wil...Abscisic acid(ABA)plays a key role in promoting the growth and development of plants,as well as mediating the responses of plants to adverse environmental conditions.Here,we measured the photosynthetic capacity of wild-type RR,mutant sitiens(sit),and ABA-pretreated sit tomato seedlings following exposure to low-temperature(LT)stress.We found that the net photosynthetic rate,intercellular carbon dioxide concentration,transpiration rate,and stomatal conductance of sit seedlings were lower than those of RR seedlings under LT stress.The chloroplast width,area,and number of osmiophilic granules were significantly larger in sit seedlings than in RR seedlings,while the chloroplast length/width ratio was significantly lower in sit seedlings than in RR seedlings.The photochemical activity of sit seedlings was lower,and the expression of photosynthesis-related genes in sit seedlings was altered following exposure to LT stress.ABA pretreatment significantly alleviated the above phenomenon.We also conducted an RNA sequencing analysis and characterized the expression patterns of genes in tomato seedlings following exposure to LT stress.We constructed 15 cDNA libraries and identified several differentially expressed genes involved in photosynthesis,plant hormone signaling transduction,and primary and secondary metabolism.Additional analyses of genes encoding transcription factors and proteins involved in photosynthesis-related processes showed pronounced changes in expression under LT stress.Luciferase reporter assay and electrophoretic mobility shift assay revealed that WRKY22 regulates the expression of PsbA.The PSII of WRKY22 and PsbA-silenced plants was inhibited.Our findings indicate that ABA plays a role in regulating the process of photosynthesis and protecting PSII in tomato under LT stress through the WRKY22-PsbA complex.展开更多
Porous molecular sieve catalysts,including aluminosilicate zeolites and silicoaluminophosphate(SAPO)molecular sieves,have found widespread use in heterogeneous catalysis and are expected to play a key role in advancin...Porous molecular sieve catalysts,including aluminosilicate zeolites and silicoaluminophosphate(SAPO)molecular sieves,have found widespread use in heterogeneous catalysis and are expected to play a key role in advancing carbon neutrality and sustainable development.Given the ubiquitous presence of water during catalyst synthesis,storage,and application,the interactions between water and molecular sieves as well as their consequent effects on frameworks and catalytic reactions have attracted considerable attention.These effects are inherently complex and highly dependent on various factors such as temperature,water phase,and partial pressure.In this review,we provide a comprehensive overview of the current understanding of water-molecular sieve interactions and their roles in catalysis,based on both experimental and theoretical calculation results.Special attention is paid to water-induced reversible and irreversible structural changes in aluminosilicate and SAPO frameworks at the atomic level,underscoring the dynamic and labile nature of these frameworks in water environments.The influence of water on catalytic performance and reaction kinetics in molecular sieve-catalyzed reactions is discussed from two perspectives:(1)its participation in reaction through hydrogen bonding interactions,such as competitive adsorption at active sites,stabilization of ground and transition states,and proton transfer bridge;(2)its role as a direct reactant forming new species via reactions with other vip molecules.Recent advancements in this area provide valuable insights for the rational design and optimization of catalysts for water-involved reactions.展开更多
基金support of the National Natural Science Foundation of China(22075131 and 22078265)the Shaanxi Fundamental Science Research Project for Mathematics and Physics under Grants(No.22JSZ005)the State-Key Laboratory of Multiphase Complex Systems(No.MPCS-2021-A).
文摘Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties.In this work,we propose an autogenously transformed CoWO_(4)/WO_(2) heterojunction catalyst,integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity.CoWO_(4) effectively captures polysulfides,while the CoWO_(4)/WO_(2) interface facilitates their S-S bond activation on heterogenous catalytic sites.Benefiting from its directional intercalation channels,CoWO_(4) not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport.Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite.As a result,the CoWO_(4)/WO_(2) heterostructure demonstrates significantly enhanced catalytic performance,delivering a high capacity of 1262 mAh g^(−1) at 0.1 C.Furthermore,its rate capability and high sulfur loading performance are markedly improved,surpassing the limitations of its single-component counterparts.This study provides new insights into the catalytic mechanisms governing Li-S chemistry and offers a promising strategy for the rational design of high-performance Li-S battery catalysts.
基金the financial support from the Key Project of Shaanxi Provincial Natural Science Foundation-Key Project of Laboratory(2025SYS-SYSZD-117)the Natural Science Basic Research Program of Shaanxi(2025JCYBQN-125)+8 种基金Young Talent Fund of Xi'an Association for Science and Technology(0959202513002)the Key Industrial Chain Technology Research Program of Xi'an(24ZDCYJSGG0048)the Key Research and Development Program of Xianyang(L2023-ZDYF-SF-077)Postdoctoral Fellowship Program of CPSF(GZC20241442)Shaanxi Postdoctoral Science Foundation(2024BSHSDZZ070)Research Funds for the Interdisciplinary Projects,CHU(300104240913)the Fundamental Research Funds for the Central Universities,CHU(300102385739,300102384201,300102384103)the Scientific Innovation Practice Project of Postgraduate of Chang'an University(300103725063)the financial support from the Australian Research Council。
文摘Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.
基金financially supported by the National Natural Science Foundation of China(No.22309067)the Open Project Program of the State Key Laboratory of Materials-Oriented Chemical Engineering,China(No.KL21-05)the Marine Equipment and Technology Institute,Jiangsu University of Science and Technology,China(No.XTCX202404)。
文摘This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.1)Mo_(0.05)O_(3-δ)(B S CNM_(0.05)),Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.05)Mo_(0.1)O_(3-δ)(BSCNM_(0.1)),and Ba_(0.6)Sr_(0.4)Co_(0.85)Mo_(0.15)O_(3-δ)(BSCM)—with Mo doping contents of 5mol%,10mol%,and15mol%,respectively,were successfully prepared using the sol-gel method.The effects of Mo doping on the crystal structure,conductivity,thermal expansion coefficient,oxygen reduction reaction(ORR)activity,and electrochemical performance were systematically evaluated using X-ray diffraction analysis,thermally induced characterization,electrochemical impedance spectroscopy,and single-cell performance tests.The results revealed that Mo doping could improve the conductivity of the materials,suppress their thermal expansion effects,and significantly improve the electrochemical performance.Surface chemical state analysis using X-ray photoelectron spectroscopy revealed that 5mol%Mo doping could facilitate a high adsorbed oxygen concentration leading to enhanced ORR activity in the materials.Density functional theory calculations confirmed that Mo doping promoted the ORR activity in the materials.At an operating temperature of 600℃,the BSCNM_(0.05)cathode material exhibited significantly enhanced electrochemical impedance characteristics,with a reduced area specific resistance of 0.048Ω·cm~2,which was lower than that of the undoped BSCN matrix material by 32.39%.At the same operating temperature,an anode-supported single cell using a BSCNM_(0.05)cathode achieved a peak power density of 1477 mW·cm^(-2),which was 30.71%,56.30%,and 171.50%higher than those of BSCN,BSCNM_(0.1),and B SCM,respectively.The improved ORR activity and electrochemical performance of BSCNM_(0.05)indicate that it can be used as a cathode material in low-temperature solid oxide fuel cells.
基金supported by the National Natural Science Foundation(52302284,22002086,22204096)Shanghai Sailing Program(23YF1412200)the Fundamental Research Funds for the Central Universities(22120240314).
文摘Single-atom catalysts(SACs)have garnered significant attention in lithium-sulfur(Li-S)batteries for their potential to mitigate the severe polysulfide shuttle effect and sluggish redox kinetics.However,the development of highly efficient SACs and a comprehensive understanding of their structure-activity relationships remain enormously challenging.Herein,a novel kind of Fe-based SAC featuring an asymmetric FeN_(5)-TeN_(4) coordination structure was precisely designed by introducing Te atom adjacent to the Fe active center to enhance the catalytic activity.Theoretical calculations reveal that the neighboring Te atom modulates the local coordination environment of the central Fe site,elevating the d-band center closer to the Fermi level and strengthening the d-p orbital hybridization between the catalyst and sulfur species,thereby immobilizing polysulfides and improving the bidirectional catalysis of Li-S redox.Consequently,the Fe-Te atom pair catalyst endows Li-S batteries with exceptional rate performance,achieving a high specific capacity of 735 mAh g^(−1) at 5 C,and remarkable cycling stability with a low decay rate of 0.038%per cycle over 1000 cycles at 1 C.This work provides fundamental insights into the electronic structure modulation of SACs and establishes a clear correlation between precisely engineered atomic configurations and their enhanced catalytic performance in Li-S electrochemistry.
文摘Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent catalysis,supramolecular systems can create dynamic and adaptable microenvironments tailored to specific substrates,similar to how enzymes work.This strategy has shown great promise in asymmetric catalysis,cascade reactions,and green chemistry applications.Recent advances focus on leveraging less conventional noncovalent forces to expand the toolbox of supramolecular strategies in catalysis.
基金financial support from the Department of Science and Technology of Jilin Province(20240304104SF,20240304103SF)the Research and Innovation Fund of the Beihua University for the Graduate Student(Major Project 2023012)。
文摘Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-forming properties and high dielectric constant.However,the elevated freezing point,high viscosity,and strong solvation energy of EC significantly hinder the transport rate of Li^(+)and the desolvation process at low temperatures.This leads to substantial capacity loss and even lithium plating on graphite anodes.Herein,we have developed an efficient electrolyte system specifically designed for lowtemperature conditions,which consists of 1.0 M lithium bis(fluorosulfonyl)imide(LiFSI)in isoxazole(IZ)with fluorobenzene(FB)as an uncoordinated solvent and fluoroethylene carbonate(FEC)as a filmforming co-solvent.This system effectively lowers the desolvation energy of Li^(+)through dipole-dipole interactions.The weak solvation capability allows more anions to enter the solvation sheath,promoting the formation of contact ion pairs(CIPs)and aggregates(AGGs)that enhance the transport rate of Li^(+)while maintaining high ionic conductivity across a broad temperature range.Moreover,the formation of inorganic-dominant interfacial phases on the graphite anode,induced by fluoroethylene carbonate,significantly enhances the kinetics of Li^(+)transport.At a low temperature of-20℃,this electrolyte system achieves an impressive reversible capacity of 200.9 mAh g^(-1)in graphite half-cell,which is nearly three times that observed with conventional EC-based electrolytes,demonstrating excellent stability throughout its operation.
基金support by the National Natural Science Foundation of Inner Mongolia (2022SHZR1885)Natural Science Foundation of Hebei province (E2022402101,E2022402105)。
文摘To completely recover valuable elements and reduce the amount of waste,the impact of phosphoric acid on the decomposition of rare earth,fluorine and phosphorus during cyclic leaching was studied based on the characteristics of low-tempe rature sulfuric acid deco mposition.When a single monazite was leached using 75 wt% H_(2)SO_(4) solution with phosphoric acid,the size and number of monazite particles in the washing slag gradually decrease with the increase in phosphoric acid content in the leaching solution.The monazite phase can hardly be found in the slag when the phosphoric acid content reaches 70 g/L,which indicates that phosphoric acid is favorable for monazite decomposition.The mixed rare earth concentrate was leached by 75 wt% H_(2)SO_(4) containing 70 g/L phosphoric acid,the mineral compositions of the washing slag are only gypsum and unwashed rare earth sulfuric acid.After cyclic leaching of75 wt% H_(2)SO_(4),the mineral compositions of the primary leaching washing slag are mainly undecomposed monazite,rare earth sulfate and calcium sulfate.However,monazite is not found in the mineral phase of the second and third leaching washing slag.The leaching rates of rare earth and phosphorus gradually increase with the increase in cyclic leaching times.In addition,the phosphoric acid content in the leaching solution increases with the increase in the number of cyclic leaching time.However,the rising trend decreases when the phosphoric acid content reaches 50 g/L by adsorption and crystallization of phosphoric acid.A small amount of water can be used to clean the leaching residue before washing to recover the more soluble phosphorus acid according to the difference of dissolution between phosphoric acid and rare earth sulfuric acid.
基金supported by The National Key R&D Program of China(No.2021YFB3500700)National Natural Science Foundation of China(Nos.21677010 and 51808037)Special fund of Beijing Key Laboratory of Indoor Air Quality Evaluation and Control(No.BZ0344KF21-04)。
文摘Researchers have recently developed various surface engineering approaches to modify environmental catalysts and improve their catalytic activity.Defect engineering has proved to be one of the most promising modification methods.Constructing defects on the surface of catalytic materials can effectively modulate the coordination environment of the active sites,affecting and changing the electrons,geometry,and other important properties at the catalytic active sites,thus altering the catalytic activity of the catalysts.However,the conformational relationship between defects and catalytic activity remains to be clarified.This dissertation focuses on an overview of recent advances in defect engineering in environmental catalysis.Based on defining the classification of defects in catalytic materials,defect construction methods,and characterization techniques are summarized and discussed.Focusing on an overview of the characteristics of the role of defects in electrocatalytic,photocatalytic,and thermal catalytic reactions and the mechanism of catalytic reactions.An elaborate link is given between the reaction activity and the structure of catalyst defects.Finally,the existing challenges and possible future directions for the application of defect engineering in environmental catalysis are discussed,which are expected to guide the design and development of efficient environmental catalysts and mechanism studies.
基金the financial support provided by the National Natural Science Foundation of China(No.51932005)the Liaoning Revitalization Talents Program(No.XLYC1807175)+1 种基金the Development Plan of Science and Technology of Jilin Province,China(YDZJ202301ZYTS280)the Natural Science Foundation of Jilin Province(YDZJ202401316ZYTS)。
文摘Lithium-sulfur(Li-S)chemistry reaction opens a new battery era with high energy density;meanwhile,multiple electrons migration leads to the complex phase transition of sulfur species.To manipulate the binding strength of multiple key intermediates more efficiently,the bimetallic TiVC MXene is utilized to realize multi-dimensional catalysis.Based on the macroscopic three-dimensional(3D)structure using two-dimensional(2D)MXene architecture,electron conductivity and sulfur utilization are improved.Microscopically,Ti-V catalytic systems regulate multiple reaction intermediates through intermetallic synergies customized surface properties and atomic scale coordination,thereby improving electronic and ionic conductivity.In-situ Raman spectroscopy and electrochemical analysis show that the conversion rate of polysulfides was accelerated during the charge-discharge process.The Ti-V interaction exhibits unique catalytic activity and regulates multiple continuous processes of sulfur species phase transformation,which are essential for the excellent energy performance of Li-S batteries.This study not only clarifies the catalytic mechanism of Ti-V at different dimensions but also proposes a promising strategy for the design of advanced catalytic systems in energy storage technology.
基金financially supported by National Key R&D Program of China(2021YFB3500702)National Natural Science Foundation of China(Nos.21677010 and 51808037)Special fund of Beijing Key Laboratory of Indoor Air Quality Evaluation and Control(No.BZ0344KF21-04).
文摘With the ongoing depletion of fossil fuels,energy and environmental issues have become increasingly critical,necessitating the search for effective solutions.Catalysis,being one of the hallmarks of modern industry,offers a promising avenue for researchers.However,the question of how to significantly enhance the performance of catalysts has gradually drawn the attention of scholars.Defect engineering,a commonly employed and effective approach to improve catalyst activity,has become a significant research focus in the catalysis field in recent years.Nonmetal vacancies have received extensive attention due to their simple form.Consequently,exploration of metal vacancies has remained stagnant for a considerable period,resulting in a scarcity of comprehensive reviews on this topic.Therefore,based on the latest research findings,this paper summarizes and consolidates the construction strategies for metal vacancies,characterization techniques,and their roles in typical energy and environmental catalytic reactions.Additionally,it outlines potential challenges in the future,aiming to provide valuable references for researchers interested in investigating metal vacancies.
基金financially supported by the National Natural Science Foundation of China(No.52231007)the Natural Science Foundation of Shaanxi Province(No.2022JM-248)+1 种基金the Creative Research Foundation of the Science and Technology on Thermostructural Composite Materials Laboratorythe Doctoral Scientific Research Foundation of Shaanxi University of Science&Technology(No.BJ16-06).
文摘The dielectric loss of carbon materials is closely related to the microstructure and the degree of crystallization,and the microstructure modulation of electromagnetic wave absorbing carbon materials is the key to enhancing absorption properties.In this work,a porous elastic Co@CNF-PDMS composite was prepared by freeze-drying and confined catalysis.The graphitization degree and conductivity loss of carbon nanofibers(CNFs)were regulated by heat treatment temperature and Co catalyst content.The construction of a heterointerface between Co and C enhances the interfacial polarization loss.The Co@CNF-PDMS composite with 4.5 mm achieves the minimum reflection loss(RLmin)of-81.0 dB at 9.9 GHz and RL no higher than-12.1 dB in the whole of the X-band.After applying a load of up to 40% strain and 100 cycles to Co@CNF-PDMS,the dielectric properties of the composite remain stable.With the increase of compression strain,the distribution density of the absorbent increases,and the CNF sheet layer extrusion contact forms a conductive path,which leads to the conductive loss increase,finally,the absorption band moves to a high frequency.The absorption band can be bi-directionally regulated by loading and strain with good stability,which provides a new strategy for the development of intelligent electromagnetic wave absorbing materials.
基金supported by the National Natural Science Foundation of PR China(Nos.52071287,52125104 and 52072342)Natural Science Foundation of Zhejiang Province,PR China(No.LZ23E010002).
文摘MgH_(2)is a promising solid-state hydrogen storage material.However,its high thermodynamics and sluggish kinetics hinder its practical application.Catalytic strategy is effective in improving its kinetic performance.Nevertheless,the highly efficient catalysts or additives are normally of low-yield in fabrication with high cost.In this work,a novel structural LaVO_(4)fabricated by a low-cost method of spraying dry followed by a calcination is used as a catalytic additive for the hydrogen storage of MgH_(2).With an optimized addition of LaVO_(4),the overall hydrogen storage performances of MgH_(2)are significantly improved.An onset dehydrogenation temperature of only 183℃is obtained after an initial activation of dehydrogenation and hydrogenation.The system can desorb 5.7 wt%H_(2)at 250℃within 10 min and maintains a dehydrogenation capacity of 5.0 wt%H_(2)after 50 cycles.It is found that LaVO_(4)is transferred to lanthanum hydride and metallic vanadium in the initial dehydrogenation process,the former acts as a highly effective catalyst for the hydrogen storage of MgH_(2)and the latter undergoes reversible hydrogenation and dehydrogenation in the subsequent cycles.The structural design of the catalyst and its scalable fabrication are highly valuable in realizing the practical application of catalytic strategy for the hydrogen storage of MgH_(2).
文摘The production of renewable methanol(CH_(3)OH)via the photocatalytic hydrogenation of CO_(2) is an ideal method to ameliorate energy shortages and mitigate CO_(2) emissions:however,the highly selective synthesis of methanol at atmospheric pressure remains challenging owing to the competing reverse water-gas shift(RWGS)reaction.Herein,we present a novel approach for the synthesis of CH_(3)OH via photocatalytic CO_(2) hydrogenation using a catalyst featuring highly dispersed Au nanoparticles loaded on oxygen vacancy(OV)-rich molybdenum dioxide(MoO_(2)),resulting in a remarkable selectivity of 43.78%.The active sites in the Au/MoO_(2) catalyst are high-density Au-oxygen vacancies,which synergistically promote the tandem methanol synthesis via an initial RWGS reaction and subsequent CO hydrogenation.This work provides comprehensive insights into the design of metal-vacancy synergistic sites for the highly selective photocatalytic hydrogenation of CO_(2) to CH_(3)OH.
基金partially supported by the National Natural Science Foundation of China(22479022)Liaoning Revitalization Talents Program(XLYC2007129)。
文摘Aqueous zinc metal batteries(ZMBs)which are environmentally benign and cheap can be used for grid-scale energy storage,but have a short cycling life mainly due to the poor reversibility of zinc metal anodes in mild aqueous electrolytes.A zincophilic carbon(ZC)layer was deposited on a Zn metal foil at 450°C by the up-stream pyrolysis of a hydrogen-bonded supramolecular substance framework,as-sembled from melamine(ME)and cyanuric acid(CA).The zincophilic groups(C=O and C=N)in the ZC layer guide uniform zinc plating/stripping and eliminate dendrites and side reactions.so that assembled symmetrical batteries(ZC@Zn//ZC@Zn)have a long-term service life of 2500 h at 1 mA cm^(−2) and 1 mAh cm^(−2),which is much longer than that of bare Zn anodes(180 h).In addition,ZC@Zn//V2O5 full batteries have a higher capacity of 174 mAh g^(−1) after 1200 cycles at 2 A g^(−1) than a Zn//V_(2)O_(5) counterpart(100 mAh g^(−1)).The strategy developed for the low-temperat-ure deposition of the ZC layer is a new way to construct advanced zinc metal anodes for ZMBs.
基金supported by Southern Marine Science and Engineering Guangdong Laboratory(Zhuhai)(No.SML2023SP243)the National Key Research and Development Program of China(No.2022YFC2906100)the National Natural Science Foundation of China(No.92475202)are acknowledged.
文摘Electrochemical metallurgy at low temperature(<473 K)shows promise for the extraction and refinement of metals and alloys in a green and sustainable manner.However,the kinetics of the electrodeposition process is generally slow at low temperature,resulting in large overpotential and low current efficiency.Thus,the application of external physical fields has emerged as an effective strategy for improving the mass and charge transfer processes during electrochemical reactions.This review highlights the challenges associated with low-temperature electrochemical processes and briefly discusses recent achievements in optimizing electrodeposition processes through the use of external physical fields.The regulating effects on the optimization of the electrodeposition process and the strategies for select-ing various external physical fields,including magnetic,supergravity,and ultrasonic fields are summarized from the perspectives of equipment and mechanisms.Finally,advanced methods for in-situ characterization of external physical field-assisted electrodeposition processes are reviewed to gain a deeper understanding of metallic electrodeposition.An in-depth exploration of the mechanism by which external physical fields affect the electrode process is essential for enhancing the efficiency of metal extraction at low temperatures.
基金support by the Ministry of Science and Higher Education(075-15-2024-531)。
文摘Catalysis is a cornerstone of modern chemistry,enabling the development of sustainable processes and the production of essential chemicals.However,a fundamental challenge in catalysis lies in understanding the nature of the catalytic species and active centers,particularly the key mechanistic understanding of homogeneous and heterogeneous systems.This review describes the concept of“cocktail”-type catalysis,demonstrating that catalytic active species are not static but evolve through the interconversion of molecular complexes,clusters,and nanoparticles.By bridging homogeneous and heterogeneous catalysis,this paradigm challenges conventional mechanistic views and initiates discussions for a universal theory of catalysis.The findings highlight the importance of adaptive catalyst behavior,leading to more efficient,selective,and robust catalytic systems.The impact of the“cocktail”-type approach extends beyond fundamental research,offering practical applications in industrial catalysis,green chemistry,and synthetic methodologies.By embracing catalytic dynamics,new opportunities arise for designing next-generation catalysts that are both versatile and highly effective in diverse transformations.
基金supported by the Key Research and Development Project of Heilongjiang Province(2022ZX02B01)the Natural Science Foundation Project of Heilongjiang Province(YQ2022C009)the Natural Science Foundation of Shandong Province(K22LB56)。
文摘Maize(Zea mays L.),a globally significant cereal crop,is produced in vast quantities worldwide.However,its growth is severely constrained by low temperatures,particularly during seed germination,which significantly impairs seedling emergence.In this study,genetic diversity across six germination-associated phenotypic traits(RGR,RSL,RTL,RRSA,RRV,and RSVI)of 304 inbred lines was analyzed,to evaluate the capacity of these lines for low-temperature tolerance.Genome-wide association study(GWAS)was carried out by combining six germination-associated phenotypic traits and genotypic data from 30-fold resequencing.The gene ZmBARK1 was identified through integrated GWAS and RNA-seq analyses,and its association with low-temperature tolerance during maize germination was validated by quantitative real-time PCR(qRT-PCR).ZmBARK1,encoding BRASSINOSTEROID INSENSITIVE 1-associated receptor kinase 1,was located on the bin 4.09 region of maize chromosome 4.Amino acid comparison and subcellular localization analyses revealed that ZmBARK1 is highly homologous to AtBAK1 and is localized to the plasma membrane of the cell,which may be involved in regulating brassinosteroid(BR)signaling.In addition,we revealed the role of ZmBARK1 in low-temperature tolerance during maize germination.Compared with wild-type(WT),the ethyl methanesulfonate(EMS)mutant zmbark1 was characterized by substantially enhanced low-temperature tolerance.Overall,these findings provide promising candidate genes,improve low-temperature tolerance in maize,and advance the understanding of regulatory mechanisms underlying maize's response to low-temperature stress.
基金sponsored by the National Natural Science Foundation of China(Nos.52175143,and 51571150).
文摘Magnesium alloys are widely used in aerospace and automotive industries due to their lightweight.However,their poor fatigue performance limits the broader application,especially in dynamic stress environments.This study explores novel coupled pretreatments of free-end largeangle pre-torsion and low-temperature aging to improve the fatigue resistance of rolled ZK60 magnesium alloy.STA(pre-torsion followed by low-temperature aging)and SAT(low-temperature aging followed by pre-torsion)samples were prepared to investigate the influences of pretreatment coupling sequences.The results of microstructure characterization reveal that pre-torsion significantly enhances the formation of tensile twins and introduces a gradient microstructure with increased dislocation density from the center to the edges.STA process resulted in the highest twinning area fraction of 35.2% and a kernel average misorientation of 0.94 at the edge.Mechanical testing demonstrated that the coupled pre-treatment obtained a better combination of strength and plasticity,significantly improved the yield strength in the compression stage,and increased the tensile-compressive yield ratio to>0.9.In the low-cycle fatigue test,the STA samples exhibited lower cyclic mean stress,a smaller cyclic hardening trend,and better hysteretic symmetry,leading to an improvement in fatigue life of up to 256%.The findings suggest that the combined pre-torsion and low-temperature aging treatments offer a promising approach to enhance the mechanical properties and fatigue resistance of ZK60 magnesium alloy,making it suitable for structural applications in demanding environments.
基金supported by the National Natural Science Foundation of China(32272791 and 32072651)the earmarked fund for CARS(CARS-23)+1 种基金the Joint Fund for Innovation Enhancement of Liaoning Province,China(2021-NLTS-11-01)the support program for Young and Middle-aged Scientific and Technological Innovation Talents,China(RC210293)。
文摘Abscisic acid(ABA)plays a key role in promoting the growth and development of plants,as well as mediating the responses of plants to adverse environmental conditions.Here,we measured the photosynthetic capacity of wild-type RR,mutant sitiens(sit),and ABA-pretreated sit tomato seedlings following exposure to low-temperature(LT)stress.We found that the net photosynthetic rate,intercellular carbon dioxide concentration,transpiration rate,and stomatal conductance of sit seedlings were lower than those of RR seedlings under LT stress.The chloroplast width,area,and number of osmiophilic granules were significantly larger in sit seedlings than in RR seedlings,while the chloroplast length/width ratio was significantly lower in sit seedlings than in RR seedlings.The photochemical activity of sit seedlings was lower,and the expression of photosynthesis-related genes in sit seedlings was altered following exposure to LT stress.ABA pretreatment significantly alleviated the above phenomenon.We also conducted an RNA sequencing analysis and characterized the expression patterns of genes in tomato seedlings following exposure to LT stress.We constructed 15 cDNA libraries and identified several differentially expressed genes involved in photosynthesis,plant hormone signaling transduction,and primary and secondary metabolism.Additional analyses of genes encoding transcription factors and proteins involved in photosynthesis-related processes showed pronounced changes in expression under LT stress.Luciferase reporter assay and electrophoretic mobility shift assay revealed that WRKY22 regulates the expression of PsbA.The PSII of WRKY22 and PsbA-silenced plants was inhibited.Our findings indicate that ABA plays a role in regulating the process of photosynthesis and protecting PSII in tomato under LT stress through the WRKY22-PsbA complex.
文摘Porous molecular sieve catalysts,including aluminosilicate zeolites and silicoaluminophosphate(SAPO)molecular sieves,have found widespread use in heterogeneous catalysis and are expected to play a key role in advancing carbon neutrality and sustainable development.Given the ubiquitous presence of water during catalyst synthesis,storage,and application,the interactions between water and molecular sieves as well as their consequent effects on frameworks and catalytic reactions have attracted considerable attention.These effects are inherently complex and highly dependent on various factors such as temperature,water phase,and partial pressure.In this review,we provide a comprehensive overview of the current understanding of water-molecular sieve interactions and their roles in catalysis,based on both experimental and theoretical calculation results.Special attention is paid to water-induced reversible and irreversible structural changes in aluminosilicate and SAPO frameworks at the atomic level,underscoring the dynamic and labile nature of these frameworks in water environments.The influence of water on catalytic performance and reaction kinetics in molecular sieve-catalyzed reactions is discussed from two perspectives:(1)its participation in reaction through hydrogen bonding interactions,such as competitive adsorption at active sites,stabilization of ground and transition states,and proton transfer bridge;(2)its role as a direct reactant forming new species via reactions with other vip molecules.Recent advancements in this area provide valuable insights for the rational design and optimization of catalysts for water-involved reactions.
