In this study,the commonly used Cu or Mn-based low-temperature SCR catalysts were employed to investigate their different reaction behaviors in the presence of high-content water vapor.Experimental results reveal that...In this study,the commonly used Cu or Mn-based low-temperature SCR catalysts were employed to investigate their different reaction behaviors in the presence of high-content water vapor.Experimental results reveal that CuCeTi sample possesses superior water re sistance at low temperature compared with MnCeTi catalyst.Upon the introduction of water vapor,both catalysts exhibit a quick loss in deNOxefficiency,while that is more pronounced on MnCeTi sample.In addition,unlike CuCeTi sample,MnCeTi catalyst also shows a gradual deactivation tendency after initial quick activity loss.Characterization and simulation results indicate that H_(2)O is more easily adsorbed and dissociated on MnCeTi catalyst,showing stronger suppression on NH3adsorption,causing more serious initial deactivation.Furthermore,more abundant hydroxyl groups derived from dissociative adsorption of water on MnCeTi catalyst will lead to more NH4NO3deposition and the decrease in redox capacity.This is the main reason of gradual deactivation of MnCeTi catalyst at high-content water vapor.Such findings could pave a new way for development of highly efficient SCR catalysts with good water resistance for real application.展开更多
Among multitudinous metal‐oxide catalysts for the selective catalytic reduction of NOx with NH3(NH3‐SCR),Mn‐based catalysts have become very popular and developed rapidly in recent years because of its superior low...Among multitudinous metal‐oxide catalysts for the selective catalytic reduction of NOx with NH3(NH3‐SCR),Mn‐based catalysts have become very popular and developed rapidly in recent years because of its superior low‐temperature denitrification activity,mainly originating from multi‐valence of Mn.Most studies suggest that the catalytic activity of multi‐component oxides is superior to that of single‐component catalysts owing to the synergistic effect among the metallic elements in such materials,of which more attentions have been given to Ce as an additive owing to its powerful oxygen storage capacity,redox ability and its ready availability.As the core of SCR technology,the research points in catalyst development at the present stage of all researchers in countries mainly centralize on the optimization of active components,carriers,calcination temperature,calcination time and temperature‐raising procedure,giving little thought to the effects of the calcination atmosphere.In the present work,Ce‐modified Mn‐based catalysts were prepared by a simple impregnation method.The effects of the calcination atmosphere(N2,air or O2)on the performance of the resulting materials during NH3‐SCR and its causes of the differences were subsequently investigated and characterized using various analytical methods.Data obtained from X‐ray diffraction,thermogravimetry and temperature‐programmed reduction with hydrogen show that calcination under N2reduces both the degree of oxidation and crystallization of the MnOx.Scanning electron microscopy also demonstrates that the use of N2inhibits the growth of grains and increases the dispersion of the catalysts.In addition,the results of temperature‐programmed desorption with ammonia indicate that catalysts calcined under N2exhibit a greater quantity of acid sites.Finally,X‐ray photoelectron spectrometry and activity results demonstrate that MnOx in the lower valence states is more favorable for NH3‐SCR reactions.In conclusion,catalysts calcined under N2show superior performance during NH3‐SCR for NOx removal,allowing NO conversions up to94%at473K.展开更多
Catalytic ozonation is a potential technology to eliminate refractory organic contaminants with the low concentration in secondary effluent from industrial park wastewater treatment plants(IPWWTPs).In this study,the c...Catalytic ozonation is a potential technology to eliminate refractory organic contaminants with the low concentration in secondary effluent from industrial park wastewater treatment plants(IPWWTPs).In this study,the catalytic ozonation over the Mn-based catalyst significantly improved the chemical oxygen demand(COD),total organic carbon(TOC),and UV254 removals of secondary effluent from IPWWTPs.The Mn-based catalyst/Og system achieved 84.8%,69.8%,and 86.4% removals of COD,TOC,and UY254,which were 3.3,5.7,and 1.1 times that in ozonation alone,respectively.Moreover,the Mn-based catalytic ozonation process exhibited excellent pH tolerance ranging from pH 4.0 to 9.0.Additionally,the depth analysis based on fluorescence excitation-emission matrix(EEM)confirmed that the catalytic ozonation process preferred to degrade toxic aromatic hydrocarbons.The existence of the Mn-based catalyst/O_(3) system enhanced 21.4%-38.3% more fluorescent organic matters removal,compared to that in ozonation alone.Mechanistic studies proved that the abundant Lewis acid sites(Mn/Mn(n+1)+and adsorbed oxygen)on the surface of the Mn-based catalyst effectively promoted O_(3) decomposition into reactive oxygen species(ROS),and-O_(2)-/HO_(2):and ^(1)O_(2) were the main ROS for degrading refractory organic contaminants.The contributions of ROS oxidation(91.2%)was much higher than that of direct O_(3) oxidation(8.8%).Thus,this work provides an effective advanced treatment process for purifying secondary effluent from IPWWTPs.展开更多
The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the ...The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the long-cycling stability of batteries needs to be improved.Herein,the Mn-based Li-rich cathode materials with small amounts of Li2 MnO3 crystal domains and gradient doping of Al and Ti elements from the surface to the bulk have been developed to improve the structure and interface stability.Then the batteries with a high energy density of 600 Wh kg^(-1),excellent capacity retention of 99.7%with low voltage decay of 0.03 mV cycle^(-1) after 800 cycles,and good rates performances can be achieved.Therefore,the structure and cycling stability of low voltage Mn-based Li-rich cathode materials can be significantly improved by the bulk structure design and interface regulation,and this work has paved the way for developing low-cost and high-energy Mn-based energy storage batteries with long lifetime.展开更多
Li-rich Mn-based oxides(LRMO)are of great significance in achieving high energy density all-solid-state lithium batteries(ASSLBs),owing to their high theoretical capacity and high operation voltage.Unfortunately,their...Li-rich Mn-based oxides(LRMO)are of great significance in achieving high energy density all-solid-state lithium batteries(ASSLBs),owing to their high theoretical capacity and high operation voltage.Unfortunately,their practical application is hindered by severe interface degradation due to the chemical oxidation and electrochemical decomposition of solid electrolytes(SEs),driven by high-active oxygen and electron sources from LRMO.Herein,an interfacial modification strategy is proposed to stabilize the surface lattice oxygen of LRMO and reduce electronic conduction between LRMO and SEs,synergistically.Accordingly,the byproducts from chemical oxidation(InO^(-))and electrochemical decomposition(LiCl^(-))are largely suppressed,leading to superior interfacial transport with the lowest resistance.Consequently,the ASSLB achieves a high reversible capacity of 227.9 mA h g^(-1)at 0.1 C,a cycling stability of 90.1%capacity retention after 200 cycles at 0.1 C,and a superior rate capability with a capacity of81.7 m A h g^(-1)at 3.0 C.This study enriches the fundamental understanding of LRMO/SEs interfacial evolution during the electrochemical cycling and the proposed interfacial modification strategy benefits the future design of Li-rich compounds for ASSLBs.展开更多
Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prep...Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.展开更多
Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting t...Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.展开更多
Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen e...Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.展开更多
Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon...Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.展开更多
To elucidate the effect of calcite-regulated activated carbon(AC)structure on low-temperature denitrification performance of SCR catalysts,this work prepared a series of Mn-Ce/De-AC-xCaCO_(3)(x is the calcite content ...To elucidate the effect of calcite-regulated activated carbon(AC)structure on low-temperature denitrification performance of SCR catalysts,this work prepared a series of Mn-Ce/De-AC-xCaCO_(3)(x is the calcite content in coal)catalysts were prepared by the incipient wetness impregnation method,followed by acid washing to remove calcium-containing minerals.Comprehensive characterization and low-temperature denitrification tests revealed that calcite-induced structural modulation of coal-derived AC significantly enhances catalytic activity.Specifically,NO conversion increased from 88.3%of Mn-Ce/De-AC to 91.7%of Mn-Ce/De-AC-1CaCO_(3)(210℃).The improved SCR denitrification activity results from the enhancement of physicochemical properties including higher Mn^(4+)content and Ce^(4+)/Ce^(3+)ratio,an abundance of chemisorbed oxygen and acidic sites,which could strengthen the SCR reaction pathways(richer NH_(3)activated species and bidentate nitrate active species).Therefore,NO removal is enhanced.展开更多
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catal...Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.展开更多
Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction...Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.展开更多
Lithium-sulfur(Li-S)batteries boast a theoretical energy density as high as 2600 Wh·kg^(−1),positioning them as a highly attractive option for future advanced energy storage systems.Challenges such as slow transf...Lithium-sulfur(Li-S)batteries boast a theoretical energy density as high as 2600 Wh·kg^(−1),positioning them as a highly attractive option for future advanced energy storage systems.Challenges such as slow transformation kinetics and shuttle effects associated with lithium polysulfides(LiPSs)have seriously hindered their practical applications.In this paper,we present a new method for the synthesis of hollow carbon-sphere-supported Co monatomic catalysts(Co-N-C).This new synthesis method achieves pyrolytic coordination using a precursor rich in imide(-RC=N-)polymers.This synthesis method not only improves the adsorbability and catalytic activity of LiPS but also significantly weakens the shuttle effect and generates Co-N-C with superior conductivity,abundant hollow structures,and a high specific surface area,thus efficiently capturing and restricting the movement of LiPS intermediates.The dispersed Co monoatomic catalysts(Co SACs)were anchored to a highly conductive nitrogen-doped carbon framework and exhibited symmetric N-coordination active sites(Co-N_(4))to ensure fast redox kinetics of LiPS and Li_(2)S_(2)/Li_(2)S solid-state products.The lithium-sulfur battery with Co-N-C as the sulfur carrier showed excellent discharging capacity of 1146.6 mAh·g^(−1) at a discharge rate of 0.5 C and maintained excellent performance at a high discharge rate of 2 C.The capacity decay rate in 500 cycles was only 0.086%per cycle,reflecting excellent long-term cycle stability.This study highlights the key role of the synergistic effect between single-atom cobalt catalysts and hollow carbon spheres in enhancing the efficiency of lithium-sulfur(Li-S)batteries.It also provides valuable insights into the construction and fabrication of highly active monatomic catalysts.The catalytic conversion efficiency of lithium polysulfides is significantly enhanced when embedded in hollow carbon architectures,which serves as a critical strategy for optimizing the electrochemical behavior of next-generation Li-S batteries.展开更多
High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environm...High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environments,tunable electronic structures,abundant unsaturated active sites,and dynamic structural reassembly—collectively enhance electrochemical activity and durability under operating conditions.This review summarizes recent advances in HEACs for hydrogen evolution,oxygen evolution,and overall water splitting,highlighting their disorder-driven advantages over crystalline counterparts.Catalytic performance benchmarks are presented,and mechanistic insights are discussed,focusing on how multimetallic synergy,amorphization effect,and in‐situ reconstruction cooperatively regulate reaction pathways.These insights provide guidance for the rational design of next‐generation amorphous high‐entropy electrocatalysts with improved efficiency and durability.展开更多
Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespr...Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespread attention for CO_(2)RR due to their high catalytic activity,selectivity,excellent stability,and low cost.However,they still need to be further improved to meet the needs of industrial applications.This review article comprehensively summarizes the recent advances in regulation strategies of Bi-based catalysts and can be divided into six categories:(1)defect engineering,(2)atomic doping engineering,(3)organic framework engineering,(4)inorganic heterojunction engineering,(5)crystal face engineering,and(6)alloying and polarization engineering.Meanwhile,the corresponding catalytic mechanisms of each regulation strategy will also be discussed in detail,aiming to enable researchers to understand the structure-property relationship of the improved Bibased catalysts fundamentally.Finally,the challenges and future opportunities of the Bi-based catalysts in the photoelectrocatalytic CO_(2)RR application field will also be featured from the perspectives of the(1)combination or synergy of multiple regulatory strategies,(2)revealing formation mechanism and realizing controllable synthesis,and(3)in situ multiscale investigation of activation pathways and uncovering the catalytic mechanisms.On the one hand,through the comparative analysis and mechanism explanation of the six major regulatory strategies,a multidimensional knowledge framework of the structure-activity relationship of Bi-based catalysts can be constructed for researchers,which not only deepens the atomic-level understanding of catalytic active sites,charge transport paths,and the adsorption behavior of intermediate products,but also provides theoretical guiding principles for the controllable design of new catalysts;on the other hand,the promising collaborative regulation strategies,controllable synthetic paths,and the in situ multiscale characterization techniques presented in this work provides a paradigm reference for shortening the research and development cycle of high-performance catalysts,conducive to facilitating the transition of photoelectrocatalytic CO_(2)RR technology from the laboratory routes to industrial application.展开更多
Developing a high-efficiency catalyst with both superior low-temperature activity and good N_(2)selectivity is still challenging for the NH_(3)selective catalytic reduction(SCR)of NO_(x)from mobile sources.Herein,we d...Developing a high-efficiency catalyst with both superior low-temperature activity and good N_(2)selectivity is still challenging for the NH_(3)selective catalytic reduction(SCR)of NO_(x)from mobile sources.Herein,we demonstrate the improved low-temperature activity and N_(2)selectivity by regulating the redox and acidic properties of MnCe oxides supported on etched ZSM-5 supports.The etched ZSM-5 enables the highly dispersed state of MnCeOx species and strong interaction between Mn and Ce species,which promotes the reduction of CeO2,facilitates electron transfer from Mn to Ce,and generates more Mn^(4+)and Ce^(3+)species.The strong redox capacity contributes to forming the reactive nitrate species and-NH_(2)species from oxidative dehydrogenation of NH_(3).Moreover,the adsorbed NH_(3)and-NH_(2)species are the reactive intermediates that promote the formation of N_(2).This work demonstrates an effective strategy to enhance the low-temperature activity and N_(2)selectivity of SCR catalysts,contributing to the NO_(x)control for the low-temperature exhaust gas during the cold-start of diesel vehicles.展开更多
Mn-based oxides have been regarded as a promising family of cathode materials for high-performance lithium-ion batteries,but the practical applications have been limited because of severe capacity deterioration(such a...Mn-based oxides have been regarded as a promising family of cathode materials for high-performance lithium-ion batteries,but the practical applications have been limited because of severe capacity deterioration(such as Li Mn O_(2)and Li Mn_(2)O_(4))as well as further complications from successive structure changes during cycling,low initial coulombic efficiency(such as Li-rich cathode)and oxidization of organic carbonate solvents at high charge potential(such as Li Ni0.5 Mn1.5 O4).Large amounts of efforts have been concentrated on resolving these issues towards practical applications,and many vital progresses have been carried out.Hence,the primary target of this review is focused on different proposed strategies and breakthroughs to enhance the rate performance and cycling stability of nanostructured Mn-based oxide cathode materials for Li-ion batteries,including morphology control,ion doping,surface coatings,composite construction.The combination of delicate architectures with conductive species represents the perspective ways to enhance the conductivity of the cathode materials and further buffer the structure transformation and strain during cycling.At last,based on the elaborated progress,several perspectives of Mn-based oxide cathodes are summarized,and some possible attractive strategies and future development directions of Mn-based oxide cathodes with enhanced electrochemical properties are proposed.The review will offer a detailed introduction of various strategies enhancing electrochemical performance and give a novel viewpoint to shed light on the future innovation in Mn-based oxide cathode materials,which benefits the design and construction of high-performance Mn-based oxide cathode materials in the future.展开更多
The as-spun Ti_(1−x)La_(x)Fe_(0.8)Mn_(0.2)(x=0,0.01,0.03,0.06,0.09,molar fraction)alloys were prepared by melt spinning.The effects of La substitution for Ti on the microstructure,hydrogen storage kinetics and thermod...The as-spun Ti_(1−x)La_(x)Fe_(0.8)Mn_(0.2)(x=0,0.01,0.03,0.06,0.09,molar fraction)alloys were prepared by melt spinning.The effects of La substitution for Ti on the microstructure,hydrogen storage kinetics and thermodynamics of TiFe-type Ti−Fe−Mn-based alloy were investigated.The as-spun alloys hold the TiFe single phase,which transforms to TiFeH_(0.06),TiFeH,and TiFeH_(2) hydrides after hydrogenation.La substitution promotes the formation of micro-defects(such as dislocations and grain boundaries)in the alloys,thus facilitating hydrogen diffusion.In addition,the hydrogen storage kinetics properties are improved after introducing La element.With the rise of La content,the hydrogen storage capacity decreases firstly and then increases,but the absolute value of hydriding enthalpy change(|ΔH|)increases firstly and then reduces.When x=0.01,the maximum value of|ΔH|is obtained to be(25.23±0.50)kJ/mol for hydriding,and the alloy has the maximum hydrogen absorption capacity of(1.80±0.04)wt.%under the conditions of 323 K and 3 MPa.展开更多
Layered Li-rich Mn-based oxides are promising cathode materials for Li-ion batteries due to their high capacity and high operation voltage.However,their commercial applications are hindered by irreversible capacity lo...Layered Li-rich Mn-based oxides are promising cathode materials for Li-ion batteries due to their high capacity and high operation voltage.However,their commercial applications are hindered by irreversible capacity loss in the first charge-discharge process,voltage decay during cycling,inefficient cyclability and rate capability.Many attempts have been performed to solve such issues,including the mechanism study and strategies to improve the electrochemical performance.This article provides a brief review and future perspective on the main challenges of the high-capacity Li-rich Mn-based cathodes for Li-ion batteries.展开更多
The high-rate cyclability of Li-rich Mn-based oxide(LMO)is highly limited by the electrochemical polarization resulting from the slow kinetic of the Li2MnO3 phase.Herein,the Prussian blue(PB)coating layer with specifi...The high-rate cyclability of Li-rich Mn-based oxide(LMO)is highly limited by the electrochemical polarization resulting from the slow kinetic of the Li2MnO3 phase.Herein,the Prussian blue(PB)coating layer with specific redox potential is introduced as a functionalized interface to overcome the side effect and the escaping of O on the surface of LMO,especially its poor rate capability.In detail,the PB layer can restrict the large polarization of LMO by sharing overloaded current at a high rate due to the synchronous redox of PB and LMO.Consequently,an enhanced high rate performance with capacity retention of 87.8%over 300 cycles is obtained,which is superior to 50.5%of the pristine electrode.Such strategies on the high-rate cyclability of Li-rich Mn-based oxide compatible with good low-rate performances may attract great attention for pursuing durable performances.展开更多
基金Project supported by National Key R&D Program of China(2022YFC3701600)National Natural Science Foundation of China(22276162 and 22306072)+1 种基金China Postdoctoral Science Foundation(2023M731441)Young Talent Fund of Jiaxing Science and Technology Project(2023AY40030)。
文摘In this study,the commonly used Cu or Mn-based low-temperature SCR catalysts were employed to investigate their different reaction behaviors in the presence of high-content water vapor.Experimental results reveal that CuCeTi sample possesses superior water re sistance at low temperature compared with MnCeTi catalyst.Upon the introduction of water vapor,both catalysts exhibit a quick loss in deNOxefficiency,while that is more pronounced on MnCeTi sample.In addition,unlike CuCeTi sample,MnCeTi catalyst also shows a gradual deactivation tendency after initial quick activity loss.Characterization and simulation results indicate that H_(2)O is more easily adsorbed and dissociated on MnCeTi catalyst,showing stronger suppression on NH3adsorption,causing more serious initial deactivation.Furthermore,more abundant hydroxyl groups derived from dissociative adsorption of water on MnCeTi catalyst will lead to more NH4NO3deposition and the decrease in redox capacity.This is the main reason of gradual deactivation of MnCeTi catalyst at high-content water vapor.Such findings could pave a new way for development of highly efficient SCR catalysts with good water resistance for real application.
文摘Among multitudinous metal‐oxide catalysts for the selective catalytic reduction of NOx with NH3(NH3‐SCR),Mn‐based catalysts have become very popular and developed rapidly in recent years because of its superior low‐temperature denitrification activity,mainly originating from multi‐valence of Mn.Most studies suggest that the catalytic activity of multi‐component oxides is superior to that of single‐component catalysts owing to the synergistic effect among the metallic elements in such materials,of which more attentions have been given to Ce as an additive owing to its powerful oxygen storage capacity,redox ability and its ready availability.As the core of SCR technology,the research points in catalyst development at the present stage of all researchers in countries mainly centralize on the optimization of active components,carriers,calcination temperature,calcination time and temperature‐raising procedure,giving little thought to the effects of the calcination atmosphere.In the present work,Ce‐modified Mn‐based catalysts were prepared by a simple impregnation method.The effects of the calcination atmosphere(N2,air or O2)on the performance of the resulting materials during NH3‐SCR and its causes of the differences were subsequently investigated and characterized using various analytical methods.Data obtained from X‐ray diffraction,thermogravimetry and temperature‐programmed reduction with hydrogen show that calcination under N2reduces both the degree of oxidation and crystallization of the MnOx.Scanning electron microscopy also demonstrates that the use of N2inhibits the growth of grains and increases the dispersion of the catalysts.In addition,the results of temperature‐programmed desorption with ammonia indicate that catalysts calcined under N2exhibit a greater quantity of acid sites.Finally,X‐ray photoelectron spectrometry and activity results demonstrate that MnOx in the lower valence states is more favorable for NH3‐SCR reactions.In conclusion,catalysts calcined under N2show superior performance during NH3‐SCR for NOx removal,allowing NO conversions up to94%at473K.
基金supported by the National Natural Science Foundation of China(No.U22A20241).
文摘Catalytic ozonation is a potential technology to eliminate refractory organic contaminants with the low concentration in secondary effluent from industrial park wastewater treatment plants(IPWWTPs).In this study,the catalytic ozonation over the Mn-based catalyst significantly improved the chemical oxygen demand(COD),total organic carbon(TOC),and UV254 removals of secondary effluent from IPWWTPs.The Mn-based catalyst/Og system achieved 84.8%,69.8%,and 86.4% removals of COD,TOC,and UY254,which were 3.3,5.7,and 1.1 times that in ozonation alone,respectively.Moreover,the Mn-based catalytic ozonation process exhibited excellent pH tolerance ranging from pH 4.0 to 9.0.Additionally,the depth analysis based on fluorescence excitation-emission matrix(EEM)confirmed that the catalytic ozonation process preferred to degrade toxic aromatic hydrocarbons.The existence of the Mn-based catalyst/O_(3) system enhanced 21.4%-38.3% more fluorescent organic matters removal,compared to that in ozonation alone.Mechanistic studies proved that the abundant Lewis acid sites(Mn/Mn(n+1)+and adsorbed oxygen)on the surface of the Mn-based catalyst effectively promoted O_(3) decomposition into reactive oxygen species(ROS),and-O_(2)-/HO_(2):and ^(1)O_(2) were the main ROS for degrading refractory organic contaminants.The contributions of ROS oxidation(91.2%)was much higher than that of direct O_(3) oxidation(8.8%).Thus,this work provides an effective advanced treatment process for purifying secondary effluent from IPWWTPs.
基金supported by the National Key R&D Program of China(No.2022YFB2404400)the National Natural Science Foundation of China(Nos.U23A20577,52372168,92263206 and 21975006)+1 种基金the“The Youth Beijing Scholars program”(No.PXM2021_014204_000023)the Beijing Natural Science Foundation(Nos.2222001 and KM202110005009).
文摘The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the long-cycling stability of batteries needs to be improved.Herein,the Mn-based Li-rich cathode materials with small amounts of Li2 MnO3 crystal domains and gradient doping of Al and Ti elements from the surface to the bulk have been developed to improve the structure and interface stability.Then the batteries with a high energy density of 600 Wh kg^(-1),excellent capacity retention of 99.7%with low voltage decay of 0.03 mV cycle^(-1) after 800 cycles,and good rates performances can be achieved.Therefore,the structure and cycling stability of low voltage Mn-based Li-rich cathode materials can be significantly improved by the bulk structure design and interface regulation,and this work has paved the way for developing low-cost and high-energy Mn-based energy storage batteries with long lifetime.
基金supported by the National Natural Science Foundation of China with Grant No.12274176 and No.12474210supported by the relevant national program+1 种基金support from Department of Science and Technology of Jilin Province with Grant No.20210301021GXthe Fundamental Research Funds for the Center Universities with Grant No.2023-JCXK-03。
文摘Li-rich Mn-based oxides(LRMO)are of great significance in achieving high energy density all-solid-state lithium batteries(ASSLBs),owing to their high theoretical capacity and high operation voltage.Unfortunately,their practical application is hindered by severe interface degradation due to the chemical oxidation and electrochemical decomposition of solid electrolytes(SEs),driven by high-active oxygen and electron sources from LRMO.Herein,an interfacial modification strategy is proposed to stabilize the surface lattice oxygen of LRMO and reduce electronic conduction between LRMO and SEs,synergistically.Accordingly,the byproducts from chemical oxidation(InO^(-))and electrochemical decomposition(LiCl^(-))are largely suppressed,leading to superior interfacial transport with the lowest resistance.Consequently,the ASSLB achieves a high reversible capacity of 227.9 mA h g^(-1)at 0.1 C,a cycling stability of 90.1%capacity retention after 200 cycles at 0.1 C,and a superior rate capability with a capacity of81.7 m A h g^(-1)at 3.0 C.This study enriches the fundamental understanding of LRMO/SEs interfacial evolution during the electrochemical cycling and the proposed interfacial modification strategy benefits the future design of Li-rich compounds for ASSLBs.
基金Supported by National Key R&D Program of China(2022YFA1503400)。
文摘Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.
基金Supported by Innovation Capability Support Program of Shaanxi(2024RS-CXTD-53,2024ZC-KJXX-096)the Key R&D Program of Shaanxi Province(2022QCY-LL-69)Xi’an Science and Technology Project(24GXFW0089)。
文摘Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.
基金Supported by the National Natural Science Foundation of China(No.52273056)the Science and Technology Development Program of Jilin Province,China(No.YDZJ202501ZYTS305)。
文摘Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.
基金Supported by the National Key Research and Development Program of China(2023YFB4104500,2023YFB4104502)the National Natural Science Foundation of China(22138013)the Taishan Scholar Project(ts201712020).
文摘Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.
基金Supported by the Science and Technology Cooperation and Exchange special project of Cooperation of Shanxi Province(202404041101014)the Fundamental Research Program of Shanxi Province(202403021212333)+3 种基金the Joint Funds of the National Natural Science Foundation of China(U24A20555)the Lvliang Key R&D of University-Local Cooperation(2023XDHZ10)the Initiation Fund for Doctoral Research of Taiyuan University of Science and Technology(20242026)the Outstanding Doctor Funding Award of Shanxi Province(20242080).
文摘To elucidate the effect of calcite-regulated activated carbon(AC)structure on low-temperature denitrification performance of SCR catalysts,this work prepared a series of Mn-Ce/De-AC-xCaCO_(3)(x is the calcite content in coal)catalysts were prepared by the incipient wetness impregnation method,followed by acid washing to remove calcium-containing minerals.Comprehensive characterization and low-temperature denitrification tests revealed that calcite-induced structural modulation of coal-derived AC significantly enhances catalytic activity.Specifically,NO conversion increased from 88.3%of Mn-Ce/De-AC to 91.7%of Mn-Ce/De-AC-1CaCO_(3)(210℃).The improved SCR denitrification activity results from the enhancement of physicochemical properties including higher Mn^(4+)content and Ce^(4+)/Ce^(3+)ratio,an abundance of chemisorbed oxygen and acidic sites,which could strengthen the SCR reaction pathways(richer NH_(3)activated species and bidentate nitrate active species).Therefore,NO removal is enhanced.
基金financial support from the National Natural Science Foundation of China(Nos.22401274,U23B6011)the Jilin Provincial Science and Technology Department Program(No.20250102070JC)。
文摘Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.
基金funded by the Innovative Research Group Project of the National Natural Science Foundation of China(52121004)the Research Development Fund(No.RDF-21-02-060)by Xi’an Jiaotong-Liverpool University+1 种基金support received from the Suzhou Industrial Park High Quality Innovation Platform of Functional Molecular Materials and Devices(YZCXPT2023105)the XJTLU Advanced Materials Research Center(AMRC).
文摘Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.
基金supported by the National Natural Science Foundation of China(No.52064035)the Key Research and Development Program of Gansu Province,China(No.25YFGA024)the Natural Science Foundation of Zhejiang Province,China(No.LGG22E020003).
文摘Lithium-sulfur(Li-S)batteries boast a theoretical energy density as high as 2600 Wh·kg^(−1),positioning them as a highly attractive option for future advanced energy storage systems.Challenges such as slow transformation kinetics and shuttle effects associated with lithium polysulfides(LiPSs)have seriously hindered their practical applications.In this paper,we present a new method for the synthesis of hollow carbon-sphere-supported Co monatomic catalysts(Co-N-C).This new synthesis method achieves pyrolytic coordination using a precursor rich in imide(-RC=N-)polymers.This synthesis method not only improves the adsorbability and catalytic activity of LiPS but also significantly weakens the shuttle effect and generates Co-N-C with superior conductivity,abundant hollow structures,and a high specific surface area,thus efficiently capturing and restricting the movement of LiPS intermediates.The dispersed Co monoatomic catalysts(Co SACs)were anchored to a highly conductive nitrogen-doped carbon framework and exhibited symmetric N-coordination active sites(Co-N_(4))to ensure fast redox kinetics of LiPS and Li_(2)S_(2)/Li_(2)S solid-state products.The lithium-sulfur battery with Co-N-C as the sulfur carrier showed excellent discharging capacity of 1146.6 mAh·g^(−1) at a discharge rate of 0.5 C and maintained excellent performance at a high discharge rate of 2 C.The capacity decay rate in 500 cycles was only 0.086%per cycle,reflecting excellent long-term cycle stability.This study highlights the key role of the synergistic effect between single-atom cobalt catalysts and hollow carbon spheres in enhancing the efficiency of lithium-sulfur(Li-S)batteries.It also provides valuable insights into the construction and fabrication of highly active monatomic catalysts.The catalytic conversion efficiency of lithium polysulfides is significantly enhanced when embedded in hollow carbon architectures,which serves as a critical strategy for optimizing the electrochemical behavior of next-generation Li-S batteries.
基金supported by the Australian Research Council(ARC)Projects(DP220101139,DP220101142,and LP240100542).
文摘High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environments,tunable electronic structures,abundant unsaturated active sites,and dynamic structural reassembly—collectively enhance electrochemical activity and durability under operating conditions.This review summarizes recent advances in HEACs for hydrogen evolution,oxygen evolution,and overall water splitting,highlighting their disorder-driven advantages over crystalline counterparts.Catalytic performance benchmarks are presented,and mechanistic insights are discussed,focusing on how multimetallic synergy,amorphization effect,and in‐situ reconstruction cooperatively regulate reaction pathways.These insights provide guidance for the rational design of next‐generation amorphous high‐entropy electrocatalysts with improved efficiency and durability.
基金supports from the National Natural Science Foundation of China(Grant Nos.12305372 and 22376217)the National Key Research&Development Program of China(Grant Nos.2022YFA1603802 and 2022YFB3504100)+1 种基金the projects of the key laboratory of advanced energy materials chemistry,ministry of education(Nankai University)key laboratory of Jiangxi Province for persistent pollutants prevention control and resource reuse(2023SSY02061)are gratefully acknowledged.
文摘Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespread attention for CO_(2)RR due to their high catalytic activity,selectivity,excellent stability,and low cost.However,they still need to be further improved to meet the needs of industrial applications.This review article comprehensively summarizes the recent advances in regulation strategies of Bi-based catalysts and can be divided into six categories:(1)defect engineering,(2)atomic doping engineering,(3)organic framework engineering,(4)inorganic heterojunction engineering,(5)crystal face engineering,and(6)alloying and polarization engineering.Meanwhile,the corresponding catalytic mechanisms of each regulation strategy will also be discussed in detail,aiming to enable researchers to understand the structure-property relationship of the improved Bibased catalysts fundamentally.Finally,the challenges and future opportunities of the Bi-based catalysts in the photoelectrocatalytic CO_(2)RR application field will also be featured from the perspectives of the(1)combination or synergy of multiple regulatory strategies,(2)revealing formation mechanism and realizing controllable synthesis,and(3)in situ multiscale investigation of activation pathways and uncovering the catalytic mechanisms.On the one hand,through the comparative analysis and mechanism explanation of the six major regulatory strategies,a multidimensional knowledge framework of the structure-activity relationship of Bi-based catalysts can be constructed for researchers,which not only deepens the atomic-level understanding of catalytic active sites,charge transport paths,and the adsorption behavior of intermediate products,but also provides theoretical guiding principles for the controllable design of new catalysts;on the other hand,the promising collaborative regulation strategies,controllable synthetic paths,and the in situ multiscale characterization techniques presented in this work provides a paradigm reference for shortening the research and development cycle of high-performance catalysts,conducive to facilitating the transition of photoelectrocatalytic CO_(2)RR technology from the laboratory routes to industrial application.
基金the National Natural Science Foundation of China(Nos.22125604,22106100,21976117,22276119)Shanghai Rising-Star Program(No.22QA1403700).
文摘Developing a high-efficiency catalyst with both superior low-temperature activity and good N_(2)selectivity is still challenging for the NH_(3)selective catalytic reduction(SCR)of NO_(x)from mobile sources.Herein,we demonstrate the improved low-temperature activity and N_(2)selectivity by regulating the redox and acidic properties of MnCe oxides supported on etched ZSM-5 supports.The etched ZSM-5 enables the highly dispersed state of MnCeOx species and strong interaction between Mn and Ce species,which promotes the reduction of CeO2,facilitates electron transfer from Mn to Ce,and generates more Mn^(4+)and Ce^(3+)species.The strong redox capacity contributes to forming the reactive nitrate species and-NH_(2)species from oxidative dehydrogenation of NH_(3).Moreover,the adsorbed NH_(3)and-NH_(2)species are the reactive intermediates that promote the formation of N_(2).This work demonstrates an effective strategy to enhance the low-temperature activity and N_(2)selectivity of SCR catalysts,contributing to the NO_(x)control for the low-temperature exhaust gas during the cold-start of diesel vehicles.
基金financially supported by the National Natural Science Foundation of China(no.51672120)the Scientific Research Project of Mudanjiang Normal University(no.1355JG014)+1 种基金the Natural Science Foundation of Hebei Province of China(no.B2020501003)the Fundamental Research Funds for the Central Universities(no.N2023030)。
文摘Mn-based oxides have been regarded as a promising family of cathode materials for high-performance lithium-ion batteries,but the practical applications have been limited because of severe capacity deterioration(such as Li Mn O_(2)and Li Mn_(2)O_(4))as well as further complications from successive structure changes during cycling,low initial coulombic efficiency(such as Li-rich cathode)and oxidization of organic carbonate solvents at high charge potential(such as Li Ni0.5 Mn1.5 O4).Large amounts of efforts have been concentrated on resolving these issues towards practical applications,and many vital progresses have been carried out.Hence,the primary target of this review is focused on different proposed strategies and breakthroughs to enhance the rate performance and cycling stability of nanostructured Mn-based oxide cathode materials for Li-ion batteries,including morphology control,ion doping,surface coatings,composite construction.The combination of delicate architectures with conductive species represents the perspective ways to enhance the conductivity of the cathode materials and further buffer the structure transformation and strain during cycling.At last,based on the elaborated progress,several perspectives of Mn-based oxide cathodes are summarized,and some possible attractive strategies and future development directions of Mn-based oxide cathodes with enhanced electrochemical properties are proposed.The review will offer a detailed introduction of various strategies enhancing electrochemical performance and give a novel viewpoint to shed light on the future innovation in Mn-based oxide cathode materials,which benefits the design and construction of high-performance Mn-based oxide cathode materials in the future.
基金financial supports from the Inner Mongolia Natural Science Foundation,China (No.2019BS05005)the Inner Mongolia University of Science and Technology Innovation Fund,China (No.2019QDL-B11)the National Natural Science Foundation of China (Nos.51901105, 51871125, 51761032).
文摘The as-spun Ti_(1−x)La_(x)Fe_(0.8)Mn_(0.2)(x=0,0.01,0.03,0.06,0.09,molar fraction)alloys were prepared by melt spinning.The effects of La substitution for Ti on the microstructure,hydrogen storage kinetics and thermodynamics of TiFe-type Ti−Fe−Mn-based alloy were investigated.The as-spun alloys hold the TiFe single phase,which transforms to TiFeH_(0.06),TiFeH,and TiFeH_(2) hydrides after hydrogenation.La substitution promotes the formation of micro-defects(such as dislocations and grain boundaries)in the alloys,thus facilitating hydrogen diffusion.In addition,the hydrogen storage kinetics properties are improved after introducing La element.With the rise of La content,the hydrogen storage capacity decreases firstly and then increases,but the absolute value of hydriding enthalpy change(|ΔH|)increases firstly and then reduces.When x=0.01,the maximum value of|ΔH|is obtained to be(25.23±0.50)kJ/mol for hydriding,and the alloy has the maximum hydrogen absorption capacity of(1.80±0.04)wt.%under the conditions of 323 K and 3 MPa.
基金This work was supported by NSFC(21621091)National Key Research and Development of China(2016YFB0100202)+4 种基金Natural Science Foundation of Fujian Province(2015J01063)the support of National Materials Genome Project(2016YFB0700600)National Key R&D Program of China(2016YFB0700600)the Guangdong Innovation Team Project(No.2013N080)Shenzhen Science and Technology Research(Nos.JCYJ20151015162256516,JCYJ20150729111733470 and JCYJ20160226105838578)。
文摘Layered Li-rich Mn-based oxides are promising cathode materials for Li-ion batteries due to their high capacity and high operation voltage.However,their commercial applications are hindered by irreversible capacity loss in the first charge-discharge process,voltage decay during cycling,inefficient cyclability and rate capability.Many attempts have been performed to solve such issues,including the mechanism study and strategies to improve the electrochemical performance.This article provides a brief review and future perspective on the main challenges of the high-capacity Li-rich Mn-based cathodes for Li-ion batteries.
基金supported by the National Natural Science Foundation of China (51802261,52072298,and 52172228)the Natural Science Foundation of Shaanxi (2019GHJD-13 and 2020JC-41)+2 种基金the Natural Science Basic Research Plan in Shaanxi province of China (2019JLP-04)Xi'an Science and Technology Project of China (2019219714SYS012CG034)the foundation of National Key Laboratory (6142808200202),PR China.
文摘The high-rate cyclability of Li-rich Mn-based oxide(LMO)is highly limited by the electrochemical polarization resulting from the slow kinetic of the Li2MnO3 phase.Herein,the Prussian blue(PB)coating layer with specific redox potential is introduced as a functionalized interface to overcome the side effect and the escaping of O on the surface of LMO,especially its poor rate capability.In detail,the PB layer can restrict the large polarization of LMO by sharing overloaded current at a high rate due to the synchronous redox of PB and LMO.Consequently,an enhanced high rate performance with capacity retention of 87.8%over 300 cycles is obtained,which is superior to 50.5%of the pristine electrode.Such strategies on the high-rate cyclability of Li-rich Mn-based oxide compatible with good low-rate performances may attract great attention for pursuing durable performances.
