The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous me...The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.展开更多
Chemical looping oxidative dehydrogenation (CL-ODH) is an economically promising method for convertingethane into higher value-added ethylene utilizing lattice oxygen in redox catalysts, also known as oxygen carriers....Chemical looping oxidative dehydrogenation (CL-ODH) is an economically promising method for convertingethane into higher value-added ethylene utilizing lattice oxygen in redox catalysts, also known as oxygen carriers. Inthis study, perovskite-type oxide SrCoO_(3-δ) and B-site Mn ion-doped oxygen carriers (SrCo_(1-x)MnxO_(3-δ), x=0.1, 0.2, 0.3)were prepared and tested for the CL-ODH of ethane. The oxygen-deficient perovskite SrCoO_(3-δ) exhibited high ethyleneselectivity of up to 96.7% due to its unique oxygen vacancies and lattice oxygen migration rates. However, its low ethyleneyield limits its application in the CL-ODH of ethane. Mn doping promoted the reducibility of SrCoO_(3-δ) oxygen carriers,thereby improving ethane conversion and ethylene yield, as demonstrated by characterization and evaluation experiments.X-ray diffraction results confirmed the doping of Mn into the lattice of SrCoO_(3-δ), while X-ray photoelectron spectroscopy(XPS) indicated an increase in lattice oxygen ratio upon incorporation of Mn into the SrCoO_(3-δ) lattice. Additionally, H2temperature-programmed reduction (H2-TPR) tests revealed more peaks at lower temperature reduction zones and a declinein peak positions at higher temperatures. Among the four tested oxygen carriers, SrCo0.8Mn0.2O_(3-δ) exhibited satisfactoryperformance with an ethylene yield of 50% at 710 °C and good stability over 20 redox cycles. The synergistic effect of Mnplays a key role in increasing ethylene yields of SrCoO_(3-δ) oxygen carriers. Accordingly, SrCo0.8Mn0.2O_(3-δ) shows promisingpotential for the efficient production of ethylene from ethane via CL-ODH.展开更多
In this work,a new ZnO/CoNiO_(2)/CoO/C metal oxides composite is prepared by cost-effective hydrothermal method coupled with annealing process under N_(2) atmosphere.Notably,the oxidation-defect annealing environment ...In this work,a new ZnO/CoNiO_(2)/CoO/C metal oxides composite is prepared by cost-effective hydrothermal method coupled with annealing process under N_(2) atmosphere.Notably,the oxidation-defect annealing environment is conducive to both morphology and component of the composite,which flower-like ZnO/CoNiO_(2)/CoO/C is obtained.Benefited from good chemical stability of ZnO,high energy capacity of CoNiO_(2) and CoO and good conductivity of C,the as-prepared sample shows promising electrochemical behavior,including the specific capacity of 1435 C·g^(-1) at 1 A·g^(-1),capacity retention of 87.3%at 20 A·g^(-1),and cycling stability of 90.5%for 3000 cycles at 5 A·g^(-1),respectively.Furthermore,the prepared ZnO/CoNiO_(2)/CoO/C/NF//AC aqueous hybrid supercapacitors device delivers the best specific energy of 55.9 W·h·kg^(-1) at 850 W·kg^(-1).The results reflect that the as-prepared ZnO/CoNiO_(2)/CoO/C microflowers are considered as high performance electrode materials for supercapacitor,and the strategy mentioned in this paper is benefit to prepare mixed metal oxides composite for energy conversion and storage.展开更多
Metal-to-insulator transitions (MITs),which are achieved in 3d-band correlated transitional metal oxides,trigger abrupt variations in electrical,optical,and/or magnetic properties beyond those of conventional semicond...Metal-to-insulator transitions (MITs),which are achieved in 3d-band correlated transitional metal oxides,trigger abrupt variations in electrical,optical,and/or magnetic properties beyond those of conventional semiconductors.Among such material families,iron(Fe:3d^(6)4s^(2))-containing oxides pique interest owing to their widely tunable MIT properties,which are associated with the various valence states of Fe.Their potential electronic applications also show promise,given the large abundance of Fe on Earth.Representative MIT properties triggered by critical temperature (TMIT) were reported for ReFe_(2)O_(4)(Fe^(2.5+)),ReBaFe_(2)O_(5)(Fe^(2.5+)),Fe_(3)O_(4)(Fe^(2.67+)),Re_(1/3)Sr_(2/3)FeO_(3)(Fe^(3.67+)),Re Cu_(3)Fe_(4)O_(12)(Fe^(3.75+)),and Ca_(1-x)Sr_(x)FeO_(3)(Fe^(4+))(where Re represents rare-earth elements).The common feature of MITs of these Fe-containing oxides is that they are usually accompanied by charge ordering transitions or disproportionation associated with the valence states of Fe.Herein,we review the material family of Fe-containing MIT oxides,their MIT functionalities,and their respective mechanisms.From the perspective of potentially correlated electronic applications,the tunability of the TMITand its resultant resistive change in Fe-containing oxides are summarized and further compared with those of other materials exhibiting MIT functionality.In particular,we highlight the abrupt MIT and wide tunability of TMITof Fe-containing quadruple perovskites,such as Re Cu3Fe4O12.However,their effective material synthesis still needs to be further explored to cater to potential applications.展开更多
Supported nanoparticles have attracted considerable attention as a promising catalyst for achieving unique properties in numerous applications,including fuel cells,chemical conversion,and batteries.Nanocatalysts demon...Supported nanoparticles have attracted considerable attention as a promising catalyst for achieving unique properties in numerous applications,including fuel cells,chemical conversion,and batteries.Nanocatalysts demonstrate high activity by expanding the number of active sites,but they also intensify deactivation issues,such as agglomeration and poisoning,simultaneously.Exsolution for bottomup synthesis of supported nanoparticles has emerged as a breakthrough technique to overcome limitations associated with conventional nanomaterials.Nanoparticles are uniformly exsolved from perovskite oxide supports and socketed into the oxide support by a one-step reduction process.Their uniformity and stability,resulting from the socketed structure,play a crucial role in the development of novel nanocatalysts.Recently,tremendous research efforts have been dedicated to further controlling exsolution particles.To effectively address exsolution at a more precise level,understanding the underlying mechanism is essential.This review presents a comprehensive overview of the exsolution mechanism,with a focus on its driving force,processes,properties,and synergetic strategies,as well as new pathways for optimizing nanocatalysts in diverse applications.展开更多
Cu catalysts,known for their unparalleled catalytic capabilities due to their unique electronic structure,have faced inherent challenges in maintaining long-term effectiveness under harsh hydrogenation conditions.Here...Cu catalysts,known for their unparalleled catalytic capabilities due to their unique electronic structure,have faced inherent challenges in maintaining long-term effectiveness under harsh hydrogenation conditions.Here,we demonstrate a molybdenum-mediated redispersion behavior of Cu under hightemperature oxidation conditions.The oxidized Cu nanoparticles with rich metal-support interfaces tend to dissolve into the MoO_(3)support upon heating to 600℃,which facilitates the subsequent regeneration in a reducing atmosphere.A similar redispersion phenomenon is observed for Cu nanoparticles supported on Zn O-modified MoO_(3).The modification of ZnO significantly improves the performance of the Cu catalyst for CO_(2)hydrogenation to methanol,with the high activity being well maintained after four repeated oxidation-reduction cycles.In situ spectroscopic and theoretical analyses suggest that the interaction involved in the formation of the copper molybdate-like compound is the driving force for the redispersion of Cu.This method is applicable to various Mo-based oxide supports,offering a practical strategy for the regeneration of sintered Cu particles in hydrogenation applications.展开更多
Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculate...Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculated using DMol3,since HMX and O are key substances in decomposition process.And the relationship between the adsorption energy of HMX,O on metal oxides(TiO_(2),Al_(2)O_(3),PbO,CuO,Fe_(2)O_(3),Co_(3)O_(4),Bi_(2)O_(3),NiO)and experimental T30 values(time required for the decomposition depth of HMX to reach 30%)was depicted as volcano plot.Thus,the T30 values of other metal oxides was predicted based on their adsorption energy on volcano plot and validated by previous experimental data.Further,the adsorption energy of HMX on ZrO_(2)and MnO_(2)was predicted based on the linear relationship between surface energy and adsorption energy,and T30 values were estimated based on volcano plot.The apparent activation energy data of HMX/MgO,HMX/SnO_(2),HMX/ZrO_(2),and HMX/MnO_(2)obtained from DSC experiments are basically consistent with our predicted T30 values,indicating that it is feasible to predict the catalytic activity based on the adsorption calculation,and it is expected that these simple structural properties can predict adsorption energy to reduce the large quantities of computation and experiment cost.展开更多
Anode materials are an essential part of lithium-ion batteries(LIBs),which determine the performance and safety of LIBs.Currently,graphite,as the anode material of commercial LIBs,is limited by its low theoretical cap...Anode materials are an essential part of lithium-ion batteries(LIBs),which determine the performance and safety of LIBs.Currently,graphite,as the anode material of commercial LIBs,is limited by its low theoretical capacity of 372 mA·h·g^(−1),thus hindering further development toward high-capacity and large-scale applications.Alkaline earth metal iron-based oxides are considered a promising candidate to replace graphite because of their low preparation cost,good thermal stability,superior stability,and high electrochemical performance.Nonetheless,many issues and challenges remain to be addressed.Herein,we systematically summarize the research progress of alkaline earth metal iron-based oxides as LIB anodes.Meanwhile,the material and structural properties,synthesis methods,electrochemical reaction mechanisms,and improvement strategies are introduced.Finally,existing challenges and future research directions are discussed to accelerate their practical application in commercial LIBs.展开更多
Co-free Li-rich layered oxides(LLOs)are emerging as promising cathode materials for Li-ion batteries due to their low cost and high capacity.However,they commonly face severe structural instability and poor electroche...Co-free Li-rich layered oxides(LLOs)are emerging as promising cathode materials for Li-ion batteries due to their low cost and high capacity.However,they commonly face severe structural instability and poor electrochemical activity,leading to diminished capacity and voltage performance.Herein,we introduce a Co-free LLO,Li_(1.167)Ni_(0.222)Mn_(0.611)O_(2)(Cf-L1),which features a cooperative structure of Li/Ni mixing and stacking faults.This structure regulates the crystal and electronic structures,resulting in a higher discharge capacity of 300.6 mA h g^(-1)and enhanced rate capability compared to the typical Co-free LLO,Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2)(Cf-Ls).Density functional theory(DFT)indicates that Li/Ni mixing in LLOs leads to increased Li-O-Li configurations and higher anionic redox activities,while stacking faults further optimize the electronic interactions of transition metal(TM)3d and non-bonding O 2p orbitals.Moreover,stacking faults accommodate lattice strain,improving electrochemical reversibility during charge/discharge cycles,as demonstrated by the in situ XRD of Cf-L1 showing less lattice evolution than Cf-Ls.This study offers a structured approach to developing Co-free LLOs with enhanced capacity,voltage,rate capability,and cyclability,significantly impacting the advancement of the next-generation Li-ion batteries.展开更多
Full concentration gradient lithium-rich layered oxides are catching lots of interest as the next generation cathode for lithium-ion batteries due to their high discharge voltage,reduced voltage decay and enhanced rat...Full concentration gradient lithium-rich layered oxides are catching lots of interest as the next generation cathode for lithium-ion batteries due to their high discharge voltage,reduced voltage decay and enhanced rate performance,whereas the high lithium residues on its surface impairs the structure stability and long-term cycle performance.Herein,a facile multifunctional surface modification method is implemented to eliminate surface lithium residues of full concentration gradient lithium-rich layered oxides by a wet chemistry reaction with tetrabutyl titanate and the post-annealing process.It realizes not only a stable Li_(2)TiO_(3)coating layer with 3D diffusion channels for fast Li^(+)ions transfer,but also dopes partial Ti^(4+)ions into the sub-surface region of full concentration gradient lithium-rich layered oxides to further strengthen its crystal structure.Consequently,the modified full concentration gradient lithium-rich layered oxides exhibit improved structure stability,elevated thermal stability with decomposition temperature from 289.57℃to 321.72℃,and enhanced cycle performance(205.1 mAh g^(-1)after 150 cycles)with slowed voltage drop(1.67 mV per cycle).This work proposes a facile and integrated modification method to enhance the comprehensive performance of full concentration gradient lithium-rich layered oxides,which can facilitate its practical application for developing higher energy density lithium-ion batteries.展开更多
Exploring suitable high-capacity V_(2)O_(5)-based cathode materials is essential for the rapid advancement of aqueous zinc ion batteries(ZIBs).However,the typical problem of slow Zn^(2+)diffusion kinetics has severely...Exploring suitable high-capacity V_(2)O_(5)-based cathode materials is essential for the rapid advancement of aqueous zinc ion batteries(ZIBs).However,the typical problem of slow Zn^(2+)diffusion kinetics has severely limited the feasibility of such materials.In this work,unique hydrated vanadates(CaVO,BaVO)were obtained by intercalation of Ca^(2+)or Ba^(2+)into hydrated vanadium pentoxide.In the CaVO//Zn and BaVO//Zn batteries systems,the former delivered up to a 489.8 mAh g^(-1)discharge specific capacity at 0.1 A g^(-1).Moreover,the remarkable energy density of 370.07 Wh kg^(-1)and favorable cycling stability yard outperform BaVO,pure V_(2)O_(5),and many reported cathodes of similar ionic intercalation compounds.In addition,pseudocapacitance analysis,galvanostatic intermittent titration(GITT)tests,and Trasatti analysis revealed the high capacitance contribution and Zn^(2+)diffusion coefficient of CaVO,while an in-depth investigation based on EIS elucidated the reasons for the better electrochemical performance of CaVO.Notably,ex-situ XRD,XPS,and TEM tests further demonstrated the Zn^(2+)insertion/extraction and Zn-storage mechanism that occurred during the cycle in the CaVO//Zn battery system.This work provides new insights into the intercalation of similar divalent cations in vanadium oxides and offers new solutions for designing cathodes for high-capacity aqueous ZIBs.展开更多
Undoubtedly,the enormous progress observed in recent years in the Ni-rich layered cathode materials has been crucial in terms of pushing boundaries of the Li-ion battery(LIB)technology.The achieved improvements in the...Undoubtedly,the enormous progress observed in recent years in the Ni-rich layered cathode materials has been crucial in terms of pushing boundaries of the Li-ion battery(LIB)technology.The achieved improvements in the energy density,cyclability,charging speed,reduced costs,as well as safety and stability,already contribute to the wider adoption of LIBs,which extends nowadays beyond mobile electronics,power tools,and electric vehicles,to the new range of applications,including grid storage solutions.With numerous published papers and broad reviews already available on the subject of Ni-rich oxides,this review focuses more on the most recent progress and new ideas presented in the literature references.The covered topics include doping and composition optimization,advanced coating,concentration gradient and single crystal materials,as well as innovations concerning new electrolytes and their modification,with the application of Ni-rich cathodes in solid-state batteries also discussed.Related cathode materials are briefly mentioned,with the high-entropy approach and zero-strain concept presented as well.A critical overview of the still unresolved issues is given,with perspectives on the further directions of studies and the expected gains provided.展开更多
To modify the thermodynamics and kinetic performance of magnesium hydride(MgH_(2))for solid-state hydrogen storage,Ni_(3)V_(2)O_(8)-rGO(rGO represents reduced graphene oxide)and Ni_(3)V_(2)O_(8)nanocomposites were pre...To modify the thermodynamics and kinetic performance of magnesium hydride(MgH_(2))for solid-state hydrogen storage,Ni_(3)V_(2)O_(8)-rGO(rGO represents reduced graphene oxide)and Ni_(3)V_(2)O_(8)nanocomposites were prepared by hydrothermal and subsequent heat treatment.The beginning hydrogen desorption temperature of 7 wt.%Ni_(3)V_(2)O_(8)-rGO modified MgH_(2)was reduced to 208℃,while the additive-free MgH_(2)and 7 wt.%Ni_(3)V_(2)O_(8)doped MgH_(2)appeared to discharge hydrogen at 340 and 226℃,respectively.A charging capacity of about 4.7 wt.%H_(2)for MgH_(2)+7 wt.%Ni_(3)V_(2)O_(8)-rGO was achieved at 125℃ in 10 min,while the dehydrogenated MgH_(2)took 60 min to absorb only 4.6 wt.%H_(2)at 215℃.The microstructure analysis confirmed that the in-situ generated Mg_(2)Ni/Mg_(2)N_(i)H_(4) and metallic V contributed significantly to the enhanced performance of MgH_(2).In addition,the presence of rGO in the MgH_(2)+7 wt.%Ni_(3)V_(2)O_(8)-rGO composite reduced particle aggregation tendency of Mg/MgH_(2),leading to improving the cyclic stability of MgH_(2)during 20 cycles.展开更多
P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phas...P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.展开更多
Glycerol carbonate,an important glycerol value-added product,has been widely used as an active intermediate and inert solvent in the synthesis of cosmetics,detergents,chemical intermediates,polymers,and so on.The dire...Glycerol carbonate,an important glycerol value-added product,has been widely used as an active intermediate and inert solvent in the synthesis of cosmetics,detergents,chemical intermediates,polymers,and so on.The direct carbonylation from glycerol with CO_(2)is considered a promising route,but still tough work due to the thermodynamic stability and the kinetic inertness of CO_(2).In this work,highlyselective direct carbonylation of glycerol and CO_(2)into glycerol carbonate has been achieved over highly dispersed MgInCe-mixed metal oxides(MgInCe-MMO),which were prepared through the topological transformation derived from the MgInCe-layered double hydroxides(MgInCe-LDHs).By precisely modulating the surface basic-acidic properties and the oxygen vacancies,an efficient carbonylation of glycerol with CO_(2)has been achieved with a selectivity of up to>99%to glycerol carbonate.Deep investigation into the synergistic catalysis of base-acid sites and oxygen vacancies has been clarified.展开更多
Vanadium oxides,par-ticularly hydrated forms like V_(2)O_(5)·nH_(2)O(VOH),stand out as promising cathode candidates for aqueous zinc ion batteries due to their adjustable layered structure,unique electronic chara...Vanadium oxides,par-ticularly hydrated forms like V_(2)O_(5)·nH_(2)O(VOH),stand out as promising cathode candidates for aqueous zinc ion batteries due to their adjustable layered structure,unique electronic characteristics,and high theoretical capacities.However,challenges such as vanadium dissolution,sluggish Zn^(2+)diffusion kinetics,and low operating voltage still hinder their direct application.In this study,we present a novel vanadium oxide([C_(6)H_(6)N(CH_(3))_(3)]_(1.08)V_(8)O_(20)·0.06H_(2)O,TMPA-VOH),developed by pre-inserting trimethylphenylammonium(TMPA+)cations into VOH.The incorporation of weakly polarized organic cations capitalizes on both ionic pre-intercalation and molecular pre-intercalation effects,resulting in a phase and morphology transition,an expansion of the interlayer distance,extrusion of weakly bonded interlayer water,and a substantial increase in V^(4+)content.These modifications synergistically reduce the electrostatic interactions between Zn^(2+)and the V-O lattice,enhancing structural stability and reaction kinetics during cycling.As a result,TMPA-VOH achieves an elevated open circuit voltage and operation voltage,exhibits a large specific capacity(451 mAh g^(-1)at 0.1 A g^(-1))coupled with high energy efficiency(89%),the significantly-reduced battery polarization,and outstanding rate capability and cycling stability.The concept introduced in this study holds great promise for the development of high-performance oxide-based energy storage materials.展开更多
Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structur...Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structural and dynamic details.Herein,we commence with a brief introduction to recent research on lithium-ion battery oxide materials studied using ^(17)O solid-state NMR spectroscopy.Then we delve into a review of ^(17)O isotopic labeling methods for tagging oxygen sites in both the bulk and surfaces of metal oxides.At last,the unresolved problems and the future research directions for advancing the ^(17)O labeling technique are discussed.展开更多
Fe-Mn based layer oxides cathode materials have attracted widespread attention as a potential candidate for sodium-ion batteries(SIBs)owing to the earth abundance,cost-effectiveness and acceptable specific capacity.Ho...Fe-Mn based layer oxides cathode materials have attracted widespread attention as a potential candidate for sodium-ion batteries(SIBs)owing to the earth abundance,cost-effectiveness and acceptable specific capacity.However,the irreversible phase transition often brings rapid capacity decay,which seriously hinders the practical application in large-scale energy storage.Herein,we design a nickel-doped Na_(0.70)Fe_(0.10)Cu_(0.20)Ni_(0.05)Mn_(0.65)O_(2)(NFCNM-0.05)cathode material of SIBs with activated anionic redox reaction,and then inhibit the harmful phase transition.The ex-situ X-ray diffraction patterns demonstrate the NFCNM-0.05 always keeps the P2 phase during the sodiation/desodiation process,indicating a high structure stability.The ex-situ X-ray photoelectron spectroscopy implies the redox reactions between O2-and O-occur in the charging process,which offers extra specific capacity.Thus,the NFCNM-0.05 electrode delivers a high initial discharge capacity of 148 mA h g-1and remains a prominent cycling stability with an excellent capacity retention of 95.9%after 200 cycles at 1 C.In addition,the electrochemical impedance spectroscopy and galvanostatic intermittent titration technique show the NFCNM-0.05 electrode possesses fast ion diffusion ability,which is beneficial for the enhancement of rate performance.Even at 10 C,the NFCNM-0.05 can offer a reversible discharge capacity of 81 mA h g-1.DFT calculation demonstrates the doping of appropriate amount of Ni ions is benefit for the enhancement of the electrochemical performance of the layer oxides.This work provides an effective strategy to enhance the electrochemical performance of Fe-Mn based cathode materials of SIBs.展开更多
Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still fac...Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still face relatively low NH3yield rate and poor stability. We present here a core-shell heterostructure comprising cobalt oxide anchored on copper oxide nanowire arrays(CuO NWAs@Co_(3)O_(4)) for efficient NRA. The CuO NWAs@Co_(3)O_(4)demonstrates significantly enhanced NRA performance in alkaline media in comparison with plain CuO NWAs and Co_(3)O_(4)flocs. Especially, at-0.23 V vs. RHE, NH_(3) yield rate of the CuO NWAs@Co_(3)O_(4)reaches 1.915 mmol h^(-1)cm^(-2),much higher than those of CuO NWAs(1.472 mmol h^(-1)cm^(-2)), Co_(3)O_(4)flocs(1.222 mmol h^(-1)cm^(-2)) and recent reported Cu-based catalysts.It is proposed that the synergetic effects of the heterostructure combing atom hydrogen adsorption and nitrate reduction lead to the enhanced NRA performance.展开更多
High-entropy oxides(HEOs)are gaining prominence in the field of electrochemistry due to their distinctive structural characteristics,which give rise to their advanced stable and modifiable functional properties.This r...High-entropy oxides(HEOs)are gaining prominence in the field of electrochemistry due to their distinctive structural characteristics,which give rise to their advanced stable and modifiable functional properties.This review presents fundamental preparations,incidental characterizations,and typical structures of HEOs.The prospective applications of HEOs in various electrochemical aspects of electrocatalysis and energy conversion-storage are also summarized,including recent developments and the general trend of HEO structure design in the catalysis containing oxygen evolution reaction(OER)and oxygen reduction reaction(ORR),supercapacitors(SC),lithium-ion batteries(LIBs),solid oxide fuel cells(SOFCs),and so forth.Moreover,this review notes some apparent challenges and multiple opportunities for the use of HEOs in the wide field of energy to further guide the development of practical applications.The influence of entropy is significant,and high-entropy oxides are expected to drive the improvement of energy science and technology in the near future.展开更多
基金funded by the National Natural Science Foundation of China,China (Nos.52272303 and 52073212)the General Program of Municipal Natural Science Foundation of Tianjin,China (Nos.17JCYBJC22700 and 17JCYBJC17000)the State Scholarship Fund of China Scholarship Council,China (Nos.201709345012 and 201706255009)。
文摘The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.
基金the SINOPEC Research and Development Project(No.JR22094).
文摘Chemical looping oxidative dehydrogenation (CL-ODH) is an economically promising method for convertingethane into higher value-added ethylene utilizing lattice oxygen in redox catalysts, also known as oxygen carriers. Inthis study, perovskite-type oxide SrCoO_(3-δ) and B-site Mn ion-doped oxygen carriers (SrCo_(1-x)MnxO_(3-δ), x=0.1, 0.2, 0.3)were prepared and tested for the CL-ODH of ethane. The oxygen-deficient perovskite SrCoO_(3-δ) exhibited high ethyleneselectivity of up to 96.7% due to its unique oxygen vacancies and lattice oxygen migration rates. However, its low ethyleneyield limits its application in the CL-ODH of ethane. Mn doping promoted the reducibility of SrCoO_(3-δ) oxygen carriers,thereby improving ethane conversion and ethylene yield, as demonstrated by characterization and evaluation experiments.X-ray diffraction results confirmed the doping of Mn into the lattice of SrCoO_(3-δ), while X-ray photoelectron spectroscopy(XPS) indicated an increase in lattice oxygen ratio upon incorporation of Mn into the SrCoO_(3-δ) lattice. Additionally, H2temperature-programmed reduction (H2-TPR) tests revealed more peaks at lower temperature reduction zones and a declinein peak positions at higher temperatures. Among the four tested oxygen carriers, SrCo0.8Mn0.2O_(3-δ) exhibited satisfactoryperformance with an ethylene yield of 50% at 710 °C and good stability over 20 redox cycles. The synergistic effect of Mnplays a key role in increasing ethylene yields of SrCoO_(3-δ) oxygen carriers. Accordingly, SrCo0.8Mn0.2O_(3-δ) shows promisingpotential for the efficient production of ethylene from ethane via CL-ODH.
基金supported by the National Natural Science Foundation of China(22078215)Research Project by Shanxi Scholarship Council of China(2021-055)。
文摘In this work,a new ZnO/CoNiO_(2)/CoO/C metal oxides composite is prepared by cost-effective hydrothermal method coupled with annealing process under N_(2) atmosphere.Notably,the oxidation-defect annealing environment is conducive to both morphology and component of the composite,which flower-like ZnO/CoNiO_(2)/CoO/C is obtained.Benefited from good chemical stability of ZnO,high energy capacity of CoNiO_(2) and CoO and good conductivity of C,the as-prepared sample shows promising electrochemical behavior,including the specific capacity of 1435 C·g^(-1) at 1 A·g^(-1),capacity retention of 87.3%at 20 A·g^(-1),and cycling stability of 90.5%for 3000 cycles at 5 A·g^(-1),respectively.Furthermore,the prepared ZnO/CoNiO_(2)/CoO/C/NF//AC aqueous hybrid supercapacitors device delivers the best specific energy of 55.9 W·h·kg^(-1) at 850 W·kg^(-1).The results reflect that the as-prepared ZnO/CoNiO_(2)/CoO/C microflowers are considered as high performance electrode materials for supercapacitor,and the strategy mentioned in this paper is benefit to prepare mixed metal oxides composite for energy conversion and storage.
基金financially supported by the National Key Research and Development Program of China (No.2021YFA0718900)the National Natural Science Foundation of China (No.62074014)the Xiaomi Scholar project。
文摘Metal-to-insulator transitions (MITs),which are achieved in 3d-band correlated transitional metal oxides,trigger abrupt variations in electrical,optical,and/or magnetic properties beyond those of conventional semiconductors.Among such material families,iron(Fe:3d^(6)4s^(2))-containing oxides pique interest owing to their widely tunable MIT properties,which are associated with the various valence states of Fe.Their potential electronic applications also show promise,given the large abundance of Fe on Earth.Representative MIT properties triggered by critical temperature (TMIT) were reported for ReFe_(2)O_(4)(Fe^(2.5+)),ReBaFe_(2)O_(5)(Fe^(2.5+)),Fe_(3)O_(4)(Fe^(2.67+)),Re_(1/3)Sr_(2/3)FeO_(3)(Fe^(3.67+)),Re Cu_(3)Fe_(4)O_(12)(Fe^(3.75+)),and Ca_(1-x)Sr_(x)FeO_(3)(Fe^(4+))(where Re represents rare-earth elements).The common feature of MITs of these Fe-containing oxides is that they are usually accompanied by charge ordering transitions or disproportionation associated with the valence states of Fe.Herein,we review the material family of Fe-containing MIT oxides,their MIT functionalities,and their respective mechanisms.From the perspective of potentially correlated electronic applications,the tunability of the TMITand its resultant resistive change in Fe-containing oxides are summarized and further compared with those of other materials exhibiting MIT functionality.In particular,we highlight the abrupt MIT and wide tunability of TMITof Fe-containing quadruple perovskites,such as Re Cu3Fe4O12.However,their effective material synthesis still needs to be further explored to cater to potential applications.
基金This study was supported by the National Research Foundation of Korea(NRF-2021R1C1C1010233)funded by the Korean government(MSIT)+1 种基金This research was also supported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)Grant(No.G032542411)funded by the Korea Ministry of Trade,Industry,and Energy(MOTIE).
文摘Supported nanoparticles have attracted considerable attention as a promising catalyst for achieving unique properties in numerous applications,including fuel cells,chemical conversion,and batteries.Nanocatalysts demonstrate high activity by expanding the number of active sites,but they also intensify deactivation issues,such as agglomeration and poisoning,simultaneously.Exsolution for bottomup synthesis of supported nanoparticles has emerged as a breakthrough technique to overcome limitations associated with conventional nanomaterials.Nanoparticles are uniformly exsolved from perovskite oxide supports and socketed into the oxide support by a one-step reduction process.Their uniformity and stability,resulting from the socketed structure,play a crucial role in the development of novel nanocatalysts.Recently,tremendous research efforts have been dedicated to further controlling exsolution particles.To effectively address exsolution at a more precise level,understanding the underlying mechanism is essential.This review presents a comprehensive overview of the exsolution mechanism,with a focus on its driving force,processes,properties,and synergetic strategies,as well as new pathways for optimizing nanocatalysts in diverse applications.
基金the National Key Research and Development Program of China[No.2021YFB4000700]the CAS Project for Young Scientists in Basic Research[YSBR-022]+1 种基金the National Natural Science Foundation of China[22008136,21925803]the Welsh Government funded Taith Research Mobility Programme[No.524339]。
文摘Cu catalysts,known for their unparalleled catalytic capabilities due to their unique electronic structure,have faced inherent challenges in maintaining long-term effectiveness under harsh hydrogenation conditions.Here,we demonstrate a molybdenum-mediated redispersion behavior of Cu under hightemperature oxidation conditions.The oxidized Cu nanoparticles with rich metal-support interfaces tend to dissolve into the MoO_(3)support upon heating to 600℃,which facilitates the subsequent regeneration in a reducing atmosphere.A similar redispersion phenomenon is observed for Cu nanoparticles supported on Zn O-modified MoO_(3).The modification of ZnO significantly improves the performance of the Cu catalyst for CO_(2)hydrogenation to methanol,with the high activity being well maintained after four repeated oxidation-reduction cycles.In situ spectroscopic and theoretical analyses suggest that the interaction involved in the formation of the copper molybdate-like compound is the driving force for the redispersion of Cu.This method is applicable to various Mo-based oxide supports,offering a practical strategy for the regeneration of sintered Cu particles in hydrogenation applications.
基金supported by Key Science and Technology Innovation Team of Shaanxi Province(No.2022TD-33)National Natural Science Foundation of China(Grant Nos.21373161,21504067)。
文摘Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculated using DMol3,since HMX and O are key substances in decomposition process.And the relationship between the adsorption energy of HMX,O on metal oxides(TiO_(2),Al_(2)O_(3),PbO,CuO,Fe_(2)O_(3),Co_(3)O_(4),Bi_(2)O_(3),NiO)and experimental T30 values(time required for the decomposition depth of HMX to reach 30%)was depicted as volcano plot.Thus,the T30 values of other metal oxides was predicted based on their adsorption energy on volcano plot and validated by previous experimental data.Further,the adsorption energy of HMX on ZrO_(2)and MnO_(2)was predicted based on the linear relationship between surface energy and adsorption energy,and T30 values were estimated based on volcano plot.The apparent activation energy data of HMX/MgO,HMX/SnO_(2),HMX/ZrO_(2),and HMX/MnO_(2)obtained from DSC experiments are basically consistent with our predicted T30 values,indicating that it is feasible to predict the catalytic activity based on the adsorption calculation,and it is expected that these simple structural properties can predict adsorption energy to reduce the large quantities of computation and experiment cost.
基金The authors acknowledge the support of the Shenyang University of Technology(QNPY202209-4)the National Natural Science Foundation of China(21571132)+1 种基金Jiangsu University Advanced Talent Fund(5501710002)the Education Department of Liaoning Province(JYTQN2023285).
文摘Anode materials are an essential part of lithium-ion batteries(LIBs),which determine the performance and safety of LIBs.Currently,graphite,as the anode material of commercial LIBs,is limited by its low theoretical capacity of 372 mA·h·g^(−1),thus hindering further development toward high-capacity and large-scale applications.Alkaline earth metal iron-based oxides are considered a promising candidate to replace graphite because of their low preparation cost,good thermal stability,superior stability,and high electrochemical performance.Nonetheless,many issues and challenges remain to be addressed.Herein,we systematically summarize the research progress of alkaline earth metal iron-based oxides as LIB anodes.Meanwhile,the material and structural properties,synthesis methods,electrochemical reaction mechanisms,and improvement strategies are introduced.Finally,existing challenges and future research directions are discussed to accelerate their practical application in commercial LIBs.
基金financially supported by the National Natural Science Foundation of China(52202046,51602246,and 51801144)the Natural Science Foundation of Shanxi Provincial(2021JQ-034)。
文摘Co-free Li-rich layered oxides(LLOs)are emerging as promising cathode materials for Li-ion batteries due to their low cost and high capacity.However,they commonly face severe structural instability and poor electrochemical activity,leading to diminished capacity and voltage performance.Herein,we introduce a Co-free LLO,Li_(1.167)Ni_(0.222)Mn_(0.611)O_(2)(Cf-L1),which features a cooperative structure of Li/Ni mixing and stacking faults.This structure regulates the crystal and electronic structures,resulting in a higher discharge capacity of 300.6 mA h g^(-1)and enhanced rate capability compared to the typical Co-free LLO,Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2)(Cf-Ls).Density functional theory(DFT)indicates that Li/Ni mixing in LLOs leads to increased Li-O-Li configurations and higher anionic redox activities,while stacking faults further optimize the electronic interactions of transition metal(TM)3d and non-bonding O 2p orbitals.Moreover,stacking faults accommodate lattice strain,improving electrochemical reversibility during charge/discharge cycles,as demonstrated by the in situ XRD of Cf-L1 showing less lattice evolution than Cf-Ls.This study offers a structured approach to developing Co-free LLOs with enhanced capacity,voltage,rate capability,and cyclability,significantly impacting the advancement of the next-generation Li-ion batteries.
基金financially supported by the Natural Science Foundation of Shandong Province(ZR2022QB166,ZR2020KE032)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA22010600)+3 种基金the Youth Innovation Promotion Association of CAS(2021210)the Foundation of Qingdao Postdoctoral Application Program(Y63302190F)the Natural Science Foundation of Qingdao Institute ofBioenergy and Bioprocess Technology(QIBEBT SZ202101)support from the Max Planck-POSTECH-Hsinchu Center for Complex Phase Materials
文摘Full concentration gradient lithium-rich layered oxides are catching lots of interest as the next generation cathode for lithium-ion batteries due to their high discharge voltage,reduced voltage decay and enhanced rate performance,whereas the high lithium residues on its surface impairs the structure stability and long-term cycle performance.Herein,a facile multifunctional surface modification method is implemented to eliminate surface lithium residues of full concentration gradient lithium-rich layered oxides by a wet chemistry reaction with tetrabutyl titanate and the post-annealing process.It realizes not only a stable Li_(2)TiO_(3)coating layer with 3D diffusion channels for fast Li^(+)ions transfer,but also dopes partial Ti^(4+)ions into the sub-surface region of full concentration gradient lithium-rich layered oxides to further strengthen its crystal structure.Consequently,the modified full concentration gradient lithium-rich layered oxides exhibit improved structure stability,elevated thermal stability with decomposition temperature from 289.57℃to 321.72℃,and enhanced cycle performance(205.1 mAh g^(-1)after 150 cycles)with slowed voltage drop(1.67 mV per cycle).This work proposes a facile and integrated modification method to enhance the comprehensive performance of full concentration gradient lithium-rich layered oxides,which can facilitate its practical application for developing higher energy density lithium-ion batteries.
基金the financial support from the National Key Research and Development Program of China(2022YFA1207503)the Giga Force Electronics Interdisciplinary Funding(JJHXM002208-2023)。
文摘Exploring suitable high-capacity V_(2)O_(5)-based cathode materials is essential for the rapid advancement of aqueous zinc ion batteries(ZIBs).However,the typical problem of slow Zn^(2+)diffusion kinetics has severely limited the feasibility of such materials.In this work,unique hydrated vanadates(CaVO,BaVO)were obtained by intercalation of Ca^(2+)or Ba^(2+)into hydrated vanadium pentoxide.In the CaVO//Zn and BaVO//Zn batteries systems,the former delivered up to a 489.8 mAh g^(-1)discharge specific capacity at 0.1 A g^(-1).Moreover,the remarkable energy density of 370.07 Wh kg^(-1)and favorable cycling stability yard outperform BaVO,pure V_(2)O_(5),and many reported cathodes of similar ionic intercalation compounds.In addition,pseudocapacitance analysis,galvanostatic intermittent titration(GITT)tests,and Trasatti analysis revealed the high capacitance contribution and Zn^(2+)diffusion coefficient of CaVO,while an in-depth investigation based on EIS elucidated the reasons for the better electrochemical performance of CaVO.Notably,ex-situ XRD,XPS,and TEM tests further demonstrated the Zn^(2+)insertion/extraction and Zn-storage mechanism that occurred during the cycle in the CaVO//Zn battery system.This work provides new insights into the intercalation of similar divalent cations in vanadium oxides and offers new solutions for designing cathodes for high-capacity aqueous ZIBs.
基金supported by the program“Excellence Initiative-Research University”for the AGH University of Krakow(IDUB AGH,No.501.696.7996,Action 4,ID 6354)partially supported by the AGH University of Krakow under No.16.16.210.476.
文摘Undoubtedly,the enormous progress observed in recent years in the Ni-rich layered cathode materials has been crucial in terms of pushing boundaries of the Li-ion battery(LIB)technology.The achieved improvements in the energy density,cyclability,charging speed,reduced costs,as well as safety and stability,already contribute to the wider adoption of LIBs,which extends nowadays beyond mobile electronics,power tools,and electric vehicles,to the new range of applications,including grid storage solutions.With numerous published papers and broad reviews already available on the subject of Ni-rich oxides,this review focuses more on the most recent progress and new ideas presented in the literature references.The covered topics include doping and composition optimization,advanced coating,concentration gradient and single crystal materials,as well as innovations concerning new electrolytes and their modification,with the application of Ni-rich cathodes in solid-state batteries also discussed.Related cathode materials are briefly mentioned,with the high-entropy approach and zero-strain concept presented as well.A critical overview of the still unresolved issues is given,with perspectives on the further directions of studies and the expected gains provided.
基金the financial support from the National Natural Science Foundation of China(No.51801078).
文摘To modify the thermodynamics and kinetic performance of magnesium hydride(MgH_(2))for solid-state hydrogen storage,Ni_(3)V_(2)O_(8)-rGO(rGO represents reduced graphene oxide)and Ni_(3)V_(2)O_(8)nanocomposites were prepared by hydrothermal and subsequent heat treatment.The beginning hydrogen desorption temperature of 7 wt.%Ni_(3)V_(2)O_(8)-rGO modified MgH_(2)was reduced to 208℃,while the additive-free MgH_(2)and 7 wt.%Ni_(3)V_(2)O_(8)doped MgH_(2)appeared to discharge hydrogen at 340 and 226℃,respectively.A charging capacity of about 4.7 wt.%H_(2)for MgH_(2)+7 wt.%Ni_(3)V_(2)O_(8)-rGO was achieved at 125℃ in 10 min,while the dehydrogenated MgH_(2)took 60 min to absorb only 4.6 wt.%H_(2)at 215℃.The microstructure analysis confirmed that the in-situ generated Mg_(2)Ni/Mg_(2)N_(i)H_(4) and metallic V contributed significantly to the enhanced performance of MgH_(2).In addition,the presence of rGO in the MgH_(2)+7 wt.%Ni_(3)V_(2)O_(8)-rGO composite reduced particle aggregation tendency of Mg/MgH_(2),leading to improving the cyclic stability of MgH_(2)during 20 cycles.
基金supported by the National Natural Science Foundation of China (22169002)the Chongzuo Key Research and Development Program of China (20220603)the Counterpart Aid Project for Discipline Construction from Guangxi University(2023M02)
文摘P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.
基金Financial support from the National Key Research and Development Program of China(2022YFB3805602)the National Natural Science Foundation of China(22138001,22288102)the Fundamental Research Funds for the Central Universities。
文摘Glycerol carbonate,an important glycerol value-added product,has been widely used as an active intermediate and inert solvent in the synthesis of cosmetics,detergents,chemical intermediates,polymers,and so on.The direct carbonylation from glycerol with CO_(2)is considered a promising route,but still tough work due to the thermodynamic stability and the kinetic inertness of CO_(2).In this work,highlyselective direct carbonylation of glycerol and CO_(2)into glycerol carbonate has been achieved over highly dispersed MgInCe-mixed metal oxides(MgInCe-MMO),which were prepared through the topological transformation derived from the MgInCe-layered double hydroxides(MgInCe-LDHs).By precisely modulating the surface basic-acidic properties and the oxygen vacancies,an efficient carbonylation of glycerol with CO_(2)has been achieved with a selectivity of up to>99%to glycerol carbonate.Deep investigation into the synergistic catalysis of base-acid sites and oxygen vacancies has been clarified.
基金This work was supported by the National Science Foundation(CBET-1803256)Dr.C.Liu acknowledges the support from National Natural Science Foundation of China(52102277)the Fundamental Research Funds for the Central Universities,conducted by Tongji University.
文摘Vanadium oxides,par-ticularly hydrated forms like V_(2)O_(5)·nH_(2)O(VOH),stand out as promising cathode candidates for aqueous zinc ion batteries due to their adjustable layered structure,unique electronic characteristics,and high theoretical capacities.However,challenges such as vanadium dissolution,sluggish Zn^(2+)diffusion kinetics,and low operating voltage still hinder their direct application.In this study,we present a novel vanadium oxide([C_(6)H_(6)N(CH_(3))_(3)]_(1.08)V_(8)O_(20)·0.06H_(2)O,TMPA-VOH),developed by pre-inserting trimethylphenylammonium(TMPA+)cations into VOH.The incorporation of weakly polarized organic cations capitalizes on both ionic pre-intercalation and molecular pre-intercalation effects,resulting in a phase and morphology transition,an expansion of the interlayer distance,extrusion of weakly bonded interlayer water,and a substantial increase in V^(4+)content.These modifications synergistically reduce the electrostatic interactions between Zn^(2+)and the V-O lattice,enhancing structural stability and reaction kinetics during cycling.As a result,TMPA-VOH achieves an elevated open circuit voltage and operation voltage,exhibits a large specific capacity(451 mAh g^(-1)at 0.1 A g^(-1))coupled with high energy efficiency(89%),the significantly-reduced battery polarization,and outstanding rate capability and cycling stability.The concept introduced in this study holds great promise for the development of high-performance oxide-based energy storage materials.
基金supported by National Key R&D Program of China(2021YFA1502803)the National Natural Science Foundation of China(NSFC)(21972066,91745202)+3 种基金NSFC-Royal Society Joint Program(21661130149)L.P.thanks the Royal Society and Newton Fund for a Royal Society-Newton Advanced Fellowshipsupported by the Research Funds for the Frontiers Science Centre for Critical Earth Material Cycling,Nanjing Universitya Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structural and dynamic details.Herein,we commence with a brief introduction to recent research on lithium-ion battery oxide materials studied using ^(17)O solid-state NMR spectroscopy.Then we delve into a review of ^(17)O isotopic labeling methods for tagging oxygen sites in both the bulk and surfaces of metal oxides.At last,the unresolved problems and the future research directions for advancing the ^(17)O labeling technique are discussed.
基金supported by the National Natural Science Foundation of China(U1960107)the Natural Science Foundation of Hebei Province(E2022501014)+3 种基金the “333”Talent Project of Hebei Province(A202005018)the Fundamental Research Funds for the Central Universities(N2123034)the Science and Technology Research Youth Fund Project of Higher Education Institutions of Hebei Province(QN2022196)the Performance subsidy fund for Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province(22567627H)。
文摘Fe-Mn based layer oxides cathode materials have attracted widespread attention as a potential candidate for sodium-ion batteries(SIBs)owing to the earth abundance,cost-effectiveness and acceptable specific capacity.However,the irreversible phase transition often brings rapid capacity decay,which seriously hinders the practical application in large-scale energy storage.Herein,we design a nickel-doped Na_(0.70)Fe_(0.10)Cu_(0.20)Ni_(0.05)Mn_(0.65)O_(2)(NFCNM-0.05)cathode material of SIBs with activated anionic redox reaction,and then inhibit the harmful phase transition.The ex-situ X-ray diffraction patterns demonstrate the NFCNM-0.05 always keeps the P2 phase during the sodiation/desodiation process,indicating a high structure stability.The ex-situ X-ray photoelectron spectroscopy implies the redox reactions between O2-and O-occur in the charging process,which offers extra specific capacity.Thus,the NFCNM-0.05 electrode delivers a high initial discharge capacity of 148 mA h g-1and remains a prominent cycling stability with an excellent capacity retention of 95.9%after 200 cycles at 1 C.In addition,the electrochemical impedance spectroscopy and galvanostatic intermittent titration technique show the NFCNM-0.05 electrode possesses fast ion diffusion ability,which is beneficial for the enhancement of rate performance.Even at 10 C,the NFCNM-0.05 can offer a reversible discharge capacity of 81 mA h g-1.DFT calculation demonstrates the doping of appropriate amount of Ni ions is benefit for the enhancement of the electrochemical performance of the layer oxides.This work provides an effective strategy to enhance the electrochemical performance of Fe-Mn based cathode materials of SIBs.
基金the financial support from National Natural Science Foundation of China (No. 21972102)National Key Research and Development Program of China (2021YFA0910400)+3 种基金Natural Science Foundation of Jiangsu Province (BK20200991)Suzhou Science and Technology Planning Project (SS202016)the USTS starting fund (No.332012104)the Natural Science Foundation of Suzhou University of Science and Technology (No.342134401)。
文摘Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still face relatively low NH3yield rate and poor stability. We present here a core-shell heterostructure comprising cobalt oxide anchored on copper oxide nanowire arrays(CuO NWAs@Co_(3)O_(4)) for efficient NRA. The CuO NWAs@Co_(3)O_(4)demonstrates significantly enhanced NRA performance in alkaline media in comparison with plain CuO NWAs and Co_(3)O_(4)flocs. Especially, at-0.23 V vs. RHE, NH_(3) yield rate of the CuO NWAs@Co_(3)O_(4)reaches 1.915 mmol h^(-1)cm^(-2),much higher than those of CuO NWAs(1.472 mmol h^(-1)cm^(-2)), Co_(3)O_(4)flocs(1.222 mmol h^(-1)cm^(-2)) and recent reported Cu-based catalysts.It is proposed that the synergetic effects of the heterostructure combing atom hydrogen adsorption and nitrate reduction lead to the enhanced NRA performance.
基金The authors are thankful for the financial support from the Beijing Natural Science Foundation(No.3222050)the National Natural Science Foundation of China(Nos.22075304 and 52202324).
文摘High-entropy oxides(HEOs)are gaining prominence in the field of electrochemistry due to their distinctive structural characteristics,which give rise to their advanced stable and modifiable functional properties.This review presents fundamental preparations,incidental characterizations,and typical structures of HEOs.The prospective applications of HEOs in various electrochemical aspects of electrocatalysis and energy conversion-storage are also summarized,including recent developments and the general trend of HEO structure design in the catalysis containing oxygen evolution reaction(OER)and oxygen reduction reaction(ORR),supercapacitors(SC),lithium-ion batteries(LIBs),solid oxide fuel cells(SOFCs),and so forth.Moreover,this review notes some apparent challenges and multiple opportunities for the use of HEOs in the wide field of energy to further guide the development of practical applications.The influence of entropy is significant,and high-entropy oxides are expected to drive the improvement of energy science and technology in the near future.