NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsi...NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsic activity limitations and poor stability,primarily due to the asymmetric adsorption of oxygen intermediates.To overcome this,the binding strength must be synergistically tuned to a moderate level to optimize catalytic performance.Here,we engineered NiFeCoCr LDH through Co doping to enhance electrical conductivity and controlled Cr leaching to introduce cationic vacancies for modulating intermediate binding strength in NiFe LDH.X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses reveal that NiFe-LDH with Co doping and Cr vacancies modulates the Ni oxidation state and local coordination environment,leading to a balanced electronic structure and enhanced structural complexity around the Ni sites.Additionally,these vacancies can trap OH^(-)/H_(2)O species,which can serve as a reservoir for OH^(-) transfer,facilitating the rapid formation of OER intermediates and enhancing catalytic performance at high current densities.As a result,V_(Cr)-NiFeCo LDH achieves 1.6 A cm^(-2)current density at 1.7 V vs.RHE while maintaining stable operation for over 1000 h at 500 mA cm^(-2).Density functional theory(DFT)calculations validate the synergistic effects of Co doping and Cr-induced vacancies on intermediate binding energies and improved OER kinetics.Overall,this work presents a rational design strategy to simultaneously enhance the activity and durability of NiFe-based OER catalysts for their application in high-performance alkaline water electrolysis.展开更多
Layered transition-metal compounds(LTMCs)feature stacked architectures,strong magnetic anisotropy,and tunable magnetic order,making them promising material platforms for low-power spintronic technologies and for enabl...Layered transition-metal compounds(LTMCs)feature stacked architectures,strong magnetic anisotropy,and tunable magnetic order,making them promising material platforms for low-power spintronic technologies and for enabling topological functionalities in the post-Moore era.Here we review recent progress on two-dimensional(2D)magnetism in LTMCs,emphasizing material taxonomy,intrinsic magnetic properties,and external-field controls.This review first presents a classification of LTMCs by crystal structure and chemistry—binary halides,chalcogenides,and ternary families(e.g.,MPX_(3),M_(m)X_(n)Te_(k),MnBi_(2)Te_(4))—followed by a summary of their coupling mechanisms,ordering temperatures,and dimensional effects.It then analyzes the modulation of exchange interactions,magnetic anisotropy,and topological states by electric-field gating,strain engineering,and ion intercalation,with representative experimental demonstrations.Notable advances include room-temperature ferromagnetic metals and semiconductors,observation of the quantum anomalous Hall effect(QAHE)in MnBi2Te4,and synergistic control of magnetic-topological states under multiple external stimuli.Persistent challenges involve the limited availability of intrinsic 2D magnetic semiconductors with high Curie temperatures(Tc),incomplete understanding of the microscopic couplings at interfaces and under quantum confinement,and device-level stability.We conclude by outlining opportunities that lie in the integration of multiscale characterization,first-principles theory,and cross-scale fabrication to precisely co-engineer magnetism,topology,and electronic structure,thereby advancing LTMCs toward spintronic and topological-quantum applications.展开更多
Interfacial engineering is crucial for developing high-performance Ni-rich layered cathodes for lithiumion batteries.Here,we introduce an interfacial precipitation(IP)strategy,guided by first-principles calculations,t...Interfacial engineering is crucial for developing high-performance Ni-rich layered cathodes for lithiumion batteries.Here,we introduce an interfacial precipitation(IP)strategy,guided by first-principles calculations,to create a functionally graded cathode during precursor synthesis.Based on thermodynamic principles of bulk insolubility and phase separation kinetics,we achieved the selective precipitation of Co onto the surface of a Ni-rich hydroxide precursor.Upon high-temperature lithiation,this engineered precursor spontaneously forms a unique,bifunctional Co-rich spinel-like layer on the final LiNi_(0.88)Co_(0.06)Mn_(0.06)O_(2)(NCM)cathode.This architecture suppresses detrimental Li/Ni cation mixing and protects the active material.Consequently,the IP-driven NCM cathode demonstrates vastly superior rate capability,delivering 140.8 m A h g^(-1)at 5C,compared to 112.9 mA h g^(-1)for its conventionally prepared counterpart.This enhancement is attributed to significantly lower charge-transfer resistance and faster kinetics.Remarkably,in a full-cell configuration,the IP-driven NCM cathode maintains 81.5%capacity after 1000 cycles at an aggressive 5C rate.This work presents a thermodynamically driven,scalable strategy for designing advanced cathodes with exceptional high-power performance and stability.展开更多
Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))from earth-abundant water and oxygen is a sustainable approach,however current photocatalysts suffer from low production rate and solar-to-chemical conversion ...Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))from earth-abundant water and oxygen is a sustainable approach,however current photocatalysts suffer from low production rate and solar-to-chemical conversion efficiency(<1.5%).Herein,we report that nickelchromium layered double hydroxide with intercalated nitrate(NiCrOOH-NO_(3))and a thickness of~4.4 nm is an efficient photocatalyst,enabling a H_(2)O_(2)production yield of 28.7 mmol g^(-1)h^(-1)under visible light irradiation with3.92%solar-to-chemical conversion efficiency.Experimental and computational studies have revealed an inherent facet-dependent reduction-oxidation reaction behavior and spatial separation of photogenerated electrons and holes.An unexpected role of intercalated nitrate is demonstrated,which promotes excited electron—hole spatial separation and facilitates the electron transfer to oxygen intermediate via delocalization.This work provides understandings in the impact of nanostructure and anion in the design of advanced photocatalysts,paving the way toward practical synthesis of H_(2)O_(2)using fully solar-driven renewable energy.展开更多
High-entropy layered hydroxides(HELHs),an emerging frontier in entropy-stabilized materials derived from layered double hydroxides(LDHs),have captivated attention with their unparalleled tunability,thermodynamic stabi...High-entropy layered hydroxides(HELHs),an emerging frontier in entropy-stabilized materials derived from layered double hydroxides(LDHs),have captivated attention with their unparalleled tunability,thermodynamic stability,and electrochemical performance.The integration of the high-entropy concept into LDHs empowers HELHs to surmount the constraints of conventional materials through compositional diversity,structurally disordered configurations,and synergistic multi-element interactions.This review systematically embarks on their synthesis methodologies,functional mechanisms,and applications in energy conversion/storage and biomedicine.Advanced synthesis strategies,such as plasma-assisted hydrothermal methods,facilitate precise control over HELH architectures while supporting scalable production.HELHs demonstrate superior electrochemical performance in critical reactions,including oxygen evolution reaction,water oxidation,hydrogen evolution,and glucose electrooxidation.Future directions encompass integrating in situ characterization with simulations,leveraging machine learning for composition screening,and expanding HELHs application through interdisciplinary collaborations.This work establishes a comprehensive roadmap for advancing HELHs as next-generation multifunctional platforms for sustainable energy and biomedical technologies.展开更多
Drilling and blasting in layered rock masses faces significant challenges,as pre-existing joints cause unbalanced energy distribution,leading to poor forming effects and severe over-excavation.However,a comprehensive ...Drilling and blasting in layered rock masses faces significant challenges,as pre-existing joints cause unbalanced energy distribution,leading to poor forming effects and severe over-excavation.However,a comprehensive understanding of the complex coupling mechanisms between key joint parameters and the in-situ stress field on the final blasting outcome is still lacking.The model tests are used to quantitatively analyze the macroscopic crushing characteristics and crack propagation velocity.The numerical simulation then reveals the underlying mechanisms of stress wave propagation and energy partitioning,which are validated against the experimental results.The results indicate that the joints and the in-situ stress field play distinct,competitive roles in the blasting outcome.First,the joints control the anisotropy of the damage:crack propagation is primarily guided along the joint direction(the channel effect),and the apparent crack velocity exhibits a V-shaped trend with the joint inclination angle(0°-90°).Second,the in-situ stress state controls the overall extent of the damage:Increased confining pressure(both equal and unequal)inhibits crack propagation by increasing the failure threshold of the rock mass.Mechanistically,while this locking effect enhances stress wave transmission(i.e.,reduces the locking effect),this is secondary to the dominant inhibitory effect of the increased overall rock mass strength.The primary contribution of this study is the identification of this dual control mechanism,revealing that the final blasting effect is a non-linear competition between the joint's structural guidance and the dominant strengthening effect from the in-situ stress field,which clarifies the complex energy partitioning mechanisms at the blast source.展开更多
The P2-type Fe/Mn-based layered oxides,with cost advantages and high theoretical capacity,are considered one of the promising cathode materials for sodium-ion batteries(SIBs).However,the commercial development of thes...The P2-type Fe/Mn-based layered oxides,with cost advantages and high theoretical capacity,are considered one of the promising cathode materials for sodium-ion batteries(SIBs).However,the commercial development of these materials is impeded by two main factors:the MnO_(6) structure distortion induced by the Jahn-Teller(J-T)effect of Mn^(3+),and the unfavorable phase transitions that occur during the insertion and extraction of Na^(+).Here,we present a strategy to improve structural stability by incorporating cost-effective,robust Al-O bonds.This approach induces localized adjustments in the electronic structu re and a pinning effect,which limits the deformation of the transition metal(TM)layers,strengthens the electrostatic bonding within the TM layers,and expands the Na layer spacing.Consequently,the Na_(0.67)Fe_(0.4)Mn_(0.54)Al_(0.06)O_(2) cathode demonstrates a capacity of 168.8 mAh g^(-1) at 0.1 C,maintaining89.2%of its original capacity after 200 cycles at 1 C.Through in situ electrochemical impedance spectroscopy(EIS)with dynamic resistance transformation(DRT)analysis,ex situ X-ray absorption spectroscopy(XAS),and in situ X-ray diffraction(XRD),the study demonstrates a reduction in the J-T effect,enhanced kinetic performance,and the inhibition of detrimental phase transitions.This study offers new avenues to the development and design of future low-cost Fe/Mn-based cathodes.展开更多
High-capacity O3-type layered NiFeMn-based oxides are promising cathodes for sodium-ion batteries,though their practical deployment is constrained by the inherent limitations of Fe redox chemistry.Traditional designs ...High-capacity O3-type layered NiFeMn-based oxides are promising cathodes for sodium-ion batteries,though their practical deployment is constrained by the inherent limitations of Fe redox chemistry.Traditional designs generally enforcing stoichiometric symmetry(Ni=Mn)yield low Fe redox activity.Herein,we propose a valence engineering strategy that breaks conventional Ni/Mn stoichiometry to reconfigure Fe's local chemical environment and unlock unprecedented redox depth.Density functional theory(DFT)calculations reveal that the designed NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode exhibits a reduced Bader charge on Fe(1.598 vs.1.638 in NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2))and elevated Fe 3d orbital energy,signifying enhanced Fe redox activity.This configuration enables an exceptional Fe^(2.60+)/Fe^(3.88+)redox(1.28 e~-per Fe),delivering a reversible capacity of184.3 mAh g^(-1)within 2-4.2 V at 0.2 C,markedly exceeding the benchmark NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(161.3 mAh g^(-1))with low reaction depth of Fe^(3.01+)/Fe^(3.61+).The intensified cationic redox reaction enables an ultrahigh energy density of 596 Whkg-1.The NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode demonstrates robust performance over a broad temperature range from-15℃to 60℃.In situ and ex situ characterizations unveil a reversible O3■P3■OP2 phase transition with minimal volume change(1.88%)that circumvents detrimental deleterious O'3 intermediates and intragranular cracking.This work establishes valence engineering as a paradigm to consolidate cationic redox reaction in high-energy layered sodium oxide cathodes.展开更多
Sodium layered oxides stand out as one of the most promising cathodes for sodium-ion batteries due to their high energy density,elemental abundance,and scalability.However,their practical applications are restricted b...Sodium layered oxides stand out as one of the most promising cathodes for sodium-ion batteries due to their high energy density,elemental abundance,and scalability.However,their practical applications are restricted by interplanar gliding,cation migration,and the formation of intragranular microcracks,which collectively lead to rapid structural degradation and capacity loss.Herein,we rationally design an ultrastable O3-type Na_(0.94)Ca_(0.03)Ni_(1/3)Fe_(1/3)Mn_(1/3)O_(2) cathode,in which Ca^(2+)cations act as pillars within the NaO_(2)slabs,suppressing the irreversible phase transitions and Na/TM cation migration commonly observed in layered oxides.Multiscale in situ and ex situ techniques,combined with post-mortem analysis,reveal that the Ca-pillared pinning effect not only effectively suppresses the interplanar gliding and stress accumulation within the crystal phase but also restrains Na/TM cation migration and surface reconstruction in near-surface regions.Benefiting from the combined effects of structural stabilization,the Ca-pillared cathode exhibits a superior cycling stability,retaining 81.6%of its capacity after 1000 cycles at 2 C within the voltage range of 2.0-4.0 V,along with significantly enhanced wide-temperature(from-40 to 80℃)performance.This work highlights another critical role of Ca pillars in suppressing cation migration and surface structural degradation beyond preventing adverse interplanar gliding,offering valuable insights for designing long-life and wide-temperature layered oxide cathodes.展开更多
The irreversible oxygen redox(OR)in Li-rich layered cathodes leads to severe structural degradation and voltage decay,particularly under harsh operating conditions.Although high-entropy oxides(HEOs)offer enhanced stab...The irreversible oxygen redox(OR)in Li-rich layered cathodes leads to severe structural degradation and voltage decay,particularly under harsh operating conditions.Although high-entropy oxides(HEOs)offer enhanced stability compared to conventional doping modifications,rational element selection for optimizing OR reversibility remains unexplored.Here,we propose an entropy engineering design paradigm for “oxygen-anchoring”,where optimal cation electronegativity(>Mn,1.55)and d(3d/4d)-p orbital hybridization synergistically enhance transition metal–oxygen(TM–O)covalency and stabilize the O2p state.Two high-entropy Li-rich layered oxides:Li_(1.2)Mn_(0.47)Ni_(0.115)Co_(0.115)Mg_(0.02)Ti_(0.02)Al_(0.02)Nb_(0.02)Mo_(0.02)O_(2)(MTANM)and Li_(1.2)Mn_(0.47)Ni_(0.115)Co_(0.115)Mg_(0.02)Ti_(0.02)Cu_(0.02)Nb_(0.02)Mo_(0.02)O_(2)(MTCNM)were synthesized using partial nano-scale precursors and comparatively evaluated.MTCNM exhibits enhanced electrochemical performance and superior oxygen stability compared to MTANM by replacing Al with higher-electronegativity Cu,which possesses improved orbital overlap with oxygen.Both experiments and density functional theory(DFT)calculations demonstrate that element selection changes the covalency of TM–O through altered electronegativity and d orbitals-p orbitals(d-p)hybridization.Further stepwise screening selected the optimal elemental combination Li_(1.2)Mn_(0.47)Ni_(0.115)Co_(0.115)Cr_(0.02)Cu_(0.02)Nb_(0.02)Mo_(0.02)Ru_(0.02)O_(2)(CCNMR),which achieved near 100%capacity retention after 150 cycles at 1 C,50℃,with its voltage decay effectively suppressed.This work establishes a rational element-screening paradigm for entropy-stabilized OR chemistry in high-energy cathodes.展开更多
NiFe layered double hydroxide(NiFe LDH)has emerged as a promising catalyst for the oxygen evolution reaction(OER);however,its hydrogen evolution reaction(HER)activity remains suboptimal due to unfavorable electronic s...NiFe layered double hydroxide(NiFe LDH)has emerged as a promising catalyst for the oxygen evolution reaction(OER);however,its hydrogen evolution reaction(HER)activity remains suboptimal due to unfavorable electronic structures,particularly the d-electron density of metal sites,which impede water dissociation and lead to poor hydrogen adsorption/desorption capabilities.Herein,we introduce an efficient cooperative d-electron density regulation(CDDR)engineering to comprehensively optimize the delectron density of NiFe LDH by grafting MoO_(x) -modified NiFe LDH nanosheets onto porous nickel particles(PNPs).The PNPs facilitate d-electron density modulation along the edges of the nanosheets,while the MoO_(x) species enable d-electron density modulation across the plane of the nanosheets,thus cooperatively constructing enriched d-electron density in NiFe LDH.Theoretical studies validate the CDDR process and reveal that the enriched d-electron density accelerates water dissociation and optimizes the hydrogen adsorption behavior of NiFe LDH.As a result,the engineered catalyst exhibits significantly improved HER activity,achieving an ultra-low overpotential of 38 mV at 10 mA cm^(-2)in 1 M KOH.Additionally,the CDDR-optimized catalyst also exhibits good OER performance,demonstrating excellent bifunctional performance for overall water splitting in both alkaline freshwater and seawater electrolytes.This work presents a novel CDDR strategy for engineering NiFe LDH into efficient HER catalysts without compromising its OER activity,potentially paving the way for the development of active and robust electrocatalysts for sustainable energy applications.展开更多
Owing to its excellent eco-friendliness and facile water elution properties,aluminum-based lithium adsorbents have attracted a surge of interest for selectively extracting Li^(+)from Salt Lake brines,which account for...Owing to its excellent eco-friendliness and facile water elution properties,aluminum-based lithium adsorbents have attracted a surge of interest for selectively extracting Li^(+)from Salt Lake brines,which account for more than 60%of the global lithium resources.However,structural collapse,facile deactivation during desorption process,and ultra-low actual adsorption capacity limit its further large-scale application,particularly in low-grade sulfate-type brines.Herein,considering its advantages,limitations,and structural features,the structural collapse of the aluminum-based lithium adsorbent was effectively suppressed by the in situ intercalation of VO_(3)^(-)and V_(2)O_(7)^(4-)into the interlayer of[LiAl_(2)(OH)_(6)]^(+).Evidently,the initial adsorption capacity andα_(Mg)^(Li)of as-configured adsorbents powder are 14.96 mg g^(-1) and 192.42 in real sulfate-type West Taijinar Salt Lake brines following NaCl salts removal with 800 mg L^(-1) Li^(+)and 9.56 g L^(-1) SO_(4)^(2-).Furthermore,the initial and retained adsorption capacities of these novel adsorbents granulate in brines after 100 adsorption/desorption cycles are 26.68 and 10.36 mg g^(-1),respectively,which are almost 10 times higher than those of industrially utilized products.Based on experiments and density functional theory calculations,the process and mechanism of anion intercalation control were preliminarily elucidated.Furthermore,research findings indicate that intercalated anions can influence not only interlayer interactions but also the backbone strength of LDH-type adsorbents.This work significantly overcomes the major utilization challenges of aluminum-based lithium adsorbents,thereby enabling the high-efficiency and stable extraction of Li^(+)from low-grade brines,including sulfate-type brines.展开更多
O3-types layered cathode materials in sodium-ion batteries(SIBs)suffer from the obvious lattice distortion induced by the complex phase transitions during Na^(+)intercalation/deintercalation process,leading to severe ...O3-types layered cathode materials in sodium-ion batteries(SIBs)suffer from the obvious lattice distortion induced by the complex phase transitions during Na^(+)intercalation/deintercalation process,leading to severe structural collapse and performance degradation.Herein,a series of high valence tantalum(Ta^(5+))doped Na(Ni_(0.4)Fe_(0.2)Mn_(0.4))_(1−x)Ta_(x)O_(2)(x=0/0.0025/0.005/0.01)secondary spherical particles are firstly developed,where Ta^(5+)doping enables the refined primary grain with a tightly stacked rod-like morphology.Comprehensive structural analysis via Neutron powder diffraction(NPD)and Synchrotron radiation X-ray diffraction(SXRD)reveals an expanded NaO_(2)slab and a reduction in Na site vacancy.The potential charge compensation mechanism is further illustrated by X-ray absorption spectroscopy(XAS)and X-ray photoelectron spectroscopy(XPS),unveiling a partial reduction from Ni^(3+)to Ni^(2+)with Ta^(5+)doping.In situ X-ray diffraction(in situ XRD)suggests that the decorated sample undergoes a volume change as low as 0.8%,in contrast with the pristine one(1.5%).Thus,the optimized sample with x=0.005 retains an enhanced capacity retention up to 70.4%at 1 C after 300 cycles in half-cell and delivers a high energy density of 251 Wh kg^(-1)(0.1 C)and with a good capacity retention of 81.0%at 1 C after 200 cycles in full-cell.Our findings provide new insights into the mechanism of high valence Ta^(5+)doping in stabilizing layered oxides cathode materials for SIBs.展开更多
With the continuous development of the offshore wind industry,the design concept of composite foundation has been given attention in the past decade.This paper presents an accurate method for investigating the horizon...With the continuous development of the offshore wind industry,the design concept of composite foundation has been given attention in the past decade.This paper presents an accurate method for investigating the horizontal vibration of monopile-friction wheel composite foundations in layered saturated soil.Firstly,the three-dimensional continuum mechanics theory with the range of linear elasticity is introduced to calculate the frictional resistance distributed on the upper soil surface.Then,the resistances of multilayered soils and inviscid seawater to the pile shaft under horizontal harmonic excitation are obtained using Novak's plane strain model,Biot's porous media theory and radiationwave theory.Thirdly,the expressions for the deformation,bending moment and internal force of the Euler-Bernoulli pile are derived using the boundary conditions with definitephysical meaning and transfer matrix method.By comparing with the results of 1g laboratory test and the idealized formula reported by the literature,the rationality and accuracy of the developed dynamical model can be verified.Finally,this paper conducts a series of worked examples to investigate the influencesof the elastic modulus and thickness of three-layer saturated soil and the location of interlayer soil on the horizontal dynamic vibration of composite foundation.The results show that an increase in elastic modulus of the surface soil is an effective way to improve the dynamic stability of the composite foundation in service conditions.The conclusions drawn from the numerical examples can develop some guidelines for the current foundation design of offshore wind turbines.展开更多
Layered oxides present compelling potential as cathode materials for sodium-ion batteries(SIBs).However,challenges including interfacial instability and sluggish reaction kinetics critically limit their rate capabilit...Layered oxides present compelling potential as cathode materials for sodium-ion batteries(SIBs).However,challenges including interfacial instability and sluggish reaction kinetics critically limit their rate capability and cycling performance.Herein,we introduce the water-soluble sodium polyacrylate(NaPAA)binder as a promising approach to mitigating these issues in P2-type layered oxides.The NaPAA binder facilitates the formation of a uniform Na^(+) conductive interfacial film,which protects the cathode against electrolyte-induced corrosion and effectively inhibits the dissolution of transition metals in P2-Na_(0.85)Li_(0.12)Ni_(0.22)Mn_(0.66)O_(2)(NLNMO).Furthermore,we elucidate the mechanism by which the NaPAA binder dynamically regulates the coordination of free anions at the electrode-electrolyte interface.This regulation reduces solvent decomposition and promotes the formation of a stable,ionically conductive layer.Consequently,the P2-NLNMO@NaPAA integrated electrode exhibits enhanced electrochemical performance,achieving an 89.2%capacity retention after 200 cycles at 0.2 C and delivering an initial capacity of 102.9 mA h g^(-1) even at 0℃.This study advances the fundamental understanding of binder-mediated interface engineering and demonstrates a scalable and eco-friendly manufacturing pathway for high-performance SIBs.展开更多
Conventional Tb^(3+)-doped phosphors typically suffer from concentration quenching once the doping level exceeds a critical threshold.Consequently,the development of Tb^(3+)phosphors with intrinsic resistance to conce...Conventional Tb^(3+)-doped phosphors typically suffer from concentration quenching once the doping level exceeds a critical threshold.Consequently,the development of Tb^(3+)phosphors with intrinsic resistance to concentration quenching has become a key research focus.In this work,we successfully synthesized KBi(MoO_(4))_(2):x Tb^(3+)(x=0-100 at%)(denoted as KBM:x Tb^(3+))phosphors via a high-temperature solid-state reaction.Remarkably,no concentration quenching was observed across the entire doping range.This anti-quenching behavior originates from the large Tb^(3+)-Tb^(3+)interionic distance(>5Å)inherent to the quasi-layered crystal structure,which effectively suppresses multipole-interaction-mediated energy migration.At full Tb^(3+)substitution(x=100 at%),the material undergoes a structural phase transition from the monoclinic KBM phase to the triclinicα-KTb(MoO_(4))_(2)(α-KTM)phase.Theα-KTM phosphor exhibits excellent thermal stability(activation energy=0.6129 eV)and a single-exponential decay profile,whereas KBM:x Tb^(3+)(x<100%)display double-exponential decay behaviors,attributed to dual energy transfer pathways.These findings provide new insights into the luminescence mechanisms of high-concentration rare-earth-doped systems and offer guidance for designing nextgeneration anti-quenching phosphors.展开更多
A method for the effective in-situ formation of boron-containing Mg-Al layered double hydroxides(LDHs)was developed for boron removal and stabilization.The influence of the B/Al molar ratio and pH on the formation of ...A method for the effective in-situ formation of boron-containing Mg-Al layered double hydroxides(LDHs)was developed for boron removal and stabilization.The influence of the B/Al molar ratio and pH on the formation of Mg-Al-B–LDHs was investigated.Compared with the adsorption method,under a high B/Al ratio,the coprecipitation method increased the boron sorption density from 0.256 to 0.472 of Al.The Toxicity Characteristic Leaching Procedure showed that the boron-coprecipitated LDHs exhibited higher stability than the boron-adsorption LDHs.The synthesized LDH samples were characterized by X-ray diffraction,X-ray photoelectron spectroscopy,and solid-state 11B-NMR.The results showed that boron was effectively incorporated into the LDH structure for the coprecipitation method.Combined with the experimental results,a potential in-situ formation pathway for Mg-Al-B–LDHs was elucidated through density functional theory calculations.The boron tended to directly incorporate into the LDH structure in the coprecipitation method,whereas it was predominantly adsorbed on the LDH surface in the adsorption method.The adsorption energy demonstrated that boron preferentially bonded to Mg^(2+)sites on the surface.The mechanism of boron incorporation in the LDHs for the coprecipitation method involved precipitation of amorphous aluminum hydroxide,layered boehmite transformation,nucleation,and layer stacking.During these processes,boron formed complexes to enhance its stability.Residual boron underwent further reactions with the LDHs,including surface adsorption and ion exchange.These findings provide theoretical insight into the effective removal and long-term immobilization of boron in landfill leachate self-remediation processes.展开更多
Layered rocks are widely distributed in sedimentary and metamorphic rocks and show anisotropic deformation and strength due to the layered structures with apparent weak surfaces.This study summarizes the findings on t...Layered rocks are widely distributed in sedimentary and metamorphic rocks and show anisotropic deformation and strength due to the layered structures with apparent weak surfaces.This study summarizes the findings on the deformation and damage characteristics of layered rock masses and surrounding rocks.The physicomechanical properties of layered rocks with different properties(e.g.inclination,shear strength,tensile strength,shear stiffness,roughness,and layer spacing)and different lithological and stress conditions are analyzed.The results revealed that with increasing layer inclination angles,the deformation and strength parameters of the rock masses present U-shaped,W-shaped,incremental,decremental,and basically unchanged trends,which are closely related to their strength and stress conditions.The increase in layer strength and confining pressure effectively suppresses the deformation and strength anisotropy caused by layer weakening,and the rock mass shifts from“structure-controlled”to“stress-structure-controlled”deformation mode.Water will increase the anisotropic behavior of layered rock masses due to the degradation of bedding and bedrock performance.The anisotropic behavior of the layered surrounding rocks is analyzed to reveal how it affects the deformation and failure behaviors of tunnels.The asymmetric characteristics of surrounding rock deformation are closely related to the layer weakening,layer thickness,and in situ stress.These findings are crucial for understanding layered rock mass deformation and failure mechanisms,facilitating prediction and control of tunnel deformation.展开更多
The morphological distribution of absorbent in composites is equally important with absorbents for the overall electromagnetic properties,but it is often ignored.Herein,a comprehensive consideration including electrom...The morphological distribution of absorbent in composites is equally important with absorbents for the overall electromagnetic properties,but it is often ignored.Herein,a comprehensive consideration including electromagnetic component regulation,layered arrangement structure,and gradient concentration distribution was used to optimize impedance matching and enhance electromagnetic loss.On the microscale,the incorporation of magnetic Ni nanoparticles into MXene nanosheets(Ni@MXene)endows suitable intrinsic permittivity and permeability.On the macroscale,the layered arrangement of Ni@MXene increases the effective interaction area with electromagnetic waves,inducing multiple reflection/scattering effects.On this basis,according to the analysis of absorption,reflection,and transmission(A-R-T)power coefficients of layered composites,the gradient concentration distribution was constructed to realize the impedance matching at low-concentration surface layer,electromagnetic loss at middle concentration interlayer and microwave reflection at high-concentration bottom layer.Consequently,the layered gradient composite(LG5-10-15)achieves complete absorption coverage of X-band at thickness of 2.00-2.20 mm with RL_(min) of-68.67 dB at 9.85 GHz in 2.05 mm,which is 199.0%,12.6%,and 50.6%higher than non-layered,layered and layered descending gradient composites,respectively.Therefore,this work confirms the importance of layered gradient structure in improving absorption performance and broadens the design of high-performance microwave absorption materials.展开更多
Due to excellent thermal insulation performance at room temperature and ultralow density,silica aero-gels are candidates for thermal insulation.However,at high temperatures,the thermal insulation prop-erty of silica a...Due to excellent thermal insulation performance at room temperature and ultralow density,silica aero-gels are candidates for thermal insulation.However,at high temperatures,the thermal insulation prop-erty of silica aerogels decreased greatly caused by transparency to heat radiation.Opacifiers introduced into silica sol can block heat radiation yet destroy the uniformity of aerogels.Herein,we designed and prepared a silica aerogel composite with oriented and layered silica fibers(SFs),SiC nanowires(SiC_(NWs)),and silica aerogels,which were prepared by papermaking,chemical vapor infiltration(CVI),and sol-gel respectively.Firstly,oriented and layered SFs made still air a wall to block heat transfer by the solid phase.Secondly,SiC_(NWs) were grown in situ on the surface of SFs evenly to weave into the network,and the network reduced the gaseous thermal conductivity by dividing cracks in SFs/SiC_(NWs)/SA.Thirdly,SiC_(NWs) weakened the heat transfer by radiation at high temperatures.Therefore,SFs/SiC_(NWs)/SA presented remarkable thermal insulation(0.017 W(m K)^(-1) at 25℃,0.0287 W(m K)^(-1) at 500℃,and 0.094 W(m K)^(-1) at 1000℃).Besides,SFs/SiC_(NWs)/SA exhibited remarkable thermal stability(no size transform after being heat treated at 1000℃ for 1800 s)and tensile strength(0.75 MPa).These integrated properties made SFs/SiC_(NWs)/SA a promising candidate for highly efficient thermal insulators.展开更多
基金supported by the Natural Science Foundation of China Grant No.52272289 and 5240223,and JSPS(Japan Society for the Promotion of Science)of Grant No.22K19088,23H00313,24H02202,and 24H02205。
文摘NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsic activity limitations and poor stability,primarily due to the asymmetric adsorption of oxygen intermediates.To overcome this,the binding strength must be synergistically tuned to a moderate level to optimize catalytic performance.Here,we engineered NiFeCoCr LDH through Co doping to enhance electrical conductivity and controlled Cr leaching to introduce cationic vacancies for modulating intermediate binding strength in NiFe LDH.X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses reveal that NiFe-LDH with Co doping and Cr vacancies modulates the Ni oxidation state and local coordination environment,leading to a balanced electronic structure and enhanced structural complexity around the Ni sites.Additionally,these vacancies can trap OH^(-)/H_(2)O species,which can serve as a reservoir for OH^(-) transfer,facilitating the rapid formation of OER intermediates and enhancing catalytic performance at high current densities.As a result,V_(Cr)-NiFeCo LDH achieves 1.6 A cm^(-2)current density at 1.7 V vs.RHE while maintaining stable operation for over 1000 h at 500 mA cm^(-2).Density functional theory(DFT)calculations validate the synergistic effects of Co doping and Cr-induced vacancies on intermediate binding energies and improved OER kinetics.Overall,this work presents a rational design strategy to simultaneously enhance the activity and durability of NiFe-based OER catalysts for their application in high-performance alkaline water electrolysis.
基金supported by the National KeyR&D Program of China(Grant No.2024YFB3817400)the National Natural Science Foundation of China(Grants No.12274276 and No.U24A6002)+1 种基金the Natural Science Foundation of Shanxi Province(China)(Grant No.202403021223008)Supported by Scientific and Technology Innovation Programs of Higher Education Institutions in Shanxi(Grant No.2024Q017 and No.2025L043).
文摘Layered transition-metal compounds(LTMCs)feature stacked architectures,strong magnetic anisotropy,and tunable magnetic order,making them promising material platforms for low-power spintronic technologies and for enabling topological functionalities in the post-Moore era.Here we review recent progress on two-dimensional(2D)magnetism in LTMCs,emphasizing material taxonomy,intrinsic magnetic properties,and external-field controls.This review first presents a classification of LTMCs by crystal structure and chemistry—binary halides,chalcogenides,and ternary families(e.g.,MPX_(3),M_(m)X_(n)Te_(k),MnBi_(2)Te_(4))—followed by a summary of their coupling mechanisms,ordering temperatures,and dimensional effects.It then analyzes the modulation of exchange interactions,magnetic anisotropy,and topological states by electric-field gating,strain engineering,and ion intercalation,with representative experimental demonstrations.Notable advances include room-temperature ferromagnetic metals and semiconductors,observation of the quantum anomalous Hall effect(QAHE)in MnBi2Te4,and synergistic control of magnetic-topological states under multiple external stimuli.Persistent challenges involve the limited availability of intrinsic 2D magnetic semiconductors with high Curie temperatures(Tc),incomplete understanding of the microscopic couplings at interfaces and under quantum confinement,and device-level stability.We conclude by outlining opportunities that lie in the integration of multiscale characterization,first-principles theory,and cross-scale fabrication to precisely co-engineer magnetism,topology,and electronic structure,thereby advancing LTMCs toward spintronic and topological-quantum applications.
基金supported by grants from the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(MSIT)(RS-2024-00407116)+1 种基金by the Ministry of Education(NRF-2018R1A6A1A03024231)support from the NRF grant funded by the MSIT(RS-2024-00406724)。
文摘Interfacial engineering is crucial for developing high-performance Ni-rich layered cathodes for lithiumion batteries.Here,we introduce an interfacial precipitation(IP)strategy,guided by first-principles calculations,to create a functionally graded cathode during precursor synthesis.Based on thermodynamic principles of bulk insolubility and phase separation kinetics,we achieved the selective precipitation of Co onto the surface of a Ni-rich hydroxide precursor.Upon high-temperature lithiation,this engineered precursor spontaneously forms a unique,bifunctional Co-rich spinel-like layer on the final LiNi_(0.88)Co_(0.06)Mn_(0.06)O_(2)(NCM)cathode.This architecture suppresses detrimental Li/Ni cation mixing and protects the active material.Consequently,the IP-driven NCM cathode demonstrates vastly superior rate capability,delivering 140.8 m A h g^(-1)at 5C,compared to 112.9 mA h g^(-1)for its conventionally prepared counterpart.This enhancement is attributed to significantly lower charge-transfer resistance and faster kinetics.Remarkably,in a full-cell configuration,the IP-driven NCM cathode maintains 81.5%capacity after 1000 cycles at an aggressive 5C rate.This work presents a thermodynamically driven,scalable strategy for designing advanced cathodes with exceptional high-power performance and stability.
基金support from the National Natural Science Foundation of China(NSFC 21905092,22475072 and 22075085)the Fundamental Research Funds for the Central Universities+1 种基金supported by the Shanghai Frontiers Science Center of Molecule Intelligent SynthesesEast China Normal University Multifunctional Platform for Innovation(004)。
文摘Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))from earth-abundant water and oxygen is a sustainable approach,however current photocatalysts suffer from low production rate and solar-to-chemical conversion efficiency(<1.5%).Herein,we report that nickelchromium layered double hydroxide with intercalated nitrate(NiCrOOH-NO_(3))and a thickness of~4.4 nm is an efficient photocatalyst,enabling a H_(2)O_(2)production yield of 28.7 mmol g^(-1)h^(-1)under visible light irradiation with3.92%solar-to-chemical conversion efficiency.Experimental and computational studies have revealed an inherent facet-dependent reduction-oxidation reaction behavior and spatial separation of photogenerated electrons and holes.An unexpected role of intercalated nitrate is demonstrated,which promotes excited electron—hole spatial separation and facilitates the electron transfer to oxygen intermediate via delocalization.This work provides understandings in the impact of nanostructure and anion in the design of advanced photocatalysts,paving the way toward practical synthesis of H_(2)O_(2)using fully solar-driven renewable energy.
基金the financial support by Advanced Materials-National Science and Technology Major Project(2024ZD0607400)the National Natural Science Foundation of China(No.52402305)+4 种基金the high-level innovation and entrepreneurship talent project of Qinchuangyuan(No.QCYRCXM-2023-084)the Postdoctoral Fellowship Program of CPSF under Grant Number GZB20230570 and 2024M752552Key projects of Shaanxi Province,China(2023GXLH-001)Natural Science Basic Research Program of Shaanxi(Program No.2024JCYBQN-0494,No.2022TD-27)the State Key Laboratory for Electrical Insulation and Power Equipment(No.EIPE23125)。
文摘High-entropy layered hydroxides(HELHs),an emerging frontier in entropy-stabilized materials derived from layered double hydroxides(LDHs),have captivated attention with their unparalleled tunability,thermodynamic stability,and electrochemical performance.The integration of the high-entropy concept into LDHs empowers HELHs to surmount the constraints of conventional materials through compositional diversity,structurally disordered configurations,and synergistic multi-element interactions.This review systematically embarks on their synthesis methodologies,functional mechanisms,and applications in energy conversion/storage and biomedicine.Advanced synthesis strategies,such as plasma-assisted hydrothermal methods,facilitate precise control over HELH architectures while supporting scalable production.HELHs demonstrate superior electrochemical performance in critical reactions,including oxygen evolution reaction,water oxidation,hydrogen evolution,and glucose electrooxidation.Future directions encompass integrating in situ characterization with simulations,leveraging machine learning for composition screening,and expanding HELHs application through interdisciplinary collaborations.This work establishes a comprehensive roadmap for advancing HELHs as next-generation multifunctional platforms for sustainable energy and biomedical technologies.
基金supported by funding from the National Natural Science Foundation of China(42372331,52204140)State key Laboratory of Mining Disaster Prevention and Control(Shandong University of Science and Technology)(JMDPC202302)+2 种基金the high-level talent cultivation funding program for the"Double First-Class"initiative in safety discipline at Henan Polytechnic University(AQ20250205)the Taishan Scholar Program of Shandong Province(tsqnz20240825)Open Fund of Shandong Engineering Research Center for Mine Gas Disaster Prevention and Control(No.2022-005)。
文摘Drilling and blasting in layered rock masses faces significant challenges,as pre-existing joints cause unbalanced energy distribution,leading to poor forming effects and severe over-excavation.However,a comprehensive understanding of the complex coupling mechanisms between key joint parameters and the in-situ stress field on the final blasting outcome is still lacking.The model tests are used to quantitatively analyze the macroscopic crushing characteristics and crack propagation velocity.The numerical simulation then reveals the underlying mechanisms of stress wave propagation and energy partitioning,which are validated against the experimental results.The results indicate that the joints and the in-situ stress field play distinct,competitive roles in the blasting outcome.First,the joints control the anisotropy of the damage:crack propagation is primarily guided along the joint direction(the channel effect),and the apparent crack velocity exhibits a V-shaped trend with the joint inclination angle(0°-90°).Second,the in-situ stress state controls the overall extent of the damage:Increased confining pressure(both equal and unequal)inhibits crack propagation by increasing the failure threshold of the rock mass.Mechanistically,while this locking effect enhances stress wave transmission(i.e.,reduces the locking effect),this is secondary to the dominant inhibitory effect of the increased overall rock mass strength.The primary contribution of this study is the identification of this dual control mechanism,revealing that the final blasting effect is a non-linear competition between the joint's structural guidance and the dominant strengthening effect from the in-situ stress field,which clarifies the complex energy partitioning mechanisms at the blast source.
基金financially supported by the National Natural Science Foundation of China(52274295)the Natural Science Foundation of Hebei Province(E2025501032,E2025501028)+3 种基金the Fundamental Research Funds for the Central Universities(N2523045,N2423051,N2423005,N2423019)the Science and Technology Project of Hebei Education Department(QN2024238)the Central Guided Local Science and Technology Development Fund Project of Hebei Province(254Z1102G)the Basic Research Program Project of Shijiazhuang City for Universities Stationed in Hebei Province(241790937A)。
文摘The P2-type Fe/Mn-based layered oxides,with cost advantages and high theoretical capacity,are considered one of the promising cathode materials for sodium-ion batteries(SIBs).However,the commercial development of these materials is impeded by two main factors:the MnO_(6) structure distortion induced by the Jahn-Teller(J-T)effect of Mn^(3+),and the unfavorable phase transitions that occur during the insertion and extraction of Na^(+).Here,we present a strategy to improve structural stability by incorporating cost-effective,robust Al-O bonds.This approach induces localized adjustments in the electronic structu re and a pinning effect,which limits the deformation of the transition metal(TM)layers,strengthens the electrostatic bonding within the TM layers,and expands the Na layer spacing.Consequently,the Na_(0.67)Fe_(0.4)Mn_(0.54)Al_(0.06)O_(2) cathode demonstrates a capacity of 168.8 mAh g^(-1) at 0.1 C,maintaining89.2%of its original capacity after 200 cycles at 1 C.Through in situ electrochemical impedance spectroscopy(EIS)with dynamic resistance transformation(DRT)analysis,ex situ X-ray absorption spectroscopy(XAS),and in situ X-ray diffraction(XRD),the study demonstrates a reduction in the J-T effect,enhanced kinetic performance,and the inhibition of detrimental phase transitions.This study offers new avenues to the development and design of future low-cost Fe/Mn-based cathodes.
基金supported by the National Natural Science Foundation of China(Grant Nos.52202282,52402054,22471283,and 52202327)Natural Science Foundation of Tianjin City(Grant Nos.22JCYBJC00040,24JCQNJC00970)。
文摘High-capacity O3-type layered NiFeMn-based oxides are promising cathodes for sodium-ion batteries,though their practical deployment is constrained by the inherent limitations of Fe redox chemistry.Traditional designs generally enforcing stoichiometric symmetry(Ni=Mn)yield low Fe redox activity.Herein,we propose a valence engineering strategy that breaks conventional Ni/Mn stoichiometry to reconfigure Fe's local chemical environment and unlock unprecedented redox depth.Density functional theory(DFT)calculations reveal that the designed NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode exhibits a reduced Bader charge on Fe(1.598 vs.1.638 in NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2))and elevated Fe 3d orbital energy,signifying enhanced Fe redox activity.This configuration enables an exceptional Fe^(2.60+)/Fe^(3.88+)redox(1.28 e~-per Fe),delivering a reversible capacity of184.3 mAh g^(-1)within 2-4.2 V at 0.2 C,markedly exceeding the benchmark NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(161.3 mAh g^(-1))with low reaction depth of Fe^(3.01+)/Fe^(3.61+).The intensified cationic redox reaction enables an ultrahigh energy density of 596 Whkg-1.The NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode demonstrates robust performance over a broad temperature range from-15℃to 60℃.In situ and ex situ characterizations unveil a reversible O3■P3■OP2 phase transition with minimal volume change(1.88%)that circumvents detrimental deleterious O'3 intermediates and intragranular cracking.This work establishes valence engineering as a paradigm to consolidate cationic redox reaction in high-energy layered sodium oxide cathodes.
基金supported by the National Key R&D Program of China(2023YFB2406000)the National Natural Science Foundation of China(22479057,52172201,51732005)。
文摘Sodium layered oxides stand out as one of the most promising cathodes for sodium-ion batteries due to their high energy density,elemental abundance,and scalability.However,their practical applications are restricted by interplanar gliding,cation migration,and the formation of intragranular microcracks,which collectively lead to rapid structural degradation and capacity loss.Herein,we rationally design an ultrastable O3-type Na_(0.94)Ca_(0.03)Ni_(1/3)Fe_(1/3)Mn_(1/3)O_(2) cathode,in which Ca^(2+)cations act as pillars within the NaO_(2)slabs,suppressing the irreversible phase transitions and Na/TM cation migration commonly observed in layered oxides.Multiscale in situ and ex situ techniques,combined with post-mortem analysis,reveal that the Ca-pillared pinning effect not only effectively suppresses the interplanar gliding and stress accumulation within the crystal phase but also restrains Na/TM cation migration and surface reconstruction in near-surface regions.Benefiting from the combined effects of structural stabilization,the Ca-pillared cathode exhibits a superior cycling stability,retaining 81.6%of its capacity after 1000 cycles at 2 C within the voltage range of 2.0-4.0 V,along with significantly enhanced wide-temperature(from-40 to 80℃)performance.This work highlights another critical role of Ca pillars in suppressing cation migration and surface structural degradation beyond preventing adverse interplanar gliding,offering valuable insights for designing long-life and wide-temperature layered oxide cathodes.
基金financially supported by the National Natural Science Foundation of China(no.52172209)the Shenzhen International Cooperative Research Project(GJHZ20240218113607014)。
文摘The irreversible oxygen redox(OR)in Li-rich layered cathodes leads to severe structural degradation and voltage decay,particularly under harsh operating conditions.Although high-entropy oxides(HEOs)offer enhanced stability compared to conventional doping modifications,rational element selection for optimizing OR reversibility remains unexplored.Here,we propose an entropy engineering design paradigm for “oxygen-anchoring”,where optimal cation electronegativity(>Mn,1.55)and d(3d/4d)-p orbital hybridization synergistically enhance transition metal–oxygen(TM–O)covalency and stabilize the O2p state.Two high-entropy Li-rich layered oxides:Li_(1.2)Mn_(0.47)Ni_(0.115)Co_(0.115)Mg_(0.02)Ti_(0.02)Al_(0.02)Nb_(0.02)Mo_(0.02)O_(2)(MTANM)and Li_(1.2)Mn_(0.47)Ni_(0.115)Co_(0.115)Mg_(0.02)Ti_(0.02)Cu_(0.02)Nb_(0.02)Mo_(0.02)O_(2)(MTCNM)were synthesized using partial nano-scale precursors and comparatively evaluated.MTCNM exhibits enhanced electrochemical performance and superior oxygen stability compared to MTANM by replacing Al with higher-electronegativity Cu,which possesses improved orbital overlap with oxygen.Both experiments and density functional theory(DFT)calculations demonstrate that element selection changes the covalency of TM–O through altered electronegativity and d orbitals-p orbitals(d-p)hybridization.Further stepwise screening selected the optimal elemental combination Li_(1.2)Mn_(0.47)Ni_(0.115)Co_(0.115)Cr_(0.02)Cu_(0.02)Nb_(0.02)Mo_(0.02)Ru_(0.02)O_(2)(CCNMR),which achieved near 100%capacity retention after 150 cycles at 1 C,50℃,with its voltage decay effectively suppressed.This work establishes a rational element-screening paradigm for entropy-stabilized OR chemistry in high-energy cathodes.
基金financially supported from the National Key Research and Development Program of China(2022YFB3803600)the National Natural Science Foundation of China(52301272,22309168,12564025,and 52472205)+7 种基金the Fundamental Research Funds for the Central Universities(CCNU25ZH006)the National College Student Innovation and Entrepreneurship Training Project(202510513082)the Research Program of HBNU(2025X082 and2025Y145)the Foundation of Hubei Key Laboratory of Photoelectric Materials and Devices(PMD202404)the General Program of Open Project of the State Key Laboratory of Precision Welding and Joining of Materials Structures(MSWJ-25M-18)the Key Research Project of Hubei Provincial Department of Education(No.D20252503)the Key Project of Hubei Provincial Natural Science Foundation of China(2025AFD002)the Foundation of National Laboratory of Solid State Microstructures(M37087)。
文摘NiFe layered double hydroxide(NiFe LDH)has emerged as a promising catalyst for the oxygen evolution reaction(OER);however,its hydrogen evolution reaction(HER)activity remains suboptimal due to unfavorable electronic structures,particularly the d-electron density of metal sites,which impede water dissociation and lead to poor hydrogen adsorption/desorption capabilities.Herein,we introduce an efficient cooperative d-electron density regulation(CDDR)engineering to comprehensively optimize the delectron density of NiFe LDH by grafting MoO_(x) -modified NiFe LDH nanosheets onto porous nickel particles(PNPs).The PNPs facilitate d-electron density modulation along the edges of the nanosheets,while the MoO_(x) species enable d-electron density modulation across the plane of the nanosheets,thus cooperatively constructing enriched d-electron density in NiFe LDH.Theoretical studies validate the CDDR process and reveal that the enriched d-electron density accelerates water dissociation and optimizes the hydrogen adsorption behavior of NiFe LDH.As a result,the engineered catalyst exhibits significantly improved HER activity,achieving an ultra-low overpotential of 38 mV at 10 mA cm^(-2)in 1 M KOH.Additionally,the CDDR-optimized catalyst also exhibits good OER performance,demonstrating excellent bifunctional performance for overall water splitting in both alkaline freshwater and seawater electrolytes.This work presents a novel CDDR strategy for engineering NiFe LDH into efficient HER catalysts without compromising its OER activity,potentially paving the way for the development of active and robust electrocatalysts for sustainable energy applications.
基金supported by the Sichuan Provincial Department of Science and Technology Project (2025YFHZ0271).
文摘Owing to its excellent eco-friendliness and facile water elution properties,aluminum-based lithium adsorbents have attracted a surge of interest for selectively extracting Li^(+)from Salt Lake brines,which account for more than 60%of the global lithium resources.However,structural collapse,facile deactivation during desorption process,and ultra-low actual adsorption capacity limit its further large-scale application,particularly in low-grade sulfate-type brines.Herein,considering its advantages,limitations,and structural features,the structural collapse of the aluminum-based lithium adsorbent was effectively suppressed by the in situ intercalation of VO_(3)^(-)and V_(2)O_(7)^(4-)into the interlayer of[LiAl_(2)(OH)_(6)]^(+).Evidently,the initial adsorption capacity andα_(Mg)^(Li)of as-configured adsorbents powder are 14.96 mg g^(-1) and 192.42 in real sulfate-type West Taijinar Salt Lake brines following NaCl salts removal with 800 mg L^(-1) Li^(+)and 9.56 g L^(-1) SO_(4)^(2-).Furthermore,the initial and retained adsorption capacities of these novel adsorbents granulate in brines after 100 adsorption/desorption cycles are 26.68 and 10.36 mg g^(-1),respectively,which are almost 10 times higher than those of industrially utilized products.Based on experiments and density functional theory calculations,the process and mechanism of anion intercalation control were preliminarily elucidated.Furthermore,research findings indicate that intercalated anions can influence not only interlayer interactions but also the backbone strength of LDH-type adsorbents.This work significantly overcomes the major utilization challenges of aluminum-based lithium adsorbents,thereby enabling the high-efficiency and stable extraction of Li^(+)from low-grade brines,including sulfate-type brines.
基金supported by the National Natural Science Foundation of China (52402298, 52172224, 52202228, 22479112)the Science and Technology Correspondent Project of Tianjin(24YDTPJC00240)+3 种基金Science Research Project of Hebei Education Department (BJK2022011)Central Funds Guiding the Local Science and Technology Development of Hebei Province (236Z4404G)the Beijing Tianjin Hebei Basic Research Cooperation Special Project(E2024202273)Tianjin Sci.&Tech. Program (22YFYSHZ00220)
文摘O3-types layered cathode materials in sodium-ion batteries(SIBs)suffer from the obvious lattice distortion induced by the complex phase transitions during Na^(+)intercalation/deintercalation process,leading to severe structural collapse and performance degradation.Herein,a series of high valence tantalum(Ta^(5+))doped Na(Ni_(0.4)Fe_(0.2)Mn_(0.4))_(1−x)Ta_(x)O_(2)(x=0/0.0025/0.005/0.01)secondary spherical particles are firstly developed,where Ta^(5+)doping enables the refined primary grain with a tightly stacked rod-like morphology.Comprehensive structural analysis via Neutron powder diffraction(NPD)and Synchrotron radiation X-ray diffraction(SXRD)reveals an expanded NaO_(2)slab and a reduction in Na site vacancy.The potential charge compensation mechanism is further illustrated by X-ray absorption spectroscopy(XAS)and X-ray photoelectron spectroscopy(XPS),unveiling a partial reduction from Ni^(3+)to Ni^(2+)with Ta^(5+)doping.In situ X-ray diffraction(in situ XRD)suggests that the decorated sample undergoes a volume change as low as 0.8%,in contrast with the pristine one(1.5%).Thus,the optimized sample with x=0.005 retains an enhanced capacity retention up to 70.4%at 1 C after 300 cycles in half-cell and delivers a high energy density of 251 Wh kg^(-1)(0.1 C)and with a good capacity retention of 81.0%at 1 C after 200 cycles in full-cell.Our findings provide new insights into the mechanism of high valence Ta^(5+)doping in stabilizing layered oxides cathode materials for SIBs.
基金supported by the National Natural Science Foundation of China(Grant No.52178329),the China Scholarship Council(Grant No.202306130155)the Postgraduate Scientific Research Innovation Project of Hunan Province,China(Grant No.CX20230442).
文摘With the continuous development of the offshore wind industry,the design concept of composite foundation has been given attention in the past decade.This paper presents an accurate method for investigating the horizontal vibration of monopile-friction wheel composite foundations in layered saturated soil.Firstly,the three-dimensional continuum mechanics theory with the range of linear elasticity is introduced to calculate the frictional resistance distributed on the upper soil surface.Then,the resistances of multilayered soils and inviscid seawater to the pile shaft under horizontal harmonic excitation are obtained using Novak's plane strain model,Biot's porous media theory and radiationwave theory.Thirdly,the expressions for the deformation,bending moment and internal force of the Euler-Bernoulli pile are derived using the boundary conditions with definitephysical meaning and transfer matrix method.By comparing with the results of 1g laboratory test and the idealized formula reported by the literature,the rationality and accuracy of the developed dynamical model can be verified.Finally,this paper conducts a series of worked examples to investigate the influencesof the elastic modulus and thickness of three-layer saturated soil and the location of interlayer soil on the horizontal dynamic vibration of composite foundation.The results show that an increase in elastic modulus of the surface soil is an effective way to improve the dynamic stability of the composite foundation in service conditions.The conclusions drawn from the numerical examples can develop some guidelines for the current foundation design of offshore wind turbines.
基金supported by the National Natural Science Foundation of China(52374311)National Key R&D Program of China(2023YFE0203000)+3 种基金the National Natural Science Foundation of Shaanxi(2023KXJ-262,2025SYS-SYSZD-035)the Fund of the State Key Laboratory of Solidification Processing in NPU(2025-TS-10)the Fundamental Research Funds for the Central Universities(D5000250277)the Youth Innovation Team of Shaanxi Universities。
文摘Layered oxides present compelling potential as cathode materials for sodium-ion batteries(SIBs).However,challenges including interfacial instability and sluggish reaction kinetics critically limit their rate capability and cycling performance.Herein,we introduce the water-soluble sodium polyacrylate(NaPAA)binder as a promising approach to mitigating these issues in P2-type layered oxides.The NaPAA binder facilitates the formation of a uniform Na^(+) conductive interfacial film,which protects the cathode against electrolyte-induced corrosion and effectively inhibits the dissolution of transition metals in P2-Na_(0.85)Li_(0.12)Ni_(0.22)Mn_(0.66)O_(2)(NLNMO).Furthermore,we elucidate the mechanism by which the NaPAA binder dynamically regulates the coordination of free anions at the electrode-electrolyte interface.This regulation reduces solvent decomposition and promotes the formation of a stable,ionically conductive layer.Consequently,the P2-NLNMO@NaPAA integrated electrode exhibits enhanced electrochemical performance,achieving an 89.2%capacity retention after 200 cycles at 0.2 C and delivering an initial capacity of 102.9 mA h g^(-1) even at 0℃.This study advances the fundamental understanding of binder-mediated interface engineering and demonstrates a scalable and eco-friendly manufacturing pathway for high-performance SIBs.
基金supported by the Natural Science Research Project of Anhui Province Education Department for Excellent Young Scholars(Grant No.2024AH030007)the National Natural Science Foundation of China(Grant No.52202001)。
文摘Conventional Tb^(3+)-doped phosphors typically suffer from concentration quenching once the doping level exceeds a critical threshold.Consequently,the development of Tb^(3+)phosphors with intrinsic resistance to concentration quenching has become a key research focus.In this work,we successfully synthesized KBi(MoO_(4))_(2):x Tb^(3+)(x=0-100 at%)(denoted as KBM:x Tb^(3+))phosphors via a high-temperature solid-state reaction.Remarkably,no concentration quenching was observed across the entire doping range.This anti-quenching behavior originates from the large Tb^(3+)-Tb^(3+)interionic distance(>5Å)inherent to the quasi-layered crystal structure,which effectively suppresses multipole-interaction-mediated energy migration.At full Tb^(3+)substitution(x=100 at%),the material undergoes a structural phase transition from the monoclinic KBM phase to the triclinicα-KTb(MoO_(4))_(2)(α-KTM)phase.Theα-KTM phosphor exhibits excellent thermal stability(activation energy=0.6129 eV)and a single-exponential decay profile,whereas KBM:x Tb^(3+)(x<100%)display double-exponential decay behaviors,attributed to dual energy transfer pathways.These findings provide new insights into the luminescence mechanisms of high-concentration rare-earth-doped systems and offer guidance for designing nextgeneration anti-quenching phosphors.
基金supported by the research equipment (Nos. G1006,G1010 and G1018) shared in MEXT Project for promoting public utilization of advanced research infrastructure (Program for supporting construction of core facilities)(No. JPMXS0440500023)financial support of the China Scholarship Council.
文摘A method for the effective in-situ formation of boron-containing Mg-Al layered double hydroxides(LDHs)was developed for boron removal and stabilization.The influence of the B/Al molar ratio and pH on the formation of Mg-Al-B–LDHs was investigated.Compared with the adsorption method,under a high B/Al ratio,the coprecipitation method increased the boron sorption density from 0.256 to 0.472 of Al.The Toxicity Characteristic Leaching Procedure showed that the boron-coprecipitated LDHs exhibited higher stability than the boron-adsorption LDHs.The synthesized LDH samples were characterized by X-ray diffraction,X-ray photoelectron spectroscopy,and solid-state 11B-NMR.The results showed that boron was effectively incorporated into the LDH structure for the coprecipitation method.Combined with the experimental results,a potential in-situ formation pathway for Mg-Al-B–LDHs was elucidated through density functional theory calculations.The boron tended to directly incorporate into the LDH structure in the coprecipitation method,whereas it was predominantly adsorbed on the LDH surface in the adsorption method.The adsorption energy demonstrated that boron preferentially bonded to Mg^(2+)sites on the surface.The mechanism of boron incorporation in the LDHs for the coprecipitation method involved precipitation of amorphous aluminum hydroxide,layered boehmite transformation,nucleation,and layer stacking.During these processes,boron formed complexes to enhance its stability.Residual boron underwent further reactions with the LDHs,including surface adsorption and ion exchange.These findings provide theoretical insight into the effective removal and long-term immobilization of boron in landfill leachate self-remediation processes.
基金support of the National Natural Science Foundation of China(Grant No.42207199)Zhejiang Provincial Natural Science Foundation of China(Grant Nos.ZCLMS25D0201 and LQ23D010002).
文摘Layered rocks are widely distributed in sedimentary and metamorphic rocks and show anisotropic deformation and strength due to the layered structures with apparent weak surfaces.This study summarizes the findings on the deformation and damage characteristics of layered rock masses and surrounding rocks.The physicomechanical properties of layered rocks with different properties(e.g.inclination,shear strength,tensile strength,shear stiffness,roughness,and layer spacing)and different lithological and stress conditions are analyzed.The results revealed that with increasing layer inclination angles,the deformation and strength parameters of the rock masses present U-shaped,W-shaped,incremental,decremental,and basically unchanged trends,which are closely related to their strength and stress conditions.The increase in layer strength and confining pressure effectively suppresses the deformation and strength anisotropy caused by layer weakening,and the rock mass shifts from“structure-controlled”to“stress-structure-controlled”deformation mode.Water will increase the anisotropic behavior of layered rock masses due to the degradation of bedding and bedrock performance.The anisotropic behavior of the layered surrounding rocks is analyzed to reveal how it affects the deformation and failure behaviors of tunnels.The asymmetric characteristics of surrounding rock deformation are closely related to the layer weakening,layer thickness,and in situ stress.These findings are crucial for understanding layered rock mass deformation and failure mechanisms,facilitating prediction and control of tunnel deformation.
基金support for this work by Key Research and Development Project of Henan Province(Grant.No.241111232300)the National Natural Science Foundation of China(Grant.No.52273085 and 52303113)the Open Fund of Yaoshan Laboratory(Grant.No.2024003).
文摘The morphological distribution of absorbent in composites is equally important with absorbents for the overall electromagnetic properties,but it is often ignored.Herein,a comprehensive consideration including electromagnetic component regulation,layered arrangement structure,and gradient concentration distribution was used to optimize impedance matching and enhance electromagnetic loss.On the microscale,the incorporation of magnetic Ni nanoparticles into MXene nanosheets(Ni@MXene)endows suitable intrinsic permittivity and permeability.On the macroscale,the layered arrangement of Ni@MXene increases the effective interaction area with electromagnetic waves,inducing multiple reflection/scattering effects.On this basis,according to the analysis of absorption,reflection,and transmission(A-R-T)power coefficients of layered composites,the gradient concentration distribution was constructed to realize the impedance matching at low-concentration surface layer,electromagnetic loss at middle concentration interlayer and microwave reflection at high-concentration bottom layer.Consequently,the layered gradient composite(LG5-10-15)achieves complete absorption coverage of X-band at thickness of 2.00-2.20 mm with RL_(min) of-68.67 dB at 9.85 GHz in 2.05 mm,which is 199.0%,12.6%,and 50.6%higher than non-layered,layered and layered descending gradient composites,respectively.Therefore,this work confirms the importance of layered gradient structure in improving absorption performance and broadens the design of high-performance microwave absorption materials.
基金supported by the National Natural Science Foun-dation of China(Grant No.U2167214).
文摘Due to excellent thermal insulation performance at room temperature and ultralow density,silica aero-gels are candidates for thermal insulation.However,at high temperatures,the thermal insulation prop-erty of silica aerogels decreased greatly caused by transparency to heat radiation.Opacifiers introduced into silica sol can block heat radiation yet destroy the uniformity of aerogels.Herein,we designed and prepared a silica aerogel composite with oriented and layered silica fibers(SFs),SiC nanowires(SiC_(NWs)),and silica aerogels,which were prepared by papermaking,chemical vapor infiltration(CVI),and sol-gel respectively.Firstly,oriented and layered SFs made still air a wall to block heat transfer by the solid phase.Secondly,SiC_(NWs) were grown in situ on the surface of SFs evenly to weave into the network,and the network reduced the gaseous thermal conductivity by dividing cracks in SFs/SiC_(NWs)/SA.Thirdly,SiC_(NWs) weakened the heat transfer by radiation at high temperatures.Therefore,SFs/SiC_(NWs)/SA presented remarkable thermal insulation(0.017 W(m K)^(-1) at 25℃,0.0287 W(m K)^(-1) at 500℃,and 0.094 W(m K)^(-1) at 1000℃).Besides,SFs/SiC_(NWs)/SA exhibited remarkable thermal stability(no size transform after being heat treated at 1000℃ for 1800 s)and tensile strength(0.75 MPa).These integrated properties made SFs/SiC_(NWs)/SA a promising candidate for highly efficient thermal insulators.
