The increasing global demand for clean and potable water underscores the need for advanced pollutant remediation technologies in wastewater,such as the degradation of azo dyes,which are known to be harmful to human he...The increasing global demand for clean and potable water underscores the need for advanced pollutant remediation technologies in wastewater,such as the degradation of azo dyes,which are known to be harmful to human health.To address this issue,heterogeneous photocatalysis emerges as a promising strategy for breaking down recalcitrant molecules.However,efforts are required to develop efficient and stable photocatalysts capable of operating under visible light.This study explores the photocatalytic potential of Fe-doped RE_(2)Zr_(2)O_(7-δ)(RE=Pr,Sm,Nd,Y)compositions,synthesized through the microwaveassisted solvothermal method,for the degradation of methylene blue.Characterizations,such as X-ray diffraction(XRD)and Raman spectroscopy,reveal the obtention of single-phase ordered pyrochlore for RE=Pr,Sm and Nd or defect fluorite structures for Y.Photocatalytic tests under visible light demonstrate efficient dye degradation for all Fe-doped samples,Y_(2)Zr_(1.9)Fe_(0.1)O_(6.95)(YZF)defect fluorite being the one that exhibits the highest efficiency.Radical scavenging experiments identify hydroxyl radicals as key contributors to the degradation process,along with photoinduced holes.These materials exhibit minimal leaching of iron ions,confirming their stability,and the best material,YZF,demonstrates effective reusability.The results highlight the potential of Fe-doped RE_(2)Zr_(2)O_(7)compositions as an efficient alternative for application as photocatalysts for the degradation of azo dyes under visible light.展开更多
The properties of high entropy pyrochlore have been studied extensively,but there is no consistent conclusion on its radiation tolerance.Besides,the mechanism of the high entropy effect on the radiation tolerance of p...The properties of high entropy pyrochlore have been studied extensively,but there is no consistent conclusion on its radiation tolerance.Besides,the mechanism of the high entropy effect on the radiation tolerance of pyrochlore is still unclear.In this work,combined with experiments and calculations of pyrochlores with similar cationic radius ratios,the A-site and B-site high entropy effects on structural evolution under irradiation are analyzed.In situ irradiation experiments were carried out on A-site high entropy pyrochlores such as(La_(0.2)Nd_(0.2)Sm_(0.2)Gd_(0.2)Er_(0.2))_(2)Zr_(2)O_(7),B-site Gd_(2)(Ti_(1/3)Sn_(1/3)Zr_(1/3))_(2)O_(7),and ternary pyrochlore Sm_(2)Zr_(2)O_(7) and Gd_(2)Sn_(2)O_(7) for comparison.The A-site high entropy pyrochlore can maintain a stable structure under high fluence irradiation like corresponding ternary pyrochlore,demonstrated by high angle annular dark field scanning transmission electron microscopy(HAADF-STEM),energy dispersive spectroscopy(EDS)mapping and Raman spectrum.The additional irradiation experiments on A-site high entropy pyrochlores(La_(1/3)Nd_(1/3)Gd_(1/3))_(2)Zr_(2)O_(7) and(Nd_(1/3)Sm_(1/3)Gd_(1/3))_(2)Zr_(2)O_(7) also confirm the similarity under irradiation between A-site high entropy and ternary pyrochlores.However,the B-site high entropy pyrochlore Gd_(2)(Ti_(1/3)Sn_(1/3)Zr_(1/3))_(2)O_(7) becomes amorphous at exceptionally low irradiation fluences,indicating a significantly distinct radiation tolerance compared with the A-site high entropy.The difference between the A-site and B-site high entropy effect is analyzed from cationic lattice distortion,bond strength,and inner electron binding energy by first-principles calculations.The results reveal the role and mechanism of the high entropy effect in pyrochlores and lay a foundation for material design and future applications.展开更多
Various excellent properties of rare earth zirconate and stannate pyrochlores are close related with their native point defects.First-principles calculations are performed to systematically investigate the point defec...Various excellent properties of rare earth zirconate and stannate pyrochlores are close related with their native point defects.First-principles calculations are performed to systematically investigate the point defect mechanism and the oxygen diffusion behavior of A_(2)B_(2)O_(7)(A=La,Ce,Pr,Nd,Pm,Sm,Eu,Gd;B=Zr,Sn).The possible defect complexes and their associated reactions under stoichiometric and nonstoichiometric conditions are explored.The O Frenkel pairs are the most stable defect structure in stoichiometric zirconates,whereas the cation antisite defects are the predominant one in stoichiometric stannates.In the case of BO_(2) excess zirconates and stannates,the BA cation antisite defect with the A vacancy and/or the oxygen interstitial is energetically favorable,whereas the ABantisite defect together with the oxygen vacancy and/or the A interstitial is preferable under the A_(2)O_(3) excess condition.Meanwhile,the maximum point defect concentrations of zirconates are much higher than those of stannates.Furthermore,the oxygen migration barriers are similar in these compounds,ranging in 0.68 eV–0.80 eV.The predicted point defects and oxygen diffusion mechanisms play the critical role in their engineering applications and are expected to guide the future property improvement of pyrochlores through the control of point defects and/or composition.展开更多
Mesoporous structured metal oxides exhibit many active applications.However,the synthesis of crystalline metal oxides with a ternary composition while maintaining satisfactory pore features is challeng-ing.Typically,h...Mesoporous structured metal oxides exhibit many active applications.However,the synthesis of crystalline metal oxides with a ternary composition while maintaining satisfactory pore features is challeng-ing.Typically,high temperatures are required which inhibit control of pore structure properties including surface area,pore volume,and pore size.Herein,the synthesis of ternary metal oxides Ln_(2)Ti_(2)O_(7)pos-sessing pyrochlore crystal structure is achieved using a novel technique which combines‘soft’and hard colloid templating strategies.The formed materials are of submicron size and composed of∼25-30 nm product‘building blocks’with good chemical and phase stability.The polycrystalline powders have a high specific surface area(up to 70 m^(2)·g^(-1))and pore volume(∼0.35 cm^(3)·g^(-1))which result in a good adsorp-tion capacity(U uptake closing to 60 mg·g^(-1)).Remarkably,the material exhibits a significant portion of mesopores(mainly 10-40 nm)which facilitate fast adsorption of the cations due to high accessibility.The synthetic methodology described herein produces highly homogenous powders and can be applied to other compositions and structures.展开更多
The comparative analysis of the dielectric properties of bismuth-containing pyrochlores with different manifestation of atomic order/disorder was carried out.We examined the dielectric properties(including behavior in...The comparative analysis of the dielectric properties of bismuth-containing pyrochlores with different manifestation of atomic order/disorder was carried out.We examined the dielectric properties(including behavior in electric fields)of two pyrochlore compounds:BZN(presumably a composition close to Bi_(1.5)Zn_(0.5)Nb_(1.5)O_(6.5))ceramics with chemical disorder in both A and B cation sublattices and Bi_(2)Ti_(2)O_(7)single crystal with fully chemical ordered structure.The fundamental differences between the dielectric properties of the BZN ceramics and Bi_(2)Ti_(2)O_(7)single crystal were shown.In particular,in the dielectric relaxation behavior(which cannot be described via Arrhenius law in the Bi_(2)Ti_(2)O_(7))or in the influence of the electric fields on the dielectric permittivity(split-ting of the field-cooled and zero-field-cooled behaviors was observed for Bi_(2)Ti_(2)O_(7)below estimated freezing temperature).The results of this study highlights the special role of Bi_(2)Ti_(2)O_(7)as a candidate material for studying aspects of geometric frustration related with pyrochlore structure in non-magnetic medium and specifies the future directions of research.展开更多
The quantum phase transition between Z_(2) plaquette valence bound solid(PVBS) and superfluid(SF) phases on the planar pyrochlore lattice(square ice) is under debate. To gain further insight, here, we focus on the dyn...The quantum phase transition between Z_(2) plaquette valence bound solid(PVBS) and superfluid(SF) phases on the planar pyrochlore lattice(square ice) is under debate. To gain further insight, here, we focus on the dynamical features of the hard-core Bose–Hubbard model on this lattice and study the excitation spectra by combining stochastic analytic continuation and quantum Monte Carlo simulation. In both PVBS and SF phases,a flat band with bow-tie structure is observed and can be explained by certain symmetries. At the transition point,the spectra turn to be continuous and gapless. A(2+1)-dimensional Abelian–Higgs model with mixed 't Hooft anomaly is proposed to describe the transition, where the anomaly matching predicts that the deconfinement can exist on the domain walls. From the snapshot of the spin configuration in real space, we found the existence of the domain wall. We also found that the spectrum along a specific path in momentum space from PVBS phase to the transition point can be well described by an XXZ spin chain, and the critical theory of XXZ spin chain matches the anomaly. The two-spinon continuum along this specific path implies additional domain walls(point defect) can emerge in the domain walls(line defect) and take the role of deconfinement at the transition point.展开更多
Low thermal conductivity and excellent mechanical strength are essential to pyrochlore A2B2O7 ceramic for environmental/thermal barrier coating applications.To collaboratively tailor the mechanical and thermal propert...Low thermal conductivity and excellent mechanical strength are essential to pyrochlore A2B2O7 ceramic for environmental/thermal barrier coating applications.To collaboratively tailor the mechanical and thermal properties of A2B2O7 ceramic,a novel high entropy pyrochlore ceramic(La_(0.3)Gd_(0.3)Ca_(0.4))_(2)(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))_(2)O_(7) with significant atomic radius and mass fluctuation is proposed by simultaneously introducing various elements with different valence states at A and B cation sites.The as-synthesized(La_(0.3)Gd_(0.3)Ca_(0.4))_(2)(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))_(2)O_(7) exhibits enhanced fracture toughness(1.68 MPa m^(1/2)),amorphous-like low thermal conductivity(1.45 W m^(-1) K^(-1) at 900℃)and matched thermal expansion coefficient(9.0×10^(-6) K^(-1) at 1200℃)with Al_(2)O_(3)/Al_(2)O_(3) CMCs.The extensive misfits in atomic weight,ionic radius among the substitutional cations in combination with the intrinsic oxygen vacancies in the anion sublattice play significant roles in the thermal conductivity reduction of(La_(0.3)Gd_(0.3)Ca_(0.4))_(2)(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))_(2)O_(7) ceramic.The combination of outstanding mechanical and thermal properties indicates that this type of material has a good application prospect for environmental/thermal barrier coatings.展开更多
Pyrochlore oxide(Y_(2)Ru_(2)O_(7))has been identified as a promising catalyst for the oxygen evolution reaction(OER)in advanced green energy strategies.However,its electrochemical inertness necessitates the exploratio...Pyrochlore oxide(Y_(2)Ru_(2)O_(7))has been identified as a promising catalyst for the oxygen evolution reaction(OER)in advanced green energy strategies.However,its electrochemical inertness necessitates the exploration of an effective strategy to facilitate electronic modulation.This study proposes a surface modification approach involving the integration of defective NiFe(D-NiFe)nanoparticles onto a Y_(2)Ru_(2)O_(7)(YRO)support(YRO@D-NiFeP/Ru)using a Prussian blue analog(PBA).Numerous cyanide(CN)vacancies are generated through the oxidation treatment of the NiFe PBA grown on the YRO support,yielding a defective PBA precursor(YRO@D-PBA).Subsequent annealing facilitates the transformation to the D-NiFe nanoparticles on the YRO support(YRO@D-NiFeP/Ru),which augments the exposure of Ni3+active sites beneficial for the OER.Moreover,the reduction of Ru cations from YRO results in the exsolution of Ru nanoparticles,which promotes synergistic charge transfer from the nanoparticles to the interior of Y_(2)Ru_(2)O_(7).Consequently,YRO@D-NiFeP/Ru exhibits a remarkable voltage of 1.49 V at 10 mA·cm^(−2) and the lowest Tafel slope of 42.4 mV·dec^(−1).In addition,a Zn–air battery constructed with YRO@D-NiFeP/Ru exhibits an outstanding power density of 136.2 mW·cm^(−2) and high charge–discharge stability,confirming the applicability of YRO@D-NiFeP/Ru in metal-air batteries.展开更多
The cubic pyrochlore Tl_(2)Ru_(2)O_(7) undergoes concurrently a metal–insulator transition (MIT) and a first-order structural transition at T_(MIT)≈120 K,below which the system was found to form one-dimensional spin...The cubic pyrochlore Tl_(2)Ru_(2)O_(7) undergoes concurrently a metal–insulator transition (MIT) and a first-order structural transition at T_(MIT)≈120 K,below which the system was found to form one-dimensional spin-one Haldane chains associated with an orbital ordering of Ru-4d electrons.With an aim to tune and access distinct ground states with strong entanglements of multiple degrees of freedom,i.e.,spin,orbital,charge,and lattice,we utilize a high-pressure approach to regulate the MIT of this system.Our detailed resistivityρ(T) measurements on the polycrystalline Tl_(2)Ru_(2)O_(7) samples under various hydrostatic pressures indeed reveal an unusual evolution of the electronic ground states.At first,the MIT is suppressed monotonically from 120 K at ambient to about 70 K at 1.5 GPa and then vanishes suddenly at about 1.8 GPa without achieving a metallic ground state.Meanwhile,the system evolves into a semiconducting ground state with magnitude ofρ(T) in the entire temperature range enhanced gradually by further increasing pressure.Prior to the abrupt disappearance of MIT,a new electronic order manifested as a kink-like anomaly inρ(T) emerges at T_(0)>T_(MIT) at 1.2 GPa and it continues to increase with pressure,producing a tricritical-point-like behavior in the T–P phase diagram of Tl_(2)Ru_(2)O_(7).The presence of two successive transitions at T_(0 )and T_(MIT )in the pressure range 1.2–1.5 GPa indicates an inhomogeneous electronic state nearby the tricritical point.At P≥3 GPa,another broad anomaly emerges inρ(T) at T_(1)>T_(0),and T_(1)continuously increases with pressure,dividing the semiconductingρ(T) into distinct thermally activated regions.These rich phenomena in the pressurized Tl_(2)Ru_(2)O_(7) should originate from the complex interplay of strongly entangled multiple quantum degrees of freedom in the system near the localized-to-itinerant crossover regime.展开更多
High-entropy pyrochlore-type structures based on rare-earth zirconates are successfully produced by conventional solid-state reaction method. Six rare-earth oxides(La2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, and Y2O3) and ZrO2...High-entropy pyrochlore-type structures based on rare-earth zirconates are successfully produced by conventional solid-state reaction method. Six rare-earth oxides(La2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, and Y2O3) and ZrO2 are used as the raw powders. Five out of the six rare-earth oxides with equimolar ratio and ZrO2 are mixed and sintered at different temperatures for investigating the reaction process. The results demonstrate that the high-entropy pyrochlores(5RE1/5)2 Zr2O7 have been formed after heated at 1000 ℃. The(5RE1/5)2Zr2O7 are highly sintering resistant and possess excellent thermal stability. The thermal conductivities of the(5RE1/5)2Zr2O7 high-entropy ceramics are below 1 W·m–1·K–1 in the temperature range of 300–1200 ℃. The(5RE1/5)2Zr2O7 can be potential thermal barrier coating materials.展开更多
Lattice engineering and distortion have been considered one kind of effective strategies for discovering advanced materials.The instinct chemical flexibility of high-entropy oxides(HEOs)motivates/accelerates to tailor...Lattice engineering and distortion have been considered one kind of effective strategies for discovering advanced materials.The instinct chemical flexibility of high-entropy oxides(HEOs)motivates/accelerates to tailor the target properties through phase transformations and lattice distortion.Here,a hybrid knowledge-assisted data-driven machine learning(ML)strategy is utilized to discover the A_(2)B_(2)O_(7)-type HEOs with low thermal conductivity(κ)through 17 rare-earth(RE=Sc,Y,La-Lu)solutes optimized A-site.A designing routine integrating the ML and high throughput first principles has been proposed to predict the key physical parameter(KPPs)correlated to the targetedκof advanced HEOs.Among the smart-designed 6188(5RE_(0.2))_(2)Zr_(2)O_(7)HEOs,the best candidates are addressed and validated by the princi-ples of severe lattice distortion and local phase transformation,which effectively reduceκby the strong multi-phonon scattering and weak interatomic interactions.Particularly,(Sc_(0.2)Y_(0.2)La_(0.2)Ce_(0.2)Pr_(0.2))_(2)Zr_(2)O_(7)with predictedκbelow 1.59 Wm^(−1)K^(−1)is selected to be verified,which matches well with the ex-perimentalκ=1.69 Wm^(−1)K^(−1)at 300 K and could be further decreased to 0.14 Wm^(−1)K^(−1)at 1473 K.Moreover,the coupling effects of lattice vibrations and charges on heat transfer are revealed by the cross-validations of various models,indicating that the weak bonds with low electronegativity and few bond-ing charge density and the lattice distortion(r∗)identified by cation radius ratio(r A/r B)should be the KPPs to decreaseκefficiently.This work supports an intelligent designing strategy with limited atomic and electronic KPPs to accelerate the development of advanced multi-component HEOs with proper-ties/performance at multi-scales.展开更多
The increasing anthropogenic emissions of greenhouse gases(GHG)is encouraging extensive research in CO_(2)utilisation.Dry reforming of methane(DRM)depicts a viable strategy to convert both CO_(2)and CH4into syngas,a w...The increasing anthropogenic emissions of greenhouse gases(GHG)is encouraging extensive research in CO_(2)utilisation.Dry reforming of methane(DRM)depicts a viable strategy to convert both CO_(2)and CH4into syngas,a worthwhile chemical intermediate.Among the different active phases for DRM,the use of nickel as catalyst is economically favourable,but typically deactivates due to sintering and carbon deposition.The stabilisation of Ni at different loadings in cerium zirconate inorganic complex structures is investigated in this work as strategy to develop robust Ni-based DRM catalysts.XRD and TPR-H2analyses confirmed the existence of different phases according to the Ni loading in these materials.Besides,superficial Ni is observed as well as the existence of a CeNiO_(3)perovskite structure.The catalytic activity was tested,proving that 10 wt.%Ni loading is the optimum which maximises conversion.This catalyst was also tested in long-term stability experiments at 600and 800℃in order to study the potential deactivation issues at two different temperatures.At 600℃,carbon formation is the main cause of catalytic deactivation,whereas a robust stability is shown at 800℃,observing no sintering of the active phase evidencing the success of this strategy rendering a new family of economically appealing CO_(2)and biogas mixtures upgrading catalysts.展开更多
Pyrochlore structure La2Sn2O7：Eu3＋ microcrystals with uniform octahedron shape were successfully synthesized via a hydrothermal route at 180 °C for 36 h. The crystal structure, particle size, morphologies, and ...Pyrochlore structure La2Sn2O7：Eu3＋ microcrystals with uniform octahedron shape were successfully synthesized via a hydrothermal route at 180 °C for 36 h. The crystal structure, particle size, morphologies, and optical properties of the as-synthesized products were investigated by XRD, TEM, SEM, EDS, FT-IR, Raman spectroscopy and PL. The effects of pH of precursor solution, precursor concentration, reaction temperature, and time were investigated. The results reveal that pH of the precursor solution not only plays an important role in determining the phase of the as-synthesized products, but also has a significant influence on the morphologies of the samples. High-quality and uniform octahedrons with an average size of about 700 nm could be easily obtained at the pH value of 12. The possible formation mechanism of octahedral-like La2Sn2O7：Eu3＋ microcrystals was briefly proposed. The photoluminescence spectra show that La2Sn2O7：Eu3＋ micro-octahedra display stronger emission in the range of 582-592 nm compared with the samples with other shapes.展开更多
The Eu3＋-doped La2Zr207 phosphor with rod-like morphology was successfully synthesized by conventional solid state reaction and hydrothermal method. X-ray diffraction patterns, transmission electron microscopy, and p...The Eu3＋-doped La2Zr207 phosphor with rod-like morphology was successfully synthesized by conventional solid state reaction and hydrothermal method. X-ray diffraction patterns, transmission electron microscopy, and photoluminescence spectra were employed to charac- terize its structure and morphology as well as luminescent properties. The results indicated that the red-emitting phosphor La2Zr207：Eu3＋ had well crystallized and belonged to the cubic structure with space group of Fd3m. The as-obtained product mainly appeared as straight nanorods with an average diameter of 47 nm and length of 50-700 nm. The pos- sible growth mechanism was also discussed. It was found that under blue excitation with a wavelength of 466 nm, the La2Zr2OT：Eu3＋ phosphor exhibited a characteristic red emission at 616 nm that was attributed to the hypersensitive 5D0--＊TF2 electric dipole transition of Eu3＋ ions. Meanwhile, it was more interesting to note that the emission of 5D1--＊TFj （J=0, 1, 2） transitions and the splitting patterns of 5D0---＋TFJ （J--l, 2, 4） transitions of Eu3＋ ions can be observed in the luminescent spectra of La2Zr207：Eu3＋. It was demonstrated that Eu3＋ preferred to occupy a low symmetry site.展开更多
A density functional theory(DFT)study was employed to investigate the mechanical property,thermal conductivity,Debye temperature,electronic structure and defect chemistry of(Gd_(1-x)Sm_(x))_(2)Zr_(2)O_(7).All the(Gd_(...A density functional theory(DFT)study was employed to investigate the mechanical property,thermal conductivity,Debye temperature,electronic structure and defect chemistry of(Gd_(1-x)Sm_(x))_(2)Zr_(2)O_(7).All the(Gd_(1-x)Sm_(x))_(2)Zr_(2)O_(7) compounds exhibit an excellent structural and mechanical stability(Gd_(0.25)Sm_(0.75))_(2)Zr_(2)O_(7) has the lowest Young’s modulus of 213.7 GPa,the largest Possion’s ratio of 0.292,the lowest Debye temperature of 491.8 K and the lowest thermal conductivity.The calculated thermal conductivities of(Gd_(1-x)Sm_(x))_(2)Zr_(2)O_(7) are 1.17-1.21 W/(m·K)by the Clark’s model and 1.32-1.36 W/(m·K)by the Cahall’s model,respectively.The formation energies of O vacancies at 48f site are negative,which increase with the Sm content,however,the formation energies of O vacancies at 8b site are almost invariable.In addition,Sm partly occupying the Gd-site reduces distinctly the formation energies of defects such as A-site vacancies,cation antisite defects,anion Frenkel pairs of oxygen at 8b site and cation interstitials,which suggests that Sm-doped Gd_(2)Zr_(2)O_(7),especially equimolar GdSmZr_(2)O_(7),has a better irradiation tolerance.After the 16 MeVTa-ion irradiation at a fluence of 1×10^(14) or 2×10^(14) ions/cm^(2),the crystal structure of GdSmZr_(2)O_(7) transforms from pyrochlore to a defect fluorite without obvious amorphous phase.展开更多
High entropy pyrochlores(HEP)are potential candidates as dispersoids in the oxide dispersed strengthened steels or alloys,which can be used in nuclear reactors and supercritical boilers.For the first time,HEP oxides Y...High entropy pyrochlores(HEP)are potential candidates as dispersoids in the oxide dispersed strengthened steels or alloys,which can be used in nuclear reactors and supercritical boilers.For the first time,HEP oxides Y_(2)(TiZrHfMoV)_(2)O_(7) were synthesized with Y_(2)Ti_(2)O_(7) as a base structure with the B site(Ti)substituted with five cations through reverse co-precipitation technique in the nanocrystalline form at lowest synthesis temperature.The synthesis parameters for Y_(2)(TiZrHfMoV)_(2)O_(7)(5C)and other derived compositions(five compositions of four cationic systems with each cation eliminated at B site from 5 C)are optimised to obtain lower crystallite and particle sizes.5C has a smaller crystallite size(27 nm)than other single-phase compositions.The cation’s influence,oxidation state,and oxygen vacancy in the phase formation were analysed through XPS.The single-phase HEPs are consolidated through spark plasma sintering.Y_(2)(TiZrHfMo)_(2)O_(7)(4 C-V)shows the highest hardness among the compositions reported so far due to its finer grain size,and Y_(2)(TiHfMoV)_(2)O_(7)(4 C-Zr)has a higher Young’s modulus compared to other single-phase composition due to its higher degree of order in the structure.展开更多
A Density functional theory method within generalized gradient approximation has been performed to obtain the static lattice parameters, oxygen positional parameter, bond length and bond angle and electronic propertie...A Density functional theory method within generalized gradient approximation has been performed to obtain the static lattice parameters, oxygen positional parameter, bond length and bond angle and electronic properties of ideal Lu2Sn207 pyrochlore. The results are in excellent agreement with available experimental measurements. Density of states （DOS） of this compound was presented and analysed. We also notice the presence of the hybridization between oxygen and Lu metal. The band structure calculations show that the compound has direct band gap of 2.67 eV at the F point in the Brillouin zone and this indicates that the material has a semi-conducting feature.展开更多
This paper performs the density functional theory calculations to obtain some factors influencing the response of pyrochlores Gd2B207 （B = Ti, Sn, Zr） to ion irradiation-induced amorphization. The 48f oxygen positio...This paper performs the density functional theory calculations to obtain some factors influencing the response of pyrochlores Gd2B207 （B = Ti, Sn, Zr） to ion irradiation-induced amorphization. The 48f oxygen position parameter x, cohesive energy, bond type and defect-formation energy are discussed. The results show that parameter x can be used to indicate the disordering tendencies within a given pyrochlore family. Bond type, cohesive energy and defect-formation energies can be used to explain some experimental observations, but they are not determined exclusively by radiation ＂resistance＂ for a different pyrochlore family.展开更多
Pyrochlore oxides of general compositions, A2Zr2O7, where A is a 3＋ cation （La to Lu）, are promising candidate materials for applications as high temperature thermal barrier coatings because of their high melting p...Pyrochlore oxides of general compositions, A2Zr2O7, where A is a 3＋ cation （La to Lu）, are promising candidate materials for applications as high temperature thermal barrier coatings because of their high melting points, high thermal expansion coefficients, and low thermal conductivities. In this study, oxides of Sm2Zr2O7, （Smo.75La0.25）2Zr2O7, （Sm0.5 La0.5）2 ZreO7, （Sm0.25La0.75）eZr2O7 and La2Zr2O7 were prepared by solid reactions at 1600℃ for 10 h using Sm2O3, La2O3 and ZrO2 as the reactants. The phase compositions of these ceramic materials were analyzed by X-ray diffractometer （XRD） and fourier transform infrared spectroscopy （FT-IR） methods, respectively. The microstructure was observed by scanning electron microscope （SEM）. The thermal conductivities of these ceramic materials were measured using laser-flash method. XRD and FT-IR results showed that pure ceramic materials with pyrochlore structure were prepared successfully. SEM results indicated that microstructures of these ceramic materials were dense and grain boundaries were very clean. The La2O3 doped Sm2Zr2O7 pyrochlores （Sm0.75 La0.25）2Zr2O7 and （Sm0.5 La0.5）2 Zr2O7 had lower thermal conductivity than the undoped Sm2Zr2O7. The thermal conductivity of （Sm0.25La0.75）2Zr2O7 was found to be lower than that of La2Zr2O7. The results showed that these ceramic materials had the potential to be used as candidate materials for TBCs.展开更多
The effect of rare earth doping on thermo-physical properties of lanthanum zirconate was investigated. Oxide powders of various compositions La2Zr2O7 were synthesized by coprecipitation-calcination method. High-temper...The effect of rare earth doping on thermo-physical properties of lanthanum zirconate was investigated. Oxide powders of various compositions La2Zr2O7 were synthesized by coprecipitation-calcination method. High-temperature dilatometer, DSC, and laser thermal diffusivity methods were used to analyze thermal expansion coefficient （TEC）, specific heat, and thermal diffusivity. The results showed that CeO2 doped pyrochlores La2（Zr1.8Ce0.2）2O7 and La1.7（DyNd）0.15（Zr0.8Ce0.2）2O7 had higher TEC than La2Zr2O7 and La1.7Dy0.3Zr2O7. La2（Zr1.8Ce0.2）2O7, La1.7Dy0.3Zr2O7, and La1.7（DyNd）0.15（Zr0.8Ce0.2）2O7 had lower thermal conductivity than undoped La2Zr2O7. The Dy2O3, Nd2O3, and CeO2 codoped composition showed the lowest thermal conductivity and the highest TEC. Thermo-physical results also indicated that TEC of rare earth oxide doped La2Zr2O7 ceramic was slightly higher than that of conventional ZrO2-8Wt.% Y2O3 （8YSZ）, and its thermal conductivity was lower than that of 8YSZ.展开更多
基金Project supported by the Spanish Government and the Ministerio de Ciencia e Innovacion(PID2020-116149 GB-I00)Generalitat Valenciana(GRISOLIA/2019/054)the Brazilian National Council for Scientific and Technological Development(306567/2021-0)。
文摘The increasing global demand for clean and potable water underscores the need for advanced pollutant remediation technologies in wastewater,such as the degradation of azo dyes,which are known to be harmful to human health.To address this issue,heterogeneous photocatalysis emerges as a promising strategy for breaking down recalcitrant molecules.However,efforts are required to develop efficient and stable photocatalysts capable of operating under visible light.This study explores the photocatalytic potential of Fe-doped RE_(2)Zr_(2)O_(7-δ)(RE=Pr,Sm,Nd,Y)compositions,synthesized through the microwaveassisted solvothermal method,for the degradation of methylene blue.Characterizations,such as X-ray diffraction(XRD)and Raman spectroscopy,reveal the obtention of single-phase ordered pyrochlore for RE=Pr,Sm and Nd or defect fluorite structures for Y.Photocatalytic tests under visible light demonstrate efficient dye degradation for all Fe-doped samples,Y_(2)Zr_(1.9)Fe_(0.1)O_(6.95)(YZF)defect fluorite being the one that exhibits the highest efficiency.Radical scavenging experiments identify hydroxyl radicals as key contributors to the degradation process,along with photoinduced holes.These materials exhibit minimal leaching of iron ions,confirming their stability,and the best material,YZF,demonstrates effective reusability.The results highlight the potential of Fe-doped RE_(2)Zr_(2)O_(7)compositions as an efficient alternative for application as photocatalysts for the degradation of azo dyes under visible light.
基金supported by the National Natural Science Foundation of China(Grant Nos.12275009,12192280,and 11935004)the National Magnetic Confinement Fusion Energy Research Project(No.2021YFE031100).
文摘The properties of high entropy pyrochlore have been studied extensively,but there is no consistent conclusion on its radiation tolerance.Besides,the mechanism of the high entropy effect on the radiation tolerance of pyrochlore is still unclear.In this work,combined with experiments and calculations of pyrochlores with similar cationic radius ratios,the A-site and B-site high entropy effects on structural evolution under irradiation are analyzed.In situ irradiation experiments were carried out on A-site high entropy pyrochlores such as(La_(0.2)Nd_(0.2)Sm_(0.2)Gd_(0.2)Er_(0.2))_(2)Zr_(2)O_(7),B-site Gd_(2)(Ti_(1/3)Sn_(1/3)Zr_(1/3))_(2)O_(7),and ternary pyrochlore Sm_(2)Zr_(2)O_(7) and Gd_(2)Sn_(2)O_(7) for comparison.The A-site high entropy pyrochlore can maintain a stable structure under high fluence irradiation like corresponding ternary pyrochlore,demonstrated by high angle annular dark field scanning transmission electron microscopy(HAADF-STEM),energy dispersive spectroscopy(EDS)mapping and Raman spectrum.The additional irradiation experiments on A-site high entropy pyrochlores(La_(1/3)Nd_(1/3)Gd_(1/3))_(2)Zr_(2)O_(7) and(Nd_(1/3)Sm_(1/3)Gd_(1/3))_(2)Zr_(2)O_(7) also confirm the similarity under irradiation between A-site high entropy and ternary pyrochlores.However,the B-site high entropy pyrochlore Gd_(2)(Ti_(1/3)Sn_(1/3)Zr_(1/3))_(2)O_(7) becomes amorphous at exceptionally low irradiation fluences,indicating a significantly distinct radiation tolerance compared with the A-site high entropy.The difference between the A-site and B-site high entropy effect is analyzed from cationic lattice distortion,bond strength,and inner electron binding energy by first-principles calculations.The results reveal the role and mechanism of the high entropy effect in pyrochlores and lay a foundation for material design and future applications.
基金supported by the National Natural Science Foundation of China(No.51602188)the Program for Professor of Special Appointment(Eastern Scholar)by Shanghai Municipal Education Commission(No.TP2015040)。
文摘Various excellent properties of rare earth zirconate and stannate pyrochlores are close related with their native point defects.First-principles calculations are performed to systematically investigate the point defect mechanism and the oxygen diffusion behavior of A_(2)B_(2)O_(7)(A=La,Ce,Pr,Nd,Pm,Sm,Eu,Gd;B=Zr,Sn).The possible defect complexes and their associated reactions under stoichiometric and nonstoichiometric conditions are explored.The O Frenkel pairs are the most stable defect structure in stoichiometric zirconates,whereas the cation antisite defects are the predominant one in stoichiometric stannates.In the case of BO_(2) excess zirconates and stannates,the BA cation antisite defect with the A vacancy and/or the oxygen interstitial is energetically favorable,whereas the ABantisite defect together with the oxygen vacancy and/or the A interstitial is preferable under the A_(2)O_(3) excess condition.Meanwhile,the maximum point defect concentrations of zirconates are much higher than those of stannates.Furthermore,the oxygen migration barriers are similar in these compounds,ranging in 0.68 eV–0.80 eV.The predicted point defects and oxygen diffusion mechanisms play the critical role in their engineering applications and are expected to guide the future property improvement of pyrochlores through the control of point defects and/or composition.
文摘Mesoporous structured metal oxides exhibit many active applications.However,the synthesis of crystalline metal oxides with a ternary composition while maintaining satisfactory pore features is challeng-ing.Typically,high temperatures are required which inhibit control of pore structure properties including surface area,pore volume,and pore size.Herein,the synthesis of ternary metal oxides Ln_(2)Ti_(2)O_(7)pos-sessing pyrochlore crystal structure is achieved using a novel technique which combines‘soft’and hard colloid templating strategies.The formed materials are of submicron size and composed of∼25-30 nm product‘building blocks’with good chemical and phase stability.The polycrystalline powders have a high specific surface area(up to 70 m^(2)·g^(-1))and pore volume(∼0.35 cm^(3)·g^(-1))which result in a good adsorp-tion capacity(U uptake closing to 60 mg·g^(-1)).Remarkably,the material exhibits a significant portion of mesopores(mainly 10-40 nm)which facilitate fast adsorption of the cations due to high accessibility.The synthetic methodology described herein produces highly homogenous powders and can be applied to other compositions and structures.
基金The authors are grateful to L.A.Shilkina for X-ray phase analysis of the BZN samples.The reported study was funded by Russian Science Foundation(RSF)-research projects no.20-72-00086(BZN ceramics preparation,dielectric mea-surements)At RTU MIREA,the work was supported by the Ministry of Science and Higher Education of Russia(project FSFZ 0706-2020-2022,Bi2Ti2O7 single crystal growth),the equipment of the Center for Collective Use of RTU MIREA was used.
文摘The comparative analysis of the dielectric properties of bismuth-containing pyrochlores with different manifestation of atomic order/disorder was carried out.We examined the dielectric properties(including behavior in electric fields)of two pyrochlore compounds:BZN(presumably a composition close to Bi_(1.5)Zn_(0.5)Nb_(1.5)O_(6.5))ceramics with chemical disorder in both A and B cation sublattices and Bi_(2)Ti_(2)O_(7)single crystal with fully chemical ordered structure.The fundamental differences between the dielectric properties of the BZN ceramics and Bi_(2)Ti_(2)O_(7)single crystal were shown.In particular,in the dielectric relaxation behavior(which cannot be described via Arrhenius law in the Bi_(2)Ti_(2)O_(7))or in the influence of the electric fields on the dielectric permittivity(split-ting of the field-cooled and zero-field-cooled behaviors was observed for Bi_(2)Ti_(2)O_(7)below estimated freezing temperature).The results of this study highlights the special role of Bi_(2)Ti_(2)O_(7)as a candidate material for studying aspects of geometric frustration related with pyrochlore structure in non-magnetic medium and specifies the future directions of research.
基金supported by the start-up funding of CQNU (Grant No. 24XLB010)supported by the Science and Technology Research Program of Chongqing Municipal Education Commission (Grant No. KJQN202100514)+3 种基金funding from Chongqing Natural Science Foundation under Grant No. CSTB2022NSCQ-JQX0018the Fundamental Research Funds for the Central Universities Grant No. 2021CDJZYJH-003Xiaomi Foundation/Xiaomi Young Talents Programfunding from the National Science Foundation of China under Grant Nos. 12404169, 12147172, 12274046, 11874094, 12147102, and 12347101。
文摘The quantum phase transition between Z_(2) plaquette valence bound solid(PVBS) and superfluid(SF) phases on the planar pyrochlore lattice(square ice) is under debate. To gain further insight, here, we focus on the dynamical features of the hard-core Bose–Hubbard model on this lattice and study the excitation spectra by combining stochastic analytic continuation and quantum Monte Carlo simulation. In both PVBS and SF phases,a flat band with bow-tie structure is observed and can be explained by certain symmetries. At the transition point,the spectra turn to be continuous and gapless. A(2+1)-dimensional Abelian–Higgs model with mixed 't Hooft anomaly is proposed to describe the transition, where the anomaly matching predicts that the deconfinement can exist on the domain walls. From the snapshot of the spin configuration in real space, we found the existence of the domain wall. We also found that the spectrum along a specific path in momentum space from PVBS phase to the transition point can be well described by an XXZ spin chain, and the critical theory of XXZ spin chain matches the anomaly. The two-spinon continuum along this specific path implies additional domain walls(point defect) can emerge in the domain walls(line defect) and take the role of deconfinement at the transition point.
基金support from the National Natural Science Foundation of China under grant No.52302065the Yunnan Fundamental Research Projects under grant Nos.202201BE070001-008 and 202201AU070142the National Key Research and Development Program of China under grant No.2023YFB3711200.
文摘Low thermal conductivity and excellent mechanical strength are essential to pyrochlore A2B2O7 ceramic for environmental/thermal barrier coating applications.To collaboratively tailor the mechanical and thermal properties of A2B2O7 ceramic,a novel high entropy pyrochlore ceramic(La_(0.3)Gd_(0.3)Ca_(0.4))_(2)(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))_(2)O_(7) with significant atomic radius and mass fluctuation is proposed by simultaneously introducing various elements with different valence states at A and B cation sites.The as-synthesized(La_(0.3)Gd_(0.3)Ca_(0.4))_(2)(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))_(2)O_(7) exhibits enhanced fracture toughness(1.68 MPa m^(1/2)),amorphous-like low thermal conductivity(1.45 W m^(-1) K^(-1) at 900℃)and matched thermal expansion coefficient(9.0×10^(-6) K^(-1) at 1200℃)with Al_(2)O_(3)/Al_(2)O_(3) CMCs.The extensive misfits in atomic weight,ionic radius among the substitutional cations in combination with the intrinsic oxygen vacancies in the anion sublattice play significant roles in the thermal conductivity reduction of(La_(0.3)Gd_(0.3)Ca_(0.4))_(2)(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))_(2)O_(7) ceramic.The combination of outstanding mechanical and thermal properties indicates that this type of material has a good application prospect for environmental/thermal barrier coatings.
基金supported by Korea Institute of Energy Technology Evaluation and Planning(KETEP)grant funded by the Korea government(MOTIE)(No.RS-2024-00398346,ESS BigData-Based O&M and Asset Management Technical Manpower Training)the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.RS-2024-00350658).
文摘Pyrochlore oxide(Y_(2)Ru_(2)O_(7))has been identified as a promising catalyst for the oxygen evolution reaction(OER)in advanced green energy strategies.However,its electrochemical inertness necessitates the exploration of an effective strategy to facilitate electronic modulation.This study proposes a surface modification approach involving the integration of defective NiFe(D-NiFe)nanoparticles onto a Y_(2)Ru_(2)O_(7)(YRO)support(YRO@D-NiFeP/Ru)using a Prussian blue analog(PBA).Numerous cyanide(CN)vacancies are generated through the oxidation treatment of the NiFe PBA grown on the YRO support,yielding a defective PBA precursor(YRO@D-PBA).Subsequent annealing facilitates the transformation to the D-NiFe nanoparticles on the YRO support(YRO@D-NiFeP/Ru),which augments the exposure of Ni3+active sites beneficial for the OER.Moreover,the reduction of Ru cations from YRO results in the exsolution of Ru nanoparticles,which promotes synergistic charge transfer from the nanoparticles to the interior of Y_(2)Ru_(2)O_(7).Consequently,YRO@D-NiFeP/Ru exhibits a remarkable voltage of 1.49 V at 10 mA·cm^(−2) and the lowest Tafel slope of 42.4 mV·dec^(−1).In addition,a Zn–air battery constructed with YRO@D-NiFeP/Ru exhibits an outstanding power density of 136.2 mW·cm^(−2) and high charge–discharge stability,confirming the applicability of YRO@D-NiFeP/Ru in metal-air batteries.
基金supported by the National Key Research and Development Program of China (Grant Nos. 2023YFA1406100 and 2021YFA1400200)the National Natural Science Foundation of China (Grant Nos. 12025408 and 12174424)+2 种基金the Youth Innovation Promotion Association of Chinese Academy of Scineces (Grant No. 2023007)support from the National Natural Science Foundation of China (Grant No. 11904272)the Open Fund of Hubei Provincial Key Laboratory of Metallurgical Industry Process Systems Science (Grant No. Z202202)。
文摘The cubic pyrochlore Tl_(2)Ru_(2)O_(7) undergoes concurrently a metal–insulator transition (MIT) and a first-order structural transition at T_(MIT)≈120 K,below which the system was found to form one-dimensional spin-one Haldane chains associated with an orbital ordering of Ru-4d electrons.With an aim to tune and access distinct ground states with strong entanglements of multiple degrees of freedom,i.e.,spin,orbital,charge,and lattice,we utilize a high-pressure approach to regulate the MIT of this system.Our detailed resistivityρ(T) measurements on the polycrystalline Tl_(2)Ru_(2)O_(7) samples under various hydrostatic pressures indeed reveal an unusual evolution of the electronic ground states.At first,the MIT is suppressed monotonically from 120 K at ambient to about 70 K at 1.5 GPa and then vanishes suddenly at about 1.8 GPa without achieving a metallic ground state.Meanwhile,the system evolves into a semiconducting ground state with magnitude ofρ(T) in the entire temperature range enhanced gradually by further increasing pressure.Prior to the abrupt disappearance of MIT,a new electronic order manifested as a kink-like anomaly inρ(T) emerges at T_(0)>T_(MIT) at 1.2 GPa and it continues to increase with pressure,producing a tricritical-point-like behavior in the T–P phase diagram of Tl_(2)Ru_(2)O_(7).The presence of two successive transitions at T_(0 )and T_(MIT )in the pressure range 1.2–1.5 GPa indicates an inhomogeneous electronic state nearby the tricritical point.At P≥3 GPa,another broad anomaly emerges inρ(T) at T_(1)>T_(0),and T_(1)continuously increases with pressure,dividing the semiconductingρ(T) into distinct thermally activated regions.These rich phenomena in the pressurized Tl_(2)Ru_(2)O_(7) should originate from the complex interplay of strongly entangled multiple quantum degrees of freedom in the system near the localized-to-itinerant crossover regime.
基金Financial support from the National Natural Science Foundation of China (Nos. 51532009, 51602324, and 51872405) are gratefully acknowledged.
文摘High-entropy pyrochlore-type structures based on rare-earth zirconates are successfully produced by conventional solid-state reaction method. Six rare-earth oxides(La2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, and Y2O3) and ZrO2 are used as the raw powders. Five out of the six rare-earth oxides with equimolar ratio and ZrO2 are mixed and sintered at different temperatures for investigating the reaction process. The results demonstrate that the high-entropy pyrochlores(5RE1/5)2 Zr2O7 have been formed after heated at 1000 ℃. The(5RE1/5)2Zr2O7 are highly sintering resistant and possess excellent thermal stability. The thermal conductivities of the(5RE1/5)2Zr2O7 high-entropy ceramics are below 1 W·m–1·K–1 in the temperature range of 300–1200 ℃. The(5RE1/5)2Zr2O7 can be potential thermal barrier coating materials.
基金supported by National defense ba-sic scientific research(Grant Nos.2022-JCKY-JJ-1086 and 211-CXCY-N103-03-04-00).
文摘Lattice engineering and distortion have been considered one kind of effective strategies for discovering advanced materials.The instinct chemical flexibility of high-entropy oxides(HEOs)motivates/accelerates to tailor the target properties through phase transformations and lattice distortion.Here,a hybrid knowledge-assisted data-driven machine learning(ML)strategy is utilized to discover the A_(2)B_(2)O_(7)-type HEOs with low thermal conductivity(κ)through 17 rare-earth(RE=Sc,Y,La-Lu)solutes optimized A-site.A designing routine integrating the ML and high throughput first principles has been proposed to predict the key physical parameter(KPPs)correlated to the targetedκof advanced HEOs.Among the smart-designed 6188(5RE_(0.2))_(2)Zr_(2)O_(7)HEOs,the best candidates are addressed and validated by the princi-ples of severe lattice distortion and local phase transformation,which effectively reduceκby the strong multi-phonon scattering and weak interatomic interactions.Particularly,(Sc_(0.2)Y_(0.2)La_(0.2)Ce_(0.2)Pr_(0.2))_(2)Zr_(2)O_(7)with predictedκbelow 1.59 Wm^(−1)K^(−1)is selected to be verified,which matches well with the ex-perimentalκ=1.69 Wm^(−1)K^(−1)at 300 K and could be further decreased to 0.14 Wm^(−1)K^(−1)at 1473 K.Moreover,the coupling effects of lattice vibrations and charges on heat transfer are revealed by the cross-validations of various models,indicating that the weak bonds with low electronegativity and few bond-ing charge density and the lattice distortion(r∗)identified by cation radius ratio(r A/r B)should be the KPPs to decreaseκefficiently.This work supports an intelligent designing strategy with limited atomic and electronic KPPs to accelerate the development of advanced multi-component HEOs with proper-ties/performance at multi-scales.
基金supported by grant PID2019-108502RJ-I00 and grant IJC2019-040560-I both funded by MCIN/AEI/10.13039/501100011033RYC2018-024387-I funded by MCIN/AEI/10.13039/501100011033 and by ESF Investing in your future。
文摘The increasing anthropogenic emissions of greenhouse gases(GHG)is encouraging extensive research in CO_(2)utilisation.Dry reforming of methane(DRM)depicts a viable strategy to convert both CO_(2)and CH4into syngas,a worthwhile chemical intermediate.Among the different active phases for DRM,the use of nickel as catalyst is economically favourable,but typically deactivates due to sintering and carbon deposition.The stabilisation of Ni at different loadings in cerium zirconate inorganic complex structures is investigated in this work as strategy to develop robust Ni-based DRM catalysts.XRD and TPR-H2analyses confirmed the existence of different phases according to the Ni loading in these materials.Besides,superficial Ni is observed as well as the existence of a CeNiO_(3)perovskite structure.The catalytic activity was tested,proving that 10 wt.%Ni loading is the optimum which maximises conversion.This catalyst was also tested in long-term stability experiments at 600and 800℃in order to study the potential deactivation issues at two different temperatures.At 600℃,carbon formation is the main cause of catalytic deactivation,whereas a robust stability is shown at 800℃,observing no sintering of the active phase evidencing the success of this strategy rendering a new family of economically appealing CO_(2)and biogas mixtures upgrading catalysts.
基金Project (07C26214301746) supported by Innovation Foundation of Ministry of Science and Technology, ChinaProject (2010GXNSFB013008) supported by Guangxi Natural Science Foundation, ChinaProject (2009bsxt001) supported by the Graduate Degree Thesis Innovation Foundation of Central South University, China
文摘Pyrochlore structure La2Sn2O7：Eu3＋ microcrystals with uniform octahedron shape were successfully synthesized via a hydrothermal route at 180 °C for 36 h. The crystal structure, particle size, morphologies, and optical properties of the as-synthesized products were investigated by XRD, TEM, SEM, EDS, FT-IR, Raman spectroscopy and PL. The effects of pH of precursor solution, precursor concentration, reaction temperature, and time were investigated. The results reveal that pH of the precursor solution not only plays an important role in determining the phase of the as-synthesized products, but also has a significant influence on the morphologies of the samples. High-quality and uniform octahedrons with an average size of about 700 nm could be easily obtained at the pH value of 12. The possible formation mechanism of octahedral-like La2Sn2O7：Eu3＋ microcrystals was briefly proposed. The photoluminescence spectra show that La2Sn2O7：Eu3＋ micro-octahedra display stronger emission in the range of 582-592 nm compared with the samples with other shapes.
文摘The Eu3＋-doped La2Zr207 phosphor with rod-like morphology was successfully synthesized by conventional solid state reaction and hydrothermal method. X-ray diffraction patterns, transmission electron microscopy, and photoluminescence spectra were employed to charac- terize its structure and morphology as well as luminescent properties. The results indicated that the red-emitting phosphor La2Zr207：Eu3＋ had well crystallized and belonged to the cubic structure with space group of Fd3m. The as-obtained product mainly appeared as straight nanorods with an average diameter of 47 nm and length of 50-700 nm. The pos- sible growth mechanism was also discussed. It was found that under blue excitation with a wavelength of 466 nm, the La2Zr2OT：Eu3＋ phosphor exhibited a characteristic red emission at 616 nm that was attributed to the hypersensitive 5D0--＊TF2 electric dipole transition of Eu3＋ ions. Meanwhile, it was more interesting to note that the emission of 5D1--＊TFj （J=0, 1, 2） transitions and the splitting patterns of 5D0---＋TFJ （J--l, 2, 4） transitions of Eu3＋ ions can be observed in the luminescent spectra of La2Zr207：Eu3＋. It was demonstrated that Eu3＋ preferred to occupy a low symmetry site.
基金Project supported by the National Natural Science Foundation of China(51621091,51321061,51021002)the National Science and Technology Major Project(2017-Ⅵ-0020-0093)。
文摘A density functional theory(DFT)study was employed to investigate the mechanical property,thermal conductivity,Debye temperature,electronic structure and defect chemistry of(Gd_(1-x)Sm_(x))_(2)Zr_(2)O_(7).All the(Gd_(1-x)Sm_(x))_(2)Zr_(2)O_(7) compounds exhibit an excellent structural and mechanical stability(Gd_(0.25)Sm_(0.75))_(2)Zr_(2)O_(7) has the lowest Young’s modulus of 213.7 GPa,the largest Possion’s ratio of 0.292,the lowest Debye temperature of 491.8 K and the lowest thermal conductivity.The calculated thermal conductivities of(Gd_(1-x)Sm_(x))_(2)Zr_(2)O_(7) are 1.17-1.21 W/(m·K)by the Clark’s model and 1.32-1.36 W/(m·K)by the Cahall’s model,respectively.The formation energies of O vacancies at 48f site are negative,which increase with the Sm content,however,the formation energies of O vacancies at 8b site are almost invariable.In addition,Sm partly occupying the Gd-site reduces distinctly the formation energies of defects such as A-site vacancies,cation antisite defects,anion Frenkel pairs of oxygen at 8b site and cation interstitials,which suggests that Sm-doped Gd_(2)Zr_(2)O_(7),especially equimolar GdSmZr_(2)O_(7),has a better irradiation tolerance.After the 16 MeVTa-ion irradiation at a fluence of 1×10^(14) or 2×10^(14) ions/cm^(2),the crystal structure of GdSmZr_(2)O_(7) transforms from pyrochlore to a defect fluorite without obvious amorphous phase.
文摘High entropy pyrochlores(HEP)are potential candidates as dispersoids in the oxide dispersed strengthened steels or alloys,which can be used in nuclear reactors and supercritical boilers.For the first time,HEP oxides Y_(2)(TiZrHfMoV)_(2)O_(7) were synthesized with Y_(2)Ti_(2)O_(7) as a base structure with the B site(Ti)substituted with five cations through reverse co-precipitation technique in the nanocrystalline form at lowest synthesis temperature.The synthesis parameters for Y_(2)(TiZrHfMoV)_(2)O_(7)(5C)and other derived compositions(five compositions of four cationic systems with each cation eliminated at B site from 5 C)are optimised to obtain lower crystallite and particle sizes.5C has a smaller crystallite size(27 nm)than other single-phase compositions.The cation’s influence,oxidation state,and oxygen vacancy in the phase formation were analysed through XPS.The single-phase HEPs are consolidated through spark plasma sintering.Y_(2)(TiZrHfMo)_(2)O_(7)(4 C-V)shows the highest hardness among the compositions reported so far due to its finer grain size,and Y_(2)(TiHfMoV)_(2)O_(7)(4 C-Zr)has a higher Young’s modulus compared to other single-phase composition due to its higher degree of order in the structure.
基金supported by the Scientific Research Foundation of the Education Bureau of Sichuan Province of China (Grant No.2010ZC119)
文摘A Density functional theory method within generalized gradient approximation has been performed to obtain the static lattice parameters, oxygen positional parameter, bond length and bond angle and electronic properties of ideal Lu2Sn207 pyrochlore. The results are in excellent agreement with available experimental measurements. Density of states （DOS） of this compound was presented and analysed. We also notice the presence of the hybridization between oxygen and Lu metal. The band structure calculations show that the compound has direct band gap of 2.67 eV at the F point in the Brillouin zone and this indicates that the material has a semi-conducting feature.
文摘This paper performs the density functional theory calculations to obtain some factors influencing the response of pyrochlores Gd2B207 （B = Ti, Sn, Zr） to ion irradiation-induced amorphization. The 48f oxygen position parameter x, cohesive energy, bond type and defect-formation energy are discussed. The results show that parameter x can be used to indicate the disordering tendencies within a given pyrochlore family. Bond type, cohesive energy and defect-formation energies can be used to explain some experimental observations, but they are not determined exclusively by radiation ＂resistance＂ for a different pyrochlore family.
基金supported by Doctoral Fund of Henan Institute of Engineering (D2007012)
文摘Pyrochlore oxides of general compositions, A2Zr2O7, where A is a 3＋ cation （La to Lu）, are promising candidate materials for applications as high temperature thermal barrier coatings because of their high melting points, high thermal expansion coefficients, and low thermal conductivities. In this study, oxides of Sm2Zr2O7, （Smo.75La0.25）2Zr2O7, （Sm0.5 La0.5）2 ZreO7, （Sm0.25La0.75）eZr2O7 and La2Zr2O7 were prepared by solid reactions at 1600℃ for 10 h using Sm2O3, La2O3 and ZrO2 as the reactants. The phase compositions of these ceramic materials were analyzed by X-ray diffractometer （XRD） and fourier transform infrared spectroscopy （FT-IR） methods, respectively. The microstructure was observed by scanning electron microscope （SEM）. The thermal conductivities of these ceramic materials were measured using laser-flash method. XRD and FT-IR results showed that pure ceramic materials with pyrochlore structure were prepared successfully. SEM results indicated that microstructures of these ceramic materials were dense and grain boundaries were very clean. The La2O3 doped Sm2Zr2O7 pyrochlores （Sm0.75 La0.25）2Zr2O7 and （Sm0.5 La0.5）2 Zr2O7 had lower thermal conductivity than the undoped Sm2Zr2O7. The thermal conductivity of （Sm0.25La0.75）2Zr2O7 was found to be lower than that of La2Zr2O7. The results showed that these ceramic materials had the potential to be used as candidate materials for TBCs.
基金supported by the Postdoctoral Foundation of China (20060400261)the Special Finance Scheme of Post Doctoral Foundation of China (200801350)
文摘The effect of rare earth doping on thermo-physical properties of lanthanum zirconate was investigated. Oxide powders of various compositions La2Zr2O7 were synthesized by coprecipitation-calcination method. High-temperature dilatometer, DSC, and laser thermal diffusivity methods were used to analyze thermal expansion coefficient （TEC）, specific heat, and thermal diffusivity. The results showed that CeO2 doped pyrochlores La2（Zr1.8Ce0.2）2O7 and La1.7（DyNd）0.15（Zr0.8Ce0.2）2O7 had higher TEC than La2Zr2O7 and La1.7Dy0.3Zr2O7. La2（Zr1.8Ce0.2）2O7, La1.7Dy0.3Zr2O7, and La1.7（DyNd）0.15（Zr0.8Ce0.2）2O7 had lower thermal conductivity than undoped La2Zr2O7. The Dy2O3, Nd2O3, and CeO2 codoped composition showed the lowest thermal conductivity and the highest TEC. Thermo-physical results also indicated that TEC of rare earth oxide doped La2Zr2O7 ceramic was slightly higher than that of conventional ZrO2-8Wt.% Y2O3 （8YSZ）, and its thermal conductivity was lower than that of 8YSZ.
