Mechanical properties,thermal conductivity and defect formation energies of samarium immobilization in Gd2Zr2O7:First-principles study and irradiation experiment

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-xSm_x)₂Zr₂O₇.All the(Gd_1-xSm_x)₂Zr₂O₇ compounds exhibit an excellent structural and mechanical stability(Gd_0.25Sm_0.75)₂Zr₂O₇ has the lowest Young’s modulus of...     

Effects of Er3+ doping on structure and thermal properties of (Sm1–xErx)2Zr2O7 ceramics for thermal barrier coating

Rare earth Er³⁺ doped (Sm_1–xEr_x)₂Zr₂O₇ (x = 0.1, 0.2, and 0.3) ceramic samples were synthesized using a solid state reaction method. The microstructure and thermal properties of these ceramics were investigated to evaluate their potential as thermal barrier coating materials. The results show that ceramics are compact with regular-shaped grains of 1–5 μm size. (Sm_1–xEr_x)₂Zr₂O₇ has a pyrochlore structure mainly determined by ionic radius ratio, but the ordering degree decreases with increase of the Er₂O₃ content. There is no phase transformation from 1000 to 1200 °C, and the (Sm_1–xEr_x)₂Zr₂O₇ ceramics exhibit excellent phase stability during thermal treatment at 1200 °C for 100 h and 1400 °C for 50 h. The thermal conductivities of dense (Sm_1–xEr_x)₂Zr₂O₇ ceramics range from 1.52 to 1.59 W/(m·K), which is lower than that of Sm₂Zr₂O₇, and decrease as the Er₂O₃ content increases. Besides, the thermal expansion coefficient of (Sm_1–xEr_x)₂Zr₂O₇ is higher than that of Sm₂Zr₂O₇.     

Optical and electrical conductivity properties of rare earth elements (Sm,Y, La,Er) co-doped CeO2

In this research, un-doped CeO₂ and Ce_0.85La_0.10M_0.05O₂ (M: Sm, Er, Y) compounds were synthesized by hydrothermal method and the multi-functional properties are reported. Oxygen defects were created with the additives of rare earth ions. The electrical and luminescence behaviors of the synthesized compounds were investigated in accord with the types of additives. The synthesized products were characterized by X-ray diffraction (XRD) analysis, Brunauer–Emmett–Teller (BET) measurement, UV–vis diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy and electrochemical impedance spectroscopic (EIS). All synthesized compounds are found to be nano-structured and have cubic phase. The total conductivity of all samples was calculated. Hence, the total conductivity of un-doped CeO₂, Ce_0.85La_0.10Y_0.05O₂, Ce_0.85La_0.10Er_0.05O₂ and Ce_0.85La_0.10Sm_0.05O₂ is found to be 2.07 × 10^?10, 5.70 × 10^?4, 1.0 × 10^?3 and 0.0747 S/cm, respectively. Also, bandgap energy (E_g) of these samples calculated from UV visible absorption spectra is discussed, and the optical results show variation between 3.2 and 2.15 eV. Additionally, the luminescence properties of the compounds were investigated and different emissions occur depending on the additive type. Accordingly, photoluminescent emission spectra of Ce_0.85La_0.10Y_0.05O₂, Ce_0.85La_0.10Er_0.05O₂ and Ce_0.85La_0.10Sm_0.05O₂ phosphors indicate that these phosphors have red, green and orange-red colors, respectively.     

Synthesis,crystal structure and photoluminescence properties of novel double perovskite La2CaSnO6:Eu3+ red-emitting phosphors

A series of new double perovskite La_2–xEu_xCaSnO₆ (0 ≤ x ≤ 0.8) red phosphors were synthesized by traditional solid-state reaction. The phase, microstructure, photoluminescence (PL) properties, quantum efficiency, and thermal stability of the phosphors were investigated. La₂CaSnO₆ matrix has a monoclinic double perovskite structure with space group P2₁/n. Under near-ultraviolet (UV) light at 395 nm, La_2–xEu_xCaSnO₆ phosphors exhibit the most typical red emission peak at 614 nm, which corresponds to ⁵D₀→⁷F₂ electric dipole transition of Eu³⁺. The optimum Eu³⁺ doping content is attained at x = 0.5, and the La_1.5Eu_0.5CaSnO₆ phosphor shows a moderate quantum efficiency (32.3%) and high color purity (92.2%). Besides, the temperature-dependent spectrum of the phosphor was studied. The emission intensity of Eu³⁺ at 423 K decreases to 70.94% of the initial intensity at 303 K, and the activation energy ΔE is estimated to be 0.232 eV, suggesting that the phosphors possess good thermal stability. The fabricated w-LED based on the phosphors has higher R_a (89), lower CCT (4539K), and better chromaticity coordinates (0.371, 0.428). These results prove that the Eu³⁺-doped La₂CaSnO₆ red phosphor has great potential applications in w-LEDs.     

Catalytic combustion of toluene over Pd-based monolithic catalysts with a novel washcoat Ce0.8Zr0.15La0.05Oδ

Two novel washcoats Ce_0.8Zr_0.15La_0.05O_δ and Ce_0.8Zr_0.2O₂ was prepared by an impregnation method, which acted as a host for the active Pd component to prepare Pd/Ce_0.8Zr_0.15La_0.05O_δ/substrate and Pd/Ce_0.8Zr_0.2O₂/substrate monolithic catalysts for toluene combustion. The washcoats was characterized by X-ray diffraction (XRD), Raman spectroscopy, Brunauner-Emmett-Teller (BET), and H₂-temperature-programmed reduction (H₂-TPR). The result indicated that both the washcoats had strong vibration-shock resistance according to ultrasonic test. Doping La³⁺ into CeO₂-ZrO₂ solid solution could generate more oxygen vacancies, and could inhibit the sinter of CeO₂-ZrO₂ solid solution when calcined at high temperatures (800, 900 and 1000 °C). The washcoat Ce_0.8Zr_0.15La_0.05O_δ had much better redox properties. The reductive temperature of Ce⁴⁺ species shifted to low temperature by 60 °C when the washcoats calcined at high temperatures (800, 900 and 1000 °C). The Pd/Ce_0.8Zr_0.15La_0.05O_δ/substrate monolithic catalyst calcination at 500 °C had the best catalytic activity and the 95% toluene conversion at a temperature as low as 190 °C. When calcined at low temperature (500 and 700 °C), the catalytic activity has little improvement, however, when calcined at high temperature, the catalytic activity of Pd/Ce_0.8Zr_0.15La_0.05O_δ/substrate monolithic catalysts had significant improvement. As catalyst washcoat, the Ce_0.8Zr_0.15La_0.05O_δ had better thermal stability than the washcoat Ce_0.8Zr_0.2O₂, the developed Pd/Ce_0.8Zr_0.15La_0.05O_δ/substrate monolithic catalyst in this work was promising for eliminating Volatile organic compounds.     

Effect of erbium doping on phase composition,mechanical and thermal properties of ZrO2-based ceramics

Er_xTi_0.1Zr_0.9–xO_2–1.5x (x = 0.04, 0.05, 0.06, 0.07, 0.08) ceramics were synthesized by a solid-state reaction method. The influence of the Er³⁺ addition on the phase composition, Vickers hardness, fracture toughness, and thermal conductivity of this ceramic material was investigated. The X-ray diffraction results reveal that the c-ZrO₂ content increases from 1.85 vol% to 33.89 vol%, and the percentage of t-ZrO₂ decreases from 98.15 vol% to 66.11 vol% with the increase in Er³⁺ content from 4 mol% to 8 mol%. Moreover, the addition of Er³⁺ is beneficial to the volume expansion of the unit cell. At the same time, the incorporation of Er³⁺ weakens the coordination of oxygen ions around the metal cations, resulting in a corresponding decrease in the tetragonality of the t-ZrO₂. The Vickers hardness and fracture toughness of the Er_xTi_0.1Zr_0.9–xO_2–1.5x ceramics show increasing and decreasing trends, respectively. The thermal conductivity has a significant decline due to point defects caused by the Er³⁺ doping. The 8ETZ ceramic exhibits the highest Vickers hardness (12.7 GPa), the lowest fracture toughness (7.6 MPa?m^1/2), and the lowest average thermal conductivity (1.85 W/(m·K)) in the temperature range of 200–1000 °C. All of the above properties are higher than those of the Y₂O₃-stabilized ZrO₂ ceramic.     

Catalysis of Ce_xZr_(1–x)O_2 for di-iso-propyl-ether hydration

The catalytic potential of CexZr1–xO2 in isopropyl ether(DIPE) hydration was explored. While the acidic H-zeolite catalyst was favorable for propylene formation through carbenium ion mechanism, Ce-ZSM-5 and CexZr1–xO2 catalysts improved product selectivity of isopropyl alcohol(IPA) through redox mechanism. The catalytic property of CexZr1–xO2 depended on the preparation method and variable, type of cerium precursor and Ce/Zr ratio. By means of characterizations with X-ray diffraction, N2 adsorption isotherms and NH3 temperature programmed desorption, tetragonal phase of CexZr1–xO2 was proposed as the active phase in which CeO2 and ZrO2 catalyzed synergistically the DIPE hydration with IPA product selectivity. The CexZr1–xO2 prepared from cerium sulfate precursor with co-precipitation hydrothermal method exhibited maximum catalytic activity and IPA product selectivity. The precursor effect was attributed to the stabilization of SO42– species on the tetragonal phase of CexZr1–xO2 and super solid acidity.     

Luminescent ionic lattice occupation and wide tunable emission spectra of La2MgZrO6:Bi3+,Eu3+ double perovskite phosphors for white light LED

La₂Mg_1-x/2Zr_1-x/2O₆:xBi³⁺(x=0.01-0.035,abbreviated as LMZ:Bi³⁺) and La_2-yMg_0.99Zr_0.99O₆:0.02Bi³⁺,yEu³⁺(y=0.1-0.11,abbreviated as LMZ:Bi³⁺,Eu³⁺) double-perovskite phosphors were prepared through high-temperature solid-phase method.The emission spectrum of LMZ:xBi³⁺(x=0.01-0.035)phosphors excited at 353 nm is asymmetric in the range be...     

Effects of different introduction methods of Ce4+ and Zr4+ on denitration performance and anti-K poisoning performance of V2O5-WO3/TiO2 catalyst

The purpose of this work is to explore the effects of the introduction methods of Ce⁴⁺ and Zr⁴⁺ on the physicochemical properties, activity, and K tolerance of V₂O₅-WO₃/TiO₂ catalyst for the selective catalytic reduction of NO_x by NH₃. Four different methods, namely pre-impregnation, post-impregnation, co-impregnation, and co-precipitation, were used to synthesize a series of V₂O₅-WO₃-TiO₂-CeO₂-ZrO₂ catalysts. The catalysts were characterized by XRD, BET, NH₃-TPD, XPS, and H₂-TPR techniques. Moreover, the activity and anti-K poisoning performance were tested by an NH₃-SCR model reaction. The results show that the introduction of Ce⁴⁺ and Zr⁴⁺ can improve the catalytic performance of V₂O₅-WO₃/TiO₂ catalyst, but the impregnation method cannot enhance the anti-K poisoning performance. Ce⁴⁺ and Zr⁴⁺ introduced by co-precipitation method can effectively improve the tolerance of K, which is mainly due to the incorporation of Ce⁴⁺ and Zr⁴⁺ into TiO₂ lattice to form a uniform TiO₂-CeO₂-ZrO₂ solid solution, resulting in the optimal surface acidity and redox performance, and reducing the decreases caused by K-poisoning. Furthermore, based on the best introduction method, we further optimized the molar ratio of Ce⁴⁺/Zr⁴⁺. It is found that the catalyst exhibits the best anti-K poisoning performance when the molar ratio of Ce⁴⁺/Zr⁴⁺ is 2:1.     

Effect of Metal Oxide Doping into Ce0.5Zr0.5O2 on Catalytic Activity of MnOx/γ-Al2O3/Ce0.45Zro.45M0.1Ox （M = Y, La, Mn） Honeycomb Catalysts

This article showed that the catalytic activity of MnOx/γ-Al2O3/Ce0.5Zr0.5O2 monolithic catalyst toward the catalytic combustion of ethanol in a fixed bed reactor could be greatly improved by doping three metal oxides into Ce0.5Zr0.5O2. The catalytic activity of MnOx/γ-Al2O3/Ce0.45Zr0.45M0.1 Ox （M = Y, La, Mn） is better than that of MnOx/γ-Al2O3/Ce0.5 Zr0.5O2. The order of activity of the catalysts is as follows： MnOx/γ-Al2O3/Ce0.45Zr0.45Y0.1Ox 〉 MnOc/γ-Al2O3/Ce0.45 Zr0.45La0.1Ox 〉 MnOx/γT-Al2O3/Ce0.45Zr0.45Mn0.1Ox 〉 MnOx/y-Al2O3/Ce0.5Zr0.5O2. The influence of the loading amount of manganese oxide in enhancing the catalytic activity of MnOx/γ-Al2O3/Ce0.45Zr0.45Y0.1 Ox was investigated. The results showed that when MnO2 loading amount was 10% （mass fraction）, the MnOx/Al2O3/Ce0.45Zr0.45Y0.1Ox catalyst recorded the highest activity.     

Helium ion irradiation effects on neodymium and cerium co-doped Gd2Zr2O7 pyrochlore ceramic

This paper studies the helium ions irradiation effects on Nd and Ce co-doped Gd_2 Zr_2 O_7 ceramics. where Nd replaces the Gd site and Ce replaces the Zr site respectively. A series of(Gd_(1-x)Nd_x)_2(Zr_(1-y)Ce_y)_2 O_7(0 ≤ x, y ≤ 1) ceramics were irradiated with a 500 keV He ions at room temperature at fluences ranging from 1 × 10~(15) to 1 × 10~(17) ions/cm~2. The irradiated samples were characterized using GIXRD, Raman and SEM measurements. From the GIXRD and Raman observations, the results indicate that all the samples display a deficient fluorite structure after irradiation. The irradiation toleration increases with the irradiation depth increasing under experimental conditions, and Nd_2 Ce_2 O_7 has the best irradiation stability in the(Gd_(1-x)Nd_x)_2(Zr_(1-y)Ce_y)_2 O_7(0≤ x. y≤1). Based on SEM results, the irradiated samples are still relatively dense and uniform, and no second phase exists.     

Influence of surface Ce/Zr ratio on formation of κ-Ce2Zr2O8 superstructure and its application in three-way catalysis

Ceria-zirconia based(CZ) materials are still a crucial component of three-way catalysts(TWCs) now.Compared with traditional cubic or tetragonal phase,CZ material with pyrochlore-type κ-Ce₂Zr₂O₈ phase shows an excellent oxygen storage capacity,and thus is examined as a promising material for developing TWCs.Considering the remarkable surface Ce/Zr ratio change during the κ-Ce₂Zr₂O₈ formation,we investigated the effects of surface C...     

Structural and electrical properties of La2-xSrxMo2O9-δ

Sr-doped La2Mo2O9 were prepared by solid state reaction and characterized by XRD,impedance spectroscopy and HebbWagner polarization method.XRD patterns of the samples indicated that the solubility limit of Sr2+ in La2-xSrxMo2O9-δ was in the range of 7 mol.% to 7.5 mol.%,i.e.,the maximum stoichiometric coefficient x in La2-xSrxMo2O9-δ was larger than 0.14 and less than 0.15.The cubic lattice parameter of La2-xSrxMo2O9-δ(0相似文献   

Lewis acid-oxygen vacancy interfacial synergistic catalysis over SO42−/Ce0.84Zr0.16O2–WO3–ZrO2 for N,N-diethylation of aniline with ethanol

Herein, a new mechanism involving Lewis acid-oxygen vacancy interfacial synergistic catalysis for aniline N,N-diethylation with ethanol was proposed, and the SO₄²⁻/Ce_0.84Zr_0.16O₂–WO₃–ZrO₂ catalyst (SCWZ) with both Lewis acid sites and oxygen vacancies was synthesized by the hydrothermal method, which shows better catalytic activity than the reported solid acidic catalysts. Besides, the SO₄²⁻/ZrO₂ (SZ) and SO₄²⁻/WO₃–ZrO₂ (SWZ) catalysts were also prepared and compared with SCWZ to investigate the synergistic effect of each component. The SO₄²⁻ and WO₃ mainly generate Lewis acid by bonding with ZrO₂, which is beneficial for the fracture of the N–H bond in aniline. The Ce_0.84Zr_0.16O₂ solid solution mainly plays a vital role in generating the oxygen vacancies as the interface active species, which can participate in stripping –OH from ethanol, then the carbocation will also be released, which only needs 1.3805 kcal/mol energy, calculated by density functional theory (DFT), to be input. In comparison, the traditional reaction mechanism needs the Brønsted acidic sites to promote the protonation of ethanol, then dehydration and subsequent formation of carbocation followed, and 108.6846 kcal/mol energy needs to be input, which is far higher than that of the new mechanism. The apparent activation energy (E_a) over SCWZ was measured by experiment to be 34.09 kJ/mol, which is much lower than that of SWZ (47.10 kJ/mol) and SZ (54.37 kJ/mol), illustrating comparatively preferable kinetics for SCWZ than that of SWZ and SZ. Besides, the conversion of aniline and selectivity to N,N-diethylaniline over SCWZ reach almost 100% and 73%, respectively. The SCWZ can be renewed for 4 times without rapid deactivation, and the longevity of SCWZ is longer than that of SWZ and SZ, as the loaded SO₄²⁻ and tetragonal ZrO₂ are stabilized by Ce_0.84Zr_0.16O₂ and WO₃, respectively.     

Highly transparent ytterbium doped yttrium lanthanum oxide ceramics

To prepare ytterbium doped lanthania yttria nanopowder a method of laser evaporation of mixed oxides was used. After calcinations of the powder at 1200 °C a pure single-phase solid solution Yb3+:(LaxY1–x)2O3 was formed in the nanoparticles. Influence of lanthanum oxide as an isovalent additive on the yttria structure was investigated. The lanthanium ions were proved to be a good aid to sinter yttria ceramics doped with Yb3+ at moderate temperatures about 1650 °С. The ceramics with relative density higher than 99.99% and grain size about 40 μm were fabricated. Full transmittance of 1.8 mm thick Yb0.11La0.23Y1.66O3 ceramics reached 82.5% at 800 nm. This material could be a good gain medium for ytterbium high power pulse lasers.     

Influence of manganese rate on structural,optical and electrochemical properties of CeO2 thin films deposited by spray pyrolysis: Supercapacitor applications

The present work aimed to investigate the electrochemical properties of ITO substrates in propylene carbonate (PC) with 0.5 mol/L lithium perchlorate (LiClO₄) medium in the presence of elaborated thin films of cerium dioxide pure and doped with manganese at varying percentages. Ce_1–xMn_xO₂ (x = 0 wt%, 2 wt%, 4 wt% and 6 wt%) were successfully deposited by the spray pyrolysis (SP) technique on the glass substrate and ITO at 450 °C. The effects of manganese (Mn) doped thin films Ce_1–xMn_xO₂ were studied and investigated by using different analyses namely X-ray diffraction (XRD) analysis, Raman spectroscopy method, UV–Vis spectrophotometer technique, atomic force microscopy (AFM) analysis and electrochemical properties. XRD data obtained present a polycrystalline with a face-centred cubic structure of fluorite type. Raman results of undoped and Mn doped thin films show two peaks at 465 and 600 cm^?1, due to the formation of extrinsic oxygen vacancies by the incorporation of Mn into Ce_1–xMn_xO₂ matrix. Energy dispersive spectroscopy (EDS) data show the presence of Ce, O, and Mn elements in the elaborated films. The AFM results reveal that the surface roughness decreases with increasing Mn rate. Further, band gap energy of thin films decreases with increasing in Mn rate due to the formation of defect state between valence and conduction band. The storage capacity of the elaborated Ce_1–xMn_xO₂/ITO/PC + LiClO₄ electrode reaches a maximum of 1.997 mF in the presence of 6 wt% of Mn.     

Energy transfer and luminescent properties of Tb3+ and Tb3+, Yb3+ doped CNGG phosphors

In this work,calcium niobium gallium garnet(Ca₃ Nb_1.6875Ga_3.1875O₁₂-CNGG) ceramic samples singledoped with Tb³⁺ and co-doped with Tb³⁺ and Yb³⁺ ions were sintered by the solid-state reaction method.The structural characterization of the samples was carried out by X-ray diffraction measurements.The optimal concentration of Tb³⁺ ions corresponding to the maximum luminescence in the green spectral range in CNGG:...     

Fabrication and long persistent luminescence of Ce3+-Cr3+ co-doped yttrium aluminum gallium garnet transparent ceramics

Persistent luminescence (PersL) materials are widely used in safety indication, traffic and transportation signs, architectural decoration and other fields. In this paper, (Y_1?xCe_x)₃(Al_0.9995Cr_0.0005)₂Ga₃O₁₂ (x = 0.001, 0.002, 0.003, 0.005) transparent ceramics were successfully prepared by solid-state reaction method in air followed by HIP post-treatment. With the increase of Ce³⁺ doping concentration, the optical quality of the as-prepared ceramics is improved and the morphology is denser. Luminescent quenching occurs when the Ce³⁺ concentration is more than 0.2%. The as-prepared transparent ceramics were annealed in different atmospheres. From the PersL decay curves, the transparent ceramics after air annealing show the best PersL performance: luminance with 4424.0 mcd/m² and PersL duration over 865 min after ceasing 365 nm excitation, respectively. The effects of Ce³⁺ doping concentration and annealing atmospheres are also discussed in detail.     

Preparation and characterization of Ce_(0.8)La_(0.2–x)Y_xO_(1.9) as electrolyte for solid oxide fuel cells

In this study, ultrafine Ce0.8La0.2–x Y x O1.9（for x=0, 0.05, 0.10, 0.15, 0.20） powders were successfully prepared by the sol-gel method.The samples were characterized by fourier transform infrared（FTIR）, thermogravimetric and differential scanning calorimetry（TG-DSC）, X-ray diffraction（XRD）, scanning electron microscopy（SEM）, AC impedance and thermal expansion measurements.Experimental results indicated that highly phase-pure cubic fluorite electrolyte Ce0.8La0.2–x Y x O1.9 powders were obtained after calcining at 600 °C.The as-synthesized powders exhibited high sintering activity, the Ce0.8La0.2–x Y x O1.9 series electrolytes which have higher relative densities over 96% could be obtained after sintered at 1400 °C for 4 h.Ce0.8La0.15Y0.05O1.9 electrolyte sintered at 1400 °C for 4 h exhibited higher oxide ionic conductivity（σ800 oC=0.057 S/cm）, lower electrical activation energy（E a=0.87 e V） and moderate thermal expansion coefficient（TEC=15.5×10-6 K-1, temperature range 25–800 °C）.     

Tailoring thermal stability of ceria-zirconia mixed oxide by doping of rare earth elements: From theory to experiment

Ceria-zirconia mixed oxides(CZMO) are widely used in many important catalysis fields.However,pure CZMO is known to have poor thermal stability.In this paper,a strategy was proposed to design Ce_0.475Zr_0.475M_0.05O₂(M=La,Y,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Er,Lu,and,Yb) oxide surface with high thermal stability by using first-principles molecular dynamics(FPMD) simulation and experiment method.Through the structure stability analysis at different temperatures,the surf...