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1.
《Solid State Ionics》2006,177(26-32):2363-2368
The mechanism and kinetics of water incorporation in the double perovskites Ва4Ca2Nb2O11 and Sr6Ta2O11 has been investigated (T = 300÷500 °C and aH2O = 1 · 10 3÷2.2 · 10 2). The formation of hydration products Ba4Ca2Nb2O11·xH2O and Sr6Ta2O11·xH2O (0.2 < x < 0.50) was limited by the diffusion of H2O. It has been found that the concentration dependences of H2O are the same for both samples: small increasing of H2O with increasing x. The temperature dependences of the chemical diffusion coefficients of water for compositions of Ba4Ca2Nb2O11·0.35H2O and Sr6Ta2O11·0.35H2O could be described with close activation energies of Ea = 0.38 ± 0.03 eV and Ea = 0.49 ± 0.03 eV, respectively. The chemical diffusion coefficients of water are nearly one order of magnitude smaller for tantalate Sr6Ta2O11. This result correlates with lower oxygen and proton conductivities in Sr6Ta2O11 as the consequence of lower mobilities.  相似文献   

2.
The high-resolution infrared spectrum of N212C18O2 has been observed in the ν3 band (2314 cm?1) region of 12C18O2 with diode laser absorption spectroscopy of pulsed molecular beam. The geometry of N212C18O2 is similar to N212C16O2, a T-shaped structure with the nitrogen molecular axis pointing towards the carbon atom. The geometrical parameters of the T-shaped ground-state structure are determined as RNcmC = 3.7285(5) Å and (90?ΘNcmCO) = 6.85(3)°. The vibrational band origin of N212C18O2 corresponding to the ν3 mode of 12C18O2 shows a shift of 0.52499(10) cm?1 with respect to that of 12C18O2.  相似文献   

3.
High-purity specimens of Li6CaLa2Ta2O12 and Li6BaLa2Ta2O12 have been successfully synthesized by solid-state reactions. The analytical chemical compositions of these samples were in good agreement with the nominal compositions of Li6CaLa2Ta2O12 and Li6BaLa2Ta2O12. The Rietveld refinements verified that these compounds have the garnet-type framework structure with the lattice constants of a = 12.725(2) Å for Li6CaLa2Ta2O12 and a = 13.001(4) Å for Li6BaLa2Ta2O12. All of the diffraction peaks of X-ray powder diffraction patterns were well indexed on the basis of cubic symmetry with space group Ia-3d. To make a search for Li sites, the electron density distributions were precisely examined by using the maximum entropy method. Li+ ions occupy partially two types of crystallographic site in these compounds: (i) tetrahedral 24d sites, and (ii) distorted octahedral 96h sites, the latter of which are the vacant sites of the ideal garnet-type structure. The present Li6CaLa2Ta2O12 and Li6BaLa2Ta2O12 samples exhibit the conductivity σ = 2.2 × 10? 6 S cm? 1 at 27 °C (Ea = 0.50 eV) and σ = 1.3 × 10? 5 S cm? 1 at 25 °C (Ea = 0.44 eV), respectively.  相似文献   

4.
The series of Gd4 ? xMxAl2O9 ? x/2 (M = Ca, Sr) with x = 0, 0.01, 0.05, 0.10 and 0.25 was prepared by the citrate complexation method. Both Gd4 ? xCaxAl2O9 ? x/2 and Gd4 ? xSrxAl2O9 ? x/2 show the monoclinic cuspidine structure with space group of P21/c up to 0.05–0.1 and 0.01–0.05 mol for Ca and Sr, respectively. Beyond the substitution limit of Gd4Al2O9, GdAlO3 and SrGd2Al2O7 appear as additional phases. The highest electrical conductivity obtained at 900 °C yielded σ = 1.49 × 10? 4 S/cm for Gd3.95Ca0.05Al2O8.98. In comparison, the conductivity of pure Gd4Al2O9 was σ = 1.73 × 10? 5 S/cm. The conductivities determined are in a similar range as those of other cuspidine materials investigated previously. The thermal expansion coefficient of Gd4Al2O9 at 1000 °C was 7.4 × 10? 6 K? 1. The phase transition between 1100 and 1200 °C reported earlier changes with increasing substitution of Ca and Sr.  相似文献   

5.
Shanwen Tao 《Solid State Ionics》2009,180(2-3):148-153
SnP2O7 and In-doped SnP2O7 have been prepared by an aqueous solution method using (NH4)2HPO4 as phosphorous source. It was found that the solid solution limit in Sn1 ? xInx(P2O7)1 ? δ was at least x = 0.12. All pyrophosphates in the Sn1 ? xInx(P2O7)1 ? δ (x  0.12) series exhibit 3 × 3 × 3 superlattice structures. The conductivities of Sn0.92In0.08(P2O7)1 ? δ in air are 6.5 × 10? 6 and 8.0 × 10? 9 S/cm at 900 and 400 °C, respectively, when prepared by an aqueous solution method and annealed at 1000 °C. The conductivity of undoped SnP2O7 is slightly lower. However, it was also found that the low-temperature conductivities of pyrophosphates annealed only at 650 °C are several orders of magnitude higher than those annealed at 1000 °C, which could be related to a trace amount of an amorphous secondary phase. The peak conductivity was in this case observed at around 250 °C, which is the same temperature as previously observed in In-doped SnP2O7 although the conductivity is still three orders of magnitude lower in the present study. These differences can be related to large differences in particle size and morphology, and all in all, the conductivities of SnP2O7-based materials are very sensitive to the synthetic history.  相似文献   

6.
Magnetic CoFe2O4@ZnS core-shell nanocomposite was successfully synthesized via one-step hydrothermal decomposition of zinc(II) diethanoldithiocarbamate complex over CoFe2O4 nanoparticles at low temperature of 200 °C. The obtained nanocomposite was characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, UV–Vis spectroscopy, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, magnetic measurements, and Brunauere-Emmette-Teller. The results confirmed the formation of CoFe2O4@ZnS nanocomposite with the average crystallite size of 18 nm. The band gap of 3.4 eV was obtained using UV–vis absorption of CoFe2O4@ZnS nanocomposite, which made it a suitable candidate for sono-/photo catalytic processes. This nanocomposite was applied as a novel sonocatalyst for the degradation of organic pollutants under ultrasound irradiation. The results showed complete degradation of methylene blue (MB) (25 mg/L) within 70 min in the presence of CoFe2O4@ZnS nanocomposite and H2O2 (4 mM). The trapping experiments indicated that OH radicals are the main active species in dye degradation. In addition, sonocatalytic activity of the CoFe2O4@ZnS nanocomposite was higher than those of pure ZnS and CoFe2O4, showing that the combining ZnS with magnetic CoFe2O4 could be an excellent choice to improve its sonocatalytic activity. The nanocomposite could be magnetically separated and reused without any observable change in its structure and performance even after five consecutive runs.  相似文献   

7.
A protonated Ba6Mn24O48 phase with an original tunnel crystal structure and mixed-valent manganese has been prepared in the form of powders and millimeter-long fibrous crystals (whiskers). A combined study either by impedance spectroscopy or transport measurements revealed that the Ba6Mn24O48 phase demonstrates mixed conductivity with both proton and electronic components reaching ~ 10? 3 Ω? 1?cm? 1 at room temperature.  相似文献   

8.
W.G. Wang  X.P. Wang  Y.X. Gao  Q.F. Fang 《Solid State Ionics》2009,180(23-25):1252-1256
The electrical properties and the mechanism of lithium ionic diffusion in the Li7La3Ta2O13 compounds were investigated. The bulk and total conductivity at 300 K of the Li7La3Ta2O13 compound are about 3.3 × 10? 6 S/cm and 2.6 × 10? 6 S/cm, respectively. The activation energy of bulk and total conductivity is in the range of 0.38–0.4 eV. A prominent internal friction peak in Li7La3Ta2O13 compounds was observed around 280 K at 0.5 Hz, which is actually composed of two subpeaks (P1 peak at lower temperature and P2 peak at higher temperature). From the shift of peak position with frequency, the activation energy of 1.0 eV and the pre-exponential factor of relaxation time in the order of 10? 18–10? 21 s were obtained if one assumes Debye relaxation processes. These values of relaxation parameters strongly suggest the existence of interaction between the relaxation species (here lithium ions or vacancies). Based on the coupling model, the relaxation activation energies are deduced as 0.45 eV and the pre-exponential factor of relaxation time as 10? 15 s. Judging from these relaxation parameters and the similarity of structure between Li7La3Ta2O13 and Li5La3Ta2O12 compounds, the P1 and P2 peaks are suggested to be related with the lithium ionic diffusion between 48g?48g and 24d?48g.  相似文献   

9.
Hydrogen peroxide (H2O2) and hydroperoxy (HO2) reactions present in the H2O2 thermal decomposition system are important in combustion kinetics. H2O2 thermal decomposition has been studied behind reflected shock waves using H2O and OH diagnostics in previous studies (Hong et al. (2009) [9] and Hong et al. (2010) [6,8]) to determine the rate constants of two major reactions: H2O2 + M  2OH + M (k1) and OH + H2O2  H2O + HO2 (k2). With the addition of a third diagnostic for HO2 at 227 nm, the H2O2 thermal decomposition system can be comprehensively characterized for the first time. Specifically, the rate constants of two remaining major reactions in the system, OH + HO2  H2O + O2 (k3) and HO2 + HO2  H2O2 + O2 (k4) can be determined with high-fidelity.No strong temperature dependency was found between 1072 and 1283 K for the rate constant of OH + HO2  H2O + O2, which can be expressed by the combination of two Arrhenius forms: k3 = 7.0 × 1012 exp(550/T) + 4.5 × 1014 exp(?5500/T) [cm3 mol?1 s?1]. The rate constants of reaction HO2 + HO2  H2O2 + O2 determined agree very well with those reported by Kappel et al. (2002) [5]; the recommendation therefore remains unchanged: k4 = 1.0 × 1014 exp(?5556/T) + 1.9 × 1011+exp(709/T) [cm3 mol?1 s?1]. All the tests were performed near 1.7 atm.  相似文献   

10.
This study synthesized Fe3O4 nanoparticles of 30–40 nm by a sonochemical method, and these particles were uniformly dispersed on the reduced graphene oxide sheets (Fe3O4/RGO). The superparamagnetic property of Fe3O4/RGO was evidenced from a saturated magnetization of 30 emu/g tested by a sample-vibrating magnetometer. Based on the testing results, we proposed a mechanism of ultrasonic waves to explain the formation and dispersion of Fe3O4 nanoparticles on RGO. A biosensor was fabricated by modifying a glassy carbon electrode with the combination of Fe3O4/RGO and hemoglobin. The biosensor showed an excellent electrocatalytic reduction toward H2O2 at a wide, linear range from 4 × 10?6 to 1 × 10?3 M (R2 = 0.994) as examined by amperometry, and with a detection limit of 2 × 10?6 M. The high performance of H2O2 detection is attributed to the synergistic effect of the combination of Fe3O4 nanoparticles and RGO, promoting the electron transfer between the peroxide and electrode surface.  相似文献   

11.
We examined the electric field-assisted thermionic emission of atomic oxygen radical anion (O?) in a vacuum from fluorine-substituted derivatives of 12CaO·7Al2O3 (C12A7) with a composition of (12 ? x)CaO·7Al2O3·xCaF2 (0  x  0.8). Unsubstituted C12A7 easily decomposed into 5CaO?3Al2O3 (C5A3) and 3CaO?Al2O3 (C3A) above 830 °C during the emission experiment in a vacuum. The decomposition temperature range became narrower as the amount of F? ion substitution increased, e.g. the sample with x = 0.4 kept a single phase after the emission experiment at 900 °C. The emitted anionic species from the x = 0.4 sample were dominated by O? ions (~ 92%) together with a small amount of O2? ions (~ 4%) and F? ions (~ 4%). The absence of an O2 gas supply to the opposite side of the emission surface led to a nearly steady co-emission of O? ions and electrons with a ratio of < 1/1. The O2 gas supply markedly enhanced the O? ion emission, and suppressed the electron emission. A sustainable and high-purity O? ion emission with a current density of 11 nA cm? 2 was achieved at 830 °C with the supply of 40 Pa O2 gas. The similarity in these emission features to the unsubstituted C12A7, together with the improved thermal stability demonstrates that the F? ion-substituted C12A7 is a promising material for higher intensity O? ion emission at higher temperatures.  相似文献   

12.
A highly sensitive chemiluminescence (CL) method for the determination of nitrofurans (NFs) was developed based on the enhancement of CL intensity of luminol–H2O2–NFs system by silver nanoparticles (AgNPs). It was supposed that the oxygen-related radicals of OH and superoxide radical (O2?) could be produced when NFs reacted with H2O2. Furthermore, the enhancement mechanism was originated from the reinforcer of AgNPs, which could catalyze the generation of the OH radical. Then OH radicals reacted with luminol anion and HO2? to form luminol radical (L?) and O2?. The excited state 3-aminophthalate anion was obtained in the reaction of L? and O2?, which was the emitter (luminophor) in the luminol–H2O2 CL reaction system and the maximal emission of the CL spectrum was at 425 nm. The experiments of scavenging oxygen-related radicals were done to confirm these reactive oxygen species participated in the CL reaction. The limits of detection (LOD) (S/N=3) were 8×10?7 g mL?1 for furacilin, 8×10?8 g mL?1 for furantoin, 4×10?8 g mL?1 for furazolidone and 2×10?7 g mL?1 for furaltadone. The proposed method was successfully applied to the determination of NFs in feeds and pharmaceutical samples.  相似文献   

13.
Fe3O4 magnetic nanoparticles (Fe3O4 MNPs) with much improved peroxidase-like activity were successfully prepared through an advanced reverse co-precipitation method under the assistance of ultrasound irradiation. The characterizations with XRD, BET and SEM indicated that the ultrasound irradiation in the preparation induced the production of Fe3O4 MNPs possessing smaller particle sizes (16.5 nm), greater BET surface area (82.5 m2 g?1) and much higher dispersibility in water. The particle sizes, BET surface area, chemical composition and then catalytic property of the Fe3O4 MNPs could be tailored by adjusting the initial concentration of ammonia water and the molar ratio of Fe2+/Fe3+ during the preparation process. The H2O2-activating ability of Fe3O4 MNPs was evaluated by using Rhodamine B (RhB) as a model compound of organic pollutants to be degraded. At pH 5.4 and temperature 40 °C, the sonochemically synthesized Fe3O4 MNPs were observed to be able to activate H2O2 and remove ca. 90% of RhB (0.02 mmol L?1) in 60 min with a apparent rate constant of 0.034 min?1 for the RhB degradation, being 12.6 folds of that (0.0027 min?1) over the Fe3O4 MNPs prepared via a conventional reverse co-precipitation method. The mechanisms of the peroxidase-like catalysis with Fe3O4 MNPs were discussed to develop more efficient novel catalysts.  相似文献   

14.
《Solid State Ionics》2006,177(1-2):73-76
Ionic conduction in fluorite-type structure oxide ceramics Ce0.8M0.2O2−δ (M = La, Y, Gd, Sm) at temperature 400–800 °C was systematically studied under wet hydrogen/dry nitrogen atmosphere. On the sintered complex oxides as solid electrolyte, ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in the solid states proton conducting cell reactor by electrochemical methods, which directly evidenced the protonic conduction in those oxides at intermediate temperature. The rate of evolution of ammonia in Ce0.8M0.2O2−δ (M = La, Y, Gd, Sm) is up to 7.2 × 10 9, 7.5 × 10 9, 7.7 × 10 9, 8.2 × 10 9 mol s 1 cm 2, respectively.  相似文献   

15.
《Solid State Ionics》2006,177(11-12):1027-1031
LiNi0.8Co0.2O2 and Ca-doped LiNi0.8Co0.2O2 cathode materials were synthesized via a rheological phase reaction method. It is found that the Ca doping significantly improves reversible capacity, cycling performance, thermal stability and rate capability. The Ca-doped LiNi0.8Co0.2O2 cathode material maintains nearly its initial discharge capacity up to 100 cycles at room temperature. It also delivers an initial discharge capacity of 183 mA h g 1 and still keeps 131 mA h g 1 even after 120 cycles at 60 °C. These results, together with the X-ray diffraction and electrochemical impedance spectroscopy analysis, reveal that Ca2+ ions occupy Li+ ion sites to form CaLi defects and lithium vacancies (VLi′), which reduce the resistance and increases conductivity of LiNi0.8Co0.2O2.  相似文献   

16.
Ferrimagnetism has been extensively studied in garnets, whereas it is rare to find the antiferromagnet. Present work will demonstrate antiferromagnetism in the two Mn–V-garnets. Antiferromagnetic phase transition in AgCa2Mn2V3O12 and NaPb2Mn2V3O12 has been found, where the magnetic Mn2+ ions locate only on octahedral A site. The heat capacity shows sharp peak due to antiferromagnetic order with the Néel temperature TN=23.8 K for AgCa2Mn2V3O12 and TN=14.2 K for NaPb2Mn2V3O12. The magnetic entropy change over a temperature range 0–50 K is 13.9 J K?1 mol-Mn2+-ions?1 for AgCa2Mn2V3O12 and 13.6 J K?1 mol-Mn2+-ions?1 for NaPb2Mn2V3O12, which are in good agreement with calculated value of Mn2+ ion with spin S=5/2. The magnetic susceptibility shows the Curie–Weiss behavior over the range 29–350 K. The effective magnetic moment μeff and the Weiss constant θ are μeff=6.20 μB Mn2+-ion?1 and θ=?34.1 K (antiferromagnetic sign) for AgCa2Mn2V3O12 and μeff=6.02 μB Mn2+-ion?1 and θ=?20.8 K for NaPb2Mn2V3O12.  相似文献   

17.
The oxygen tracer diffusion coefficient (D?) has been measured for 9 mol% scandia 2 mol% yttria co-doped zirconia solid solution, (Y2O3)2(Sc2O3)9(ZrO2)89, using isotopic exchange and line scanning by Secondary Ion Mass Spectrometry, as a function of temperature. The values of the tracer diffusion coefficient are in the range of 10? 8–10? 7 cm2 s? 1 and the Arrhenius activation energy was calculated to be 0.9 eV; both valid in the temperature range of 600–900 °C. Electrical conductivity measurements were carried out using 2-probe and 4-probe AC impedance spectroscopy, and a 4-point DC method at various temperatures. There is a good agreement between the measured tracer diffusion coefficients (D?, Ea = 0.9 eV) and the diffusion coefficients calculated from the DC total conductivity data (Dσ, Ea = 1.0 eV), the latter calculated using the Nernst–Einstein relationship.  相似文献   

18.
Lu2O3:Tb,Hf ceramics containing 0.1% of Tb and 0–1.5% of Hf were prepared in reducing atmosphere at 1700 °C and their thermoluminescence properties were systematically studied. For comparison Tb,Ca co-doped specimen was also fabricated and investigated. The Tb,Hf ceramics shows basically a single TL band located around 180 °C as found with heating rate of 15 °C/min. Ceramics singly doped with Tb show complex TL glow curves indicating the presence of traps of very different depths. On the other hand Tb,Ca co-doping is beneficial for the development of shallow traps with the main TL band around 70 °C. Hence, the aliovalent impurities, Ca2+ and Hf4+, strongly influenced the traps structure in Lu2O3:Tb ceramics, each of them in its own specific way. Isothermal decay of Lu2O3:Tb,Hf at 185 °C was recorded and its shape suggest that multiple hole trapping occurs in the Lu2O3:Tb,Hf ceramics. Due to the different traps depths the Lu2O3:Tb,Hf ceramics possess properties typical for storage phosphors, while Lu2O3:Tb,Ca is a persistent luminescent material rather.  相似文献   

19.
Chemical interactions between the Ba2YCu3O6+x superconductor and the LaMnO3 buffer layers employed in coated conductors have been investigated experimentally by determining the phases formed in the Ba2YCu3O6+x–LaMnO3 system. The Ba2YCu3O6+x–LaMnO3 join within the BaO–(Y2O3–La2O3)–MnO2–CuOx multi-component system is non-binary. At 810 °C (pO2 = 100 Pa) and at 950 °C in purified air, four phases are consistently present along the join, namely, Ba2?x(La1+x?yYy)Cu3O6+z, Ba(Y2?xLax)CuO5, (La1?xYx)MnO3, (La,Y)Mn2O5. The crystal chemistry and crystallography of Ba(Y2?xLax)CuO5 and (La1?xYx)Mn2O5 were studied using the X-ray Rietveld refinement technique. The Y-rich and La-rich solid solution limits for Ba(Y2?xLax)CuO5 are Ba(Y1.8La0.2)CuO5 and Ba(Y0.1La1.9)CuO5, respectively. The structure of Ba(Y1.8La0.2)CuO5 is Pnma (No. 62), a = 12.2161(5) Å, b = 5.6690(2) Å, c = 7.1468(3) Å, V = 494.94(4) Å3, and Dx = 6.29 g cm?3. YMn2O5 and LaMn2O5 do not form solid solution at 810 °C (pO2 = 100 Pa) or at 950 °C (in air). The structure of YMn2O5 was confirmed to be Pbam (No. 55), a = 7.27832(14) Å, b = 8.46707(14) Å, c = 5.66495(10) Å, and V = 349.108(14) Å3. A reference X-ray pattern was prepared for YMn2O5.  相似文献   

20.
The growth of ultrathin films of Y2O3(111) on Pt(111) has been studied using scanning tunneling microscopy (STM), X-ray photoemission spectroscopy (XPS), and low energy electron diffraction (LEED). The films were grown by physical vapor deposition of yttrium in a 10? 6 Torr oxygen atmosphere. Continuous Y2O3(111) films were obtained by post-growth annealing at 700 °C. LEED and STM indicate an ordered film with a bulk-truncated Y2O3(111)–1 × 1 structure exposed. Furthermore, despite the lattices of the substrate and the oxide film being incommensurate, the two lattices exhibit a strict in-plane orientation relationship with the [11?0] directions of the two cubic lattices aligning parallel to each other. XPS measurements suggest hydroxyls to be easily formed at the Y2O3 surface at room temperature even under ultra high vacuum conditions. The hydrogen desorbs from the yttria surface above ~ 200 °C.  相似文献   

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