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1.
Partial conductivities in the SrCe(Y)O3−δ system have been studied in oxidising conditions in the temperature range 923–1273 K. Compositions with variable Y content (5 and 10 at.%), Sr deficiency (3 at.%), and with the addition of Fe2O3 as sintering aid (2 mol%) were analysed. A modified Faradaic efficiency method and oxygen permeation measurements were employed to appraise the oxide-ionic transport. Oxide-ion transference numbers in air lie in the range 0.19–0.80 and decrease with increasing temperature in the range 973–1223 K. Modelling of total conductivity as a function of oxygen partial pressure (p(O2)) confirmed that protonic transport is minor under the studied conditions. SrCe0.95Y0.05O3−δ exhibits greater oxide-ion conductivity than SrCe0.9Y0.1O3−δ, indicative of dopant–vacancy association at high dopant contents. Conversely, oxygen permeability is slightly higher for SrCe0.9Y0.1O3−δ as a result of faster surface-exchange kinetics. The oxygen flux through Fe-free membranes is dominated by the bulk in low p(O2) gradients, when the permeate-side p(O2) is higher than 0.03 atm, but surface exchange plays an increasing role with increasing p(O2) gradient. Addition of Fe2O3 to SrCe(Y)O3−δ lowers the sintering temperature by 100 K but results in the formation of intergranular second phases which block oxide-ionic and electronic transport, and thus oxygen permeation. The average thermal expansion coefficients (TECs) are (10.8–11.6) × 10−6 K−1 in the temperature range 373–1373 K for all studied compositions.  相似文献   

2.
The sintering behavior and dielectric properties of the monoclinic zirconolite-like structure compound Bi2(Zn1/3Nb2/3)2O7 (BZN) and Bi2(Zn1/3Nb2/3−xVx)2O7 (BZNV, x = 0.001) sintered under air and N2 atmosphere were investigated. The pure phase were obtained between 810 and 990 °C both for BZN and BZNV ceramics. The substitution of V2O5 and N2 atmosphere accelerated the densification of ceramics slightly. The influences on microwave dielectric properties from different atmosphere were discussed in this work. The best microwave properties of BZN ceramics were obtained at 900 °C under N2 atmosphere with r = 76.1, Q = 850 and Qf = 3260 GHz while the best properties of BZNV ceramics were got at 930 °C under air atmosphere with r = 76.7, Q = 890 and Qf = 3580 GHz. The temperature coefficient of resonant frequency τf was not obviously influenced by the different atmospheres. For BZN ceramics the τf was −79.8 ppm/°C while τf is −87.5 ppm/°C for BZNV ceramics.  相似文献   

3.
In the present study, the C3H8 decomposition reaction is studied in a double-chamber proton-conducting cell-reactor. The proton conductor was a strontia–ceria–ytterbia perovskite disk of the form: SrCe0.95Yb0.05O3−. The working electrode-catalyst was either Pt or Pd, in the form of a polycrystalline film. The reaction temperature varied between 923 and 1023 K and the partial pressure of propane in the feed gas was 2 kPa. The hydrogen produced by the reaction was electrochemically transported through the walls of the proton-conducting disk, to the outer reactor-chamber. The two electrodes (Pt and Pd) are compared in terms of their catalytic and electrocatalytic activities.  相似文献   

4.
In order to elucidate the superior start-up activity of LaFePdOx catalysts in practical automotive emission control, the redox property of Pd species in a Perovskite-type LaFe0.95Pd0.05O3 catalyst was studied at temperatures ranging from 100 to 400 °C using X-ray spectroscopic techniques. In a reductive atmosphere, and even at temperatures as low as 100 °C, Pd0 species is partially segregated out onto the catalyst surface from the B-site of the Perovskite-type matrix of LaFe0.95Pd0.05O3. Passing through successive oxidizing atmospheres, the segregated Pd0 species is re-oxidized into Pd2+ at 200–300 °C. The formation of a solid solution between the re-oxidized Pd species and the Perovskite-type matrix begins to be seen at around 400 °C and accelerates at higher temperatures. Thus a quasi-reversible redox reaction between the surface Pd0 and the cationic Pd in the LaFe0.95Pd0.05O3 matrix takes place. The start-up activity of LaFePdxOx catalysts can be attributed to Pd0 that segregates under the reductive atmosphere which is a natural part of the redox fluctuation in automotive exhaust gases at 100–200 °C.  相似文献   

5.
Nanometer perovskite-type oxides La1−xSrxMO3−δ (M = Co, Mn; x = 0, 0.4) have been prepared using the citric acid complexing-hydrothermal-coupled method and characterized by means of techniques, such as X-ray diffraction (XRD), BET, high-resolution scanning electron microscopy (HRSEM), X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption (TPD), and temperature-programmed reduction (TPR). The catalytic performance of these nanoperovskites in the combustion of ethylacetate (EA) has also been evaluated. The XRD results indicate that all the samples possessed single-phase rhombohedral crystal structures. The surface areas of these nanomaterials ranged from 20 to 33 m2 g−1, the achievement of such high surface areas are due to the uniform morphology with the typical particle size of 40–80 nm (as can be clearly seen in their HRSEM images) that were derived with the citric acid complexing-hydrothermally coupled strategy. The XPS results demonstrate the presence of Mn4+ and Mn3+ in La1−xSrxMnO3−δ and Co3+ and Co2+ in La1−xSrxCoO3−δ, Sr substitution induced the rises in Mn4+ and Co3+ concentrations; adsorbed oxygen species (O, O2, or O22−) were detected on the catalyst surfaces. The O2-TPD profiles indicate that Sr doping increased desorption of the adsorbed oxygen and lattice oxygen species at low temperatures. The H2-TPR results reveal that the nanoperovskite catalysts could be reduced at much lower temperatures (<240 °C) after Sr doping. It is observed that under the conditions of EA concentration = 1000 ppm, EA/oxygen molar ratio = 1/400, and space velocity = 20,000 h−1, the catalytic activity (as reflected by the temperature (T100%) for EA complete conversion) increased in the order of LaCoO2.91 (T100% = 230 °C) ≈ LaMnO3.12 (T100% = 235 °C) < La0.6Sr0.4MnO3.02 (T100% = 190 °C) < La0.6Sr0.4CoO2.78 (T100% = 175 °C); furthermore, there were no formation of partially oxidized by-products over these catalysts. Based on the above results, we conclude that the excellent catalytic performance is associated with the high surface areas, good redox properties (derived from higher Mn4+/Mn3+ and Co3+/Co2+ ratios), and rich lattice defects of the nanostructured La1−xSrxMO3−δ materials.  相似文献   

6.
Bearing in mind the excellent dielectric properties at high frequency of some niobates like ZnNb2O6, Zn3Nb2O8, BaNb2O6, Ba5Nb4O15 (r 20–45, tan δ < 10 × 10−4 and ρi > 1010 Ω cm), synthesis, sintering and properties of these oxides are reported. The lowering of their sintering temperature has been investigated for these four ceramics using sintering aids. Using appropriate additive, it is possible to densify these ceramics at a temperature for which base metal electrodes, e.g. Cu and Ag can be employed. Two formulations were found to be sinterable at 1000 °C (lower than the copper melting point) whereas a third formulation is co-sinterable with silver electrodes. For this later, the dielectric properties are globally maintained in comparison with the pure compound sintered at 1200 °C. This result makes this formulation suitable for silver based passive components devices manufacturing.  相似文献   

7.
The water gas shift (WGS) reaction was studied in a double-chamber high temperature proton conducting cell (HTPC). The proton conductor was a strontia–ceria–ytterbia (SCY) disk of the form: SrCe0.95Yb0.05O3− and the working electrode was a polycrystalline Fe film. The reaction temperature and the inlet partial pressure of CO varied between 823 and 973 K, and between 1.0 and 10.6 kPa, respectively. The inlet partial pressure of steam (PH2O) was kept constant at 2.3 kPa. An increase in the production of H2 was observed upon “pumping” protons away from the catalyst surface. The Faradaic efficiency (Λ) was lower than unity, indicating a sub-Faradaic effect. The highest value of rate enhancement ratio (ρ) was approximately 3.2, at T = 823 K. The proton transport number (PTN) varied between 0.45 and 1.0. An up to 99% of the produced H2 was electrochemically separated from the reaction mixture.  相似文献   

8.
Ten weight percent BBZS (Bi2O3, B2O3, ZnO and SiO2) glass was added to x(Ba4Nd9.333Ti18O54) − (1 − x)(BaLa4Ti4O15) (BNLT, 0 ≤ x ≤ 1) composite dielectric ceramics to lower their sintering temperature whilst retaining microwave properties useful for low temperature co-fired ceramic and antenna core technology. With the addition of 10 wt% BBZS glass, dense BNLT composite ceramics were produced at temperatures between 950 and 1140 °C, depending on composition (x), an average reduction of sintering temperature by 350 °C. X-ray diffraction, scanning and transmission electron microscopy and Raman spectroscopy studies revealed that there was limited inter-reaction between BLT/BNT and the BBZS glass. Microwave property measurement showed that the addition of BBZS glass to BNLT ceramics had a negligible effect on r and τf, although deterioration in the measured quality factor (Qf) was observed. The optimised composition (xBNT − (1 − x)BLT)/0.1BBZS (x = 0.75) had r  61, τf  38 ppm/°C and Qf  2305 GHz.  相似文献   

9.
SrCe1 − xYxO3 − δ (x = 0.1, 0.2) high temperature proton conductors (HTPC) have been fabricated by directional solidification using a laser-heated float zone (LHFZ) method. The resulting microstructures have been studied using scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and electron backscatter diffraction (EBSD). The LHFZ method produces a cellular microstructure consisting of crystalline cells embedded in an amorphous matrix, showing a strong biaxial texture. EBSD studies show that all the crystalline cells have their <0 0 1> axis as described in the cubic Pm3m prototype unit cell parallel to the growth direction. The observed microstructural features are explained in terms of the fabrication process.  相似文献   

10.
To clarify the effect of substitutional electron doping on the thermoelectric figure of merit (ZT = S2σTκ−1) of Ruddlesden–Popper phase SrO(SrTiO3)n (or Srn+1TinO3n+1), measurements were conducted for several thermoelectric parameters, e.g. electrical conductivity (σ), Seebeck coefficient (S) and thermal conductivity (κ), of (Sr1−xREx)n+1TinO3n+1 (n = 1 or 2, RE (rare earth): La or Nd, x = 0.05 and 0.1) dense ceramics prepared by a conventional solid-state reaction and hot-pressing technique. Crystal structures of the resultant ceramics were represented as (Sr1−xREx)n+1 TinO3n+1 evaluated by powder X-ray diffraction followed by the Rietveld analysis. All the ceramics exhibited electrical conductivity and the σ values simply depended on the dopant concentration, indicating that both La3+ and Nd3+ ions act as electron donors. The |S| values increased with temperature due to decrease in the chemical potential. Significant reduction of the κ values was observed as compared to cubic-perovskite SrTiO3. The ZT value increased with temperature and reached 0.15 at 1000 K for (Sr0.95La0.05)3Ti2O7.  相似文献   

11.
Nanoparticles of CexZr1−xO2 (x = 0.75, 0.62) were prepared by the oxidation-coprecipitation method using H2O2 as an oxidant, and characterized by N2 adsorption, XRD and H2-TPR. CexZr1−xO2 prepared had single fluorite cubic structure, good thermal stability and reduction property. With the increasing of Ce/Zr ratio, the surface area of CexZr1−xO2 increased, but thermal stability of CexZr1−xO2 decreased. The surface area of Ce0.62Zr0.38O2 was 41.2 m2/g after calcination in air at 900 °C for 6 h. TPR results showed the formation of solid solution promoted the reduction of CeO2, and the reduction properties of CexZr1−xO2 were enhanced by the cycle of TPR-reoxidation. The Pd-only three-way catalysts (TWC) were prepared by the impregnation method, in which Ce0.75Zr0.25O2 was used as the active washcoat and Pd loading was 0.7 g/L. In the test of Air/Fuel, the conversion of C3H8 was close to 100% and NO was completely converted at λ < 1.025. The high conversion of C3H8 was induced by the steam reform and dissociation adsorption reaction of C3H8. Pd-only catalyst using Ce0.75Zr0.25O2 as active washcoat showed high light off activity, the reaction temperatures (T50) of 50% conversion of CO, C3H8 and NO were 180, 200 and 205 °C, respectively. However, the conversions of C3H8 and NO showed oscillation with continuously increasing the reaction temperature. The presence of La2O3 in washcoat decreased the light off activity and suppressed the oscillation of C3H8 and NO conversion. After being aged at 900 °C for 4 h, the operation windows of catalysts shifted slightly to rich burn. The presence of La2O3 in active washcoat can enhance the thermal stability of catalyst significantly.  相似文献   

12.
The catalytic oxidation of unsymmetrical dimethylhydrazine (UDMH) by air has been studied in a vibro-fluidized catalyst bed laboratory kinetic setup over catalysts CuxMg1−xCr2O4/γ-Al2O3, 32.9%Ir/γ-Al2O3 and β-Si3N4 in a temperature range 150–400 °C. The catalyst CuxMg1−xCr2O4/γ-Al2O3 was found to be optimal regarding high yields of CO2 and low yields of NOx. A probable mechanism of UDMH heterogeneous catalytic oxidation is proposed. Catalyst CuxMg1−xCr2O4/γ-Al2O3 has been further used in the pilot plant specially designed for the destruction of UDMH. Results of testing the main fluidized bed catalytic reactor for UDMH oxidation and the reactor for selective catalytic reduction of NOx with NH3 are presented. These results prove that the developed UDMH destruction technology is highly efficient and environmentally safe.  相似文献   

13.
Compounds with the general formula SrCe1−xYbxO3-0.5x have been characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), temperature programmed reduction (TPR) and BET, and tested for catalytic activity with respect to dehydrogenation of ethane to ethene. XRD indicates that the solubility limit of Yb2O3 in SrCeO3 is about 10 %, above which a second phase is formed. Furthermore, Yb:SrCeO3 is unstable in the presence of CO2 as it reacts to SrCO3 and Yb:CeO2. TPR measurements indicate that Ce may be reduced from tetra- to the trivalent state. BET measurements yielded specific surface areas of approximately 1m2/g. The different catalyst compositions were tested in a continuous flow tubular reactor with two different partial pressures of oxygen at 500, 600 and 700 °C. A maximum yield of 49 % was obtained at 700 °C. Possible reaction mechanisms are discussed.  相似文献   

14.
An aqueous (NH4)2CO3 coprecipitation method, based on that of Groppi et al. [Appl. Catal. A 104 (1993) 101–108] was used to synthesize Sr1−xLaxMnAl11O19− hexaaluminates. These materials were first synthesized by alkoxide hydrolysis. This synthesis route requires special handling of the starting materials and is not likely to be commercially practical. The materials prepared by (NH4)2CO3 coprecipitation have similar surface areas as those prepared by the alkoxide hydrolysis method. Their CH4 oxidation activity, measured as the temperature needed for 10% conversion of methane, is higher than those prepared by alkoxide hydrolysis. The La-substantiated material, LaMnAl11O19−, shows high surface area with 19.3 m2/g after calcination at 1400°C for 2 h. It is active for CH4 oxidation with T10% at 450°C using 1% CH4 in air and 70 000 cm3/h g space velocity. The stability and activity of LaMnAl11O19− prepared by (NH4)2CO3 coprecipitation method is a simple and important step forward for the application of CH4 catalytic combustion for gas turbines.  相似文献   

15.
Several hexaaluminate-related materials were prepared via hydrolysis of alkoxide and powder mixing method for high temperature combustion of CH4 and C3H8, in order to investigate the effect of the concentration of the fuels, O2 and H2O on NOx emission and combustion characteristics. Among the hexaaluminate catalysts, Sr0.8La0.2MnAl11O19− prepared by the alkoxide method exhibited the highest activity for methane combustion and low NOx emission capability. NOx emission at 1500 °C was increased linearly with O2 concentration, whereas water vapor addition decreased NOx emission in CH4 combustion over the Sr0.8La0.2MnAl11O19− catalyst. In the catalytic combustion of C3H8 over the Sr0.8La0.2MnAl11O19− catalyst, the amount of NOx emitted was raised in the temperature range between 1000 and 1500 °C when the C3H8 concentration increased from 1 to 2 vol.%. It was found that NOx emission in this temperature range was reduced effectively by adding water vapor.  相似文献   

16.
Supported LaCoO3 perovskites with 10 and 20 wt.% loading were obtained by wet impregnation of different Ce1−xZrxO2 (x = 0–0.3) supports with a solution prepared from La and Co nitrates, and citric acid. Supports were also prepared using the “citrate method”. All materials were calcined at 700 °C for 6 h and investigated by N2 adsorption at −196 °C, XRD and XPS. XRD patterns and XPS measurements evidenced the formation of a pure perovskite phase, preferentially accumulated at the outer surface. These materials were comparatively tested in benzene and toluene total oxidation in the temperature range 100–500 °C. All catalysts showed a lower T50 than the corresponding Ce1−xZrxO2 supports. Twenty weight percent LaCoO3 catalysts presented lower T50 than bulk LaCoO3. In terms of reaction rates per mass unit of perovskite calculated at 300 °C, two facts should be noted (i) the activity order is more than 10 times higher for toluene and (ii) the reverse variation with the loading as a function of the reactant, a better activity being observed for low loadings in the case of benzene. For the same loading, the support composition influences drastically the oxidative abilities of LaCoO3 by the surface area and the oxygen mobility.  相似文献   

17.
The influence of catalyst pre-treatment temperature (650 and 750 °C) and oxygen concentration (λ = 8 and 1) on the light-off temperature of methane combustion has been investigated over two composite oxides, Co3O4/CeO2 and Co3O4/CeO2–ZrO2 containing 30 wt.% of Co3O4. The catalytic materials prepared by the co-precipitation method were calcined at 650 °C for 5 h (fresh samples); a portion of them was further treated at 750 °C for 7 h, in a furnace in static air (aged samples).

Tests of methane combustion were carried out on fresh and aged catalysts at two different WHSV values (12 000 and 60 000 mL g−1 h−1). The catalytic performance of Co3O4/CeO2 and Co3O4/CeO2–ZrO2 were compared with those of two pure Co3O4 oxides, a sample obtained by the precipitation method and a commercial reference. Characterization studies by X-ray diffraction (XRD), BET and temperature-programmed reduction (TPR) show that the catalytic activity is related to the dispersion of crystalline phases, Co3O4/CeO2 and Co3O4/CeO2–ZrO2 as well as to their reducibility. Particular attention was paid to the thermal stability of the Co3O4 phase in the temperature range of 750–800 °C, in both static (in a furnace) and dynamic conditions (continuous flow). The results indicate that the thermal stability of the phase Co3O4 heated up to 800 °C depends on the size of the cobalt oxide crystallites (fresh or aged samples) and on the oxygen content (excess λ = 8, stoichiometric λ = 1) in the reaction mixture. A stabilizing effect due to the presence of ceria or ceria–zirconia against Co3O4 decomposition into CoO was observed.

Moreover, the role of ceria and ceria–zirconia is to maintain a good combustion activity of the cobalt composite oxides by dispersing the active phase Co3O4 and by promoting the reduction at low temperature.  相似文献   


18.
Nanosized particles dispersed uniformly on Al2O3 particles were prepared from the decomposition of precursor Cr(CO)6 by metal organic chemical vapor deposition (MOCVD) in a fluidized chamber. These nanosized particles consisted of Cr2O3, CrC1−x, and C. A solid solution of Al2O3–Cr2O3 and an Al2O3–Cr2O3/Cr3C2 nanocomposite were formed when these fluidized powders were pre-sintered at 1000 and 1150 °C before hot-pressing at 1400 °C, respectively. In addition, an Al2O3–Cr2O3/Cr-carbide (Cr3C2 and Cr7C3) nanocomposite was formed when the particles were directly hot pressed at 1400 °C. The interface between Cr3C2 and Al2O3 is non-coherent, while the interface between Cr7C3 and Al2O3 is semi-coherent.  相似文献   

19.
Ceramics with a composition close to BaZn2Ti4O11 were synthesized according to various substitutional mechanisms in order to verify an existence of a homogeneity range in the vicinity of this composition. Structural and microstructural investigations showed that the crystal structure of BaZn2Ti4O11 was formed in the homogeneity range corresponding to the formula BaZn2 − xTi4O11 − x (0 < x < 0.1). Densely sintered BaZn2 − xTi4O11 − x (0 < x < 0.1) ceramics exhibited a dielectric constant around 30, τf = −30 ppm/K and high Q × f values, which increased from 68,000 GHz at x = 0 to 83,000 GHz at x = 0.05. Structurally, the deficiency of Zn in BaZn2 − xTi4O11 − x (0 < x < 0.1) resulted in a slight decrease in the unit-cell volume. The influence of secondary phases in the BaZn2Ti4O11-based materials on the microwave dielectric properties was also investigated. A presence of small amounts of ZnO, BaTiO3, hollandite-type solid solutions (BaxZnxTi8 − xO16) and BaTi4O9 caused a decrease in Q × f values.  相似文献   

20.
Zr-substituted,Tm-doped SrCeO3(SrCe0.95-xZrxTm0.05O3-δ,0≤x≤0.40)were synthesized via citrate complexing method,and the membranes of SrCe0.95-xZrxTm0.05O3-δwere prepared by pressing followed by sintering. X-ray diffraction(XRD)was used to characterize the phase structure of sintered membrane.The microstructure of the sintered membranes was studied by scanning electron microscopy(SEM).Protonic and electronic conductivities were measured under different circumstance.Hydrogen permeation through the SrCe0.75Zr0.20Tm0.05O3-δmembranes was carried out using gas permeation setup.Hydrogen permeation fluxes( 2H J)of the SrCe0.75Zr0.20Tm0.05O3-δ membrane reach up to 0.042 ml·min -1 ·cm-2 at H 2 partial pressure of 0.4×10 5 Pa at 900°C.The hydrogen permea- tion fluxes( 2H J)obtained in this paper are slightly lower than that of SrCe0.95Tm0.05O3-δon the same orders,and Zr doping can increase chemical stability of the SrCe0.75Zr0.20Tm0.05O3-δmembranes.  相似文献   

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