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1.
Partial conductivities in the SrCe(Y)O 3−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 Fe 2O 3 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(O 2)) confirmed that protonic transport is minor under the studied conditions. SrCe 0.95Y 0.05O 3−δ exhibits greater oxide-ion conductivity than SrCe 0.9Y 0.1O 3−δ, indicative of dopant–vacancy association at high dopant contents. Conversely, oxygen permeability is slightly higher for SrCe 0.9Y 0.1O 3−δ as a result of faster surface-exchange kinetics. The oxygen flux through Fe-free membranes is dominated by the bulk in low p(O 2) gradients, when the permeate-side p(O 2) is higher than 0.03 atm, but surface exchange plays an increasing role with increasing p(O 2) gradient. Addition of Fe 2O 3 to SrCe(Y)O 3−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.
Moderate additions of Al 2O 3 to strontium ferrite-based mixed conductors, such as SrFe 0.7Al 0.3O 3−δ and La 0.2Sr 0.8Fe 0.8Ga 0.2O 3−δ with the composition close to the solid solution formation limits, make it possible to improve ceramics sinterability, to increase oxygen permeability and to decrease thermal expansion. These effects are associated with the segregation of alumina-rich phases, primarily SrAl 2O 4, and the formation of A-site cation-deficient perovskite. The improved properties of the SrFe 0.7Al 0.3O 3-based material were used to fabricate high-quality tubular membranes for methane conversion reactors. Similar enhancement in sinterability is also observed for another promising parent material of mixed-conducting membranes, La 0.5Sr 0.5FeO 3−δ. However, extensive dissolution of Al 3+ cations in the iron sublattice, creation of A-site vacancies and changing the La:Sr concentration ratio all lead to decreasing ionic transport in La 0.5Sr 0.5FeO 3−δ. As a result, additions of either Al 2O 3 or SrAl 2O 4 have a deteriorating influence on the oxygen permeation fluxes through La 0.5Sr 0.5FeO 3-based ceramics. 相似文献
3.
Nanometer perovskite-type oxides La 1−xSr xMO 3−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 m 2 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 Mn 4+ and Mn 3+ in La 1−xSr xMnO 3−δ and Co 3+ and Co 2+ in La 1−xSr xCoO 3−δ, Sr substitution induced the rises in Mn 4+ and Co 3+ concentrations; adsorbed oxygen species (O −, O 2−, or O 22−) were detected on the catalyst surfaces. The O 2-TPD profiles indicate that Sr doping increased desorption of the adsorbed oxygen and lattice oxygen species at low temperatures. The H 2-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 LaCoO 2.91 ( T100% = 230 °C) ≈ LaMnO 3.12 ( T100% = 235 °C) < La 0.6Sr 0.4MnO 3.02 ( T100% = 190 °C) < La 0.6Sr 0.4CoO 2.78 ( 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 Mn 4+/Mn 3+ and Co 3+/Co 2+ ratios), and rich lattice defects of the nanostructured La 1−xSr xMO 3−δ materials. 相似文献
4.
The sintering properties of La 1−xSr xFeO 3−δ ( x = 0.1, 0.25) mixed conductors have been investigated with particular emphasis on the effect of secondary phases due to cation non-stoichiometry (±5 mol% La excess and deficiency). Secondary phases, located at grain boundaries in cation non-stoichiometric materials, increased the sintering temperature compared to single-phase materials. Extensive swelling in final stage of sintering was observed in all materials, which resulted in micro-porous materials. The swelling was most pronounced in the phase pure and two-phase materials due to La-deficiency, while refractory secondary phases in La-excess materials inhibited both sintering, grain growth and swelling. In La-deficient materials, formation of molten secondary phases resulted in rapid swelling due to viscous flow. The present findings demonstrated the importance of controlling sintering temperature and time, as well as careful control of the cation stoichiometry of La 1−xSr xFeO 3−δ in order to achieve fully dense and homogenous La 1−xSr xFeO 3−δ ceramics. 相似文献
5.
This paper reports the application of mixed conducting perovskite membranes for simultaneous in situ O 2 separation and catalytic oxidation of ammonia to nitric oxide. Calcium and strontium-substituted lanthanum ferrite perovskites (La 1−xA xFeO 3−δ, with A = Ca, Sr and x = 0.1–0.2) were prepared by a conventional wet complexation route with citric acid. Dense membrane disks were obtained by uniaxial pressing of the calcined powders followed by sintering. The oxidation of ammonia over these catalytic membranes in the temperature range of 1000–1333 K leads to NO selectivities up to 98% with no N 2O production, showing stable performance during several days on stream. This novel process demonstrates the great potential for intensification of nitric acid manufacture into miniaturized plants and is considered to be particularly attractive for on-site production of this important bulk chemical. 相似文献
6.
Powders of pure and 5% ytterbium substituted strontium cerate (SrCeO 3/SrCe 0.95Yb 0.05O 3−δ) were prepared by spray pyrolysis of nitrate salt solutions. The powders were single phase after calcination in nitrogen atmosphere at 1100 °C (SrCeO 3) and 1200 °C (SrCe 0.95Yb 0.05O 3−δ). Dense SrCeO 3 and SrCe 0.95Yb 0.05O 3−δ materials were obtained by sintering at 1350–1400 °C in air. Heat treatment at 850 and 1000 °C, respectively, was necessary prior to sintering to obtain high density. The dense materials had homogenous microstructures with grain size in the range 6–10 μm for SrCeO 3 and 1–2 μm for SrCe 0.95Yb 0.05O 3−δ. The electrical conductivity of SrCe 0.95Yb 0.05O 3−δ was in good agreement with reported data, showing mixed ionic–electronic conduction. The ionic contribution was dominated by protons below 1000 °C and the proton conductivity reached a maximum of 0.005 S/cm above 900 °C. In oxidizing atmosphere the p-type electronic conduction was dominating above 700 °C, while the contribution from n-type electronic conduction only was significant above 1000 °C in reducing atmosphere. 相似文献
7.
Defective structures, surface textures, oxygen mobility, oxygen storage capacity (OSC), and redox properties of RE 0.6Zr 0.4O 2 and of RE 0.6Zr 0.4−xY xO 2 (RE=Ce, Pr; x=0, 0.05) solid solutions have been investigated using X-ray diffraction (XRD), temperature-programmed desorption (TPD), temperature-programmed reduction (TPR), O 2−H 2 and O 2−CO titration, 18O/ 16O isotope exchange, CO pulsing reaction, and X-ray photoelectron spectroscopy (XPS) techniques. The effects of doping noble metal onto RE 0.6Zr 0.4−xY xO 2 on oxygen mobility and surface oxygen activities have also been studied. Based on the experimental outcomes, we conclude that: (i) a Pr-based solid solution has better redox behavior than a Ce-based one; (ii) incorporation of yttrium ions in the lattices of CZ and PZ solid solutions could result in an enhancement in oxygen vacancy concentration, Ce 4+/Ce 3+ and Pr 4+/Pr 3+ redox properties, lattice oxygen mobility, and oxygen storage capacity; and (iii) doping the noble metal (Rh, Pt, and Pd) onto RE-based solid solution has positive effect on the properties concerned in this work. 相似文献
8.
Direct nitric oxide decomposition over perovskites is fairly slow and complex, its mechanism changing dramatically with temperature. Previous kinetic study for three representative compositions (La 0.87Sr 0.13Mn 0.2Ni 0.8O 3−δ, La 0.66Sr 0.34Ni 0.3Co 0.7O 3−δ and La 0.8Sr 0.2Cu 0.15Fe 0.85O 3−δ) has shown that depending on the temperature range, the inhibition effect of oxygen either increases or decreases with temperature. This paper deals with the effect of CO 2, H 2O and CH 4 on the nitric oxide decomposition over the same perovskites studied at a steady-state in a plug-flow reactor with 1 g catalyst and total flowrates of 50 or 100 ml/min of 2 or 5% NO. The effect of carbon dioxide (0.5–10%) was evaluated between 873 and 923 K, whereas that of H 2O vapor (1.6 or 2.5%) from 723 to 923 K. Both CO 2 and H 2O inhibit the NO decomposition, but inhibition by CO 2 is considerably stronger. For all three catalysts, these effects increase with temperature. Kinetic parameters for the inhibiting effects of CO 2 and H 2O over the three perovskites were determined. Addition of methane to the feed (NO/CH 4=4) increases conversion of NO to N 2 about two to four times, depending on the initial NO concentration and on temperature. This, however, is still much too low for practical applications. Furthermore, the rates of methane oxidation by nitric oxide over perovskites are substantially slower than those of methane oxidation by oxygen. Thus, perovskites do not seem to be suitable for catalytic selective NO reduction with methane. 相似文献
9.
(Mg 1−xZn x) 2SiO 4 ceramics were prepared and characterized. The densification temperatures of the present ceramics are much lower than those for Mg 2SiO 4 and Zn 2SiO 4 end-members. Small solid solution limits of Zn in Mg 2SiO 4 and Mg in Zn 2SiO 4 are observed, and the bi-phase structure is confirmed in (Mg 1−xZn x) 2SiO 4 ceramics with x = 0.1–0.9. Even though, it is clear that the Qf value of Zn 2SiO 4 ceramics can be significantly improved together with a suppressed temperature coefficient of resonant frequency τf by substituting Mg for Zn. (Mg 0.4Zn 0.6) 2SiO 4 ceramics indicate a good combination of microwave dielectric characteristics: r = 6.6 Qf = 95,650 GHz, and τf = −60 ppm/°C. 相似文献
10.
Catalytic methane combustion and CO oxidation were investigated over AFeO 3 (A=La, Nd, Sm) and LaFe 1−xMg xO 3 ( x=0.1, 0.2, 0.3, 0.4, 0.5) perovskites prepared by citrate method and calcined at 1073 K. The catalysts were characterized by X-ray diffraction (XRD). Redox properties and the content of Fe 4+ were derived from temperature programmed reduction (TPR). Specific surface areas (SA) of perovskites were in 2.3–9.7 m 2 g −1 range. XRD analysis showed that LaFeO 3, NdFeO 3, SmFeO 3 and LaFe 1−xMg xO 3 ( x·0.3) are single phase perovskite-type oxides. Traces of La 2O 3, in addition to the perovskite phase, were detected in the LaFe 1−xMg xO 3 catalysts with x=0.4 and 0.5. TPR gave evidence of the presence in AFeO 3 of a very small fraction of Fe 4+ which reduces to Fe 3+. The fraction of Fe 4+ in the LaFe 1−xMg xO 3 samples increased with increasing magnesium content up to x=0.2, then it remained nearly constant. Catalytic activity tests showed that all samples gave methane and CO complete conversion with 100% selectivity to CO 2 below 973 and 773 K, respectively. For the AFeO 3 materials the order of activity towards methane combustion is La>Nd>Sm, whereas the activity, per unit SA, of the LaFe 1−xMg xO 3 catalysts decreases with the amount of Mg at least for the catalysts showing a single perovskite phase ( x=0.3). Concerning the CO oxidation, the order of activity for the AFeO 3 materials is Nd>La>Sm, while the activity (per unit SA) of the LaFe 1−xMg xO 3 catalysts decreases at high magnesium content. 相似文献
11.
The impact of oxygen permeability using an ionic oxygen conducting membrane reactor with surface catalyst was investigated for the oxidative coupling of methane to higher hydrocarbons. Dense Ba 0.5Sr 0.5Co 0.8Fe 0.2O 3−δ (BSCFO), Ba 0.5Sr 0.5Mn 0.8Fe 0.2O 3−δ (BSMFO) and BaBi 0.4Fe 0.6O 3 (BBFO) membrane disks with Pt/MgO catalysts were prepared by sol–gel deposition or wash-coating. It is demonstrated that the oxygen supply by permeation needs to fit to the consumption during the coupling reaction. In case of insufficient oxygen supply comparably poor conversions are observed while higher oxygen fluxes lead to increased methane conversions, especially in the presence of an efficient catalyst. Generally, increasing catalytic activity leads to lower C 2 selectivity, especially for low oxygen permeation fluxes. The concept of a reactor employing dense catalytic membranes is viable, but the present study identifies further potential when the activity of the catalyst for the oxidative coupling is improved, leading to an overall enhanced performance of the membrane reactor. 相似文献
12.
The emissions of CO 2, NO x and SO 2 from the combustion of a high-volatile coal with N 2- and CO 2-based, high O 2 concentration (20, 50, 80, 100%) inlet gases were investigated in an electrically heated up-flow-tube furnace at elevated gas temperatures (1123–1573 K). The fuel equivalence ratio, φ, was varied in the range of 0.4–1.6. Results showed that CO 2 concentrations in flue gas were higher than 95% for the processes with O 2 and CO 2-based inlet gases. NO x emissions increased with φ under fuel-lean conditions, then declined dramatically after φ=0.8, and the peak values increased from about 1000 ppm for the air combustion process and 500 ppm for the O 2(20%)+CO 2(80%) inlet gas process to about 4500 ppm for the oxygen combustion process. When φ>1.4 the emissions decreased to the same level for different O 2 concentration inlet gas processes. On the other hand, NO x emission indexes decreased monotonically with φ under both fuel-lean and fuel-rich combustion. SO 2 emissions increased with φ under fuel-lean conditions, then declined slightly after φ>1.2. Temperature has a large effect on the NO x emission. Peak values of the NO x emission increased by 50–70% for the N 2-based inlet gas processes and by 30–50% for the CO 2-based inlet gas process from 1123 to 1573 K. However, there was only a small effect of temperature on the SO 2 emission. 相似文献
13.
Catalytic combustion of methane has been investigated over AMnO 3 (A = La, Nd, Sm) and Sm 1−xSr xMnO 3 ( x = 0.1, 0.3, 0.5) perovskites prepared by citrate method. The catalysts were characterized by chemical analysis, XRD and TPR techniques. Catalytic activity measurements were carried out with a fixed bed reactor at T = 623–1023 K, space velocity = 40 000 N cm 3 g −1 h −1, CH 4 concentration = 0.4% v/v, O 2 concentration = 10% v/v. Specific surface areas of perovskites were in the range 13–20 m2 g−1. XRD analysis showed that LaMnO3, NdMnO3, SmMnO3 and Sm1−xSrxMnO3 (x = 0.1) are single phase perovskite type oxides. Traces of Sm2O3 besides the perovskite phase were detected in the Sm1−xSrxMnO3 catalysts for x = 0.3, 0.5. Chemical analysis gave evidence of the presence of a significant fraction of Mn(IV) in AMnO3. The fraction of Mn(IV) in the Sm1−xSrxMnO3 samples increased with x. TPR measurements on AMnO3 showed that the perovskites were reduced in two steps at low and high temperature, related to Mn(IV) → Mn(III) and Mn(III) → Mn(II) reductions, respectively. The onset temperatures were in the order LaMnO3 > NdMnO3 > SmMnO3. In Sm1−xSrxMnO3 the Sr substitution for Sm caused the formation of Mn(IV) easily reducible to Mn(II) even at low temperature. Catalytic activity tests showed that all samples gave methane complete conversion with 100% selectivity to CO2 below 1023 K. The activation energies of the AMnO3 perovskites varied in the same order as the onset temperatures in TPR experiments suggesting that the catalytic activity is affected by the reducibility of manganese. Sr substitution for Sm in SmMnO3 perovskites resulted in a reduction of activity with respect to the unsubstituted perovskite. This behaviour was related to the reduction of Mn(IV) to Mn(II), occurring under reaction conditions, hindering the redox mechanism. 相似文献
14.
Graded Pb(Zr x,Ti 1−x)O 3 films with Zr compositions varied across the thickness direction were deposited on Pt/Ti/SiO 2/Si substrate using a conventional spin-coating method. The up- and down-graded PZT films exhibited the perovskite polycrystalline structure. Microstructure investigations of the films showed a dense texture and successive layers of different compositions. The relative permittivities of the up- and down-graded PZT films measured at 1 kHz and room temperature were 1846 and 1019, respectively. Good dielectric and ferroelectric properties as well as the low-temperature processing suggested that the compositionally graded PZT films were promising for memory device applications. 相似文献
15.
With an aim to improve the 5 V capacity and cyclability of the LiMn 1.5Ni 0.5O 4 spinel oxide, three series of Cr substitutions have been pursued with y ≤ 0.2: LiMn 1.5Ni 0.5−yCr yO 4, LiMn 1.5−0.5yNi 0.5−0.5yCr yO 4, and LiMn 1.5−0.33yLi 0.33yNi 0.5−yCr yO 4. While the first series involves an increase in the Mn 3+ content, the second and third series are designed to maintain charge neutrality (Mn 4+, Ni 2+, Cr 3+, and Li +) without introducing Mn 3+ ions. The LiMn 1.5Ni 0.5−yCr yO 4 series experiences a widening of the 4 V plateau and a decrease in the 5 V capacity compared to LiMn 1.5Ni 0.5O 4 due to an increase in the Mn 3+ content. On the other hand, the LiMn 1.5−0.5yNi 0.5−0.5yCr yO 4 series shows a suppression of the 4 V plateau and an increase in the 5 V capacity due to the elimination of the Mn 3+ions. The LiMn 1.5−0.33yLi 0.33yNi 0.5−yCr yO 4 series shows a suppression of the 4 V plateau at low Cr contents, but an increase in the 4 V plateau as the Cr content increases above 0.1. Among the various compositions investigated, LiMn 1.45Ni 0.45Cr 0.1O 4 exhibits the best combination of high 5 V capacity (128 mAh/g at 5–4.2 V) and excellent capacity retention (98% in 50 cycles) compared to 118 mAh/g and 92% for LiMn 1.5Ni 0.5O 4. 相似文献
16.
Based on the Ibl penetration model mass transfer equations for gas-evolving electrodes were derived and compared to the effect of forced convection. Experimental studies were conducted in a rectangular flow channel with the working electrode facing downward. The variables were linear bubble velocity, linear electrolyte velocity, nature of the gas and electrode position. Up to bubble velocities ( Ux) of 2 and 6 cm s −1 for O 2 and H 2 gases respectively, the thickness of the Nernst diffusion layer (δ av) was described well by the equation δ av = [ DdeL/( Ux) av] 1/3. Intermediate slopes between − 1/3 and − 1 were observed for O 2 bubble velocities between 2 and 6 cm s −1. A theoretical derivation suggests that in the absence of bubble coalescence, the mass transfer effect due to laminar flow induced by electrolytically evolved gas exceeds that due to forced external laminar flow for all practical channel designs. 相似文献
17.
Effect of substitution of CuO and WO 3 on the microwave dielectric properties of BiNbO 4 ceramics and the co-firing between ceramics and copper electrode were investigated. The (Bi 1−xCu x)(Nb 1−xW x)O 4 ( x = 0.005, 0.01, 0.015, 0.02) composition can be densified between 900 and 990 °C. The microwave dielectric constants lie between 36 and 45 and the pores in ceramics were found to be the main influence. The Q values changes between 1400 and 2900 with different x values and sintering temperatures while Qf values lie between 6000 and 16,000 GHz. The microwave dielectric losses, mainly affected by the grain size, pores, and the secondary phase, are discussed. The (Bi 1−xCu x)(Nb 1−xW x)O 4 ceramics and copper electrode was co-fired under N 2 atmosphere at 850 °C and the EDS analysis showed no reaction between the dielectrics and copper electrodes. This result presented the (Bi 1−xCu x)(Nb 1−xW x)O 4 dielectric materials to be good candidates for LTCC applications with copper electrode. 相似文献
18.
The first oxygen permeation data of a dense hollow fiber perovskite membrane based on BaCo xFe yZr zO 3 − δ are reported. The hollow fiber was prepared by a phase inversion process. Dense fibers were obtained with the following typical geometries: outer diameter, 800–900 μm; inner diameter, 500–600 μm; length, 30 cm. The O 2-permeation through the hollow fiber perovskite membrane was studied in a high-temperature gas permeation cell under different operation conditions. The increase of the helium gas flow rate reduces the oxygen partial pressure ( pO2) on the core side and a higher oxygen permeation flux is observed. High oxygen flux of 0.73 m 3 (O 2)/(m 2 (membrane) h) was achieved at 850 °C under the operation parameters Fair (shell side) = 150 ml/min and FHe (core side) = 30 ml/min. The oxygen partial pressure dependence of the O 2 permeation flux indicated an interplay of both surface reaction and bulk diffusion as rate limiting steps. During 5 days of permeation a high and stable oxygen flux was observed. X-ray diffraction patterns of fresh and spent membranes after the permeation measurements revealed that no degradation after oxygen permeation appears. 相似文献
19.
We have obtained mass spectra of negative ions produced by rays in artificial air at atmospheric pressure (N 2: 80%, O 2: 20%, H 2O: 20–1500 ppm, CO 2: 0.2–300 ppm, NO, NO 2 0.02 ppm). We observed two main categories: hydrates built on simple ions (O 2−, O 3−, OH −, CO 3−, CO 4−, HCO 3−, NO 2−, NO 3−), hydrates built on complex ions (NO x−, HNO γ, HCO 3−HNO x, x = 2,3; Y = 2, 3). For high values of hygrometry, CO 2 content and ageing time (5 msec) we observe the disappearance of O 2−, O 3−, OH − hydrates whereas the major part of the spectrum consists of complex ions. 相似文献
20.
The effect of carbon dioxide on the chemical stability of a Ba 0.5Sr 0.5Co 0.8Fe 0.2O 3−δ cathode in the real reaction environment at 450 °C was investigated by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), temperature programmed desorption (TPD), X-ray diffraction (XRD) and electrochemical impedance spectra (EIS) techniques. It was found that the presence even of very small quantities of CO 2 seriously deteriorates the fuel cell performance at 450 °C. XPS, TPD and XRD results strongly evidenced the formation of carbonates involving strontium and possibly barium after the BSCF cathode was operated in 1% CO 2/O 2 gas mixture at 450 °C for 24 h. SEM-EDX analysis of the BSCF cathode surface, after treatment in CO 2/O 2 environment at 450 °C, showed small particles on the surface probably associated with a carbonate phase and a segregated phase of the perovskite. The corresponding EDX spectra confirmed the presence of a carbonate layer and also revealed the surface enrichment of strontium and barium elements. EIS results indicated that both ohmic and polarization resistances increased gradually with the introduction of carbon dioxide in the oxidant stream, which could be interpreted by the decreased oxygen reduction kinetics and the formation of carbonate insulating layer. 相似文献
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