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1.
A series of the Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts (x = 0–1) were prepared. The structure of the catalysts was characterized using XRD, SEM and H2-TPR. The catalytic activity of the catalysts for the combustion of methane was evaluated. The results indicated that in the Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts the surface phase structure were the Ce1−xCuxO2−x solid solution, -Al2O3 and γ-Al2O3. The surface particle shape and size were different with the variety of the molar ratio of Ce to Cu in the Ce1−xCuxO2−x solid solution. The Cu component of the Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts played an important role to the catalytic activity for the methane combustion. There were the stronger interaction among the Ce1−xCuxO2−x solid solution and the Al2O3 washcoats and the FeCrAl support.  相似文献   

2.
The binary systems ReS2–TaS2 and OsS2-TaS2 are studied. Mixed layer structure (MLS) phases are found in RexTa1−xS2 with a composition range of 0.25x0.5, as well as in the OsxTa1−xS2 with a composition range of 0.26x0.33. The MLSs of both phases are constructed by a random and mixed stacking of the 2Hb-layers and 3R-layers. The magnetic susceptibilities of samples from both phases show a weak Pauli-paramagnetism. The paramagnetic moment and the electrical conductivity of both phases decrease as the composition x increases. The behaviour of the paramagnetic moment and the electrical conductivity of those phases offer us a good example of the number of conduction electrons and their effect.  相似文献   

3.
Structural, redox and catalytic deep oxidation properties of LaAl1−xMnxO3 (x=0.0, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0) solid solutions prepared by the citrate method and calcined at 1073 K were investigated. XRD analysis showed that all the LaAl1−xMnxO3 samples are single phase perovskite-type solid solutions. Particle sizes and surface areas (SA) are in the 280–1180 Å and 4–33 m2 g−1 ranges, respectively. Redox properties and the content of Mn4+ were derived from temperature programmed reduction (TPR) with H2. Two reduction steps are observed by TPR for pure LaMnO3, the first attributed to the reduction of Mn4+ to Mn3+ and the second due to complete reduction of Mn3+ to Mn2+. The presence of Al in the LaAl1−xMnxO3 solid solutions produces a strong promoting effect on the Mn4+→Mn3+ reducibility and inhibits the further reduction to Mn2+. Both for methane combustion and CO oxidation all Mn-containing perovskites are much more active than LaAlO3, so pointing to the essential role of the transition metal ion in developing highly active catalysts. Partial dilution with Al appears to enhance the specific activity of Mn sites for methane combustion.  相似文献   

4.
Catalytic methane combustion and CO oxidation were investigated over AFeO3 (A=La, Nd, Sm) and LaFe1−xMgxO3 (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 Fe4+ were derived from temperature programmed reduction (TPR). Specific surface areas (SA) of perovskites were in 2.3–9.7 m2 g−1 range. XRD analysis showed that LaFeO3, NdFeO3, SmFeO3 and LaFe1−xMgxO3 (x·0.3) are single phase perovskite-type oxides. Traces of La2O3, in addition to the perovskite phase, were detected in the LaFe1−xMgxO3 catalysts with x=0.4 and 0.5. TPR gave evidence of the presence in AFeO3 of a very small fraction of Fe4+ which reduces to Fe3+. The fraction of Fe4+ in the LaFe1−xMgxO3 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 CO2 below 973 and 773 K, respectively. For the AFeO3 materials the order of activity towards methane combustion is La>Nd>Sm, whereas the activity, per unit SA, of the LaFe1−xMgxO3 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 AFeO3 materials is Nd>La>Sm, while the activity (per unit SA) of the LaFe1−xMgxO3 catalysts decreases at high magnesium content.  相似文献   

5.
Effect of substitution of CuO and WO3 on the microwave dielectric properties of BiNbO4 ceramics and the co-firing between ceramics and copper electrode were investigated. The (Bi1−xCux)(Nb1−xWx)O4 (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 (Bi1−xCux)(Nb1−xWx)O4 ceramics and copper electrode was co-fired under N2 atmosphere at 850 °C and the EDS analysis showed no reaction between the dielectrics and copper electrodes. This result presented the (Bi1−xCux)(Nb1−xWx)O4 dielectric materials to be good candidates for LTCC applications with copper electrode.  相似文献   

6.
The structural and electronic properties of selected compositions of SnxTi1−xO2 solid solutions (x=0, 1/24, 1/16, 1/12, 1/8, 1/6, 1/4, 1/2, 3/4, 5/6, 7/8, 11/12, 15/16, 23/24 and 1) were investigated by means of periodic density functional theory (DFT) calculations at B3LYP level. The calculations show that the corresponding lattice parameters vary non-linearly with composition, supporting positive deviations from Vegard’s law in the SnxTi1−xO2 system. Our results also account for the fact that chemical decomposition in SnxTi1−xO2 system is dominated by composition fluctuations along [0 0 1] direction. A nearly continuous evolution of the direct band gap and the Fermi level with the growing value of x is predicted. Ti 3d states dominate the lower portion of the conduction band of SnxTi1−xO2 solid solutions. Sn substitution for Ti in TiO2 increases the oxidation–reduction potential of the oxide as well as it renders the lowest energy transition to be indirect. These two effects can be the key factors controlling the rate for the photogenerated electron–hole recombination. These theoretical results are capable to explain the enhancement of photoactivity in SnxTi1−xO2 solid solutions.  相似文献   

7.
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   

8.
Electrical resistivity and Seebeck (S) measurements were performed on (La1−xSrx)MnO3 (0.02x0.50) and (La1−xSrx)CoO3 (0x0.15) in air up to 1073 K. (La1−xSrx)MnO3 (x0.35) showed a metal-to-semiconductor transition; the transition temperature almost linearly increased from 250 to 390 K with increasing Sr content. The semiconductor phase above the transition temperature showed negative values of S. (La1−xSrx)CoO3 (0x0.10) showed a semiconductor-to-metal transition at 500 K. Dominant carriers were holes for the samples of x0.02 above room temperature. LaCoO3 showed large negative values of S below ca. 400 K, indicative of the electron conduction in the semiconductor phase.  相似文献   

9.
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   

10.
The aim of the present work is to obtain ceramic materials with a hexagonal structure and high density, hardness and mechanical strength at lower synthesis temperature. Ceramic samples with nominal composition La1−xCaxAl11−yzMgyTizO18 (x=0–1; y=0–3; z=0–3,5) are prepared. The samples are sintered at temperature 1500 °C by one-stage and two-stage ceramic technology. By X-ray diffraction and scanning electron microscopy, predominant phase LaAl11O18 and second phases LaAlO3 and -Al2O3 are identified. Ceramic materials are characterized with high physico-mechanical properties and may be find application for production of mill bodies and materials for immobilization of nuclear waste.  相似文献   

11.
Attrition and ball milling are used as mechanical means to reduce grain size of optimized fast oxide-ion conductors La2−xRxMo2−yWyO9 (R: rare earths). Dilatometry is used to determine the optimal sintering conditions in order to obtain high density samples (greater than 96% of relative density) with help of scanning electron microscopy to characterize their microstructure. The optimal sintering temperatures are highly dependent on the chemical composition, and therefore identical annealing temperatures do not warrant similar relative densities. Complex impedance spectroscopy show that above the transition temperature of La2Mo2O9 at 580 °C, the conductivity of all the studied compounds is lower than that of the parent compound, whereas just below the transition, in most cases the stabilization of the cubic phase increases conductivity. An interesting result is that tungsten substitution, which stabilizes La2Mo2O9 against reduction, does not affect significantly the oxide ion conduction.  相似文献   

12.
Perovskites of different La1−xSrxAl1−yyFeyMgyO3−δ compositions (x=0, 0.1, 0.15, 0.2 and y=0.1, 0.3, 0.5, 0.8) were prepared from a reactive precursor slurry of hydrated oxides. Each sample was aged between 16 and 26 h up to 1473 K. Activity in methane combustion (1%/air) was determined in a plug-flow reactor, with 1 g catalyst and 24 l/h flowrate. Gradual decrease in activity due to thermal aging was observed, the degree of activity loss being composition dependent. Nevertheless, activity of samples aged at 1370 K was nearly independent of composition. The best thermal stability showed LaAl0.65Fe0.15Mg0.2O3 perovskite. None of the magnesium substituted perovskites performed better than a La0.85Sr0.15Al0.87Fe0.13O3 reference sample.  相似文献   

13.
The weight and plaque diameter change following trermal treatment, and the density and lattice constant of lithium-rich LixNi1−xO solid solutions obtained by heat treatment at 750°C of Li2CO3---LiyNi1−yO (y < x) mixtures were measured as a function of time. It was found that densification of the solid solutions depends on the method of obtaining the Li2CO3---LiyNi1−yO mixtures. When a large amount of carbonate is put into the starting mixtures Ni---Li2CO3-binder, and the powders are milled together, sintering occurs; in contrast, when the carbonate is added after the formation of LiyNi1−yO solid solution, so that the interstices of the plaque are filled with molten carbonate, the resulting mixtures exhibit no densification. For densification to occur, Li2CO3 must be in intimate contact with the lithium-doped NiO grains.  相似文献   

14.
We have used a complex sol–gel process to synthesize a family of compounds LiNixCo1−xO2 (x = 0, 0.25, 0.5, 0.75, 1). These compounds are candidates for electrode materials in high-energy-density batteries. Starting sols were prepared from xNi2+ + (1 − x) Co2+ acetates/ascorbic acid aqueous solutions by alkalizing with LiOH and NH3. With thermal treatment in air, nickel carbonates formed in quantities roughly proportional to Ni concentration. The carbonate impurities could not be fully removed by heating in air to high temperatures. Because formation of pure layered oxides was inhibited by the presence of the carbonates, we developed a new way to remove them from just-formed precursors by treating the intermediate phases (those formed after calcination at 750 °C) with concentrated HNO3 and H2O2. All resulting powders were phase pure by X-ray diffraction and were easily friable. Various electrochemical properties of compacts prepared from these powders were measured.  相似文献   

15.
This study focuses on the direct sulfur recovery process (DSRP), in which SO2 can be directly converted into elemental sulfur using a variety of reducing agents over Ce1−xZrxO2 catalysts. Ce1−xZrxO2 catalysts (where x = 0.2, 0.5, and 0.8) were prepared by a citric complexation method. The experimental conditions used for SO2 reduction were as follow: the space velocity (GHSV) was 30,000 ml/g-cat h and the ratio of [CO (or H2, H2 + CO)]/[SO2] was 2.0. It was found that the catalyst and reducing agent providing the best performance were the Ce0.5Zr0.5O2 catalyst and CO, respectively. In this case, the SO2 conversion was about 92% and the sulfur yield was about 90% at 550 °C. Also, a higher efficiency of SO2 removal and elemental sulfur recovery was achieved in the reduction of SO2 with CO as a reducing agent than that with H2. In the reduction of SO2 by H2 over the Ce0.5Zr0.5O2 catalyst, SO2 conversion and sulfur yield were about 92.7% and 73%, respectively, at 800 °C. Also, the reduction of SO2 using synthetic gas with various [CO]/[H2] molar ratios over the Ce0.5Zr0.5O2 catalyst was performed, in order to investigate the possibility of using coal-derived gas as a reducing agent in the DSRP. It was found that the reactivity of the SO2 reduction using the synthetic gas with various [CO]/[H2] molar ratios was increased with increasing CO content of the synthetic gas. Therefore, it was found that the Ce1−xZrxO2 catalysts are applicable to the DSRP using coal-derived gas, which contains a larger percentage of CO than H2.  相似文献   

16.
The structure evolution, and microwave dielectric properties of Nd(2−x)/3LixTiO3 ceramics (0 ≤ x ≤ 0.5) were investigated in this paper. X-ray diffraction (XRD) and scanning electron microscopy (SEM) results show that samples with x = 0.2–0.4 exhibit single phase. Multi-phases of Nd2Ti2O7, Nd2/3TiO3 and Nd2Ti4O11 were observed when x = 0 and 0.1. The concentration and ordering degree of A-site decrease with the increase of x value. The dielectric constant increases up to x = 0.2 and then decreases with the further increase of x value. The Qf value decreases with the increase of x value. The temperature coefficient of resonant frequency exhibits negative value and the absolute value decreases greatly with the decrease of x value.  相似文献   

17.
Catalytic combustion of methane has been investigated over AMnO3 (A = La, Nd, Sm) and Sm1−xSrxMnO3 (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 cm3 g−1 h−1, CH4 concentration = 0.4% v/v, O2 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   


18.
Layered Li[Ni(1−x)/3Mn(1−x)/3Co(1−x)/3Crx]O2 materials with x = 0, 0.01, 0.02, 0.03, 0.05 are prepared by a solid-state pyrolysis method. The oxide compounds were calcined with various Cr-doped contents, which result in greater difference in morphological (shape, particle size and specific surface area) and the electrochemical (first charge profile, reversible capacity and rate capability) differences. The Li[Ni(1−x)/3Mn(1−x)/3Co(1−x)/3Crx]O2 powders were characterized by means of X-ray diffraction (XRD), charge/discharge cycling, cyclic voltammetry, and SEM. XRD experiment revealed that the Li[Ni(1−x)/3Mn(1−x)/3Co(1−x)/3Crx]O2 (x = 0, 0.01, 0.02, 0.03, 0.05) were crystallized to well layered -NaFeO2 structure. The first specific discharge capacity and coulombic efficiency of the electrode of Cr-doped materials were higher than that of pristine material. When x = 0.02, the sample showed the highest first discharge capacity of 241.9 mAh g−1 at a current density of 30 mA g−1 in the voltage range 2.3–4.6 V, and the Cr-doped samples exhibited higher discharge capacity and better cycleability under medium and high current densities at room temperature.  相似文献   

19.
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   

20.
Mixed oxides with compositions SrTi1−xyZrxMnyO3, with 0 ≤ x ≤ 1 and 0 ≤ y ≤ 0.2 have been prepared with a conventional coprecipitation method. Some of them are constituted by very pure perovskite-type solid solution phases, with tetravalent Zr and Mn substituting for Ti in the B site. The addition of Zr to SrTiO3 tends to increase the surface areas, while the insertion of Mn tends to decrease it. Mn-containing materials are active in the catalytic combustion of 1% methane in air at temperatures higher than 700 K and can be competitive with pure manganite perovskites like LaMnO3 in spite of the lower Mn content. Pyridine adsorption experiments show that medium strength Lewis acid sites are located at the surface of these materials, and could be involved in the hydrocarbon CH bond activation.  相似文献   

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