Nanosized perovskite-type oxides La1−xSrxMO3−δ (M = Co, Mn; x = 0, 0.4) for the catalytic removal of ethylacetate

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 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 La_1−xSr_xMnO_3−δ and Co³⁺ and Co²⁺ in La_1−xSr_xCoO_3−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 (T_100%) for EA complete conversion) increased in the order of LaCoO_2.91 (T_100% = 230 °C) ≈ LaMnO_3.12 (T_100% = 235 °C) < La_0.6Sr_0.4MnO_3.02 (T_100% = 190 °C) < La_0.6Sr_0.4CoO_2.78 (T_100% = 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 La_1−xSr_xMO_3−δ materials.     

Electrical resistivity and thermopower of (La1−xSrx)MnO3 and (La1−xSrx)CoO3 at elevated temperatures

Electrical resistivity and Seebeck (S) measurements were performed on (La_1−xSr_x)MnO₃ (0.02x0.50) and (La_1−xSr_x)CoO₃ (0x0.15) in air up to 1073 K. (La_1−xSr_x)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. (La_1−xSr_x)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.     

Performance of La1−xSrxAl1−y−y′FeyMgy′O3−δ perovskites in methane combustion: effect of aluminum and magnesium content

Perovskites of different La_1−xSr_xAl_1−y−y′Fe_yMg_y′O_3−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 LaAl_0.65Fe_0.15Mg_0.2O₃ perovskite. None of the magnesium substituted perovskites performed better than a La_0.85Sr_0.15Al_0.87Fe_0.13O₃ reference sample.     

Synthesis and properties of lanthanum hexaaluminate ceramic La1−xCaxAl11−y−zMgyTizO18

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 La_1−xCa_xAl_11−y−zMg_yTi_zO₁₈ (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.     

Microwave dielectric properties and co-firing with copper of (Bi1−xCux)(Nb1−xWx)O4 ceramics

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 (Bi_1−xCu_x)(Nb_1−xW_x)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 Q_f 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)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 (Bi_1−xCu_x)(Nb_1−xW_x)O₄ dielectric materials to be good candidates for LTCC applications with copper electrode.     

Catalytic behavior of La–Sr–Ce–Fe–O mixed oxidic/perovskitic systems for the NO+CO and NO+CH4+O2 (lean-NOx) reactions

Mixed oxides of the general formula La_0.5Sr_xCe_yFeO_z were prepared by using the nitrate method and characterized by XRD and Mössbauer techniques. The crystal phases detected were perovskites LaFeO₃ and SrFeO_3−x and oxides -Fe₂O₃ and CeO₂ depending on x and y values. The low surface area ceramic materials have been tested for the NO+CO and NO+CH₄+O₂ (“lean-NO_x”) reactions in the temperature range 250–550°C. A noticeable enhancement in NO conversion was achieved by the substitution of La³⁺ cation at A-site with divalent Sr⁺² and tetravalent Ce⁺⁴ cations. Comparison of the activity of the present and other perovskite-type materials has pointed out that the ability of the La_0.5Sr_xCe_yFeO_z materials to reduce NO by CO or by CH₄ under “lean-NO_x” conditions is very satisfying. In particular, for the NO+CO reaction estimation of turnover frequencies (TOFs, s⁻¹) at 300°C (based on NO chemisorption) revealed values comparable to Rh/-Al₂O₃ catalyst. This is an important result considering the current tendency for replacing the very active but expensive Rh and Pt metals. It was found that there is a direct correlation between the percentage of crystal phases containing iron in La_0.5Sr_xCe_yFeO_z solids and their catalytic activity. O₂ TPD (temperature-programmed desorption) and NO TPD studies confirmed that the catalytic activity for both tested reactions is related to the defect positions in the lattice of the catalysts (e.g., oxygen vacancies, cationic defects). Additionally, a remarkable oscillatory behavior during O₂ TPD studies was observed for the La_0.5Sr_0.2Ce_0.3FeO_z and La_0.5Sr_0.5FeO_z solids.     

Lanthanum ferrite membranes in ammonia oxidation: Opportunities for ‘pocket-sized’ nitric acid plants

This paper reports the application of mixed conducting perovskite membranes for simultaneous in situ O₂ 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 N₂O 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.     

Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts for catalytic combustion of methane

A series of the Ce_1−xCu_xO_2−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 Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts the surface phase structure were the Ce_1−xCu_xO_2−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 Ce_1−xCu_xO_2−x solid solution. The Cu component of the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts played an important role to the catalytic activity for the methane combustion. There were the stronger interaction among the Ce_1−xCu_xO_2−x solid solution and the Al₂O₃ washcoats and the FeCrAl support.     

Synthesis of La2−xNiO4+δ oxides by polymeric route: non-stoichoimetry control

The synthesis of La_2−xNiO_4+δ oxides has been done via a polymeric route. This method allows the preparation of a wide range of non-stoichoimetry values. Oxides with values as high as 0.25 have been synthesised. Correlations between processing parameters such as sol composition and heat treatment have been done with structural and microstructural properties of the oxides. In our synthesis conditions, the higher the mean grain size, the higher the non-stoichoimetry level.

Transmission electron microscopy on these oxides has shown that whatever the non-stoichoimetry level, the extra-oxygen arranges in the structure according to two superstructures which correspond to δ=0.25 and δ=0.17. This shows that our grains consist of a mixture of these compositions.     

Sintering and electrical conductivity in fast oxide ion conductors La2−xRxMo2−yWyO9 (R: Nd, Gd, Y)

Attrition and ball milling are used as mechanical means to reduce grain size of optimized fast oxide-ion conductors La_2−xR_xMo_2−yW_yO₉ (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.     

AMnO3 (A=La, Nd, Sm) and Sm1−xSrxMnO3 perovskites as combustion catalysts: structural, redox and catalytic properties

Catalytic combustion of methane has been investigated over AMnO₃ (A = La, Nd, Sm) and Sm_1−xSr_xMnO₃ (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 Sm_1−xSr_xMnO₃ (x = 0.1) are single phase perovskite type oxides. Traces of Sm₂O₃ besides the perovskite phase were detected in the Sm_1−xSr_xMnO₃ 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 Sm_1−xSr_xMnO₃ 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 Sm_1−xSr_xMnO₃ 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.     

Oxygen transport in ferrite-based ceramic membranes: Effects of alumina sintering aid

Moderate additions of Al₂O₃ 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 SrAl₂O₄, and the formation of A-site cation-deficient perovskite. The improved properties of the SrFe_0.7Al_0.3O₃-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 Al³⁺ 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 Al₂O₃ or SrAl₂O₄ have a deteriorating influence on the oxygen permeation fluxes through La_0.5Sr_0.5FeO₃-based ceramics.     

Synthesis, characterisation and properties of (Ba1 − xSrx) (Nd1/2Nb1/2) O3 ceramics for application as dielectric resonators in microwave circuits

The (Ba_{1 − x}Sr_x) (Nd_1/2Nb_1/2) O₃ ceramics have been prepared by the conventional ceramic route for different values of x. Addition of a small amount of CeO₂ (1 wt%) as a sintering aid increased the density of the samples. The structure and microstructure of the sintered samples are studied by X-ray diffraction and SEM methods. The dielectric properties of the samples are measured in the microwave frequency region as a function of composition. The dielectric constant decreases as x increases. The coefficient of thermal variation of resonant frequency decreases as the Sr content increases and goes to the negative side. The dielectric properties of (Ba_{1 − x}Sr_x) (Nd_1/2Nb_1/2) O₃ are in the range suitable for application as dielectric resonators in microwave circuits.     

Catalytic combustion of CH4 and CO on La1−xMxMnO3 perovskites

The activities of perovskites depend on compositions and preparation methods. Various perovskites, La_1−xM_xMnO₃ (M=Ag, Sr, Ce, La), have been prepared by two different methods (co-precipitation and spray decomposition). The new preparation method, spray decomposition, produced perovskites of a high surface area of over 10 m²/g. The catalytic activities for CH₄ and CO oxidation have been studied on a series of catalysts, La_1−xM_xMnO₃. The perovskite-type oxide, La_0.7Ag_0.3MnO₃, shows the highest catalytic activity: the complete conversion of CO and CH₄ at 370 and 825 K, respectively.     

The NO selective reduction on the La1−xSrxMnO3 catalysts

La_1−xSr_xMnO₃ (x=0, 0.1, 0.3, 0.5, 0.7) perovskite-type oxides (PTOs) were prepared by coprecipitation under various calcination temperature, and their performances for the NO reduction were evaluated under a simulated exhaust gas mixture. The X-ray diffraction (XRD) and thermogravimetric analysis were carried out to find the formation process of the perovskite. The NO reduction rate under different reaction temperature, the concentration of oxygen and the presence of hydrocarbon were observed by the input/output analysis. In the presence of 10% excess oxygen, the catalyst La_0.7Sr_0.3MnO₃ calcined at 900 °C showed a NO reduction rate of 61% at 380 °C. The study of the reaction curves showed that C₃H₈ could act as the reducer for the NO reduction below 400 °C. The NO reduction is highly affected by increasing the O₂ concentration from 0.5 to 10%, especially at high temperatures when oxygen becomes more competitive than NO on the oxidation of C₃H₈, leading to a decrease of the NO reduction from 100% to zero at 560 °C.     

Oxygen storage capacity of La1−xBO3 perovskites (with A′ = Sr, Ce; B = Co, Mn)—relation with catalytic activity in the CH4 oxidation reaction

The aim of this work was to study the effect of cation-substitution on the reducibility of the perovskite, as well as the effect on the catalytic activity for the CH₄ oxidation reaction. Six perovskites (LaCoO₃, LaMnO₃, La_1−xSr_xMnO₃ (x = 0.2, 0.4), and La_1−xCe_xMnO₃ (x = 0.05, 0.1)) were synthesized by reactive grinding. The reducibility of the perovskite was studied by means of the oxygen storage capacity (OSC) measurement. OSC was performed at different temperatures on LaCoO₃ and LaMnO₃, in order to elucidate the different mechanisms of reduction involved at each temperature. The substituted samples showed that reduction profile is modified at high-substitution degrees; however, no differences were observed on the OSC values (amount of most active oxygen, calculated after one pulse of CO) between the pure lanthanum sample and the substituted ones.

Tested in the CH₄ oxidation reaction, the LaCoO₃ sample was found to present a little higher activity than LaMnO₃, even if the cobalt-based sample presented a smaller specific surface area. Moreover, all the substituted samples presented very slightly higher activities than the pure LaMnO₃ solid. Because of the supposed redox oxidation mechanism (Mars-Van-Krevelen), this agrees well with the OSC results obtained for the reducibility of the manganese on these samples, by which it was observed that substitution does not clearly affect the immediate reduction of the manganese.     

Preparation of CexZr1−xO2 (x = 0.75, 0.62) solid solution and its application in Pd-only three-way catalysts

Nanoparticles of Ce_xZr_1−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. Ce_xZr_1−xO₂ prepared had single fluorite cubic structure, good thermal stability and reduction property. With the increasing of Ce/Zr ratio, the surface area of Ce_xZr_1−xO₂ increased, but thermal stability of Ce_xZr_1−xO₂ decreased. The surface area of Ce_0.62Zr_0.38O₂ 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 Ce_xZr_1−xO₂ were enhanced by the cycle of TPR-reoxidation. The Pd-only three-way catalysts (TWC) were prepared by the impregnation method, in which Ce_0.75Zr_0.25O₂ 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 Ce_0.75Zr_0.25O₂ 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.     

AFeO3 (A=La, Nd, Sm) and LaFe1−xMgxO3 perovskites as methane combustion and CO oxidation catalysts: structural, redox and catalytic properties

Catalytic methane combustion and CO oxidation were investigated over AFeO₃ (A=La, Nd, Sm) and LaFe_1−xMg_xO₃ (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 LaFe_1−xMg_xO₃ (x·0.3) are single phase perovskite-type oxides. Traces of La₂O₃, in addition to the perovskite phase, were detected in the LaFe_1−xMg_xO₃ 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 LaFe_1−xMg_xO₃ 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 LaFe_1−xMg_xO₃ 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 LaFe_1−xMg_xO₃ catalysts decreases at high magnesium content.     

Microwave absorption materials — IV Preparation of the mixed layer structure phases, RexTa1−xS2 and OsxTa1−xS2, and some electrical and magnetic properties

The binary systems ReS₂–TaS₂ and OsS₂-TaS₂ are studied. Mixed layer structure (MLS) phases are found in Re_xTa_1−xS₂ with a composition range of 0.25x0.5, as well as in the Os_xTa_1−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.     

Processing and characterization of sol–gel fabricated mixed metal aluminates

Nanocrystalline lanthanum aluminate (LaAlO₃, LAP) and Sr-substituted LAP ceramics were synthesized by sol–gel processes using mixtures of inorganic salts of the respective elements. The metal ions, generated by dissolving metal nitrates or acetates in acetic acid and/or water were complexed by 1,2-ethanediol to obtain the precursor for LAP. The XRD patterns of the LaAlO₃ and La_1−xSr_xAlO_3−δ (x ≤ 0.50) ceramic sintered at 1000 °C were almost identical with the perovskite LAP composition. The phase transformations, composition and microstructural features in the gels and polycrystalline samples were studied by thermal analysis (TG/DTA), powder X-ray diffraction analysis (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and inductively coupled argon plasma emission spectroscopy (ICP). The quality of the resulting products (homogeneity, crystallisation temperature, grain size and grain size distribution, etc.) of the “chimie douce” synthetic route is discussed.