Catalytic activity of nanometer La1−xSrxCoO3 (x = 0, 0.2) perovskites towards VOCs combustion

Combustive oxidation of volatile organic compounds (VOCs), such as propyl alcohol, toluene and cyclohexane, were studied. The combustion was catalyzed by nanoparticles of La_1−xSr_xCoO₃ (x = 0, 0.2) perovskites prepared by a co-precipitation method. The results showed high activities of the perovskite catalysts. Compared to LaCoO₃, in particular, La_0.8Sr_0.2CoO₃ was much higher in catalytic ability. The total oxidation of VOCs followed the increasing order: cyclohexane < toluene < propyl alcohol. The T_99% of cyclohexane was 40 °C lower than that of toluene, which appeared to be determined by the bond strengths of the weakest C–H and C–C bonds. The 100-h stability experiments showed that La_1−xSr_xCoO₃ (x = 0, 0.2) perovskite was highly stable.     

Synthesis and Characterization of Perovskite-Type Oxides La1−xMxCoO3 (M = Ce,Sr) for the Selective CO Oxidation (SELOX)

Perovskite-type oxides La_1?xM_xCoO₃ (M = Ce, Sr) were prepared by citrate method, characterized and evaluated in the selective CO oxidation (SELOX-CO). The insertion of low Cerium or Strontium content generated solids with a single phase related LaCoO₃ perovskite. For higher contents we observed segregation of CeO₂ and SrCO₃. The iso-structural substitution favors the formation of vacancies. The SELOX-CO showed 100 % CO conversion at 200 °C. Higher temperatures favored hydrogen oxidation and methanation.     

Visible-light sensitive La1−xBaxCoO3 photocatalyst for malachite green degradation

In this study, a series of photocatalyst La_1?xBa_xCoO₃ (x=0, 0.1, 0.3, 0.5, 0.7) powders were successfully prepared using the sol–gel method. The crystal structure and band gap of La_1?xBa_xCoO₃ were characterized by X-ray diffraction and Ultraviolet–visible diffuse reflection spectroscopy for photocatalysis investigation. The results showed that the Ba-doped LaCoO₃ exhibited obvious absorption characteristics in visible light regions. In addition, the effect of La_1?xBa_xCoO₃ on the photocatalytic degradation of malachite green under different light sources was also investigated. Ba-doped LaCoO₃ showed excellent visible-light sensitive photocatalytic activities and a maximum photocatalytic degradation of malachite green could be achieved with a degradation degree of 97% by La_0.7Ba_0.3CoO₃ in visible light for 60 min.     

Sol–gel synthesis of La0.6Sr0.4CoO3−x and Sm0.5Sr0.5CoO3−x cathode nanopowders for solid oxide fuel cells

Nano-powders of La_0.6Sr_0.4CoO_3?x (LSC) and Sm_0.5Sr_0.5CoO_3?x (SSC) compositions, which are being investigated as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs) with La(Sr)Ga(Mg)O_3?x (LSGM) as the electrolyte, were synthesized by low-temperature sol–gel method using metal nitrates and citric acid. Thermal decomposition of the citrate gels was followed by simultaneous DSC/TGA methods. Development of phases in the gels, on heat treatments at various temperatures, was monitored by X-ray diffraction. Sol–gel powders calcined at 550–1000 °C consisted of a number of phases. Single perovskite phase La_0.6Sr_0.4CoO_3?x or Sm_0.5Sr_0.5CoO_3?x powders were obtained at 1200 °C and 1300 °C, respectively. Morphological analysis of the powders calcined at various temperatures was done by scanning electron microscopy. The average crystallite size of the powders was ～15 nm after 700 °C calcinations and slowly increased to 70–100 nm after heat treatments at 1300–1400 °C.     

Catalytic Post-Treatment of Automotive Exhaust Gas from Natural Gas Combustion Engines: Potential Interest of Perovskite Materials

This study reports an investigation of the surface properties of Pd-modified perovskite catalysts for NO _x removal from Natural Gas engines. H₂ production from reforming and water-gas-shift reactions can be profitably used for the reduction of NO _x . Particular attention has been paid to the nature of interactions between Pd and LaCoO₃ according to in situ reductive thermal treatments. The catalytic properties have been investigated by temperature-programmed NO desorption and temperature-programmed NO/H₂ reaction. Different experiments performed on partially and extensively reduced catalysts lead to changes in surface reactivity. Interestingly, beneficial interactions with a significant selectivity enhancement to the production of nitrogen is observed on pre-reduced Pd/LaCoO₃ under smooth conditions at 250 °C particularly in the presence of oxygen. More extensive reduction at 450 °C leads to the loss of the structural properties of LaCoO₃ accompanied with partial segregation of CoO _x and La₂O₃. Such structural changes lead to a detrimental effect on the catalytic performances.     

Electrical and magnetic properties of La1−xSrxMnO3 (0.1 ≤ x≤ 0.25) ceramics prepared by sol–gel technique

La_1−xSr_xMnO₃ (0.1 ≤ x ≤ 0.25) high density ceramics were prepared by sol-gel method using methanol as solvent. X-ray diffraction analysis showed that all samples exhibited single perovskite structure and no second phase was detected. Scanning electron microscopy images exhibited good particle connectivity on the surface of sample, and grain size increased with the increase in Sr doping. Resistivity-temperature curves of samples were measured by standard four-probe method, and curves exhibited significant differences in studied range of Sr doping. Magnetic measurement results indicated that the variation of susceptibility of different samples was quite different, and the Curie temperature of samples increased with the increase in Sr content. For x = 0.2, temperature coefficient of resistance value of the sample was larger, and corresponding peak TCR temperature was 307.1 K, which is very close to room temperature. Thus, La_0.8Sr_0.2MnO₃ ceramics exhibited high TCR value close to room temperature. Combined with its excellent magnetic properties, La_0.8Sr_0.2MnO₃ ceramics may potentially act as effective candidates for uncooled radiation calorimeter and uncooled magnetic sensor. Applications of La_0.8Sr_0.2MnO₃ ceramics in uncooled infrared radiation calorimeter at room temperature will be highly beneficial.     

Non-congruence of high-temperature mechanical and structural behaviors of LaCoO3 based perovskites

This paper presents the mechanical behavior of LaCoO₃ and La_0.8Ca_0.2CoO₃ ceramics under four-point bending in which the two cobaltites are subjected to a low stress of ∼8 MPa at temperatures ranging from room temperature to 1000 °C. Unexpected stiffening is observed in pure LaCoO₃ in the 700–900 °C temperature range, leading to a significant increase in the measured Young’s modulus, whereas La_0.8Ca_0.2CoO₃ exhibits softening from 100 °C to 1000 °C, as expected for most materials upon heating. Neutron diffraction, X-ray diffraction and micro-Raman spectroscopy are used to study the crystal structure of the two materials in the RT–1000 °C temperature range. Despite a detailed study, there is no conclusive evidence to explain the stiffening behavior observed in pure LaCoO₃ as opposed to the softening behavior in La_0.8Ca_0.2CoO₃ at high temperatures (above 500 °C).     

Highly Active La1−x K x CoO3 Perovskite-type Complex Oxide Catalysts for the Simultaneous Removal of Diesel Soot and Nitrogen Oxides Under Loose Contact Conditions

The nanometric La_1?x K _x CoO₃ (x = 0–0.30) perovskite-type oxides were prepared by a citric acid-ligated method. The catalysts were characterized by means of XRD, IR, BET, XPS and SEM. The catalytic activity for the simultaneous removal of soot and nitrogen oxides was evaluated by a technique of the temperature-programmed oxidation reaction. In the LaCoO₃ catalyst, the partial substitution of La³⁺ at A-site by alkali metal K⁺ enhanced the catalytic activity for the oxidation of soot particle and reduction of NO _x . The La_0.70K_0.30CoO₃ oxides are good candidate catalysts for the simultaneous removal of soot particle and NO _x . The combustion temperatures for soot particles over the La_0.70K_0.30CoO₃ catalyst are in the range from 289 to 461 °C, the selectivity of CO₂ is 98.4% and the conversion of NO to N₂ is 34.6% under loose contact conditions. The possible reasons that can lead to the activity enhancement for the K-substitution samples compared to the unsubstituted sample (LaCoO₃) were given. The particle size has a large effect on its catalytic performance for the simultaneous removal of diesel soot and nitrogen oxides.     

Synthesis of La1−xSrxMnO3 powders by polymerizable complex method: Evaluation of structural, morphological and electrical properties

Lanthanum strontium manganite (La_1−xSr_xMnO₃, LSM) powders were synthesized by polymerizable complex method, based on complexation of metal ions (MI) with citric acid (CA) and polyesterification between CA and ethylene glycol (EG). Firstly, the effect of the molar ratio of CA:MI (=1–3) was investigated on the synthesis of La_0.7Sr_0.3MnO₃ powders, which were characterized by thermal analysis (TGA/DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The results indicated that the molar ratio CA:MI = 3 is adequate for a good crystallization of pure perovskite phase after calcination, with nanometric crystallite sizes and porous microstructure. For the La_0.7Sr_0.3MnO₃ sample synthesized with CA:MI ratio of 3, it was investigated the effect of calcination temperature, showing that the perovskite structure is better crystallized at 900 °C, without secondary phase formation. Using this same CA:MI ratio and calcination temperature, powders with different Sr content (x = 0.2–0.4) were synthesized, with surface areas of 4–10 m² g⁻¹. These powders were sintered at 1100 °C to produce porous pellets. The porosity of the sintered pellets and the electrical conductivity, measured by two-probe technique, increased with increasing Sr content.     

Enhanced photocatalytic activity of La1-xSrxCoO3/Ag3PO4 induced by the synergistic effect of doping and heterojunction

This study sought to design and synthesize a series of perovskite-based La_1-xSr_xCoO₃/Ag₃PO₄ (with x = 0–1) heterojunction photocatalysts with different Strontium (Sr) doping contents by a simple sol-gel method and properties of the material were comprehensively characterized. Moreover, tetracycline (TC) was chosen as the target pollutant to assess the effect of Sr doping on the catalytic performance of LaCoO₃/Ag₃PO₄. Our results demonstrated that the partial replacement of La³⁺ with Sr²⁺ coupled with shifting Co³⁺ to the mixed-valence state of Co³⁺-Co⁴⁺ led to the formation of substantially more oxygen vacancies in the crystal lattice of La_1-xSr_xCoO₃/Ag₃PO₄. Therefore, the doped catalyst La_1-xSr_xCoO₃/Ag₃PO₄ exhibited enhanced photocatalytic performance. When x = 0.9, the obtained La_0·1Sr_0·9CoO₃/Ag₃PO₄ exhibit an optimal performance for TC degradation. Kinetic analyses demonstrated that the degradation rate constant of TC in La_0·1Sr_0·9CoO₃/Ag₃PO₄ system was 0.0098 min^?1, which is 1.78 times that of LaCoO₃/Ag₃PO₄, and 2.45 times that of SrCoO₃/Ag₃PO₄. Additionally, free radical sequestration experiments indicated that OH^?, h⁺, and O₂^?? all participated in the degradation of TC in the following order: h⁺>O₂^??>OH^?. Finally, analyses of photocatalytic mechanisms suggested that the enhanced photocatalytic activity of La_0·1Sr_0·9CoO₃/Ag₃PO₄ was due to its strong electron transfer properties and the formation of substantially more surface oxygen vacancies in Sr-doped La_0·1Sr_0·9CoO₃.     

Oxygen nonstoichiometry in Pr1−xSrxCo0.2B0.8O3−δ (B = Mn,Fe, x = 0.2, 0.4) perovskite oxides

Thermogravimetric analysis was applied to the study of oxygen nonstoichiometry of perovskite oxides of the compositions Pr_0.8Sr_0.2Co_0.2Mn_0.8O_3−δ and Pr_1−xSr_xCo_0.2Fe_0.8O_3−δ (x = 0.2, 0.4). The measurements were performed in the temperature range from room temperature to 1200 °C in various atmospheres: oxygen, air and argon. The recorded weight loss corresponds to the loss of lattice oxygen. The magnitude of oxygen loss increased and the temperature at which oxygen loss became significant decreased with increasing Sr content. The loss of lattice oxygen became more significant as the oxygen partial pressure decreased. For the same pO₂ and level of Sr doping, the Fe-containing composition became more easily oxygen deficient than the corresponding Mn-containing one, suggesting that Fe is more resistant to oxidation from the trivalent to the tetravalent state than Mn. Electrical conductivity measurements, performed in air, showed that the temperature ranges at which conductivity decrease was observed, correspond fairly well with those ranges where weight loss was detected.     

Microstructure of Ba1−xLaxTiO3−δ ceramics sintered by Spark Plasma Sintering

Nano-sized Ba_1−xLa_xTiO₃ (0.00 ≤ x ≤ 0.14) powders were prepared by a coprecipitation method and calcined at 850 °C in air. The corresponding ceramics were obtained by Spark Plasma Sintering (SPS) at 1050 °C. These ceramics are oxygen deficient and are marked as Ba_1−xLa_xTiO_3−δ. Both powders and ceramics were characterized by X-ray diffraction (XRD) and Transmission Electron Microscopy (TEM). The effect of lanthanum concentration on the densification behavior, on the structure and the microstructure of the oxides was investigated. Average grain sizes are comprised between 54 (3) nm and 27 (2) nm for powders, and 330 (11) nm and 36 (1) nm for ceramics according to the La-doping level. Powders crystallize in the cubic (or pseudo-cubic) perovskite phase. The structure of ceramics consists in a mixture of cubic (or pseudo-cubic) and tetragonal perovskite type phases. As the lanthanum content increases, the tetragonality of the samples decreases, as well as the grain size.     

Effect of strontium and cerium doping on the structural characteristics and catalytic activity for C3H6 combustion of perovskite LaCrO3 prepared by sol–gel

Two series of Sr- or Ce-doped La_1−xM_xCrO₃ (x = 0.0, 0.1, 0.2 and 0.3) catalysts were prepared by thermal decomposition of amorphous citrate precursors followed by annealing at 800 °C in air atmosphere. The effect of Ce and Sr on the morphological/structural properties of LaCrO₃ was investigated by means of thermogravimetric/differential thermal analysis (TG/DTA) of the precursors decomposition under air, X-ray diffraction (XRD), electron paramagnetic resonance (EPR), transmission electron microscopy–X-ray energy dispersive spectroscopy (TEM–XEDS), S_BET determination, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) techniques. The characterization results are employed to explain catalytic activity results for C₃H₆ combustion. It is shown that the lanthanum chromite perovskite structure is obtained upon thermal treatment of the sol–gel derived precursors at T > ca. 800 °C. The presence of the dopant generally induces the formation of segregated oxide phases in the samples calcined at 800 °C although some introduction of the Sr in the perovskite structure is inferred from EPR measurements. The oxidation activity becomes maximised upon formation of such doped perovskite structure.     

Influence of Na doping on the magnetic properties of LaFeO3 powders and dielectric properties of LaFeO3 ceramics prepared by citric sol-gel method

The emergence of ferromagnetism in perovskite oxide LaFeO₃ nanoparticles and colossal dielectric response in ceramics has inspired researchers to study the effect of various dopants on the magnetic and dielectric properties of LaFeO₃ powders and ceramics. However, the influence of alkali element Na doping has not been studied yet, and the origin of such ferromagnetic behavior is still ambiguous. The primary objective of the present work is to elucidate the effect of Na doping on the magnetic properties of La_1−xNa_xFeO₃ (x=0, 0.1 and 0.2) powders and dielectric properties of corresponding ceramics prepared by citric sol-gel method. FE-SEM results showed that the introduction of Na dopant actually resulted in the formation of nonstoichiometric La_1−xFeO₃ and x/2 Na₂O. Compared to the canted AFM behavior for the pure powder, ferromagnetic behavior with enhanced magnetization of 2.11 emu/g at 10 kOe could be obviously observed at room temperature for the powder with x=0.2. XPS measurement suggested nonstoichiometric Fe/La ratio which leads to the distortion of lattice structure and enlarged canting angle between the two AFM coupled Fe sublattice should be responsible for the enhancement of magnetization in the Na-doped samples. Meanwhile, the introduction of Na dopant lowered the growth temperature of grains of the parent LFO and resulted in larger average grain size, which in turn leaded to great enhancement of ε′ into the order of 10⁵ at 100 Hz at the cost of high tanδ for the Na-doped ceramics.     

The effect of Zn addition on the structure and transport properties of BaCe0.9−xZrxY0.1O3−δ

BaCe_0.9−xZr_xY_0.1O_3−δ (0.1 ≤ x ≤ 0.9) are ceramic proton conductors widely investigated for different electrochemical devices, such as Solid Oxide Fuel Cell (SOFC) electrolytes, however, their applications are limited by the high sintering temperatures necessary to achieve densification. Polycrystalline powders of BaCe_0.9−xZr_xY_0.1O_3−δ (BCZ) have been prepared by freeze-drying precursor method at 1000 °C. These powders were mixed with a zinc nitrate solution to decrease the sintering temperature to 1200–1300 °C. The addition of Zn has several effects on the structure and microstructure of BCZ: the densification and grain growth are enhanced at lower temperature and a reduction of the crystallographic symmetry is observed for samples with low Zr-content (x ≤ 0.3). Furthermore, the bulk and specific grain boundary conductivities are only slightly affected by the addition of Zn.     

Perovskite forming ceramics of the system SrxLa1−x TiIVx+yCoIIyCoIII1−x−2yO3 for NTC thermistor applications

The paper reports the preparation, structure and electrical properties of oxide ceramic semiconductors based on the series Sr_xLa_1−x Ti^IV_x+yCo^II_yCo^III_1−x−2yO₃ with perovskite type stucture: 0<x<1, 0<y<(1−x)/2. The study starts from LaCoO₃ which is highly conductive yielding metallic condutivity above 330°C. The upset trigonal distortion of LaCoO₃ is reduced when Sr^II/Ti^IV is substituted for La^III/Co^III corresponding to increasing values of x and also when 2 Co^III are introduced for Ti^IV/Co^II into the lattice corresponding to increasing values of y. At high values of x and y othorhombic distortion occurs. At the same time, the interaction between the Co^III atoms of LaCoO₃ is increasingly interrupted providing increasing values of the the resistivity value ρ_25°C and of the B_25/100°C value deduced from measurements at 25 and 100°C according to ρ(T )=ρ_25°C e^B/T. The range of variation of x an y makes possible to prepare ceramics with desired electrical properties within the limits of ρ_25°C=1.1 Ωcm, B=1910 K and ρ_25°C=1 bis 8×10⁶ Ωcm at B-values up to 6500 K. Dependent on composition, NTC ceramics for thermistor or insurance applications are accessible. Thermistors do not show aging even at higher temperature, e.g. at 500°C, provided the single phase state is achieved as a result of mixed oxide preparation and sintering. Hence, high temperature thermistor applications are also made possible. The semiconductor behavior can be understood using the conventional polaron state hopping model.     

Synthesis,Characterization, and Catalytic Activity of Mn‐doped Perovskite Oxides for Three‐Way Catalysis

Mn‐doped La_0.8Sr_0.2CoO₃ perovskite oxides (La_0.8Sr_0.2Co_1–xMn_xO₃; x = 0, 0.1, 0.3, 0.5) were synthesized by a modified sol‐gel method. The phase‐pure oxides were obtained. CoO and carbonates were formed on the surface of La_0.8Sr_0.2CoO₃. With increasing doping content, these impurities were reduced while the stability of the perovskite structure was improved. The valence state of B‐site ions and the amount of absorbed oxygen were influenced by Mn doping. The catalytic activity of the perovskite catalysts was investigated for CO oxidation and simultaneous removal of CO, C₃H₈, and NO. For CO and NO removal, La_0.8Sr_0.2Co_0.9Mn_0.1O₃ exhibited the best performance. For C₃H₈ removal, the reactivity was promoted linearly with the doping content. The structure‐activity relationship is also discussed.     

Preparation and thermal stability of oxynitride perovskite solid solution Sr1-xLaxTa1-xTixO2N

The thermal stability of oxynitride perovskites is very important for the fabrication of their dense ceramics. In this study, a solid solution of the oxynitride perovskite Sr_1-xLa_xTa_1-xTi_xO₂N was prepared via the ammonia nitridation of oxide precursors. The oxynitrides products obtained at x ≤ 0.2 and x ≥ 0.7 had tetragonal and triclinic perovskite-type structures, respectively. A neutron diffraction study on the oxynitride product obtained at x = 0.2 indicated that this tetragonal perovskite had a cis-type anion distribution similarly to SrTaO₂N. The tetragonal perovskite released a part of nitrogen at approximately 1000 °C in a nitrogen atmosphere while maintaining the perovskite structure at least to 1450 °C. The oxynitride perovskites at x ≥ 0.5 gradually decomposed to a mixture of LaTiO₂N, LaTiO₃, La(OH)₃, La₂O₃, TiN and TaO above 1100 °C.     

Evaluation of the La0.75Sr0.25Mn0.8Co0.2O3−δ system as cathode material for ITSOFCs with La9Sr1Si6O26.5 apatite as electrolyte

In the past years, a major interest has been devoted to decrease the working temperature of solid oxide fuel cells (SOFCs) down to about 700 °C.Apatite materials (La_10?xSr_xSi₆O_27?x/2) are attractive candidates for solid electrolytes, with a high ionic conductivity at 700 °C, a chemical and a dimensional stability for a pO₂ ranging from 10^?25 to 0.2 atm. A perovskite oxide (La_0.75Sr_0.25Mn_0.8Co_0.2O_3?δ) has been used as a cathode material.Symmetrical cathode/electrolyte/cathode cells were fabricated by stacking layers obtained by tape casting of apatite and perovskite powders and co-sintering at 1400 °C for 2 h in air.Impedance spectroscopy measurements were performed on these cells in order to determine the electrode resistance. It has been shown that the latter decreases with the porosity content of the cathode and with the use of a composite material (apatite/perovskite) instead of a simple perovskite.     

Lanthanum-doped PZT synthesized by the oxidant peroxide method and sintered by conventional and microwave routes

Lanthanum-doped lead zirconate titanate (Pb_0.95La_0.05Zr_1−xTi_xO₃) with two different compositions, x=0.20 (PLZT20) and 0.80 (PLZT80), were successfully obtained by the oxidant peroxide method (OPM). This environmental friendly synthetic route showed to be very attractive to prepare lead based ferroelectric powders since no carbon or halides compounds were used. Tetragonal perovskite structure was observed for PLZT80 and rhombohedral perovskite for PLZT20, with single phase identified in the powders calcined at temperatures higher than 700 °C. Powders crystallized at 700 °C were used to produce ceramic samples that were sintered at 1000 °C for 2 h by conventional and microwaves techniques. The composition of the fractured surface of ceramics were quite close to the nominal molar composition, indicating that the OPM promotes the formation of materials with high compositional homogeneity and similar microstructures regardless the sintering method used.