Search Results (29)

Metallic Pd/Ni gauzes, located downstream of the Pt/Rh ammonia oxidation catalyst nets in the Ostwald process, is the current technology for capturing volatile gas phase platinum and rhodium species lost from the Pt/Rh combustion catalyst through evaporation. In this screening study, we explore four oxide families, ABO₃ perovskites, (ABO₃)_n(AO) Ruddlesden–Popper (RP) phases, AO rock salt, and A₂O₃ sesquioxide type oxides, as alternative materials for platinum capture. It was found that all the tested nickelates, LaNiO₃, NdNiO₃, La₂NiO₄, and La₄Ni₃O₁₀, captured platinum well and formed A₂NiPtO₆. In contrast, La_0.85Sr_0.15FeO₃, LaFeO₃, and LaCoO₃ did not capture platinum. CaO, SrO, and Nd₂O₃ formed low-dimensional platinates such as Ca_xPt₃O₄, Sr₄PtO₆, and a newly discovered neodymium platinate, Nd_10.67Pt₄O₂₄. Gd₂O₃ did not capture platinum in bench-scale experiments in dry air, but did, however, seem to capture platinum under pilot plant conditions, likely due to the co-capture of Co lost from the N₂O abatement catalyst. The catalytic activity of both oxides and platinum-containing products were studied, toward NO_x and N₂O decomposition. None of the oxides showed significant activity toward NO_x decomposition, and all showed activity toward N₂O decomposition, but to different extents. An overall assessment of the screened oxides with respect to potential use in industrial Ostwald conditions is provided. All tested oxides except CaO and SrO withstood industrial conditions. From our assessments, the nickelates and A₂O₃ (A = Nd, Gd) stand out as superior oxides for platinum capture. Full article

Perovskite-type proton conductors exist in two structural forms, ABO₃ and ${\mathrm{A}}_2{\mathrm{B}}^{\prime }{\mathrm{B}}^{″}{\mathrm{O}}_6$. In this study, novel A-site double-perovskite proton conductors (${\mathrm{A}}^{\prime }{\mathrm{A}}^{″}{\mathrm{B}}_2{\mathrm{O}}_6$) were proposed. Na_1+xLa_1-xZr₂O_6-δ (x = 0, 0.1, 0.2) perovskites were prepared by a solid-state reaction at 1200 °C. However, raising the sintering temperature to 1300 °C resulted in the Na to volatilize, converting the Na_1.1La_0.9Zr₂O_6-δ into La_0.9Zr₂O_6-δ. The conductivities of these materials in a humid atmosphere were tested using electrochemical impedance spectroscopy, and their carrier transport numbers were measured using the defect equilibria model and concentration cell method. Na_1.1La_0.9Zr₂O_6-δ and Na_1.2La_0.8Zr₂O_6-δ are predominantly proton conductors, with Na_1.1La_0.9Zr₂O_6-δ exhibiting the highest proton transport number of 0.52 at 800 °C. In contrast, NaLaZr₂O₆ is predominantly an electronic conductor, while La_0.9Zr₂O_6-δ functions as an oxide ion conductor. Due to their high protonic transport numbers, these Na_1+xLa_1-xZr₂O_6-δ A-site double-perovskite oxides present a promising avenue for the development of proton conductors. Full article

Mixed oxides featuring perovskite-type structures (ABO₃) offer promising catalytic properties for applications focused on the control of atmospheric pollution. In this work, a series of Ba_xMnO₃ (x = 1, 0.9, 0.8 and 0.7) samples have been synthesized, characterized and tested as catalysts for CO oxidation reaction in conditions close to that found in the exhausts of last-generation automotive internal combustion engines. All samples were observed to be active as catalysts for CO oxidation during CO-TPRe tests, with Ba_0.7MnO₃ (B0.7M) being the most active one, as it presents the highest amount of oxygen vacancies (which act as active sites for CO oxidation) and Mn (IV), which features the highest levels of reducibility and the best redox properties. B0.7M has also showcased a high stability during reactions at 300 °C, even though a slightly lower CO conversion is achieved during the second consecutive reaction cycle. This performance appears to be related to the decrease in the Mn (IV)/Mn (III) ratio. Full article

The rapid discovery of photocatalysts with desired performance among tens of thousands of potential perovskites represents a significant advancement. To expedite the design of perovskite-oxide-based photocatalysts, we developed a model of ABO₃-type perovskites using machine learning methods based on atomic and experimental parameters. This model can be used to predict specific surface area (SSA), a key parameter closely associated with photocatalytic activity. The model construction involved several steps, including data collection, feature selection, model construction, web-service development, virtual screening and mechanism elucidation. Statistical analysis revealed that the support vector regression model achieved a correlation coefficient of 0.9462 for the training set and 0.8786 for the leave-one-out cross-validation. The potential perovskites with higher SSA than the highest SSA observed in the existing dataset were identified using the model and our computation platform. We also developed a webserver of the model, freely accessible to users. The methodologies outlined in this study not only facilitate the discovery of new perovskites but also enable exploration of the correlations between the perovskite properties and the physicochemical features. These findings provide valuable insights for further research and applications of perovskites using machine learning techniques. Full article

Engineering of oxygen vacancies (Vo) in nanomaterials allows diligent control of their physicochemical properties. SrTiO₃ possesses the typical ABO₃ structure and has attracted considerable attention among the titanates due to its chemical stability and its high conduction band energy. This has resulted in its extensive use in photocatalytic energy-related processes, among others. Herein, we introduce the use of Flame Spray Pyrolysis (FSP); an industrial and scalable process to produce Vo-rich SrTiO₃ perovskites. We present two types of Anoxic Flame Spray Pyrolysis (A-FSP) technologies using CH₄ gas as a reducing source: Radial A-FSP (RA-FSP); and Axial A-FSP (AA-FSP). These are used for the control engineering of oxygen vacancies in the SrTiO_3-x nanolattice. Based on X-ray photoelectron spectroscopy, Raman and thermogravimetry-differential thermal analysis, we discuss the role and the amount of the Vos in the so-produced nano-SrTiO_3-x, correlating the properties of the nanolattice and energy-band structure of the SrTiO_3-x. The present work further corroborates the versatility of FSP as a synthetic process and the potential future application of this process to engineer photocatalysts with oxygen vacancies in quantities that can be measured in kilograms. Full article

Perovskite-type oxides (ABO₃) are a highly versatile class of materials. They are compositionally flexible, as their constituents can be chosen from a wide range of elements across the periodic table with a vast number of possible combinations. This flexibility enables the tuning of the materials’ properties by doping the A- and/or B-sites of the base structure, facilitating the application-oriented design of materials. The ability to undergo exsolution under reductive conditions makes perovskite-type oxides particularly well-suited for catalytic applications. Exsolution is a process during which B-site elements migrate to the surface of the material where they form anchored and finely dispersed nanoparticles that are crucially important for obtaining a good catalytic performance, while the perovskite base provides a stable support. Recently, exsolution catalysts have been investigated as possible materials for CO₂ utilization reactions like reverse water–gas shift reactions or methane dry reforming. Full article

Bismuth-based oxides with chemical formula ABiO₃, where A = Ca, Zn, Mg, have been recently synthesized and suggested to host ferroelectricity. As these materials possess favorable optical properties, the presence of ferroelectricity with large polarization would further enhance the possible applications, for example, in photovoltaics by improving the separation of charge carriers. In this work, first-principles Density Functional Theory (DFT) calculations are performed to study the relative stability of the different polymorphs and to investigate the structural, electronic, and ferroelectric properties. Furthermore, the effect of compressive and tensile in-plane strain on the polarization and electronic properties is also considered. Our study suggests that CaBiO₃ should have a large electric polarization (1.8 C/m²) comparable to the one of BiFeO₃. Interestingly, the very high polarization appears with only slightly anomalous values of Born effective charges, which would point out a dominant ionic contribution. Our results call for further studies, both from experimental and theoretical sides, to confirm the large electric polarization CaBiO₃ predicted in this work. For ZnBiO₃ and MgBiO₃, we have demonstrated that, up to large values of strain, the perovskite structure retains favorable ferroelectric and electronic (band gap) properties. Full article

Lead-free ceramics 0.96(Na_0.52K_0.48)_0.95Li_0.05NbO₃-0.04CaZrO₃ (NKLN-CZ) are prepared by using the solid-state procedure and two-step synthesis technique. The crystal structure and thermal stability of NKLN-CZ ceramics sintered at 1140–1180 °C are investigated. All the NKLN-CZ ceramics are ABO₃-type perovskite phases without impure phases. With the increase in sintering temperature, a phase transition occurs in NKLN-CZ ceramics from the orthorhombic (O) phase to the concomitance of O-tetragonal (T) phases. Meanwhile, ceramics become dense because of the presence of liquid phases. In the vicinity of ambient temperature, an O-T phase boundary is obtained above 1160 °C, which triggers the improvement of electrical properties for the samples. The NKLN-CZ ceramics sintered at 1180 °C exhibit optimum electrical performances (d₃₃ = 180 pC/N, k_p = 0.31, dS/dE = 299 pm/V, ε_r = 920.03, tanδ = 0.0452, P_r = 18 μC/cm², T_c = 384 °C, E_c = 14 kV/cm). The relaxor behavior of NKLN-CZ ceramics was induced by the introduction of CaZrO3, which may lead to A-site cation disorder and show diffuse phase transition characteristics. Hence, it broadens the temperature range of phase transformation and mitigates thermal instability for piezoelectric properties in NKLN-CZ ceramics. The value of kp for NKLN-CZ ceramics is held at 27.7–31% (variance of k_p < 9%) in the range from −25 to 125 °C. The results indicate that lead-free ceramics NKLN-CZ is one of the hopeful temperature-stable piezoceramics for practical application in electronic devices. Full article

YMnO₃ is a P-type semiconductor with a perovskite-type structure (ABO₃). It presents two crystalline systems: rhombohedral and hexagonal, the latter being the most stable and studied. In the hexagonal system, Mn³⁺ ions are coordinated by five oxygen ions forming a trigonal bipyramid, and the Y³⁺ ions are coordinated by five oxygen ions. This arrangement favors its ferroelectric and ferromagnetic properties, which have been widely studied since 1963. However, applications based on their optical properties have yet to be explored. This work evaluates the photoelectric response and the photocatalytic activity of yttrium manganite in visible spectrum wavelengths. To conduct this, a rod-obelisk-shaped yttrium manganite with a reduced indirect bandgap value of 1.43 eV in its hexagonal phase was synthesized through the precipitation method. The synthesized yttrium manganite was elucidated by solid-state techniques, such as DRX, XPS, and UV-vis. It was non-toxic as shown by the 100% leukocyte viability of mice BALB/c. Full article

Mixed oxides with perovskite-type structure (ABO₃) are promising catalysts for atmospheric pollution control due to their interesting and tunable physicochemical properties. In this work, two series of Ba_xMnO₃ and Ba_xFeO₃ (x = 1 and 0.7) catalysts were synthesized using the sol–gel method adapted to aqueous medium. The samples were characterized by μ-XRF, XRD, FT-IR, XPS, H₂-TPR, and O₂-TPD. The catalytic activity for CO and GDI soot oxidation was determined by temperature-programmed reaction experiments (CO-TPR and soot-TPR, respectively). The results reveal that a decrease in the Ba content improved the catalytic performance of both catalysts, as B0.7M-E is more active than BM-E for CO oxidation, and B0.7F-E presents higher activity than BF for soot conversion in simulated GDI engine exhaust conditions. Manganese-based perovskites (BM-E and B0.7M-E) achieve better catalytic performance than iron-based perovskite (BF) for CO oxidation reaction due to the higher generation of actives sites. Full article

ABO₃ perovskite materials with small cations at the A site, especially those with ordered cation arrangements, have attracted a great deal of interest because they show unusual physical properties and deviations from the general characteristics of perovskites. In this work, perovskite solid solutions (Lu_0.5Mn_0.5)(Mn_1−xTi_x)O₃ with x = 0.25, 0.50, and 0.75 were synthesized by means of a high-pressure, high-temperature method at approximately 6 GPa and approximately 1550 K. All the samples crystallize in the GdFeO₃-type perovskite structure (space group Pnma) and have random distributions of the small Lu³⁺ and Mn²⁺ cations at the A site and Mn^4+/3+/2+ and Ti⁴⁺ cations at the B site, as determined by Rietveld analysis of high-quality synchrotron X-ray powder diffraction data. Lattice parameters are a = 5.4431 Å, b = 7.4358 Å, c = 5.1872 Å (for x = 0.25); a = 5.4872 Å, b = 7.4863 Å, c = 5.2027 Å (for x = 0.50); and a = 5.4772 Å, b = 7.6027 Å, c = 5.2340 Å (for x = 0.75). Despite a significant dilution of the A and B sublattices by non-magnetic Ti⁴⁺ cations, the x = 0.25 and 0.50 samples show long-range ferrimagnetic order below T_C = 89 K and 36 K, respectively. Mn cations at both A and B sublattices are involved in the long-range magnetic order. The x = 0.75 sample shows a spin-glass transition at T_SG = 6 K and a large frustration index of approximately 22. A temperature-independent dielectric constant was observed for x = 0.50 (approximately 32 between 5 and 150 K) and for x = 0.75 (approximately 50 between 5 and 250 K). Full article

Perovskite-type ABO₃ oxides show a number of cation-ordered structures, which have significant effects on their properties. The rock-salt-type order is dominant for B cations, and the layered order for A cations. In this work, we prepared a new perovskite-type oxide, Sm₂CuMn(MnTi₃)O₁₂, with a rare columnar A-site order using a high-pressure, high-temperature method at about 6 GPa and about 1700 K. Its crystal structure was studied with synchrotron powder X-ray diffraction. The compound crystallizes in space group P4₂/nmc (No. 137) at room temperature with a = 7.53477 Å and c = 7.69788 Å. The magnetic properties of the compound were studied with dc and ac magnetic susceptibility measurements and specific heat. Spin-glass (SG) magnetic properties were found with T_SG = 7 K, while specific heat, in the form of C_p/T, showed a strong, very broad anomaly developing below 20 K and peaking at 4 K. The dielectric constant of Sm₂CuMn(MnTi₃)O₁₂ was nearly frequency and temperature independent between 8 K and 200 K, with a value of about 50. Cu²⁺ doping drastically modified the magnetic and dielectric properties of Sm₂CuMn(MnTi₃)O₁₂ in comparison with the parent compound Sm₂MnMn(MnTi₃)O₁₂, which showed a long-range ferrimagnetic order at 34–40 K. The antisite disorder of Cu²⁺ and Mn²⁺ cations between square-planar and octahedral sites was responsible for the SG magnetic properties of Sm₂CuMn(MnTi₃)O₁₂. Full article

Double oxides with the structure of the Ruddlesden–Popper (R-P) layered perovskite A_n+1B_nO_3n+1 attract attention as materials for various electrochemical devices, selective oxygen-permeable ceramic membranes, and catalytic oxidative reactions. In particular, Sr₂TiO₄ layered perovskite is considered a promising catalyst in the oxidative coupling of methane. Our high-resolution transmission electron microscopy (HRTEM) studies of Sr₂TiO₄ samples synthesized using various methods have shown that their structure often contains planar defects disturbing the periodicity of layer alternation. This is due to the crystal-chemical features of the R-P layered perovskite-like oxides whose structure is formed by n consecutive layers of perovskite (ABO₃)_n in alternating with layers of rock-salt type (AO) in various ways along the c crystallographic direction. Planar defects can arise due to a periodicity violation of the layers alternation that also leads to a violation of the synthesized phase stoichiometry. In the present work, a crystallochemical analysis of the possible structure of planar defects is carried out, structures containing defects are modeled, and the effect of such defects on the X-ray diffraction patterns of oxides of the A₂BO₄ type using Sr₂TiO₄ is established as an example. For the calculations, we used the method of constructing probabilistic models of one-dimensionally disordered structures. For the first time, the features of diffraction were established, and an approach was demonstrated for determining the concentration of layer alternation defects applicable to layered perovskite-like oxides of the A₂BO₄ type of any chemical composition. A relation has been established between the concentration of planar defects and the real chemical composition (nonstoichiometry) of the Sr₂TiO₄ phase. The presence of defects leads to the Ti enrichment of particle volume and, consequently, to the enrichment of the surface with Sr. The latter, in turn, according to the data of a number of authors, can serve as an explanation for the catalytic activity of Sr₂TiO₄ in the oxidative coupling of methane. Full article

Sr-doped lanthanum scandate La_1−xSr_xScO_3−δ (LSS) is a promising perovskite-type material for electrochemical applications such as proton conductors. Oxygen vacancy is a common defect in ABO₃-type perovskites. It controls ion transport as well as proton uptake. The energetic, structural, and electronic properties of oxygen vacancy in LSS are studied deploying the DFT method with meta-GGA functional. The vacancy formation energies in LSS were calculated for various Sr concentrations. Unlike other perovskites, in this material, the electrons are trapped at the oxygen vacancy site (the F-type centres, common in ionic oxides like MgO and Al₂O₃) rather than localised on the nearest to the vacancy B-cations. The process of oxygen vacancy formation is considered relative to Sr concentration x and oxygen nonstoichiometry factor δ. Three primary regimes are discussed: (I) localized at the vacancy electrons, x/δ < 2, (II) electron charge balanced system, x/δ = 2, and (III) delocalized electron holes, x/δ > 2. For x/δ ≥ 2 oxygen vacancy formation energy reaches the saturation level of ~3.5 eV, which is potentially beneficial for the proton uptake. Full article

Perovskite (ABO₃) nanosheets with a high carrier mobility have been regarded as the best candidates for gas-sensitive materials arising from their exceptional crystal structure and physical–chemical properties that often exhibit good gas reactivity and stability. Herein, Ag in situ modified porous LaFeO₃ nanosheets were synthesized by the simple and efficient graphene oxide (GO)-assisted co-precipitation method which was used for sensitive and selective ethanol detection. The Ag modification ratio was studied, and the best performance was obtained with 5% Ag modification. The Ag/LaFeO₃ nanomaterials with high surface areas achieved a sensing response value (R_g/R_a) of 20.9 to 20 ppm ethanol at 180 °C with relatively fast response/recovery times (26/27 s). In addition, they showed significantly high selectivity for ethanol but only a slight response to other interfering gases. The enhanced gas-sensing performance was attributed to the combination of well-designed porous nanomaterials with noble metal sensitization. The new approach is provided for this strategy for the potential application of more P-type ABO₃ perovskite-based gas-sensitive devices. Full article