Search Results (40)

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

This paper studies the structural parameters and electrophysical properties (dielectric and piezo electric, as well as currents of thermostimulated depolarization) of samples of composition 0.20BiScO₃·0.45PbTiO₃·0.35PbMg_1/3Nb_2/3O₃ (or in short 0.20BS·0.45PT·0.35PMN) obtained by ceramic and melt-hardening methods of synthesis. In the ceramic method, the samples were obtained from the starting oxides by two-stage firing. In the melt method, amorphous precursors were first obtained from heat-treated and non-heat-treated starting oxide mixtures by melting and subsequent quenching under sharply gradient temperature conditions. Samples were obtained after grinding, pressing, and thermal annealing of the synthesized precursors, and four types of samples differing in size and shape of the intermediate precursor particles (crystallites) were obtained. The X-ray phase analysis showed that the predominant phase in the studied samples is the perovskite phase; in both types of samples, up to 5 wt.% of impurity phase with pyrochlore structure was also present. The samples of 0.20BS·0.45PT·0.35PMN exhibit dielectric properties characteristic of relaxor ferroelectrics, and the polarized samples exhibit a pronounced piezo effect with a piezo modulus value of d₃₃~200 pC/N. A comparative analysis of the properties of the samples obtained by different methods has been carried out. The essential advantage of the melt method is that its use allows obtaining varieties of four kinds of ferroelectric relaxors and reduces the time of synthesis of samples by 2–3 times. Full article

Formaldehyde (HCHO) is identified as the most toxic chemical among 45 organic compounds found in industrial wastewater, posing significant harm to both the environment and human health. In this study, a novel approach utilizing the Lanthanum-manganese complex oxide (LaMnO₃)/peroxymonosulfate (PMS) system was proposed for the effective removal of HCHO from wastewater. Perovskite-Type LaMnO₃ was prepared by sol-gel method. The chemical compositions and morphology of LaMnO₃ samples were analyzed through thermogravimetric analysis (TG), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The effects of LaMnO₃ dosage, PMS concentration, HCHO concentration, and initial pH on the HCHO removal rate were investigated. When the concentration of HCHO is less than 1.086 mg/mL (5 mL), the dosage of LaMnO₃ is 0.06 g, and n(PMS)/n(HCHO) = 2.5, the removal rate of HCHO is more than 96% in the range of pH = 5–13 at 25 °C for 10 min. Compared with single-component MnO₂, the perovskite structure of LaMnO₃ is beneficial to the catalytic degradation of HCHO by PMS. It is an efficient Fenton-like oxidation process for treating wastewater containing HCHO. The LaMnO₃ promoted the formation of SO₄•⁻ and HO•, which sequentially oxidized HCHO to HCOOH and CO₂. Full article

Neutron diffraction instruments offer a platform for materials science and engineering studies at extended temperature ranges far from ambient. As one of the widely used neutron sample environment types, cryogenic furnaces are usually bulky and complex, and they may need hours of beamtime overhead for installation, configuration, cooling, and sample change, etc. To reduce the overhead time and expedite experiments at the state-of-the-art high-flux neutron source, we developed a low-cost, miniature, and easy-to-use cryogenic environment (77–473 K) for in situ neutron diffraction. A travel-size mug serves for the environment where the samples sit inside. Immediate cooling and an isothermal dwell at 77 K are realized on the sample by direct contact with liquid N₂ in the mug. The designed Al inserts serve as the holder of samples and heating elements, alleviate the thermal gradient, and clear neutron pathways. Both a single-sample continuous measurement and multi-sample high-throughput measurements are demonstrated in this environment. High-quality and refinable in situ neutron diffraction patterns are acquired on model materials. The results quantify the orthorhombic-to-cubic phase transformation process in LiMn₂O₄ and differentiate the anisotropic lattice thermal expansions and bond length evolutions between rhombohedral perovskite oxides with composition variation. Full article

Ba_1−xCe_xMnO₃ (BM-Ce_x) and Ba_1−xLa_xMn_0.7Cu_0.3O₃ (BMC-La_x) perovskite-type mixed oxides were synthesized using the sol–gel method adapted for aqueous media with different values of x (0, 0.1, 0.3, 0.6) to estimate the effect of the degree of the partial substitution of Ba by Ce or La on the structure and properties that are relevant for their use as catalysts for gasoline direct injection (GDI) soot oxidation. The samples were deeply characterized by ICP-OES, XRD, XPS, N₂ adsorption, H₂-TPR, and O₂-TPD, and their potential as catalysts for soot oxidation has been analyzed in various scenarios that replicate the exhaust conditions of a GDI engine. By comparing the catalytic performance for soot oxidation of the two tested series (BM-Cex and BMC-Lax) and in the two conditions used (100% He and 1% O₂ in He), it could be concluded that (i) in the absence of oxygen in the reaction atmosphere (100% He), BMC-La_0.1 is the best catalyst, as copper is also able to catalyze the soot oxidation; and (ii) if oxygen is present in the reaction atmosphere (1% O₂/He), BM-Ce_0.1 is the most-active catalyst as it presents a higher proportion of Mn(IV) than BMC-La_0.1. Thus, it seems that the addition of an amount of Ce or La higher than that corresponding to x = 0.1 in Ba_1−xCe_xMnO₃ and Ba_1−xLa_xCu_0.3Mn_0.7O₃ does not allow us to improve the catalytic performance of BM-Ce_0.1 and BMC-La_0.1 for soot oxidation in the tested conditions. Full article

Here, we successfully synthesized Sr-doped perovskite-type oxides of La_1−xSr_xCo_1−λO_3−δ, “LSX” (x = 0, 0.1, 0.3, 0.5, 0.7), using the glycine-assisted solution combustion method. The effect of strontium doping on the catalyst structure, NO to NO₂ conversion, NO_x adsorption and storage, and NO_x reduction performance were investigated. The physicochemical properties of the catalysts were studied by XRD, SEM-EDS, N₂ adsorption–desorption, FTIR, H₂-TPR, O₂-TPD, and XPS techniques. The NSR performance of LaCoO₃ perovskite was improved after Sr doping. Specifically, the perovskite with 50% of Sr doping (LS5 sample) exhibited excellent NO_x storage capacity within a wide temperature range (200–400 °C), and excellent stability after hydrothermal and sulfur poisoning. It also displayed the highest NO_x adsorption–storage capacity (NAC: 1889 μmol/g; NSC: 1048 μmol/g) at 300 °C. This superior performance of the LS5 catalyst can be attributed to its superior reducibility, better NO oxidation capacity, increased surface Co²⁺ concentration, and, in particular, its generation of more oxygen vacancies. FTIR results further revealed that the LSX catalysts primarily store NO_x through the “nitrate route”. During the lean–rich cycle tests, we observed an average NO_x conversion rate of over 50% in the temperature range of 200–300 °C, with a maximum conversion rate of 61% achieved at 250 °C. Full article

The poor film stability of Sn-Pb mixed perovskite film and the mismatched interface energy levels pose significant challenges in enhancing the efficiency of tin–lead (Sn-Pb) mixed perovskite solar cells. In this study, polyvinylpyrrolidone (PVP) is introduced into the PVK perovskite precursor solution, effectively enhancing the overall stability of the film. This improvement is achieved through the formation of robust coordination bonds between the carbonyl (C=O) in the pyrrole ring and the undercoordinated Sn^II and Pb^II, thereby facilitating the passivation of defects. Furthermore, the introduction of PVP inhibits the oxidation of tin (Sn), thereby enhancing the n-type characteristics of the perovskite film. This adjustment in the energy level of the PVK perovskite film proves instrumental in reducing interface energy loss, subsequently improving interface charge transfer and mitigating device recombination. Consequently, perovskite solar cells incorporating PVP achieve an outstanding champion power conversion efficiency (PCE) of 21.31%. Full article

Herein, we present an in-depth investigation into the enhancement of catalytic soot oxidation through cerium-doped three-dimensional ordered macroporous (3DOM) La-Co-Ni-based perovskites synthesized with the colloidal crystal template (CCT) method. The 3DOM structure significantly contributes to the accessibility and interaction efficiency between soot and catalyst. Based on the results of powder X-ray diffraction (XRD), N₂ adsorption-desorption measurements, scanning electron microscopy (SEM), temperature-programmed oxidation of NO (NO-TPO), temperature-programmed reduction of H₂ (H₂-TPR), in situ infrared Fourier transform spectroscopy (In-situ DRIFTS), and temperature-programmed oxidation (TPO) reactions, the role of cerium doping in modifying the structural and catalytic properties of 3DOM perovskite-type La_2−xCe_xCoNiO₆ catalysts was investigated systematically. The optimized cerium doping ratio in La_2−xCe_xCoNiO₆ catalysts can improve the microenvironment for efficient soot-catalyst contact, enhancing the catalytic activity of soot oxidation. Among the catalysts, the 3DOM La_0.8Ce_1.2CoNiO₆ catalyst shows the highest catalytic activity for soot oxidation, whose T₁₀, T₅₀, and T₉₀ values are 306 °C, 356 °C, and 402 °C, respectively. The mechanism of the cerium doping effect for boosting soot oxidation is proposed: The doping of Ce ions can increase the surface oxygen species, which is the main active species for promoting the key step of NO oxidation to NO₂ in catalyzing soot oxidation. This research provides a new strategy to develop high-efficient non-noble metal catalysts for soot oxidation in pollution control and sustainable environmental practices. Full article

Perovskite-type Sr(Ti,V)O_3-δ ceramics are promising anode materials for natural gas- and biogas-fueled solid oxide fuel cells, but the instability of these phases under oxidizing conditions complicates their practical application. The present work explores approaches to the fabrication of strontium titanate-vanadate electrodes from oxidized precursors. Porous ceramics with the nominal composition SrTi_1−yV_yO_z (y = 0.1–0.3) were prepared in air via a solid state reaction route. Thermal processing at temperatures not exceeding 1100 °C yielded composite ceramics comprising perovskite-type SrTiO₃, pyrovanadate Sr₂V₂O₇ and orthovanadate Sr₃(VO₄)₂ phases, while increasing firing temperatures to 1250–1440 °C enabled the formation of SrTi_1−yV_yO₃ perovskites. Vanadium was found to substitute into the titanium sublattice predominantly as V⁴⁺, even under oxidizing conditions at elevated temperatures. Both perovskite and composite oxidized ceramics exhibit moderate thermal expansion coefficients in air, 11.1–12.1 ppm/K at 30–1000 °C, and insignificant dimensional changes induced by reduction in a 10%H₂-N₂ atmosphere. The electrical conductivity of reduced perovskite samples remains comparatively low, ~10⁻¹ S/cm at 900 °C, whereas the transformation of oxidized vanadate phases into high-conducting SrVO_3−δ perovskites upon reduction results in enhancement in conductivity, which reaches ~3 S/cm at 900 °C in porous composite ceramics with nominal composition SrTi_0.7V_0.3O_z. The electrical performance of the composite is expected to be further improved by optimization of the processing route and microstructure to facilitate the reduction of the oxidized precursor and attain better percolation of the SrVO₃ phase. Full article

In this research work, the photocatalytic capacity shown by the nanoparticles of the CaTiO₃ system was evaluated to degrade two pollutants of emerging concern, namely methyl orange (MO)—considered an organic contaminating substance of the textile industry that is non-biodegradable when dissolved in water—and levofloxacin (LVF), an antibiotic widely used in the treatment of infectious diseases that is released mostly to the environment in its original chemical form. The synthesis process used to obtain these powders was the polymeric precursor method (Pechini), at a temperature of 700 °C for 6 h. The characterization of the obtained oxide nanoparticles of interest revealed the presence of a majority perovskite-type phase with an orthorhombic $\mathrm{P}\mathrm{b}\mathrm{n}\mathrm{m}$ structure and a minority rutile-type $\mathrm{T}\mathrm{i}{\mathrm{O}}_2$ phase, with a $\mathrm{P}42/\mathrm{m}\mathrm{n}\mathrm{m}$ structure and a primary particle size $<100\mathrm{n}\mathrm{m}$. The adsorption–desorption isotherms of the synthesized solids had H3-type hysteresis loops, characteristic of mesoporous solids, with a BET surface area of $10.01{\mathrm{m}}^2/\mathrm{g}$. The Raman and FTIR spectroscopy results made it possible to identify the characteristic vibrations of the synthesized system and the characteristic deformations of the perovskite structure, reiterating the results obtained from the XRD analysis. Furthermore, a bandgap energy of $~3.4\mathrm{e}\mathrm{V}$ and characteristic emissions in the violet (437 nm/2.8 eV) and orange (611 nm/2.03 eV) were determined for excitation lengths of 250 nm and 325 nm, respectively, showing that these systems have a strong emission in the visible light region and allowing their use in photocatalytic activity to be potentialized. The powders obtained were studied for their photocatalytic capacity to degrade methyl orange (MO) and levofloxacin (LVF), dissolved in water. To quantify the coloring concentration, UV–visible spectroscopy was used considering the variation in the intensity of the characteristic of the greatest absorption, which correlated with the change in the concentration of the contaminant in the solution. The results showed that after irradiation with ultraviolet light, the degradation of the contaminants MO and LVF was 79.4% and 98.1% with concentrations of 5 g/L and 10 g/L, respectively. Full article

There is an urgent need to develop a low-cost and high-performance gas sensor for industrial production and daily life. Perovskite-type oxides are appropriate materials for resistive gas sensors. In this paper, two gas-sensing materials of gadolinium orthoferrite (GdFeO₃) with rod and butterfly morphologies were obtained by annealing the corresponding precursors at 800 °C in a muffle furnace for 3 h. The precursors of GdFe(CN)₆·4H₂O with novel morphologies were prepared by a co-precipitation method at room temperature. The materials were evaluated in terms of their structure, morphology, and gas-sensing performance. The gas sensor based on GdFeO₃ rods showed a better sensing performance than the sensor based on GdFeO₃ butterflies. It exhibited the largest response value of 58.113 to 100 ppm n-propanol at a relatively low operating temperature of 140 °C, and the detection limit was 1 ppm. The results show that the GdFeO₃ rods-based sensor performed well in detecting low concentration n-propanol. The satisfactory gas-sensing performance of the GdFeO₃ rods-based sensor may be due to the porous structure and the large percentages of defect oxygen and adsorbed oxygen (37.5% and 14.6%) on the surface. This study broadens the application of GdFeO₃ in the gas sensor area. Full article

As we approach the limits of semiconductor technology, the development of new materials and technologies for the new era in electronics is compelling. Among others, perovskite oxide hetero-structures are anticipated to be the best candidates. As in the case of semiconductors, the interface between two given materials can have, and often has, very different properties, compared to the corresponding bulk compounds. Perovskite oxides show spectacular interfacial properties due to the the rearrangement of charges, spins, orbitals and the lattice structure itself, at the interface. Lanthanum aluminate and Strontium titanate hetero-structures (LaAlO${}_3$/SrTiO${}_3$) can be regarded as a prototype of this wider class of interfaces. Both bulk compounds are plain and (relatively) simple wide-bandgap insulators. Despite this, a conductive two-dimensional electron gas (2DEG) is formed right at the interface when a LaAlO${}_3$ thickness of $n\ge 4$ unit cells is deposited on a SrTiO${}_3$ substrate. The 2DEG is quite thin, being confined in only one or at least very few mono-layers at the interface, on the SrTiO${}_3$ side. A very intense and long-lasting study was triggered by this surprising discovery. Many questions regarding the origin and characteristics of the two-dimensional electron gas have been (partially) addressed, others are still open. In particular, this includes the interfacial electronic band structure, the transverse plane spatial homogeneity of the samples and the ultrafast dynamics of the confined carriers. Among a very long list of experimental techniques which have been exploited to study these types of interfaces (ARPES, XPS, AFM, PFM, …and many others), optical Second Harmonic Generation (SHG) was found to be suitable for investigating these types of buried interfaces, thanks to its extreme and selective interface-only sensitivity. The SHG technique has made its contribution to the research in this field in a variety of different and important aspects. In this work we will give a bird’s eye view of the currently available research on this topic and try to sketch out its future perspectives. Full article

Double-layered manganites are natural superlattices with low thermal conductivity, which is of importance for potential thermoelectric applications. The Gd_2−2xSr_1+2xMn₂O₇ (x = 0.5; 0.625; 0.75) were prepared by the solid-state reaction method. All the samples crystallize in the tetragonal I4/mmm Sr₃Ti₂O₇ type structure. The unit cell volume and the distortion in the MnO₆ octahedra increase with increasing Gd content. Their thermoelectric properties were investigated between 300 and 1200 K. All exhibit an n-type semiconducting behavior. The electrical conductivity (σ) increases while the absolute value of the Seebeck coefficient (|S|) decreases with increasing Gd content. Simultaneous increases in σ and |S| with increasing temperature are observed at temperatures approximately higher than 600 K, and the power factor reaches a maximum value of 18.36 μW/(m K²) for x = 0.75 at 1200 K. The thermal conductivity (κ) is lower than 2 W/(m K) over the temperature range of 300–1000 K for all the samples and a maximum dimensionless figure of merit ZT of 0.01 is obtained for x = 0.75 at 1000 K. Full article

Photoelectrochemical (PEC) solar water splitting is favourable for transforming solar energy into sustainable hydrogen fuel using semiconductor electrodes. Perovskite-type oxynitrides are attractive photocatalysts for this application due to their visible light absorption features and stability. Herein, strontium titanium oxynitride (STON) containing anion vacancies of SrTi(O,N)_3−δ was prepared via solid phase synthesis and assembled as a photoelectrode by electrophoretic deposition, and their morphological and optical properties and PEC performance for alkaline water oxidation are investigated. Further, cobalt-phosphate (CoPi)-based co-catalyst was photo-deposited over the surface of the STON electrode to boost the PEC efficiency. A photocurrent density of ~138 μA/cm at 1.25 V versus RHE was achieved for CoPi/STON electrodes in presence of a sulfite hole scavenger which is approximately a four-fold enhancement compared to the pristine electrode. The observed PEC enrichment is mainly due to the improved kinetics of oxygen evolution because of the CoPi co-catalyst and the reduced surface recombination of the photogenerated carriers. Moreover, the CoPi modification over perovskite-type oxynitrides provides a new dimension for developing efficient and highly stable photoanodes in solar-assisted water-splitting reactions. Full article

The organic–inorganic lead halide hybrids comprising semiconducting perovskite components and organic modules have proven to be promising candidates for optoelectronic applications. The modulation of the inorganic components as optical centres by diverse organic cationic templates is under intense investigation. Herein, we successfully prepared new one-dimensional lead halide hybrid perovskites [L1]_2n[Pb₂Cl₆]_n∞·nH₂O (1) and [PbBr₂(L2)]_n∞·0.5nH₂O (2), and the dimeric complex [PbBr₂(L3)]₂ (3) in water media. In 1, 2-(2-hydroxyethyl)-2H-imidazo[1,5-a]pyridinium cation [L1]⁺ resulted from the oxidative condensation–cyclization between formaldehyde, ethanolamine and 2-pyridinecarbaldehyde (2-PCA); the polydentate Schiff base ligands L2 and L3 formed in the in situ condensation of 2-PCA and ethanolamine or ethylenediamine, respectively. The lead chloride hybrid 1 contains the previously unreported type of a [Pb₂Cl₆]_∞ double chain constructed from three-edge- and five-edge-sharing PbCl₆ octahedra, and cations forming π-bonded stacks aligned along the inorganic wires. In the crystal of 2, pairs of the double-side organically decorated [PbBr₂(L2)]_∞ chains built of corner-sharing PbBr₃N₂O octahedra arrange hydrophilic channels to host water molecules. In the solid state, the identically stacked dimers of 3 form columns parallel to the ab plane with the Pb₂Br₄ moieties in the column being strictly coplanar. Hirshfeld surface analysis was used to rationalize the packing patterns through hydrogen bonds of O−H···O/Cl and C−H···O/Cl types with the involvement of OH groups of [L1]⁺, L2 and water molecules in 1 and 2, as well as C–H∙∙∙Br hydrogen bonding in 2 and 3. The QTAIM analysis of non-covalent interactions in 1–3 was performed. According to the analysis of the solid-state UV–visible reflectance spectra by a Tauc plot, the optical band gap values of 1, 2 and 3 as direct gap semiconductors were estimated to be 3.36, 3.13 and 2.96 eV, respectively. Full article