Search Results (188)

Facing energy and environmental issues is recognized globally as one of the major challenges for sustainable development, to which sustainable chemistry can make significant contributions. Strontium ferrate-based materials belong to a little-known class of perovskite-type compounds in which iron is primarily stabilized in the unusual 4+ oxidation state, although some Fe³⁺ is often present, depending on the synthesis and processing conditions and the type and amount of dopant. When doped with cerium at the Sr site, the SrFeO_3−δ cubic structure is stabilized, more oxygen vacancies form and the Fe⁴⁺/Fe³⁺ redox couple plays a key role in its functional properties. Alone or combined with other materials, Ce-doped strontium ferrates can be successfully applied to wastewater treatment. Specific doping at the Fe site enhances their electronic conductivity for use as electrodes in solid oxide fuel cells and electrolyzers. Their oxygen storage capacity and oxygen mobility are also exploited in chemical looping reactions. The main limitations of these materials are SrCO₃ formation, especially at the surface; their low surface area and porosity; and cation leaching at acidic pH values. However, these limitations can be partially addressed through careful selection of synthesis, processing and testing conditions. This review highlights the high versatility and efficiency of cerium-doped strontium ferrates for energy and environmental applications, both at low and high temperatures. The main literature on these compounds is reviewed to highlight the impact of their key properties and synthesis and processing parameters on their applicability as sustainable thermocatalysts, electrocatalysts, oxygen carriers and sensors. Full article

Recently, we have described SrMo_1-xMg_xO_3-δ perovskites (x = 0.1, 0.2) as excellent anode materials for solid oxide fuel cells (SOFCs), with mixed ionic and electronic conduction (MIEC) properties. After depositing on the solid electrolyte, they were annealed for sintering at high temperatures (typically 1000 °C), giving rise to oxidized scheelite-type phases, with SrMo_1-xMg_xO_4-δ (x = 0.1, 0.2) stoichiometry. To obtain the active perovskite phases, they were reduced again in the working anode conditions, under H₂ atmosphere. Therefore, there must be an excellent reversibility between the oxidized Sr(Mo, Mg)O_4-δ scheelite and the reduced Sr(Mo, Mg)O_3-δ perovskite phases. This work describes the topotactical oxidation, by annealing at 400 °C in air, of the SrMo_0.9Mg_0.1O_3-δ perovskite oxide. The characterization by X-ray diffraction (XRD) and neutron powder diffraction (NPD) was carried out in order to determine the crystal structure features. The scheelite oxides are tetragonal, space group I4₁/a (No. 88), whereas the perovskites are cubic, s.g. Pm-3m (No. 221). The Rietveld refinement of the scheelite phase from NPD data after annealing the perovskite at 400 °C and cooling it down slowly to RT evidences the absence of intermediate phases between perovskite and scheelite oxides, as well as the presence of oxygen vacancies in both oxidized and reduced phases, essential for their performance as MIEC oxides. The topotactical relationship between both crystal structures is discussed. Full article

This work explored an electrochemical approach for synthesizing lanthanum-modified nickel oxide (NiO_x:La) as a hole transport layer (HTL) in inverted perovskite solar cells (IPSCs). By varying the La³⁺ concentration, the chemical, charge transport, structural, and morphological properties of the NiO_x:La film and the HTL/PVK interface were evaluated to enhance photovoltaic performance. X-ray photoelectron spectroscopy (XPS) confirmed La³⁺ incorporation, a higher Ni³⁺/Ni³⁺ ratio, and a valence band shift, improving p-type conductivity. Electrochemical impedance spectroscopy and Mott–Schottky analyses indicated that NiO_x:La 0.5% exhibited the lowest resistance and the highest carrier density, correlating with higher recombination resistance. The NiO_x:La 0.5% based cell achieved a PCE of 20.08%. XRD and SEM confirmed no significant changes in PVK structure, while photoluminescence extinction demonstrated improved charge extraction. After 50 days, this cell retained 80% of its initial PCE, whereas a pristine NiO_x device retained 75%. Hyperspectral imaging revealed lower optical absorption loss and better homogeneity. These results highlight NiO_x:La as a promising HTL for efficient and stable IPSCs. Full article

This study focuses on enhancing the photoelectrocatalytic (PEC) performance of LaFeO₃ photocathodes by incorporating Ag nanocrystals. LaFeO₃, a perovskite-type metal oxide semiconductor, has potential in PEC water splitting but suffers from fast charge carrier recombination. Ag nanoparticles are introduced due to their surface plasmon resonance (SPR) property and ability to form Schottky junctions with LaFeO₃. A series of Ag/LaFeO₃ materials are prepared using the molten salt method for LaFeO₃ synthesis and the direct reduction method for Ag loading. The results show that Ag nanoparticles are uniformly dispersed on LaFeO₃. The 3 mol% Ag/LaFeO₃ photocathode demonstrates a remarkable ninefold increase in photocurrent density (15 mA·cm⁻² at −0.2 V vs. RHE) compared to pure LaFeO₃ (1.7 mA·cm⁻²). The band gap of LaFeO₃ is reduced from 2.07 eV to 1.92 eV with 3 mol% Ag loading, and the charge transfer impedance is reduced by 77%, while the carrier concentration increases by 2.3 times. The novelty of this work lies in the comprehensive investigation of the interaction mechanisms between Ag nanoparticles and LaFeO₃, which lead to enhanced light absorption, improved charge separation, and increased electrochemical activity. The optimized Ag loading not only improves the photocatalytic efficiency but also enhances the stability of the photocathode. This work provides valuable insights into the interaction between Ag and LaFeO₃, and offers experimental and theoretical support for developing efficient photocatalytic materials for PEC water splitting. Full article

Volatile organic compound (VOC) emissions have become a critical environmental concern due to their contributions to photochemical smog formation, secondary organic aerosol generation, and adverse human health impacts in the context of accelerated industrialization and urbanization. Catalytic oxidation over perovskite-type catalysts is an attractive technological approach for efficient VOC abatement. This review systematically evaluates the advancements in perovskite-based catalysts for VOC oxidation, focusing on their crystal structure–activity relationships, electronic properties, synthetic methodologies, and nanostructure engineering. Emphasis is placed on metal ion doping strategies and supported catalyst configurations, which have been demonstrated to optimize catalytic performance through synergistic effects. The applications of perovskite catalysts in diverse oxidation systems, including photocatalysis, thermal catalysis, electrocatalysis, and plasma-assisted catalysis, are comprehensively discussed with critical analysis of their respective advantages and limitations. It summarizes the existing challenges, such as catalyst deactivation caused by carbon deposition, sulfur/chlorine poisoning, and thermal sintering, as well as issues like low energy utilization efficiency and the generation of secondary pollutants. By consolidating current knowledge and highlighting future research directions, this review provides a solid foundation for the rational design of next-generation perovskite catalysts for sustainable VOC management. Full article

In this work, we report the synthesis of perovskite-type Ba-doped LaFeO₃ (La_1−xBa_xFeO₃, x = 0.00, 0.02, 0.04, and 0.06) nanofibers (NFs) using the electrospinning method. The synthesized La_1−xBa_xFeO₃ materials have a fibrous structure with an average fiber diameter of 250 nm. The fibers, in turn, consist of smaller crystalline particles of 20–50 nm in size. The sensor properties of La_1−xBa_xFeO₃ nanofibers were studied when detecting 20 ppm CO, CH₄, methanol, and acetone in dry air in the temperature range of 50–350 °C. Doping with barium leads to a significant increase in sensor response and a decrease in operating temperature when detecting volatile organic compounds (VOCs). The process of acetone oxidation on the surface of the most sensitive La_0.98Ba_0.02FeO₃ material was studied using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption in combination with mass spectrometry (TPD-MS). A mechanism for the sensor signal formation is proposed. Full article

As one of the representative transparent conducting oxides, perovskite-typed La-doped BaSnO₃ (LBSO) films could be integrated with other perovskite materials to create all-perovskite oxide devices exhibiting exotic physical properties. To overcome the intricate trade-off between conductivity and transmittance in LBSO-based devices, understanding the structural modulating mechanisms of transmittance is definitely crucial. In this paper, the influences of the prevailing Ruddlesden–Popper faults (RP faults) on the transmittance of LBSO films were systematically illuminated, whose density were regulated by the oxygen partial pressures during film growth. High-angle annular dark field (HAADF) STEM and X-ray diffraction (XRD) were employed to characterize the microstructures of the films growing under various oxygen partial pressures and annealing under different oxygen partial pressures. A decrease in RP fault density was observed in the films grown and annealed at high oxygen partial pressures, which displayed improved visible light transmittance. Atomic-scale energy-dispersive spectroscopy (EDS) and electron energy-loss spectroscopy (EELS) analyses revealed the different electronic structure at RP faults compared with the bulk material, including the double concentration of La and increased M5/M4 white line ratio, which is modulative by the oxygen deficiency in LBSO film. It is revealed that the RP defaults in LBSO films annealed at low oxygen pressures displayed larger changes in electronic structure compared with the counterparts with low oxygen deficiency. This work suggests that the oxygen deficiency in LSBO films plays a crucial role in changing the density of RP faults and their electronic structures, thereby regulating the transmittance of LBSO films, which would provide guidance for fabricating high-performance LBSO films. Full article

The chemical looping reforming of methane using an SrFeO₃ oxygen carrier to produce synthesis gas from solar energy was experimentally investigated and validated. High-temperature solar heat was used to provide the reaction enthalpy, and therefore the methane feedstock was entirely dedicated to producing syngas. The two-step isothermal process encompassed partial perovskite reduction with methane (partial oxidation of CH₄) and exothermic oxidation of SrFeO_3-δ with CO₂ or H₂O splitting under the same operating temperature. The oxygen carrier material was shaped in the form of a reticulated porous foam structure for enhancing heat and mass transfer, and it was cycled in a solar-heated tubular reactor under different operating parameters (temperature: 950–1050 °C, methane mole fraction: 5–30%, and type of oxidant gas: H₂O vs. CO₂). This study aimed to assess the fuel production capacity of the two-step process and to demonstrate the potential of using strontium ferrite perovskite during solar cycling for the first time. The maximum H₂ and CO production rates during CH₄-induced reduction were 70 and 25 mL/min at 1000 °C and 15% CH₄ mole fraction. The increase in both the cycle temperature and the methane mole fraction promoted the reduction step, thereby enhancing syngas yields up to 569 mL/g during reduction at 1000 °C under 30% CH₄ (778 mL/g including both cycle steps), and thus outperforming the performance of the benchmark ceria material. In contrast, the oxidation step was not significantly affected by the experimental conditions and the material’s redox performance was weakly dependent on the nature of the oxidizing gas. The syngas yield remained above 200 mL/g during the oxidation step either with H₂O or CO₂. Twelve successive redox cycles with stable patterns in the syngas production yields validated material stability. Combining concentrated solar energy and chemical looping reforming was shown to be a promising and sustainable pathway toward carbon-neutral solar fuels. Full article

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

We report on a series of SrMo_1−xMn_xO_3−δ perovskite oxides designed as potential anode materials for solid oxide fuel cells (SOFCs). These materials were synthesized using a citrate method, yielding scheelite-type precursors with nominal SrMo_1−xMn_xO₄ compositions, which were further reduced to obtain the active perovskite oxides. Their structural evolution was examined through X-ray diffraction (XRD) and neutron powder diffraction (NPD). These techniques provided insights into the crystallographic changes upon Mn doping, revealing key factors influencing ionic conductivity. Whereas the oxidized scheelite precursors are tetragonal, space group I4₁/a, the reduced perovskite specimens are cubic, space group Pm-3m, and show the conspicuous absence of oxygen vacancies, even at the highest temperature of 800 °C. The transport properties were analyzed through electrical conductivity measurements, exhibiting a metallic-like behavior. Thermogravimetric analysis (TGA) and dilatometry give insights into the thermal stability and expansion behavior, essential for SOFC operation. Test single SOFCs were built in an electrolyte-supported configuration, on LSGM pellets of 300 μm thickness, assessing the performance of the title materials as anodes. This work emphasizes the critical relationship between the crystal structure and its electrochemical behavior, providing a deeper understanding of how doping strategies can optimize fuel cell performance. Full article

X-ray diffraction analysis of the pseudo-binary SrFe_1−xV_xO_3−δ system showed that the solid solution formation limit at atmospheric oxygen pressure corresponds to x ≈ 0.1. SrFe_0.9V_0.1O_3−δ has a cubic perovskite-type structure with the Pm$\overline{3}$m space group. The oxygen nonstoichiometry variations in SrFe_0.9V_0.1O_3−δ, measured by coulometric titration in the oxygen partial pressure range of 10⁻²¹ to 0.5 atm at 1023–1223 K, can be adequately described using an ideal solution approximation with V⁵⁺ as the main oxidation state of vanadium cations. This approach was additionally validated by statistical thermodynamic modeling. The incorporation of vanadium decreases both oxygen deficiency and the average iron oxidation state with respect to undoped SrFeO_3−δ. As a result, the electrical conductivity, thermal expansion and chemical expansivity associated with the oxygen vacancy formation all become lower compared to strontium ferrite. At 923 K, the conductivity of SrFe_0.9V_0.1O_3−δ is 14% lower than that of SrFeO_3−δ but 21% higher compared to SrFe_0.9Ta_0.1O_3−δ. The area-specific polarization resistance of the porous SrFe_0.9V_0.1O_3−δ electrode deposited onto 10 mol.% scandia- and 1 mol.% yttria-co-stabilized zirconia solid electrolyte with a protective Ce_0.9Gd_0.1O_2−δ interlayer, was 0.34 Ohm×cm² under open-circuit conditions at 1173 K in air. Full article

Direct light olefin synthesis from bio-syngas hydrogenation is a promising pathway to decarbonize the chemical industry. The present study is devoted to the investigation of co-hydrogenation of carbon oxides in the presence of complex systems with the perovskite structure GdBO₃ (B = Fe, Mn, Co). The catalyst samples were synthesized by sol-gel technology and characterized by XRD, XPS, BET and TPR. It was found that the Fe/Mn-containing samples exhibited efficient catalysis of the hydrogenation of simulated bio-syngas to light hydrocarbons. The GdMnO₃ catalyst exhibits selectivity for C₂–C₃ light olefins of up to 37% among C1+ hydrocarbons, with a maximum olefin/paraffin ratio. GdMnO₃ also exhibits high conversion of CO and CO₂, reaching up to 70–75% at 723 K. However, the GdFeO₃ catalyst shows a lower selectivity of (${\mathit{C}}_{2-3}^{=}$ = 22%, while it exhibits a higher conversion of CO₂, up to 95%, at the same temperature. Herein, we established a catalyst structure–performance relationship as a function of chemical composition. Oxygen mobilities and ratios of surface (O_s) to lattice (O_l) oxygen, forms of hydrogen adsorption, formation of -CH_x- radicals and their subsequent recombination to olefins are influenced by the nature of the element in the B position. This work provides valuable insights for the rational design of bimetallic catalysts for bio-syngas hydrogenation. Full article

In the era of artificial intelligence and Internet of Things, data storage has an important impact on the future development direction of data analysis. Resistive random-access memory (RRAM) devices are the research hotspot in the era of artificial intelligence and Internet of Things. Perovskite-type rare-earth metal oxides are common functional materials and considered promising candidates for RRAM devices because their interesting electronic properties depend on the interaction between oxygen ions, transition metals, and rare-earth metals. LaCoO₃, NdCoO₃, and SmCoO₃ are typical rare-earth cobaltates (RCoO₃). These perovskite materials were fabricated by electrospinning and the calcination method. The aim of this study was to investigate the resistive switching effect in the RCoO₃ structure. The oxygen vacancies in RCoO₃ are helpful to form conductive filaments, which dominates the resistance transition mechanism of Pt/RCoO₃/Pt. The electronic properties of RCoO₃ were investigated, including the barrier height and the shape of the conductive filaments. This study confirmed the potential application of LaCoO₃, NdCoO₃, and SmCoO₃ in memory storage devices. Full article

Early on, oxides were ruled out from superconductivity, since they are typically large-band-gap insulators. Nevertheless, a rather small number of them were found to be superconducting, with transition temperatures up to 14 K and a remarkably low carrier density. This was the starting point of K. Alex Müller (KAM) becoming interested in superconductivity in oxides. Step by step, he advanced the research on oxides and finally discovered, together with J. Georg Bednorz, high-temperature superconductivity (HTSC) in the perovskite-type compound Ba-La-Cu-O. Even though he was inspired by specific and clear ideas in his search, he added new impact in the understanding of HTSC for many years after receipt of the Nobel prize for this discovery. Full article

Amidst the swift expansion of the electric vehicle industry, the imperative for alternative battery technologies that balance economic feasibility with sustainability has reached unprecedented importance. Herein, we utilized Perovskite-based oxide compounds barium titanate (BaTiO₃) and strontium titanate (SrTiO₃) nanoparticles as anode materials for lithium-ion batteries from straightforward and standard carbonate-based electrolyte with 10% fluoroethylene carbonate (FEC) additive [1M LiPF₆ (1:1 EC: DEC) + 10% FEC]. SrTiO₃ and BaTiO₃ electrodes can deliver a high specific capacity of 80 mA h g⁻¹ at a safe and low average working potential of ≈0.6 V vs. Li/Li⁺ with excellent high-rate performance with specific capacity of ~90 mA h g⁻¹ at low current density of 20 mA g⁻¹ and specific capacity of ~80 mA h g⁻¹ for over 500 cycles at high current density of 100 mA g⁻¹. Our findings pave the way for the direct utilization of perovskite-type materials as anode materials in Li-ion batteries due to their promising potential for Li⁺ ion storage. This investigation addresses the escalating market demands in a sustainable manner and opens avenues for the investigation of diverse perovskite oxides as advanced anodes for next-generation metal-ion batteries. Full article