Search Results (33)

Lanthanide perovskite materials are promising candidates for supercapacitor applications. In this study, a series of La_1−xCa_xCrO₃ (x = 0–0.2) materials were prepared by sol-gel method, incorporating bivalent ions calcium at A-site. La_0.85Ca_0.15CrO₃ exhibited the lowest charge transfer resistance and highest specific surface area. At 1 A/g, La_0.85Ca_0.15CrO₃ achieved a maximum specific capacitance of 306 F/g, about 2.3 times higher than that of the LaCrO₃ (133 F/g). Based on the observed data, a mechanism involving oxygen anion charge storage during the charging-discharging process is proposed. After 5000 long cycle, the coulomb efficiency of the electrode remains above 94%. These results demonstrate that Ca-substituted compounds exhibit significant potential for A-site engineering in supercapacitor applications. Full article

This study comparatively evaluates the performance of ABO₃ perovskite materials (A = La, Ca, Sr; B = Mn, Fe) as oxygen carriers in three-step Chemical Looping Hydrogen (CLH) technology, focusing on redox behavior, oxygen transport capacity, hydrogen production, and selectivity under controlled pulse-mode conditions. The redox behavior of the materials is analyzed in relation to their defect chemistry. Perovskites such as (La_1−xCa_x)MnO₃, (La_1−xSr_x)MnO₃, and (La_0.6Ca_0.4)(Mn_1−xFe_x)O₃ were synthesized via wet chemical methods and tested in chemical looping cycles. Doping A-site cations with Ca or Sr enhanced oxygen delivery capacity by more than 100% upon reduction with CH₄ when dopant content (x) increased from 0 to 0.5. However, H₂ selectivity decreased from 52% to 2.5% for (La_1−xCa_x)MnO₃ and from 46% to 14% for (La_1−xSr_x)MnO₃ under the same conditions. In contrast, substituting Mn with Fe significantly improved hydrogen production, particularly in LaFeO₃, which exhibited the highest hydrogen selectivity and yield. At 1000 °C, LaFeO₃ produced nearly 10 mmol H₂ g⁻¹, with 80% generated during the reduction step at 99.9% selectivity and the remaining 20% during the water-splitting step at 100% selectivity. These results are linked to the extent of B-site cation reduction reactions (i) B⁴⁺ → B³⁺, which facilitates complete fuel oxidation and (ii) B³⁺ → B²⁺, which leads to partial fuel oxidation. The reverse of (ii) also contributes to H₂ production during water splitting. Additionally, the study assesses the materials’ microstructure and stability over prolonged cycles. The findings highlight Fe-based perovskites, particularly LaFeO₃, as promising candidates for CLH applications, emphasizing the need for structural and compositional optimization to enhance hydrogen production efficiency. Full article

Good piezoelectricity and high resistivity are prerequisites for high-temperature acceleration sensors to function correctly in high-temperature environments. Bismuth layered structure ferroelectrics (BLSFs) are promising candidates for piezoelectric ceramics with excellent piezoelectric performance at high temperatures, high electrical resistivity, and high Curie temperatures (T_c). In this study, (LiMn)⁵⁺ is substituted for Bi at the A-site, and Ce-doping is performed to replace Ti ions in Na_0.5Bi_4.5Ti₄O₁₅, which achieves the desired combination of high piezoelectric coefficients and high resistivity. Herein, we prepared Na_0.5Bi₃(LiMn)_0.9Ti_4−xCe_xO₁₅ high-temperature piezoelectric ceramics, achieving a high piezoelectric coefficient d₃₃ of 32.0 pC/N and a high resistivity ρ of 1.2 × 10⁸ Ω·cm (at 500 °C), and a high Curie temperature of 648 °C. It is important that the d₃₃ variation remains within 8% over a wide temperature range from 25 °C to 600 °C, demonstrating excellent thermal stability. Structural characterization and microstructure analysis showed that the excellent piezoelectric coefficient and high resistivity of cerium-doped Na_0.5Bi_4.5Ti₄O₁₅-based ceramics are attributable to the synergistic effects of structural characteristics, defect concentration, refined grain size and domain morphology. This study demonstrates that the superior properties of Na_0.5Bi₃(LiMn)_0.9Ti_4−xCe_xO₁₅ ceramics are crucial for the stable operation of high-temperature accelerometer sensors and for the development of high-temperature devices. Full article

High-entropy perovskite materials (HEPMs), characterized by their multi-element composition and highly disordered structure, can incorporate multiple rare earth elements at the A-site, producing perovskites with enhanced CO₂ resistance, making them stay high performance and structurally stable in the CO₂ atmosphere. However, this modification may result in reduced oxygen permeability. In this study, we investigated La_0.2Pr_0.2Nd_0.2Ba_0.2Sr_0.2Co_0.8Fe_0.2O_3-δ (L_0.2M_1.8) high-entropy perovskite materials, focusing on enhancing their oxygen permeability in both air and CO₂ atmospheres through strategic design modifications at the B-sites and A/B-sites. We prepared Ni-substituted La_0.2Pr_0.2Nd_0.2Ba_0.2Sr_0.2Co_0.7Fe_0.2Ni_0.1O_3-δ (L_0.2M_1.7N_0.1) HEPMs by introducing Ni elements at the B-site, and further innovatively introduced A-site defects to prepare La_0.2Pr_0.2Nd_0.2Ba_0.2Sr_0.2Co_0.7Fe_0.2Ni_0.1O_3-δ (L_0.1M_1.7N_0.1) materials. In a pure CO₂ atmosphere, the oxygen permeation flux of the L_0.1M_1.7N_0.1 membrane can reach 0.29 mL·cm⁻²·min⁻¹. Notably, the L_0.1M_1.7N_0.1 membrane maintained a good perovskite structure after stability tests extending up to 120 h under 20% CO₂/80% He atmosphere. These findings suggest that A-site-defect high-entropy perovskites hold great promise for applications in CO₂ capture, storage, and utilization. Full article

Hybrid organic-inorganic lead halide perovskites (LHPs) have emerged as a highly significant class of materials due to their tunable and adaptable properties, which make them suitable for a wide range of applications. One of the strategies for tuning and optimizing LHP-based devices is the substitution of cations and/or anions in LHPs. The impact of Cs substitution at the A site on the structural, vibrational, and elastic properties of MA_xCs_1−xPbCl₃-mixed single crystals was investigated using X-ray diffraction (XRD) and Raman and Brillouin light scattering techniques. The XRD results confirmed the successful synthesis of impurity-free single crystals, which exhibited a phase coexistence of dominant cubic and minor orthorhombic symmetries. Raman spectroscopy was used to analyze the vibrational modes associated with the PbCl₆ octahedra and the A-site cation movements, thereby revealing the influence of cesium incorporation on the lattice dynamics. Brillouin spectroscopy was employed to investigate the changes in elastic properties resulting from the Cs substitution. The incorporation of Cs cations induced lattice distortions within the inorganic framework, disrupting the hydrogen bonding between the MA cations and PbCl₆ octahedra, which in turn affected the elastic constants and the sound velocities. The substitution of the MA cations with smaller Cs cations resulted in a stiffer lattice structure, with the two elastic constants increasing up to a Cs content of 30%. The current findings facilitate a fundamental understanding of mixed lead chloride perovskite materials, providing valuable insights into their structural and vibrational properties. Full article

In this paper, the sol-gel method was used to synthesize powders of LaMnO₃ (LMO), La_0.85Ca_0.15MnO₃ (LCM), and La_0.85Sr_0.15MnO₃ (LSM). The effect of substituting Ca and Sr at the A-site on the perovskite crystal structure and electrochemical capabilities of LMO was investigated. LCM retained its orthogonal structure in comparison to the parent LMO components, whereas LSM transitioned to a rhombic structure. At 0.5 A/g, the specific capacitance of LCM and LSM electrodes is 185.5 F/g and 248 F/g, respectively. The specific capacitance of LCM was three times greater than that of the LMO electrode. Among the three samples (LMO, 22.25 m² g⁻¹; LSM, 31.56 m² g⁻¹), the LCM sample exhibited the highest specific surface area of 38.79 m² g⁻¹. The charge transfer resistances of the LMO, LCM, and LSM are 0.48 Ω, 0.36 Ω, and 0.38 Ω, respectively. The LCM electrode exhibits the greatest capacitance performance due to its more refined morphology, increased concentration of oxygen vacancy, and more complete utilization of the perovskite bulk structure. The above results demonstrate that Ca or Sr substitution of A-site compounds has great potential for supercapacitor applications. Full article

In recent years, there have been intense studies on hybrid organic–inorganic compounds (HOIPs) due to their tunable and adaptable features. This present study reports the vibrational, structural, and elastic properties of mixed halide single crystals of MA_xFA_1-xPbCl₃ at room temperature by introducing the FA cation at the A-site of the perovskite crystal structure. Powder X-ray diffraction analysis confirmed that its cubic crystal symmetry is similar to that of MAPbCl₃ and FAPbCl₃ with no secondary phases, indicating a successful synthesis of the MA_xFA_1-xPbCl₃ mixed halide single crystals. Structural analysis confirmed that the FA substitution increases the lattice constant with increasing FA concentration. Raman spectroscopy provided insight into the vibrational modes, revealing the successful incorporation of the FA cation into the system. Brillouin spectroscopy was used to investigate the changes in the elastic properties induced via the FA substitution. A monotonic decrease in the sound velocity and the elastic constant suggests that the incorporation of large FA cations causes distortion within the inorganic framework, altering bond lengths and angles and ultimately resulting in decreased elastic constants. An analysis of the absorption coefficient revealed lower attenuation coefficients as the FA content increased, indicating reduced damping effects and internal friction. The current findings can facilitate the fundamental understanding of mixed lead chloride perovskite materials and pave the way for future investigations to exploit the unique properties of mixed halide perovskites for advanced optoelectronic applications. Full article

BaZr_xTi_1−xO₃ (BZT) ceramics with different concentrations of Sc ions were prepared, and the effect of doping concentration on the crystal substitution type of BZT was studied. The substitution position of the Sc ion in BZT was related to its concentration. When the concentration of Sc ions was low (<1.0 mol %), it showed B-site substitution; otherwise, Sc ions showed A-site substitution. In addition, the effects of the Sc ion concentration on the sintering temperature, crystal structure, microstructure, and properties of BZT were also studied. The results showed that the introduction of Sc ions can reduce the sintering temperature to 1250 °C. When the concentration of Sc ions was 1.0 mol % and 2.0 mol %, the high dielectric constants of BZT were 14,273 and 12,747, respectively. Full article

Transition metal oxide materials are promising oxygen catalysts that are alternatives to expensive and precious metal-containing catalysts. Integration of transition metal oxides with high activity for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is an important pathway for good bifunctionality. In contrast to the conventional physical mixing and hybridization strategies, perovskite-type oxide provides an ideal structure for the integration of the transition metal element atoms on an atomic scale. Herein, B-site ordered double-perovskite-type La_1.6Sr_0.4MnCoO₆ nanocrystallites with ultra-small cubic (20–50 nm) morphology and high specific surface areas (25 m² g⁻¹) were proposed. Rational designs were integrated to promote the ORR-OER catalysis, e.g., introducing oxygen vacancies via A-site cation substitution, further increasing surface oxygen vacancies via integration of a small amount of Pt/C and nanosizing of the material via a facile molten-salt method. The batteries with the La_1.6Sr_0.4MnCoO₆ nanocrystallites and an aqueous alkaline electrolyte demonstrate decent discharge−charge voltage gaps of 0.75 and 1.10 V at 1 and 30 mA cm⁻², respectively, and good cycling stability of 250 h (1500 cycles). A coin-type battery with a gel−polymer electrolyte also presents a good performance. Full article

Lead-free Ba_1−xSr_xTiO₃ (BST) (x = 0, 0.1, 0.2, 0.3, 0.4 and 0.45) ceramics were successfully prepared via the solid-state reaction route. A pure perovskite crystalline structure was identified for all compositions by X-ray diffraction analysis. The basic phase transition temperatures in these ceramics were studied over a wide temperature range. A change in symmetry from a tetragonal to cubic phase was detected, which was further proven by phonon anomalies in composition/temperature-dependent Raman spectra. The incorporation of Sr²⁺ into BaTiO₃ (BT) lead to a shift in the phase transitions to lower temperatures, suppressing the ferroelectric properties and inducing relaxor-like behavior. Therefore, it was reasonable to suppose that the materials progressively lack long-range ordering. The initial second-harmonic generation (SHG) measurements demonstrated that the cubic phase of BST ceramics is not purely centrosymmetric over a wide temperature interval. We discussed the possible origin of the observed effects, and showed that electric field poling seems to reconstruct the structural ordering destroyed by the introduction of Sr²⁺ to BT. In the first approximation, substitution of Sr for larger Ba simply reduced the space for the off-central shift in Ti in the lattice and hence the domain polarization. A-site cation ordering in BST and its influence on the density of electronic states were also explored. The effect of doping with strontium ions in the BST compound on the density of electronic states was investigated using ab initio methods. As the calculations showed, doping BT with Sr²⁺ atoms led to an increase in the bandgap. The proposed calculations will also be used in the subsequent search for materials optimal for applications in photovoltaics. Full article

Lung cancer is one of the most common malignancies worldwide. Non-small-cell lung cancer (NSCLC) accounts for more than 80% of lung cancers, shows chemotherapy resistance, metastasis, and relapse. The phosphatidylinositol-3 kinase (PI3K)/Akt pathway has been implicated in the carcinogenesis and disease progression of NSCLC, suggesting that it may be a promising therapeutic target for cancer therapy. Although phenylurea derivatives have been reported as potent multiple kinase inhibitors, novel unsymmetrical N,Nʹ-diarylurea derivatives targeting the PI3K/Akt pathway in NSCLC cells remain unknown. Methods: N,Nʹ-substituted phenylurea derivatives CTPPU and CT-(4-OH)-PU were investigated for their anticancer proliferative activity against three NSCLC cell lines (H460, A549, and H292) by 3-(4,5-dimethythiazol-2-yl)-2,5-diphenyl tetrazolium bromide, colony formation, Hoechst33342/PI staining assays, and apoptosis analysis. The protein expressions of Akt pathway-related proteins in response to CTPPU or CT-(4-OH)-PU were detected by Western blot analysis. The Kyoto Encyclopedia of Genes and Genomes mapper was used to identify the possible signaling pathways in NSCLC treated with CTPPU. The cell cycle was analyzed by flow cytometry. Molecular docking was used to investigate the possible binding interaction of CTPPU with Akt, the mammalian target of rapamycin complex 2 (mTORC2), and PI3Ks. Immunofluorescence and Western blot analysis were used to validate our prediction. Results: The cytotoxicity of CTPPU was two-fold higher than that of CT-(4-OH)-PU for all NSCLC cell lines. Similarly, the non-cytotoxic concentration of CTPPU (25 µM) dramatically inhibited the colony formation of NSCLC cells, whereas its relative analog CT-(4-OH)-PU had no effect. Protein analysis revealed that Akt and its downstream effectors, namely, phosphorylated glycogen synthase kinase (GSK)-3β (Ser9), β-catenin, and c-Myc, were reduced in response to CTPPU treatment, which suggested the targeting of Akt-dependent pathway, whereas CT-(4-OH)-PU had no effect on such cell growth regulatory signals. CTPPU induced G1/S cell cycle arrest in lung cancer cells. Immunofluorescence revealed that CTPPU decreased p-Akt and total Akt protein levels, which implied the effect of the compound on protein activity and stability. Next, we utilized in silico molecular docking analysis to reveal the potential molecular targets of CTPPU, and the results showed that the compound could specifically bind to the allosteric pocket of Akt and three sites of mTORC2 (catalytic site, A-site, and I-site), with a binding affinity greater than that of reference compounds. The compound cannot bind to PI3K, an upstream regulator of the Akt pathway. The effect of CTPPU on PI3K and Akt was confirmed. This finding indicated that the compound could decrease p-Akt but caused no effect on p-PI3K. Conclusions: The results indicate that CTPPU significantly inhibits NSCLC cell proliferation by inducing G1/S cell cycle arrest via the Akt/GSK-3β/c-Myc signaling pathway. Molecular docking revealed that CTPPU could interact with Akt and mTORC2 molecules with a high binding affinity. These data indicate that CTPPU is a potential novel alternative therapeutic approach for NSCLC. Full article

Cu-content La_1−xSr_xNi_1−yCu_yO_3−δ perovskites with A-site strontium doping have been tuned as cobalt-free cathode materials for high-performance anode-supported SOFCs, working at an intermediate-temperature range. All obtained oxides belong to the R-3c trigonal system, and phase transitions from the R-3c space group to a Pm-3m simple perovskite have been observed by HT-XRD studies. The substitution of lanthanum with strontium lowers the phase transition temperature, while increasing the thermal expansion coefficient (TEC) and oxygen non-stoichiometry δ of the studied materials. The thermal expansion is anisotropic, and TEC values are similar to commonly used solid electrolytes (e.g., 14.1 × 10⁻⁶ K⁻¹ for La_0.95Sr_0.05Ni_0.5Cu_0.5O_3−δ). The oxygen content of investigated compounds has been determined as a function of temperature. All studied materials are chemically compatible with GDC-10 but react with LSGM and 8YSZ electrolytes. The anode-supported SOFC with a La_0.95Sr_0.05Ni_0.5Cu_0.5O_3−δ cathode presents an excellent power density of 445 mW·cm⁻² at 650 °C in humidified H₂. The results indicate that La_1−xSr_xNi_1−yCu_yO_3−δ perovskites with strontium doping at the A-site can be qualified as promising cathode candidates for anode-supported SOFCs, yielding promising electrochemical performance in the intermediate-temperature range. Full article

Higher power conversion efficiencies for photovoltaic devices can be achieved through simple and low production cost processing of ${\mathrm{APbI}}_3\left(\mathrm{A}={\mathrm{CH}}_3{\mathrm{NH}}_3,{\mathrm{CHN}}_2{\mathrm{H}}_4,\dots \right)$ perovskites. Due to their limited long-term stability, however, there is an urgent need to find alternative structural combinations for this family of materials. In this study, we propose to investigate the prospects of cation-substitution within the A-site of the ${\mathrm{APbI}}_3$ perovskite by selecting nine substituting organic and inorganic cations to enhance the stability of the material. The tolerance and the octahedral factors are calculated and reported as two of the most critical geometrical features, in order to assess which perovskite compounds can be experimentally designed. Our results showed an improvement in the thermal stability of the organic cation substitutions in contrast to the inorganic cations, with an increase in the power conversion efficiency of the Hydroxyl-ammonium (NH₃OH) substitute to η = 25.84%. Full article

The climate change impact associated with greenhouse gas emissions is a major global concern. This work investigates perovskite compounds for oxygen separation from air to supply oxygen to oxyfuel energy systems to abate these significant environmental impacts. The perovskites studied were Me_0.5Sr_0.5Co_0.8Cu_0.2O_3−δ (MeSCC) where the A-site substitution was carried out by four different cations (Me = Ca, Mg, Sr, or Ba). SEM analysis showed the formation of small particle (<1 µm) aggregates with varying morphological features. XRD analysis confirmed that all compounds were perovskites with a hexagonal phase. Under reduction and oxidation reactions (redox), Ba and Ca substitutions resulted in the highest and lowest oxygen release, respectively. In terms of real application for oxygen separation from air, Ba substitution as BaSCC proved to be preferable due to short temperature cycles for the uptake and release of oxygen of 134 °C, contrary to Ca substitution with long and undesirable temperature cycles of 237 °C. As a result, a small air separation unit of 0.66 m³, containing 1000 kg of BaSCC, can produce 18.5 ton y⁻¹ of pure oxygen by using a conservative heating rate of 1 °C min⁻¹. By increasing the heating rate by a further 1 °C min⁻¹, the oxygen production almost doubled by 16.7 ton y⁻¹. These results strongly suggest the major advantages of short thermal cycles as novel designs for air separation. BaSCC was stable under 22 thermal cycles, and coupled with oxygen production, demonstrates the potential of this technology for oxyfuel energy systems to reduce the emission of greenhouse gases. Full article

In this study, an environmentally friendly sol-gel synthetic approach was used for the preparation of yttrium-doped MgFe₂O₄. Two series of compounds with different iron content were synthesized and A-site substitution effects were investigated. In the first series, the iron content was fixed and the charge balance was suggested to be compensated by a partial reduction of Fe³⁺ to Fe²⁺ or formation of interstitial O²⁻ ions. For the second series of samples, the iron content was reduced in accordance with the substitution level to compensate for the excess of positive charge, which accumulates due to replacing divalent Mg²⁺ with trivalent Y³⁺ ions. Structural, morphological and magnetic properties were inspected. It was observed that single-phase compounds can only form when the substitution level reaches 20 mol% of Y³⁺ ions and iron content is reduced. The coercivity as well as saturation magnetization decreased with the increase in yttrium content. Mössbauer spectroscopy was used to investigate the iron content in both tetrahedral and octahedral positions. Full article