Tuning of conductive type and magnetic properties of Ca3Co2O6 ceramics through Pb‐doping

The effect of Pb doping on structural, electrical, magnetic, and thermal transport properties of Ca_3?xPb_xCo₂O₆ (x=0‐0.3) ceramics has been investigated systemically. It is found that the substituted Pb‐ions have a mixed valence state of +2 and +4, and a small amount of Co³⁺ ions will transfer into Co²⁺ due to the substitution of Pb⁴⁺ for Ca²⁺. The resistivity decreases monotonically with increasing Pb content, which is related to the variation in carrier concentration and the enhanced grain connectivity. The signs of both Hall coefficient and thermopower changed from positive to negative by a proper Pb doping, indicating the conductive type of Ca₃Co₂O₆ can be effectively tuned from p to n through the doping. The low‐temperature magnetization, the magnetic exchange coupling constant J and Weiss temperature θ decrease monotonically with the increase in Pb‐doping content, indicating the strength of the ferromagnetic interaction between adjacent high spin Co³⁺ ions has been weakened due to the reduced magnetic correlation length in these Pb‐doped samples.     

Double perovskite Sr2FeReO6 oxides: Structural,dielectric, magnetic,electrical, and optical properties

Double perovskite Sr₂FeReO₆ (SFRO) powders were synthesized by so-gel process and annealed in argon atmosphere. Their structural, dielectric, magnetic, electrical, and optical properties were comprehensively investigated. It was found that the SFRO powders possessed a tetragonal crystal structure with I4/m space group and exhibited spherical shapes with some agglomeration due to the magnetic interactions between particles of the powders. Quantitative energy dispersive X-ray spectrometer data revealed the atomic ratio of Sr, Fe, Re, and O elements close to the nominal values of 2:1:1:6. X-ray photoemission spectroscopy spectra reveal two species of Re⁵⁺ and Re^6-7+ coexist in the SFRO powders. Sr, Fe, and O elements are present as Sr²⁺, Fe³⁺, and lattice oxygen, respectively. Dielectric property measurements revealed a Maxwell–Wagner type dielectric dispersion in the SFRO ceramics. Ferromagnetic behavior was verified by the observed magnetic hysteresis loops in the SFRO powders at 2 K and 300 K. The remanent magnetization and coercive field at 2 K were 8.23 emu/g and 3152 Oe, respectively, and the saturated magnetization was estimated to be 21.8 emu/g (or 2.0 μ_B/f.u.), smaller than the theoretical value of 3.0 μ_B/f.u. owing to the presence of the anti-site defects. Magnetic Curie temperature (T_C) was estimated to be 432.3 K. Intergranular tunneling magnetoresistance and hysteresis phenomena were observed in the SFRO powders at low temperatures, and the MR (2 K, 6 T) was measured to be −15% and −10% for MR (100 K, 6 T). Electrical transport and optical absorption measurements demonstrate the semiconducting nature of the SFRO with optical band gap of 1.39 eV. The electrical transport process follows the small polaron variable range hopping theory. The unique combination of high T_C ferromagnetism with the semiconductivity enables the SFRO to be a promising candidate for spintronic devices.     

A peculiar heterotrimetallic Mn–Co–Ni complex: Synthesis, crystal structure and magnetic properties

The first complex [Mn(H₂O)₆][NiCo(TTHA)(H₂O)₂] · 4H₂O 1 (TTHA⁶⁻ = triethylenetetraminehexaacetate) containing Mn^II–Co^II–Ni^II three different 3d metal ions is synthesized and magnetic measurement suggests that ferromagnetic interactions occur between Ni²⁺ ions and rarely found low-spin Co²⁺ ions.     

Co‐synthesis of Sm0.5Sr0.5CoO3‐Sm0.2Ce0.8O1.9 Composite Cathode with Enhanced Electrochemical Property for Intermediate Temperature SOFCs

A 70 wt.% Sm_0.5Sr_0.5CoO₃ – 30 wt.% Sm_0.2Ce_0.8O_1.9 (SSC–SDC73) composite cathode was co‐synthesized by a facile one‐step sol–gel method, which showed lower polarization resistance and overpotential than those of physically mixed SSC–SDC73 cathode. The polarization resistance of co‐synthesized SSC–SDC73 cathode at 800 °C was as low as 0.03 Ω cm² in air. Scanning electron microscopy (SEM) images showed that the enhanced electrochemical property was mainly attributed to the smaller grains and good dispersion of SSC and SDC phases within the composite cathode, leading to an increase in three‐phase boundary length. The dependence of polarization resistance with oxygen partial pressure indicated that the rate‐limiting step for oxygen reduction reaction was the dissociation of molecular oxygen to atomic oxygen process. An anode supported fuel cell with a co‐synthesized SSC–SDC73 cathode exhibited a peak power density of 924 mW cm⁻² at 800 °C. Our results suggested that co‐synthesized composite was a promising cathode for intermediate temperature solid oxide fuel cells (IT‐SOFCs).     

Au and Co3O4 anchored Bi2WO6 with enhanced electron paramagnetic resonance,surface plasmon resonance,nonlinear and magnetic properties

The combination of surface plasmon resonance (SPR) effect with hetero-p–n structure shows promising benefits to optical linear and nonlinear properties. In this study, Au nanoparticles (NPs) decorated p–n hetero-structured Co₃O₄/Bi₂WO₆ composite was synthesized and characterized in terms of the optical linear and nonlinear and magnetic properties, morphology, electron transition, charge transfer, energy band gap, polarizability, SPR effect, and oxygen vacancies using scanning electron microscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, Z-scan, ultraviolet–visible spectra, and vibrating sample magnetometer. The combination of Co₃O₄ provided active 3d electrons transition and charge transfer which increased carriers’ concentration and reduced the energy band gap. Au SPR enhanced the internal polarization and strengthened the built-in electric field, yielding strong nonlinear behavior. In addition, magnetic Co₃O₄ endowed sample with room-temperature ferromagnetism which was obviously strengthened by Au NPs. The obtained sample is promising for laser and photonics applications.     

Investigation of luminescence properties of Pb2+‐doped Sr2B2O5 phosphor

A near‐UV emitting phosphor, Pb²⁺‐doped Sr₂B₂O₅ was synthesized by the solid‐state reaction method at 900°C for 3 hours in air. The structure of the phosphor was verified by X‐ray diffraction study which shows monoclinic phase. Fourier transform infrared (FTIR) analysis confirmed the formation of Sr₂B₂O₅. The excitation and emission spectra of the synthesized phosphors were investigated at room temperature with photoluminescence spectrophotometer. The emission and excitation bands of Pb²⁺‐doped Sr₂B₂O₅ were observed at 370 and 289 nm, respectively. The dependence of the PL intensities on the Pb²⁺ concentration for the Sr_2?xPb_xB₂O₅ (0.01 ≤ x ≤ 0.03) phosphors was studied and it was observed that the concentration quenching of Pb²⁺ in Sr₂B₂O₅ is 0.025 mol.     

微波辅助金属有机骨架材料制备无定形Co3O4花球及其电化学性能

以六水合硝酸钴(Co(NO3)2?6H2O)、苯甲酰丙酮（C10H10O2）为原料, 利用微波法合成了前体。前体在500℃空气条件下锻烧得到无定形Co3O4花球。通过 XRD、 SEM、TEM对目标产物进行了表征 , 研究了无定形Co3O4花球的微观结构、表面形貌。电化学测试结果表明,无定形Co3O4花球负极材料 在100mA/g的电流密度下,首次充电比容量达到826mAh/g;循环100圈后,容量保持率为89.2％,具有高的比容量、良好的循环性能和广泛的应用前景。     

High‐temperature piezoelectric properties of 0‐3 type CaBi4Ti4O15:x wt%BiFeO3 composites

The 0‐3 type CaBi₄Ti₄O₁₅:30 wt%BiFeO₃ composite shows much better high‐temperature piezoelectric properties than the single‐phase CaBi₄Ti₄O₁₅ or BiFeO₃ ceramics. The composite with 0‐3 type connectivity exhibits a high density of 7.01 g/cm³, a saturated polarization of 21.5 μC/cm² and an enhanced piezoelectric d₃₃ of 25 pC/N. After the poled composite was annealed at 600°C, its d₃₃ is 21 pC/N at room temperature. Resistance of the composite decreases slowly from 10⁹ ohm at 20°C to ~10⁵ ohm at 500°C. Furthermore, the poled composite shows strong radial and thickness dielectric resonances at 20°C‐500°C.     

Flame Spray Synthesis of Nanoscale La0.6Sr0.4Co0.2Fe0.8O3–δ and Ba0.5Sr0.5Co0.8Fe0.2O3–δ as Cathode Materials for Intermediate Temperature Solid Oxide Fuel Cells

Electrochemical performance and degradation was analysed by conductivity measurements as well as thermogravimetric analysis (TGA) under different atmospheres. CO₂ was identified as a critical parameter in terms of carbonate formation from Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3–δ and causes a strong increase in the material resistivity, whereas La_0.6Sr_0.4Co_0.2Fe_0.8O_3–δ is unaffected. The oxygen exchange kinetic of both compositions is affected by CO₂ containing atmospheres.     

Structural features and thermoelectric properties of Al‐doped (ZnO)5In2O3 homologous phases

In this work, we investigated the influence of Al doping on the structure of the (ZnO)₅In₂O₃ homologous phase and the thermoelectric characteristics of (ZnO)₅(In_1?xAl_x)₂O₃ ceramics for x=0, 0.01, 0.03, 0.05, 0.1, and 0.2, prepared using a classic ceramic procedure and sintering at 1500°C for 2 hours. The Al substituted for In on both the primary sites in the Zn₅(In_1?xAl_x)₂O₈ homologous phase, the octahedral sites in the basal‐plane inversion boundaries and the trigonal bi‐pyramidal sites in the zig‐zag inversion boundaries, which resulted in a uniformly increased shrinkage of the unit cell with the additions of Al. The a and c parameters were reduced for x=0.2 by a maximum 0.8%. All the samples had similar microstructures, so the differences in the TE characteristics mainly resulted from the effects of the substitution of Al for In, decreasing the charge‐carrier concentration and affecting their mobility. Slightly improved TE characteristics were only observed for Al additions with x=0.01‐0.05, while larger additions of Al only resulted in a reduced electrical conductivity and decreased ZT values in comparison to the un‐doped composition.     

Structural,optical, and magnetic properties of KBiFe2O5 synthesized by a sol-gel method using PVP as additive

KBiFe₂O₅ (KBFO) is a perovskite-like inorganic material that has great potential as an absorber material for active layers of photovoltaic devices; however, the synthesis conditions reported until now (pressure and temperature) are inappropriate for its direct deposition on the usual substrates of solar cells. Being able to synthesize these materials directly on the substrate avoids a second stage of deposition of this material, besides improving joining properties and consequently improving energy conversion efficiency. To decrease the synthesis temperature of KBFO, the sol-gel method was used at different times and temperatures with poly(vinylpyrrolidone) (PVP) as an accelerating agent for the kinetics of formation of the phase. Thus, the formation of the KBFO phase as powder at temperatures below 550°C and atmospheric pressure with the use of PVP as a synthesis additive is reported for the first time; however, the phase was obtained with impurities and the lower the synthesis temperature the greater the presence of impurities, but the smaller the crystallite size. Two band gaps were found for the samples: one around 2.41 and 2.07 eV and the other one around 1.76 eV. Samples synthesized at higher temperatures had a paramagnetic behavior, while samples synthesized at lower temperatures had weak ferromagnetic behavior.     

First Principles Modeling of Pd‐doped (La,Sr)(Co,Fe)O3 Complex Perovskites

(La,Sr)(Co,Fe)O₃ (LSCF) perovskites are well known promising materials for cathodes of solid oxide fuel cells. In order to reduce cathode operational temperature, doping on B‐sublattice with different metals was suggested. Indeed, as it was shown recently experimentally, doping with low Pd content increases oxygen vacancy concentration which is one of factors controlling oxygen transport in fuel cells. In this Communication, we modeled this material using first principles DFT calculations combined with supercell model. The charge density redistribution, density of states, and local lattice distortion around palladium ions are analyzed and reduction of the vacancy formation energy confirmed.     

Structural,magnetic, electrical and electrochemical properties of SrCoO2.5, Sr9Co2Mn5O21 and SrMnO3 compounds

SrCo_1−xMn_xO_3−d (0 ≤ x ≤ 1) were synthesized by conventional solid state reaction method. We found that Mn substitution hinders the decomposition of carbonate at 900 °C and increases the synthesis temperature of SrCo_1−xMn_xO_3−d to 1200 °C. Three different main phases emerge as the Mn content is increased; SrCoO_2.5, Sr₉Co₂Mn₅O₂₁ and SrMnO_3. Structural properties of the samples were investigated by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, x-ray diffraction (XRD) and scanning electron microscopy (SEM). Valance states of the transition metal (TM) ions were estimated based on lattice parameters and ionic radii of TM ions. High temperature resistivity measurements show hysteresis upon heating and cooling and is attributed to oxygen release without any endothermic/exothermic activity. The spin configurations of Co and Mn ions in SrCoO_2.5, Sr₉Co₂Mn₅O₂₁ and SrMnO₃ were estimated by Curie-Weiss fitting of χ-T curves. Electrochemical measurements show two anodic/cathodic peaks indicating two main types of oxygen sites in the unit cell.     

Transparent glass ceramics containing Lu6O5F8:Tb3+ nano‐crystals: Enhanced photoluminescence and X‐ray excited luminescence

The development of scintillators is of fundamental and industrial meaning for their diverse applications. Despite the great advance in scintillating mono‐crystals, challenge remains to search for novel scintillating materials with low cost, large volume, and high efficiency. Here, Tb³⁺‐doped glass ceramics (GC) with crystallized Lu₆O₅F₈ nano‐crystals were prepared and characterized as potential X‐ray scintillators. Their structural, optical, and luminescent properties were explored systematically. After thermal treatment, X‐ray excited luminescence (XEL) intensity from Lu₆O₅F₈:Tb³⁺ GC is greatly increased and the relative intensity is about 64% of commercial BGO scintillator, benefiting from preferential enrichment of Tb³⁺ ions into Lu₆O₅F₈ nano‐crystals with low phonon energy. Moreover, unusual decay behaviors of Tb³⁺ emissions in GC sample are observed and discussed. Our results indicate that rare earth doped GC may offer a novel platform for designing and fabricating new scintillating materials in the future.     

Selective catalytic reduction of NOx with propylene in the presence of oxygen over Co–Pt promoted H-MFI and HY

Kinetic and in situ spectroscopic studies of Co–Pt/MFI and Co–Pt/HY catalysts for the selective reduction of NO_x with propylene in the presence of oxygen were carried out. The results of catalytic tests of Co–Pt/MFI showed that the addition of Pt to Co based catalyst improved the activity, but a small increase in selectivity to N₂O (15–20%) was observed. In the case of Co–Pt/HY catalyst, the addition of Pt improved the activity more significantly and however, a larger increase in selectivity to N₂O (6–72%) was obtained. It was also found from the results of FT-IR studies of Co–Pt/MFI that the reduction of NO to N₂ was as follows: firstly the oxidation of NO to NO₂ occurred over metallic Pt and NO₂ forms Co–NO₂, Co–ONO, and/or Co–ONO₂; secondly, the partial oxidation of C₃H₆ was happened over Brønsted acid sites and the reaction of NO₂ formed on Co sites with partial oxidized C₃H₆ produced organo-nitro species. These species were dehydrated and isomerized to form isocyanate. Finally, [NCO] type intermediates react with NO from gas phase to selectively yield N₂.     

Investigation of anisotropic mechanical properties of textured KSr2Nb5O15 ceramics via ab‐initio calculation and nanoindentation

Anisotropic mechanical properties of KSr₂Nb₅O₁₅ (KSN) crystals were investigated through first‐principles calculations based on density functional theory. These properties were experimentally verified via nanoindentation on textured KSN ceramics fabricated, using a reactive template grain growth method. Nanoindentation was performed in directions parallel and perpendicular to the [001] direction of samples consisting of highly oriented grains with tetragonal symmetry. Calculations revealed that Nb‐O yields a relatively strong covalent effect and Nb‐O octahedral distortions induce spontaneous polarization in the KSN crystal. The measured indentation modulus values concurred with the predictions, based on the calculated elastic constants, as indicated by an anisotropic ratio of ~10% between the 2 tested orientations. The hardness exhibited negligible anisotropy. However, the predictions revealed a pronounced anisotropy of the Young's modulus (ratio of ~40% between the [100] direction and a direction tilted by ~45° from the [001] toward the [100]).     

Preparation, characterization and catalytic properties of Co–Nb2O5–SiO2 catalysts

Co–Nb₂O₅–SiO₂ catalysts were prepared using three different sol–gel procedures: (i) the colloidal sol–gel method using NbCl₅ and SiCl₄ as precursors; (ii) the polymeric sol–gel method using niobium ethoxide and tetraethyl-orthosilicate (TEOS); (iii) an intermediate procedure between the colloidal and polymeric sol–gel method in which the precursors were those utilized in the CSG but dissolved in a mixture of anhydrous ethanol and CCl₄. In all procedures, the elimination of the solvent carried out between 80 and 110°C was followed by a reduction in hydrogen flow (30 ml min⁻¹) at 773 K. Following these procedures, samples containing 10 wt.% Co and 15 wt.% niobium oxide (expressed as Nb₂O₅) were obtained. The characterization of the catalysts was performed using various techniques: N₂ adsorption and desorption curves at 77 K, NH₃- and H₂-chemisorption, TPO, XPS, XRD, and solid state ¹H MAS-NMR. Hydrogenolysis of butane was evaluated. The low reaction rates are assigned to the effect of the metal size, whereas the isobutane selectivity as well as the relatively high stability is due to the acidity of the support.     

Synthesis and properties of magnetic sensitive shape memory Fe3O4/poly(ε‐caprolactone)‐polyurethane nanocomposites

Fe₃O₄/poly (ε‐caprolactone)‐polyurethane (PCLU) shape memory nanocomposites were prepared by an in situ polymerization method. The thermal properties, magnetic properties, and shape memory properties of the nanocomposites were investigated systematically. The results showed that the Fe₃O₄ nanoparticles were homogeneously dispersed in the PCLU matrix, which ensured good shape memory properties of nanocomposites in both hot water and an alternating magnetic field (f = 45 kHz, H = 29.7 kA m^?1/36.7 kA m^?1). The nanocomposites started to recover near 40°C, which is slightly higher than body temperature. Thus, they would not change their deformed shape during the implanting process into the human body. Considering potential clinical applications, 45°C was chosen as shape recovery temperature which is slightly higher than 37°C, and the nanocomposites had high shape recovery rate at this temperature. With increasing content of Fe₃O₄ nanoparticles, the shape memory properties of the nanocomposites in an alternating magnetic field increased and the best recovery rate reached 97%, which proves that this kind of nanocomposites might be used as potential magnetic sensitive shape memory materials for biomedical applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013     

Fabrication of BaZr0.1Ce0.7Y0.2O3 – δ ‐Based Proton‐Conducting Solid Oxide Fuel Cells Co‐Fired at 1,150 °C

Dense proton‐conducting BaZr_0.1Ce_0.7Y_0.2O_{3 – δ} (BZCY) electrolyte membranes were successfully fabricated on NiO–BZCY anode substrates at a low temperature of 1,150 °C via a combined co‐press and co‐firing process. To fabricate full cells, the LaSr₃Co_1.5Fe_1.5O_{10 – δ}–BZCY composite cathode layer was fixed to the electrolyte membrane by two means of one‐step co‐firing and two‐step co‐firing, respectively. The SEM results revealed that the cathode layer bonded more closely to the electrolyte membrane via the one‐step co‐firing process. Correspondingly, determined from the electrochemical impedance spectroscopy measured under open current conditions, the electrode polarisation and Ohmic resistances of the one‐step co‐fired cell were dramatically lower than the other one for its excellent interface adhesion. With humidified hydrogen (2% H₂O) as the fuel and static air as the oxidant, the maximum power density of the one‐step co‐fired single cell achieved 328 mW cm^–2 at 700 °C, showing a much better performance than that of the two‐step co‐fired single cell, which was 264 mW cm^–2 at 700 °C.     

Li2ZrO3包覆LiNi0.8Co0.1Mn0.1O2的复合材料及其电化学性能

以Zr（NO₃）₄·5H₂O和CH₃COOLi·2H₂O为原料,采用湿化学法,将Li₂ZrO₃包覆在LiNi_0.8Co_0.1Mn_0.1O₂锂离子电池正极材料的表面,研究Li₂ZrO₃不同包覆比例对LiNi_0.8Co_0.1Mn_0.1O₂电化学性能的影响。SEM、TEM、EDS谱图分析表明,Li₂ZrO₃层均匀地包覆在LiNi_0.8Co_0.1Mn_0.1O₂表面,其厚度约为8 nm。与纯相相比,1%（质量分数） Li₂ZrO₃包覆的LiNi_0.8Co_0.1Mn_0.1O₂复合材料在1.0 C下首次放电比容量为184.7 mA·h·g^-1、100次循环之后放电比容量为169.5 mA·h·g^-1,其容量保持率达到91.77%,表现出良好的循环稳定性。循环伏安（CV）和电化学阻抗（EIS）测试结果表明,Li₂ZrO₃包覆层抑制了正极材料与电解液之间的副反应,减小了材料在循环过程中的电荷转移阻抗,从而提高了材料的电化学性能。