B-site ordered perovskite LaSrMnNbO6: Synthesis, structure and antiferromagnetism

LaSrMnNbO₆ has been synthesized by high temperature solid state reaction under 1% H₂/Ar dynamic flow. The structure is determined by Rietveld refinement of the powder X-ray diffraction data. It crystallizes in the monoclinic space group P2₁/n with the unit cell parameters: a=5.69187(12), b=5.74732(10), c=8.07018(15) Å and β=90.0504(29)°, which were also confirmed by electron diffraction. The Mn²⁺ and Nb⁵⁺ ions, whose valence states are confirmed by X-ray absorption near-edge spectroscopy, are almost completely ordered over the B-site (<1% inversion) of the perovskite structure due to the large differences of both cationic size (0.19 Å) and charge. The octahedral framework displays significant tilting distortion according to Glazer’s tilt system a⁻b⁻c⁺. Upon heating, LaSrMnNbO₆ decomposes at 690 °C under O₂ flow or at 775 °C in air. The magnetic susceptibility data indicate the presence of long-range antiferromagnetic ordering at T_N=8 K; the experimentally observed effective paramagnetic moment, μ_eff=5.76 μ_B for high spin Mn²⁺ (3d⁵, S=5/2) is in good agreement with the calculated value (μ_calcd=5.92 μ_B).     

Degree of order and redox balance in B-site ordered double-perovskite oxides, Sr2MMoO6−δ (M=Mg, Mn, Fe, Co, Ni, Zn)

We have investigated a series of double-perovskite oxides Sr₂MMoO_6−δ (M=Mg, Mn, Fe, Co, Ni, Zn) for redox stability, oxygen content and crystal structure. Phases with M=Co, Ni and Zn were found to be oxygen-stoichiometric and stable under oxidizing conditions, whereas those with M=Mn and Fe were oxygen-deficient and stable under reducing conditions. The M=Mg phase is stable both under reducing and oxidizing conditions, showing variable oxygen contents within 0.00≤δ≤0.04 depending on the annealing conditions. Structural data indicate somewhat depressed values for the degree of M/Mo cation order and also evidence of electron transfer from M^II to Mo^VI for M=Mn, Fe and Co.     

Effect of Copper Substitution and Preparation Methods on the LaMnO3 Structure and Catalysis of Methane Combustion and CO Oxidation

 LaMn1-xCuxO3刡冊 perovskite oxides (x = 0, 0.2, 0.4, 0.6, 0.8, 1) were prepared by two different methods, the Pechini and sol-gel methods. The catalysts were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray fluorescence spectroscopy, N2 adsorption, and temperature-programmed reduction. Their catalytic activity in the oxidation of methane and CO was evaluated. EDS and SEM results showed that the Pechini samples had more homogeneity and smaller particles (higher specific surface area). The catalytic activity for methane combustion was highest for x = 0.2. In CO oxidation, the oxides with x = 0.2 and x = 0.4 were the most active. The Pechini samples had higher activity and stability than the sol-gel samples.     

Structural and ac electrical properties of a newly synthesized single phase rare earth double perovskite oxide: Ba2CeNbO6

A single phase rare earth double perovskite oxide Ba₂CeNbO₆ (BCN) is synthesized by solid-state reaction technique for the first time. The X-ray diffraction pattern of the sample at room temperature shows monoclinic structure, with the lattice parameters, a=5.9763 Å, b=5.975 Å and c=8.48 Å and β=90.04°. Impedance spectroscopy is used to study the ac electrical behavior of this material as a function of frequency (10²-10⁶ Hz) at various temperatures (30-450 °C). A relaxation is observed in the entire temperature range. Conduction mechanism is investigated by fitting the complex impedance data to Cole-Cole equation. Complex impedance plane plots show only one semicircular arc, indicating only the grain contribution of dielectric relaxation. The scaling behavior of imaginary part of electric modulus (M″) and imaginary part of electrical impedance (Z″) suggests that the relaxation describes the same mechanism at various temperatures. The frequency dependence of conductivity is interpreted in terms of the jump relaxation model and is fitted to Jonscher's power law. The values of dc conductivities extracted from the Jonscher power law varies from 2.79×10⁻⁷ to 3.5×10⁻⁵ Sm⁻¹ with the increase in temperature from 100 to 450 °C. The activation energies (0.37 eV) extracted from M″(ω) and Z″(ω) peaks are found to follow the Arrhenius law.     

高效医学传感钙钛矿材料研究进展

卤化物钙钛矿材料作为一种新型半导体材料,具有优异的光电转换特性、能级结构可调、易于加工、结构和尺寸以及形貌可调、改性后优异的生物相容性等优点,在医学检测传感器中具有广阔的应用前景。本综述讨论了钙钛矿材料在生物医学传感领域的研究进展,钙钛矿医学传感器能通过光电转换、全光转换、电催化等多种物理或化学机制实现传感,具有可灵活选择的器件结构、性能指标和信号传递方式,用于人体代谢物质、神经递质、癌症相关物质和药物等医学物质的检测。钙钛矿医学传感器将为未来的医工多学科融合提供新希望,加快医工融合发展。     

Photo-induced effect in the layered perovskite manganite La<Subscript>1.2</Subscript>Sr<Subscript>1.8</Subscript>Mn<Subscript>1.8</Subscript>Co<Subscript>0.2</Subscript>O<Subscript>7</Subscript>

It is helpful to study the photo-induced effect in the perovskite manganites not only for elucidating the mechanism of colossal magnetoresistance (CMR) effect but also for potential applications in technology. The laser-induced effect in the Co doping layered perovskite manganites La_1.2Sr_1.8Mn_1.8Co_0.2O₇, is studied in this paper and the obtained results are also compared with that gained in the Nd-doping manganites with cubic perovskite structure.     

The Spin Modulation Stimulated Efficient Electrocatalytic Oxygen Evolution Reaction over LaCoO3 Perovskite

Perovskite is a promising non-noble catalyst and has been widely investigated for the electrochemical oxygen evolution reaction (OER). However, there is still serious lack of valid approaches to further enhance their catalytic performance. Herein, we propose a spin state modulation strategy to improve the OER electrocatalytic activity of typical perovskite material of LaCoO₃. Specifically, the electronic configuration transition was realized by a simple high temperature thermal reduction process. M-H hysteresis loop results reveal that the reduction treatment can produce more unpaired electrons in 3d orbit by promoting the electron transitions of Co from low spin state to high spin state, and thus lead to the increase of the spin polarization. Electrochemical measurements show that the catalytic performance of LaCoO₃ is strongly dependent on its electronic configuration. With the optimized reduction treatment, the overpotential for the OER process in 0.5 M KOH electrolyte solution at 10 mA cm⁻² current density was 396 mV, significantly lower than that of the original state. Furthermore, it can mediate efficient OER with an overpotential of 383 mV under an external magnetic field, which is attributed to the appropriate electron filling. Our results show that electron spin state regulation is a new way to boost the OER electrocatalytic activity.     

Transition Metal Doping Induces Ti3+ to Promote the Performance of SrTiO3@TiO2 Visible Light Photocatalytic Reduction of CO2 to Prepare C1 Product.

Transition metal Fe, Co, Ni and Cu doped strontium titanate-rich SrTiO₃@TiO₂ (STO@T) materials were prepared by hydrothermal method. The prepared doped materials exhibit better photocatalytic CO₂ reduction to CH₄ ability under visible light conditions. Among them, Fe-doped and undoped SrTiO₃@TiO₂ under visible light conditions CO₂ reduction products only CO, while M-STO@T (M=Co, Ni, Cu) samples converted CO₂ to CH₄. The average methane yield of Ni-doped STO@T samples are as high as 73.85 μmol g⁻¹ h⁻¹. The production of methane is mainly due to the increase in the response of the doped samples to visible light. And the increase in the separation rate of photogenerated electrons and holes and the efficiency of electron transport caused by the generation of impurity levels. The impurity level caused by Ti³⁺ plays an important role in the production of methane by CO₂ visible light reduction. Ni doping effectively improves the photocatalytic performance of STO@T and CO₂ reduction mechanism were explained.     

Zwitterionic Block Copolymers for the Synthesis and Stabilization of Perovskite Nanocrystals

Traditional hot injection methods for the preparation of cesium lead halide perovskite nanocrystals (CsPbX₃ PNCs, where X=Cl, Br, or I) rely on small molecule surfactants to produce PNCs with cube, plate, or rod-like morphologies. Here, we describe a new method whereby zwitterionic block copolymers are employed as macromolecular ligands in PNC synthesis, affording PNCs with excellent colloidal stability, high photoluminescence quantum yield, and in some cases distinctly non-cubic shapes. The block copolymers used in this study – composed of a poly(n-butyl methacrylate) hydrophobic block and zwitterionic methacrylate hydrophilic blocks – dissolve in useful solvents for PNC growth despite containing large mole percentages of zwitterionic groups. PNCs prepared with block copolymer ligands were found to disperse and retain their fluorescence in a range of polar organic solvents and were amenable to direct integration into optically transparent nanocomposite thin films with high PNC content.