空穴掺杂Sr2FeMoO6的晶体结构及磁性研究

采用传统高温固相反应法制备了空穴掺杂的系列样品Sr2xKxFeMoO6（0≤x≤0．04）,研究了其晶体结构和磁性质．X射线粉末衍射结果表明该系列样品均为单相,四方晶系,空间群为I4／m．碱金属K的含量可以调控反位缺陷的浓度．未掺杂样品Sr2FeM006在280K时的原胞磁矩为1．12μB．掺杂量为x=0．04样品的原胞磁矩为1．26μB．阳离子有序、晶格畸变是影响Sr2-xKxFeMoO6磁性的重要因素．     

Morphology, structure and photocatalytic performance of ZnIn2S4 synthesized via a solvothermal/hydrothermal route in different solvents

Hexagonal ZnIn₂S₄ photocatalysts with different morphology and crystallinity (micro-structures) were prepared in aqueous-, methanol- and ethylene glycol-mediated conditions via a solvothermal/hydrothermal method. The aqueous- and methanol-mediated ZnIn₂S₄ presented to be Flowering-Cherry-like microsphere, while the ethylene glycol-mediated ZnIn₂S₄ presented to be micro-cluster. In comparison with two other products, aqueous-mediated ZnIn₂S₄ possessed the best crystallinity (micro-structure), which resulted in the highest photocatalytic activity for hydrogen evolution under visible-light irradiation. Additionally, aqueous-mediated ZnIn₂S₄ was found to be more stable than the other two ZnIn₂S₄ photocatalysts while undergoing the photocatalytic process. During the photocatalytic reaction, the average rates for hydrogen production over aqueous-, methanol- and ethylene glycol-mediated ZnIn₂S₄ were determined to be 27.3, 12.4 and 9.1 μmol h^-1, respectively, in the present photocatalytic systems.     

Improving the visible light photocatalytic activity of mesoporous TiO2 via the synergetic effects of B doping and Ag loading

B-doped together with Ag-loaded mesoporous TiO₂ (Ag/B–TiO₂) was prepared by a two-step hydrothermal method in the presence of boric acid, triblock copolymer surfactant, and silver nitrate, followed by heat treatment. The obtained samples were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), UV–vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption–desorption. It was revealed that all samples consist of highly crystalline anatase with mesoporous structure. For Ag/B–TiO₂, B was doped into TiO₂ matrix in the form of both interstitial B and substitutional B while Ag was deposited on the surface of B–TiO₂ in the form of metallic silver. Compared with the single B-doped or Ag-loaded TiO₂ one, mesoporous Ag/B–TiO₂ exhibits much higher visible light photocatalytic activity for the degradation of Rhodamine 6G, which can be ascribed to the synergistic effects of B doping and Ag loading by narrowing the band gap of the photocatalyst and preventing the fast recombination of the photogenerated charge carriers, respectively.     

The adsorption site and orientation of CH3S on Ni(111)

The angle-resolved X-ray photoelectron spectra for 0.15 monolayers (ML) of sulfur, and 0.25 ML methyl thiolate formed at 100 K and annealed to 150 and 250 K, on Ni(111) are analyzed to determine the structures of these species. It is found that sulfur adsorbs on the face-centered cubic hollow site on Ni(111) with a S---Ni bond length of 2.20±0.02 Å. The thiolate species formed at 150 K has the C---S bond tilted at 35° to the surface normal with a C---S bond length of 1.85±0.02 Å and a S---Ni bond length similar to that for adsorbed sulfur (2.2 Å). The methyl group is tilted toward the bridge site and the thiolate appears to be adsorbed on the face-centered cubic site although there may also be adsorption in the hexagonal close packed site. The species formed at 250 K adsorbs on a reconstructed surface where the chemical shift of the S 2p core level indicates that it adsorbs at a four-fold site and the angle-resolved XPS data indicate that the C---S bond is oriented normal to the surface. The calculated angular variations in intensity are consistent with this interpretation but cannot distinguish between the various models proposed for the reconstructed surface.     

Growth of β-MnO2 films on TiO2(110) by oxygen plasma assisted molecular beam epitaxy

We have used oxygen plasma assisted MBE to grow epitaxial films of pyrolusite (β-MnO₂) on TiO₂(110) for thicknesses of one to six bilayers (BL). We define a bilayer to be a layer of Mn and lattice O and an adjacent layer of bridging O within the rutile structure. The resulting surfaces have been characterized in situ by reflection high-energy electron diffraction, low-energy electron diffraction, X-ray photoelectron spectroscopy and diffraction, and atomic force microscopy. Well-ordered, pseudomorphic overlayers form for substrate temperatures between 400 and 500°C. Mn–Ti intermixing occurs over the time scale of film growth (1 BL/min) for substrate temperatures in excess of 500°C. Films grown at 400–500°C exhibit island growth, whereas intermixed films grown at temperatures of 500–600°C are more laminar. 1 BL films grown at 450°C are more laminar than multilayer films grown at the same temperature, and form a well-ordered surface cation layer of Mn on the rutile structure with at most 10% indiffusion to the second cation layer.     

Synthesis and luminescence properties of Gd6MoO12:Yb3+, Er3+ phosphor with enhanced photoluminescence by Li+ doping

Yb³⁺/Er³⁺ co-doped Gd₆MoO₁₂ and Yb³⁺/Er³⁺/Li⁺ tri-doped Gd₆MoO₁₂ phosphors were prepared by adjusting the annealing temperature via the high temperature solid-state method. Under the excitation of 980 nm semiconductor, the upconversion luminescence properties were investigated and discussed. In the experimental process, we get the optimum Yb³⁺ concentration and the concentration quench effect will happen while the concentration extends the given region. According to the Yb³⁺ concentration quenching effects, the critical distance between Yb³⁺ ions had been calculated. The measured UC luminescence exhibited a strong red emission near 660 nm and green emission at 530 nm and 550 nm, which are due to the transitions of Er³⁺(⁴F_9/2, ²H_11/2, ⁴S_3/2) → Er³⁺(⁴I_15/2). Then the effect of excitation power density in different regions on the upconversion mechanisms was investigated and the calculated results demonstrate that the green and red upconversion is a two-photon process. A possible mechanism was discussed. After Li⁺ ions mixing, the upconversion emission enhanced largely, and the optimum Li⁺ concentration was obtained while fixed the Yb³⁺ and Er³⁺ on the above optimum concentration. This enhancement owns to the decrease of the local symmetry around Er³⁺ after Li⁺ ions doping into the system. This result indicates that Li⁺ is a promising candidate for improving luminescence in some case.     

The effect of CuO and NiO doping on dielectric and ferroelectric properties of Na0.5Bi0.5TiO3 lead-free ceramics

In the present work, lead-free piezoelectric ceramics (Na_0.5Bi_0.5)TiO₃ –xCuO–yNiO (for x = 0.0, 0.02, 0.04 and 0.06) have been prepared by a conventional solid-state reaction method. An investigation of CuO and NiO doping in bismuth sodium titanate (BNT) and a study of the structure, morphology, and dielectric and ferroelectric properties of the NBT–CuNi system have been conducted. Phase and microstructural analysis of the (Na_0.5Bi_0.5)TiO₃ (NBT) based ceramics has been carried out using X-ray diffraction and scanning electron microscopy (SEM) techniques. Field emission scanning electron microscopy (FE-SEM) images showed that inhibition of grain growth takes place with increasing Cu and Ni concentration. The results indicate that the co-doping of NiO and CuO is effective in improving the dielectric and ferroelectric properties of NBT ceramics. Temperature-dependent dielectric studies have also been carried out at room temperature to 400 °C at different frequencies. The NBT ceramics co-doped with x = 0.06 and y = 0.06 exhibited an excellent dielectric constant ?_r = 1514. The study suggests that there is enormous scope of application of such materials in the future for actuators, ultrasonic transducers and high-frequency piezoelectric devices.     

Synthesis,photoluminescence and thermoluminescence properties of LiNa3P2O7:Tb3+ green emitting phosphor

The alkaline phosphate based LiNa₃P₂O₇:Tb³⁺ phosphors are prepared by solid state reaction method. X-ray diffraction (XRD) analysis shows that all the powders possess orthorhombic structure. Fourier transform infrared (FTIR) spectroscopy studies suggest that the phosphor belong to the diphosphate family. The morphology of the phosphors is identified by scanning electron microscopy (SEM). Upon 378 nm excitation, the LiNa₃P₂O₇:Tb³⁺ phosphors shown emission bands at 482, 545, 588 and 620 nm corresponding to the transitions ⁵D₄→⁷F₆, ⁵D₄→⁷F₅, ⁵D₄→⁷F₄ and ⁵D₄→⁷F₃, respectively. The optimized concentration of Tb³⁺ in LiNa₃P₂O₇ phosphor is found to be 9 mol%. The concentration quenching mechanism was proved to be the exchange interaction between two nearest Tb³⁺ ions with the critical distance (R_c) of 1.18 nm. The Commission International de l'Eclairage (CIE) coordinates evidence that the phosphors emit in the green light region. Thermoluminescence properties of the prepared phosphors are studied by pre-irradiating the powders with different doses of UV irradiation. The kinetic parameters of TL glow curves are calculated using Chen's peak shape method.     

Dielectric relaxation and ac conduction in multiferroic Bi0.8Gd0.1Pb0.1Fe0.9Ti0.1O3 ceramics: impedance spectroscopy analysis

ABSTRACT

The solid solutions of Bi_0.8Gd_0.1Pb_0.1Fe_0.9Ti_0.1O₃ have been prepared by the solid-state reaction method. The preliminary structural studies were carried out by X-ray diffraction technique showing the formation of polycrystalline sample with ABO₃ type of perovskite structure with hexagonal symmetry for the Bi_0.8Gd_0.1Pb_0.1Fe_0.9Ti_0.1O₃ ceramic system at room temperature. Dielectric properties and impedance study of this ceramic have been characterized in the temperature range room temperature to 375 °C and frequency range 100 Hz–1 MHz. The maximum ferroelectric transition temperature (T_c) of this system was in the range 200 °C–260 °C with the dielectric constant of peak to be ～30,170 at 1 kHz. The complex impedance plot exhibited one impedance semicircle observed at low temperature, whereas two semicircles above 80 °C and the centres of the semicircles lie below the real axis, which indicates that the material is non-Debye type. Single semicircle is explained by the grain effect of the bulk and double semicircle is due to the bulk and grain boundary effect. The bulk resistance and grain boundary resistance of the materials decrease with the increasing temperature, showing negative temperature and a typical semiconducting property, i.e. negative temperature coefficient of resistance behaviour.     

Preparation and characterization of hollow TiO2 nanospheres: The effect of Fe3+ doping on their microstructure and electronic structure

Hollow Fe-doped TiO₂ spheres with various Fe dopant concentrations, 0.25, 0.50 and 1.0 wt%, were synthesized via a hydrothermal method using carbon spheres as templates. The prepared samples were calcined in air at temperatures of 500 and 550 °C for 3 h and characterized using XRD, SEM, TEM, SAED, EDX, XPS and UV–vis spectroscopy. The analytical results showed that the presence of a very low concentration of Fe³⁺ incorporated into hollow nanoporous TiO₂ spheres inhibited the growth of nanocrystals as well as the anatase to rutile phase transformation inside the anatase TiO₂ lattice. Doping with 1.0 wt% Fe³⁺ resulted in a reduction of the TiO₂ sphere diameter from 205.71 ± 25.29 nm to 68.70 ± 7.07 nm. The optical energy gap of the samples was determined from UV–Vis absorption spectra. The results showed that the absorption edge of TiO₂@Fe was shifted toward the visible light region with increased Fe content.     

Fabrication and efficient visible light-induced photocatalytic activity of Bi2MoO6/BiPO4 composite

Novel Bi₂MoO₆/BiPO₄ composites with heterojunction structure were fabricated by a one-step hydrothermal method. The photocatalytic properties of Bi₂MoO₆/BiPO₄ composites were evaluated by photocatalytic degradation of rhodamine B (Rh B) under visible light irradiation (λ>420 nm). The results showed that Bi₂MoO₆/BiPO₄ photocatalysts showed much higher photocatalytic activity for the Rh B degradation than the pure BiPO₄ and Bi₂MoO₆ under visible light. The best photocatalytic performance of Bi₂MoO₆/BiPO₄ with about 98.0% Rh B degradation located at molar ratio of 2:1 under visible light illumination for 30 min. The enhanced photocatalytic activity could be mainly ascribed to the formation of heterojunction interface in Bi₂MoO₆/BiPO₄ composites, which is beneficial to the transfer and separation of photogenerated electron–hole pairs, as well as the strong visible light absorption resulting from the sensitization role of Bi₂MoO₆ to BiPO₄. It was also observed that the photodegradation of Rh B is chiefly attributed to the oxidation action of the generated O₂⁻ radicals and the action of h_vb⁺ through direct hole oxidation process.     

H2S和H2S+的振动光谱和电子能谱计算

本文基于MOLPRO软件包使用从头算方法计算了星际分子H₂S及其阳离子H₂S⁺的势能面及光电子能谱.首先,在(U)CCSD/cc-pVQZ理论水平下获取了H₂S沿法线坐标展开的势能面,势能面直观描述了不同振动模式耦合对分子能量变化的影响,S-H键的非对称伸缩振动和面内弯曲振动共同作用使得系统势能变化范围明显变大.振动多组态相互作用方法被用来计算非谐振动频率和振动光谱,计算结果显示,倍频和组合频之间出现了强烈的费米共振,使得相应波段处的红外强度显著增强.最后,使用拉曼波函数和收缩不变Krylov子空间方法首次计算了H₂SΧ¹A₁→H₂S⁺ X²B₁的光电子能谱.此项研究有助于进一步理解星际分子的内部结构,并为实验研究及星际观测提供参考.     

Structure, microstructure and ionic conductivity of the solid solution LiTi2−xSnx(PO4)3

The Nasicon compounds with the composition LiTi_2−xSn_x(PO₄)₃ (x=0-1.8) were synthesised by the solid state reaction. Their structures were determined from X-ray powder diffraction using Rietveld analysis. All the compositions present the space group R-3c. The refinements show that the Ti and Sn cations are statistically distributed over the same position while the Li ones are exclusively located on the M1 site. The lattice constants a and c exhibit linear variation over the whole composition range. The bond lengths are in accordance with those of other Nasicon structures. The SEM micrographs of the samples show relative porous microstructures. The ionic conductivity is about 10⁻⁴-10⁻⁵ S cm⁻¹; for the activation energy, a typical value of 0.32 eV is obtained for x=0.6 composition whereas significant deviation from linearity in the temperature dependence of the dc conductivity, is observed for the Sn-rich ones. This tendency is discussed along with the structural features.     

Reductive-annealing-induced changes in Mo valence states on the surfaces of MoO3 single crystals and their high temperature transport

Reduction of MoO₃ in extreme reducing condition is a way to achieve Mo metal. However, effect of less extreme reductive-annealing, where it allows to keep the crystal structure, on physical and chemical properties of MoO₃ has not been well-studied. In this work, we studied the evolution of Mo valence state during reductive annealing and its effect on high temperature transport. We found the formation of oxygen vacancies on surface of MoO₃ single crystals at the low temperature, which is evidenced by increase of Mo⁵⁺ and color change. In addition, formation of Mo⁴⁺ was at the elevated temperature. For understanding the relation between bulk conductivity and Mo valence state, real-time impedance spectroscopy is employed. Use of two different gases makes it possible to distinguish impedance responses of MoO₃ from those of reduced MoO_3-x. Also, from time-dependent impedance measurements, we observed the evolution of transport behaviour by evolution of Mo valence state.     

Incorporation of iodine into the channels of AlPO4-5 crystals

Iodine molecules have been incorporated into the channels of calcined AlPO₄-5 crystals by using vapor-phase diffusion method. XRD results indicate that the iodine-loaded AlPO₄-5 crystals are of similar structure as that of as-synthesized AlPO₄-5 crystals. TG and XRF analyses reveal that the iodine molecules have not compactly filled the channels of AlPO₄-5 crystals, and the desorbing process of adsorbed iodine is quite different from that of adsorbed water. Polarized Raman spectra imply that the iodine exists in the channels of AlPO₄-5 crystals as vapor-like I₂ molecules, and the I₂ molecules orientate randomly.     

Effect of Gd doping on structural, electrical and magnetic properties of BiFeO3 electroceramic

Room temperature multiferroic electroceramics of Gd doped BiFeO₃ monophasic materials have been synthesized adopting a slow step sintering schedule. Incorporation of Gd nucleates the development of orthorhombic grain growth habit without the appearance of any significant impurity phases with respect to original rhombohedral (R3c) phase of un-doped BiFeO₃. It is observed that, the materials showed room temperature enhanced electric polarization as well as ferromagnetism when rare earth ions like Gd doping is critically optimized (x=0.15) in the composition formula of Bi_1+2xGd_2x/2Fe_1−2xO₃. We believe that magnetic moment of Gd⁺³ ions in Gd doped BiFeO₃ tends to align in the same direction with respect to ferromagnetic component associated with the iron sub lattice. The dielectric constant as well as loss factor shows strong dispersion at lower frequencies and the value of leakage current is greatly suppressed with the increase in concentration of x in the above composition. Addition of excess bismuth and Gd (x=0.1 and 0.15) caused structural transformation as well as compensated bismuth loss during high temperature sintering. Doping of Gd in BiFeO₃ also suppresses spiral spin modulation structure, which can change Fe-O-Fe bond angle or spin order resulting in enhanced ferromagnetic property.     

Preparation and photocatalytic activity of nitrogen-doped TiO2 hollow nanospheres

TiO₂ hollow nanospheres were prepared using silicon oxide as a template. N-doped titanium oxide hollow spheres, TiO_2−xN_x were synthesized by reacting TiO₂ hollow spheres with thiourea at 500 °C. XRD and XPS data showed that oxygen was successfully substituted by nitrogen through the nitrogen-doping reaction, and finally N-doped TiO₂ hollow spheres were formed. The N-doped TiO₂ hollow spheres showed new absorption shoulder in visible light region so that they were expected to exhibit photocatalytic activity in the visible light. The photocatalytic activity of N-doped TiO₂ hollow spheres under visible light was similar to that of normal spherical TiO_2−xN_x in spite of the structural difference.