Insights on the origin of the structural phase transition in BaV10O15 from electronic structure calculations and the effect of Ti-doping on its structure and electrical transport properties

Band structure calculations at the level of LMTO-ASA provide insight into the electronic structure of BaV₁₀O₁₅ and the origin of the structural phase transition. A crystal orbital Hamiltonian population/integrated crystal orbital Hamiltonian population analysis provides evidence that the crystallographic phase transition is driven by V-V bond formation. As well, the energy bands near the Fermi level are very narrow, <1 eV, consistent with the fact that the observed insulating behavior can be due to electron localization via either Mott-Hubbard correlation and/or Anderson disorder. The partial solid solution, BaV_10−xTi_xO₁₅, was examined to study the effect of Ti-doping at the V sites on the structure and electronic transport properties. In spite of the non-existence of “BaTi₁₀O₁₅”, the limiting x=8, as indicated by a monotonic increase in the cell volume and systematic changes in properties. This limit may be due to the difficulty of stabilizing Ti²⁺ in this structure. For x=0.5 both the first order structural phase transition and the magnetic transition at 40 K are quenched. The samples obey the Curie-Weiss law to x=3 with nearly spin only effective moments along with θ values which range from −1090 K (x=0.5) to −1629 K (x=3). For x>3 a very large, ∼2×10⁻³ emu/mol, temperature independent (TIP) contribution dominates. Conductivity measurements on sintered, polycrystalline samples show semiconducting behavior for all compositions. Activation energies for Mott hopping derived from high temperature data range from ∼0.1 eV for x=0-1 and fall to a plateau of 0.06 eV for x=3-7. Low temperature data for x=3, 5 and 7 show evidence for Mott variable range hoping (VRH) with a T^1/4 law and in one case between 5 and 17 K, a Efros-Shklovskii correlated hopping, T^1/2 law, was seen, in sharp contrast to BaV₁₀O₁₅ where only the E-S law was observed up to 75 K. Seebeck coefficients are small (<35 μV/K), positive, roughly TIP and increase with increasing x up to x=5. This may point to a Heikes hopping of holes but a simple single carrier model is impossible. The compositions for x>3 are remarkable in that local moment behavior is lost, yet a metallic state is not reached. The failure of this system to be driven metallic even at such high doping levels is not fully understood but it seems clear that disorder induced carrier localization plays a major role.     

乙醇 /水混合溶剂沉淀制备纳米BaF2及粒径控制

采用水和乙醇混合溶剂沉淀的方法制备了不同粒径的BaF₂纳米粉体。用XRD、TEM和FSEM表征了粉体的粒径和形貌。研究了陈化时间、水和乙醇的体积比对BaF₂纳米粉体的粒径和形貌的影响。结果表明，随混合溶剂中乙醇含量升高，沉淀粒径减小。BaF₂沉淀粒径的倒数和溶剂介电常数的倒数呈线性关系，据此关系可以控制BaF₂纳米粉体的粒径。     

Synthesis of Ultra-Fine Columbite Powder MgNb2O6 by the Polymerized Complex Method

Pure MgNb₂O₆ powders with high specific surface area and high crystallinity have been successfully synthesized by the Polymerized Complex (PC) Method. A solution of water, citric acid, ethylene glycol and niobium and magnesium ions, was polymerized at 130°C by the water elimination and was calcined at 400°C for 2 h. The precursor formed was calcined at temperatures from 700°C to 1000°C in air to obtain the columbite phase. Thermal analysis, Raman spectroscopy, x-ray diffraction, adsorption/desorption hysteresis and scanning electron microscopy were used to investigate the polymer decomposition and the columbite phase evolution. No evidence for phase separation of crystalline MgCO₃ and Nb₂O₅ in Raman spectra and x-ray diffraction pattern as distinct intermediates were found, and the MgNb₂O₆ probably is formed through a single-step decomposition of oxycarbonate intermediate, as other double oxide synthesized by the PC Method, as indicated by the thermal decomposition of the precursor.     

TiCl4-Cr还原偶联活泼卤化物及芳醛、芳酮的研究

低价钛化合物在有机合成和有机反应中有着广泛的应用。我们曾研究了低价钛对α,α,α-三卤甲基苯的脱卤偶联、对2,2-二芳     

Progress on phthalocyanine-conjugated Ag and Au nanoparticles: Synthesis,characterization, and photo-physicochemical properties

Phthalocyanine (Pc) complexes are an important class of dyes with numerous (e.g., biological, photophysical, and analytical) applications. Among the methods used to improve the properties of these complexes, one should mention the introduction of different substituents, variation of the central metal ion, ligand exchange, and conjugation to nanomaterials (e.g., carbon-based nanomaterials and metal nanoparticles (NPs)). This work briefly reviews Pc complex conjugation to Ag and Au NPs, highlights the different NP shapes, and discusses the diversity of conjugation approaches. Moreover, the use of UV–Vis spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, atomic force microscopy, dynamic light scattering and Fourier transform infrared spectroscopy to characterize Pc-NP hybrids is summarized. The effect of conjugation on Pc photo-physicochemical properties (fluorescence, singlet oxygen generation, triplet state formation, and optical limiting behavior) is discussed, and future perspectives for the synthesis and applications of new hybrids are provided.     

超临界流体干燥过程的分析

以ZrOCl2•8H2O为原料，采用超临界流体干燥（SCFD）法，在短时间内制备出大孔体积高比表面ZrO2气凝胶超细粉．该法具有良好的稳定性和可靠性．建立了醇凝胶中液相含水量的分析方法，为产品质量控制及确认体系是否处于超临界状态提供了依据．对抽提后的溶剂分析表明，SCFD过程是一物理过程．对水的抽提干燥过程亦进行了初步的理论探讨．     

Tetragonal low-temperature structure of LiAl

The cubic face-centered structure of LiAl (, at ) transforms into a tetragonal body-centered structure (I4₁/amd, , at ). This first-order phase transition at about during heating is probably the reason for the so-called “ anomalies” in some physical properties like specific heat, electrical resistivity and nuclear-spin lattice relaxation. This transition seems to be correlated with the composition Li:Al of the alloy and the amount of Li vacancies.     

负载型非晶态Cu/SiO2催化剂的非晶性质

以超细ＳｉＯ２为载体，用ＫＢＨ４还原Ｃｕ＾２＋盐溶液制备了非负载型Ｃｕ和负载型Ｃｕ／ＳｉＯ２催化剂，ＸＲＤ，ＴＥＭ和电子衍射分析结果表明，负载型Ｃｕ／ＳｉＯ２为完全非晶态，而非负载型Ｃｕ中存在着少量晶态Ｃｕ，ＤＳＣ结果表明，非晶态Ｃｕ／ＳｉＯ２的热稳定性明显高于非负载型Ｃｕ，说明超细ＳｉＯ２具有稳定非晶结构的作用，ＸＰＳ结果表明，还原产物中的铜原子呈Ｃｕ状态，ＩＣＰ分析结果表明，样品中的Ｂ含量均低     

高效液相色谱法测定糙米粉中的维生素

高效液相色谱法测定糙米粉中的维生素吴红京，唐根源，王勇（中国科学院福建物质结构研究所福州３５０００２）（福建药品检验所福州３５０００１）１前言众所周知，糙米粉有很高的营养价值，含有人体必需的多种维生素。用高效液相色谱法（ＨＰＬＣ）和薄层色谱法（ＴＬＣ...     

CuO-BaO/SiO2催化剂的结构表征

以XRD、XPS和EXAFS手段对CuO－BaO／Sic2催化剂及其还原态的结构进行了研究．结果表明，在CuO－BaO／SiO2体系中铜和钡都是以氧化态的形式存在，超细SiO2载体对所负载的CuO的结构有影响．随着样品负载量的逐渐降低，Cu－O和Cu－Cu睡的健长和配位数逐渐征小，而且低载量样品的健长和配位数减小的幅度最大．在总负载量＞13．39％的样品中，CuO以晶相的形式存在；总负载量＜13．39％的样品中，CUO呈现单层分布的高分出状态．还原态样品中钢以本价铜的形式存在，随负载量的降低，还原态Cu－Cu健的镇长和配位数也分别呈现出逐渐减小的趋势．还原态中心铜原子在催化剂表面的分布状态基本上保持了氧化态催化剂中CuO物相的分市状态．