钙钛矿型LaNiO3、LaMnO3的形成条件

用混合硝酸盐分解法和柠檬酸络合法分别制取了单一钙铁矿型多晶粉末LaNiO_3和LaMnO_3. XRD分析表明LaNiO_3的形成经历了混合氧化物转化为LaNiO_3的同相反应; 而LaMnO_3晶相直接由无定形相转化而来。根据DTA、TG、IR分析两者的形成, NO_3~-离子都起了重要作用. 同时讨论了络合剂柠檬酸的作用.     

Preparation and characterization of spherical V2O3 nanopowder

V₂O₃ nanopowder with spherical particles was prepared by reducing pyrolysis of the precursor, (NH₄)₅[(VO)₆(CO₃)₄(OH)₉]·10H₂O, in H₂ atmosphere. The thermolysis process of the precursor in a H₂ flow was investigated by thermogravimetric analysis and differential thermal analysis. The results indicate that pure V₂O₃ forms at 620°C and crystallizes at 730°C. The effects of various reductive pyrolysis conditions on compositions of V₂O₃ products were studied. Scanning electron micrographs show that the particles of the V₂O₃ powder obtained at 650°C for 1 h are spherical about 30 nm in size with more homogeneous distribution. Experiments show that nanopowder has larger adsorption capacity to gases and is more easily reoxidized by air at room temperature than micropowder. Differential scanning calorimetry experiment indicates that the temperature of phase transition of nano-V₂O₃ powder is −119.5°C on cooling or −99.2°C on heating. The transition heats are −12.55 J g⁻¹ on cooling and 11.42 J g⁻¹ on heating, respectively.     

Dodekahydro‐closo‐dodekaborate der schweren Erdalkalimetalle aus wäßriger Lösung: Ca(H2O)7[B12H12] · H2O,Sr(H2O)8[B12H12] und Ba(H2O)6[B12H12]

Dodecahydro‐ closo ‐dodecaborates of the Heavy Alkaline‐Earth Metals from Aqueous Solution: Ca(H₂O)₇[B₁₂H₁₂] · H₂O, Sr(H₂O)₈[B₁₂H₁₂], and Ba(H₂O)₆[B₁₂H₁₂] The crystalline hydrates of the heavy alkaline earth metal dodecahydro‐closo‐dodecaborates (M[B₁₂H₁₂] · n H₂O, n = 6–8; M = Ca, Sr, Ba) are easily accessible by reaction of an aqueous (H₃O)₂[B₁₂H₁₂] solution with an alkaline earth metal carbonate (MCO₃). By isothermic evaporation of the respective aqueous solution we obtained colourless single crystals which are characterized by X‐ray diffraction at room temperature. The three compounds Ca(H₂O)₇[B₁₂H₁₂] · H₂O (orthorhombic, P2₁2₁2₁; a = 1161.19(7), b = 1229.63(8), c = 1232.24(8) pm; Z = 4), Sr(H₂O)₈[B₁₂H₁₂] (trigonal, R3; a = 1012.71(6), c = 1462.94(9) pm; Z = 3) and Ba(H₂O)₆[B₁₂H₁₂] (orthorhombic, Cmcm; a = 1189.26(7) pm, b = 919.23(5) pm, c = 1403.54(9) pm; Z = 4) are neither formula‐equal nor isostructural. The structure of Sr(H₂O)₈[B₁₂H₁₂] is best described as a NaCl‐type arrangement, Ba(H₂O)₆[B₁₂H₁₂] rather forms a layer‐like and Ca(H₂O)₇[B₁₂H₁₂] · H₂O a channel‐like structure. In first sphere the alkaline earth metal cations Ca²⁺ and Sr²⁺ are coordinated by just seven and eight oxygen atoms from the surrounding water molecules, respectively. A direct coordinative influence of the quasi‐icosahedral [B₁₂H₁₂]^2– cluster anions becomes noticeable only for the Ba²⁺ cations (CN = 12) in Ba(H₂O)₆[B₁₂H₁₂]. The dehydratation of the alkaline earth metal dodecahydro‐closo‐dodecaborate hydrates has been shown to take place in several steps. Thermal treatment leads to the anhydrous compounds Ca[B₁₂H₁₂], Sr[B₁₂H₁₂] and Ba[B₁₂H₁₂] at 224, 164 and 116 °C, respectively.     

Syntheses, crystal structures, and characterization of As(III) and As(V) thioarsenates, [Mn2(phen)(As2S5)]n and [Mn3(phen)3(AsS4)2]n·nH2O

The hydrothermal reactions of As, Mn, S, phen (phen=1,10-phenanthroline), and en (en=ethylenediamine) yield two manganese As(III) and As(V) thioarsenates, [Mn₂(phen)(As^III₂S₅)]_n (1) and [Mn₃(phen)₃(As^VS₄)₂]_n·nH₂O (2), respectively. Single-crystal X-ray diffraction analyses reveal that compound 1 is a two-dimensional (2D) layer of (6,3) topology. The 18-membered rings within the 2D porous layers are formed by corner-, edge-, and face-sharing cubane-like [Mn₂As₂S₄] units along the [100] direction. Whereas compound 2 is a one-dimensional (1D) chain structure. They are both characterized by IR, elemental analysis, EDS, and X-ray powder diffraction. The thermogravimetric analysis of 1 and 2 are discussed. Both the compounds are semiconductors with the band gap of E_g (compound 1)=2.01 eV (617 nm) and E_g (compound 2)=1.97 eV (629 nm), respectively. In addition, the variable-temperature magnetic susceptibility data suggest weak antiferromagnetic interactions between the Mn²⁺ ions in these two compounds.     

槲皮素的光谱分析

槲皮素属于黄酮醇类化合物,广泛存在于蔬菜、水果、茶和葡萄酒等很多食物中。它是一种极强的天然抗氧化剂,具有抗血栓、抗炎、抗病毒、抗肿瘤等作用。本文分析了槲皮素的UV、IR、¹H NMR、¹³C NMR、MS、TG、DSC等,给槲皮素的生产、质量控制提供可靠的光谱数据。     

Decomposition of tetraalkylammonium thiotungstates characterized by thermoanalysis, mass spectrometry, X-ray diffractometry and scanning electron microscopy

Thermal decomposition reactions of tetraalkylammonium thiotungstates, (R₄N)₂WS₄ (R = methyl to heptyl), were investigated with DSC and DTA-TG coupled with mass spectroscopy (MS). The results demonstrate that the complexity of thermal decomposition reactions is significantly influenced by the alkyl group, i.e., more complex steps are observed for the materials with longer alkyl chain lengths. Tetraethyl and tetrapropyl complexes show reversible and irreversible phase transitions detected by DSC experiments combined with thermodiffractometry. The tetrapentyl compound undergoes an irreversible phase transition while the tetraheptyl sample exhibits a glass-like transition and melting prior to decomposition. The whole series of compounds decompose without forming sulfur rich WS_n (n = 3 or 4) intermediates. The final WS₂ products are nearly stoichiometric for R = methyl to pentyl but for hexyl and heptyl samples the sulfur content is significantly reduced with a W/S ratio of about 1.5. The residual carbon and hydrogen contents increase in the final decomposition products in the same order as the number of C atoms in R₄N increase. For the N content no clear trend is obvious. A general thermal decomposition mechanism is suggested which follows a bimolecular nucleophilic substitution reaction. In the SEM images only for R = heptyl the formation of macro-pores with a sponge-like morphology is seen, but for the other precursors compact materials are formed which in part display a well developed morphology. X-ray diffraction analysis of the final products shows the formation of amorphous WS₂ up to the tetrapentyl precursor. But for the tetrahexyl and tetraheptyl materials the W:S ratio is significantly smaller than 1:2 and large amounts of C and H are determined by chemical analyses. In accordance with previously reported results it can be assumed that a carbosulfide phase is formed by a mixed C-W-S sandwich layered structure.     

Tetramethylammoniumamalgam, [N(CH3)4]Hg8

Tetramethyl Ammonium Amalgam, [N(CH₃)₄]Hg₈ Crystals of tetramethyl ammonium amalgam with the composition [N(CH₃)₄]Hg₈ were prepared by electrolysis. According to temperature‐dependent X‐ray diffraction experiments the compound transforms into an amorphous product above 6 °C; the decomposition is a multi‐stage process as shown by DTA experiments. X‐ray examinations of crystalline aggregates indicate a structure of low symmetry with remarkable similarities to that of α‐Hg.     

Synthesis, Crystal Structure and Thermoanalysis of o-vanillin-ethylenediamine Schiff Base Copper( Ⅱ ) Complex

The crystal structure of the title compound [Cu (o-vanillin-ethylenediamine) (H2O)] is described. The complex crystallizes in the orthorhombic system, space group Pbn21 with formula = CuC18H20N2O5, cell dimensions are: a = 0.7490(3) nm, b = 0.9256(2) nm, c=2. 4691(6) nm, V=1.712 nm3, Z = 4, Dc=l.51 g/cm3. The kinetics of thermal decomposition of the complex was studied under the non-isothermal condition by TG. Kinetic parameters were obtained from the analysis of the TG, DTG curves by integral and differential methods. By comparison of the kinetic parameters, the most probable mechanism function is f(α) = (3/2) (1-α)[-ln(1-α)]1/3, and the mathematical expression for the kinetic compensation effect is lnA = 0. 201E+0. 531.     

Untersuchungen zur Kristallstruktur von Lithium‐dodecahydro‐closo‐dodecaborat aus wäßriger Lösung: Li2(H2O)7[B12H12]

Investigations on the Crystal Structure of Lithium Dodecahydro‐closo‐dodecaborate from Aqueous Solution: Li₂(H₂O)₇[B₁₂H₁₂] By neutralization of an aqueous solution of the acid (H₃O)₂[B₁₂H₁₂] with lithium hydroxide (LiOH) and subsequent isothermic evaporation of the resulting solution to dryness, it was possible to obtain the heptahydrate of lithium dodecahydro‐closo‐dodecaborate Li₂[B₁₂H₁₂] · 7 H₂O (≡ Li₂(H₂O)₇[B₁₂H₁₂]). Its structure has been determined from X‐ray single crystal data at room temperature. The compound crystallizes as colourless, lath‐shaped, deliquescent crystals in the orthorhombic space group Cmcm with the lattice constants a = 1215.18(7), b = 934.31(5), c = 1444.03(9) pm and four formula units in the unit cell. The crystal structure of Li₂(H₂O)₇[B₁₂H₁₂] can not be described as a simple AB₂‐structure type. Instead it forms a layer‐like structure analogous to the well‐known barium compound Ba(H₂O)₆[B₁₂H₁₂]. Characteristic feature is the formation of isolated cation pairs [Li₂(H₂O)₇]²⁺ in which the water molecules form two [Li(H₂O)₄]⁺ tetrahedra with eclipsed conformation, linked to a dimer via a common corner. The bridging oxygen atom (∢(Li‐ O ‐Li) = 112°) thereby formally substitutes Ba²⁺ in Ba(H₂O)₆[B₁₂H₁₂] according to (H₂ O )Li₂(H₂O)₆[B₁₂H₁₂]. A direct coordinative influence of the [B₁₂H₁₂]^2— cluster anions to the Li⁺ cations is not noticeable, however. The positions of the hydrogen atoms of both the water molecules and the [B₁₂H₁₂]^2— units have all been localized. In addition, the formation of B‐H^δ—···^δ+H‐O‐hydrogen bonds between the water molecules and the hydrogen atoms from the anionic [B₁₂H₁₂]^2— clusters is considered and their range and strength is discussed. The dehydratation of the heptahydrate has been investigated by DTA‐TG measurements and shown to take place in two steps at 56 and 151 °C, respectively. Thermal treatment leads to the anhydrous lithium dodecahydro‐closo‐dodecaborate Li₂[B₁₂H₁₂], eventually.     

Raman spectra and thermal analysis of a new lead–tellurium–germanate glass system

Differential scanning calorimetry (DSC) and Raman scattering studies of a new glass system, lead–tellurium–germanate glasses in the form of (90−x)GeO₂·xTeO₂·27PbO·10CaO with x=0, 10, 20, 30, and 40, are reported. The glass samples were fabricated using a conventional melt-quenching method. The Raman spectra and possible glass structures are discussed for different TeO₂ contents. The results indicate that increasing TeO₂ content up to 40 mol% in the glass system decreases the glass transition temperature and melting temperature, and suppresses the crystallization tendency in the fiber pulling temperature range. The lead–tellurium–germanate glass, GTPC, possesses a larger refractive index and a smaller maximum phonon energy than that of a lead–germanate glass, 63GeO₂·27PbO·10CaO, and shows a better thermal stability compared to a tellurite glass, 75TeO₂·20ZnO·5Na₂O (TZN). These improved properties could be beneficial for fabricating rare-earth doped fiber devices.