CsCl-TmCl3-HCl-H2O(25 ℃)的相平衡及其固相化合物

The equilibrium solubilities of the quaternary system CsCl-TmCl₃-HCl-H₂O was determined at 25 ℃ and the corresponding equilibrium diagram was constructed. The diagram is a complicated system with limited solid solutions and formation of a new compound 3CsCl·2TmCl₃·14H₂O. The new compound has been characterized by XRD, TC-DTG and fluorescence spectrometry. Results show that upconversion spectrum exhibits at 335 nm when exciting at 860 nm, and fluorescence spectrum exhibits at 295 nm and 385 nm when exciting at 240 nm. The compound loses its crystal water by four steps at 50 to 250 ℃. Using a heat conduction calorimeter, the standard molar enthalpy of dissolution of 3CsCl·2TmCl₃·14H₂O was determined to be (-11.601 ± 0.050) kJ·mol^-1 at 298.15 K.     

Fe/La2O3纳米催化剂制备碳纳米管

Nanocrystalline LaFeO₃ was synthesised by the citrate method with La(NO₃)₃·6H₂O,Fe(NO₃)₃·9H₂O and citric acid as the raw materials. Before and after reduction, its structure was characterized by means of X-ray diffraction and transmission electron microscopy(TEM). And after reduction of LaFeO₃ oxide, the rare earth oxide, La₂O₃, prevents Fe particles from agglomerating and promotes the dispersion of nano-scale Fe particles (ca.40nm), which is one of the key factors for the growth of carbon nanotube. The carbon nanotubes from the catalytic de-composition of C₂H₂ were obtained using Fe/La₂O₃ nano-scale catalyst, which was formed from LaFeO₃ oxide as the catalyst precursor. The morphological structures of the carbon nanotube obtained have been examined by TEM. The results indicate that they are multi-walled nanotubes of good quality with inter diameter ranging from 20～25nm and length ranging from 25～40μm. The yields of carbon nanotube are 1.25g·gcat^-1 at the reaction temperature of 973K for 30min.     

Lu(Et2dtc)3(phen)的生成反应焓变、摩尔热容和恒容燃烧能测定

A ternary solid complex Lu(Et₂dtc)₃(phen) has been obtained from the reaction of hydrated lutetium chloride with sodium diethyldithiocarbamate (NaEt₂dtc), and 1,10-phenanthroline (o-phen·H₂O) in absolute ethanol. IR spectrum of the complex indicates that Lu³⁺ binds with sulfur atom in the Na(Et₂dtc)₃ and nitrogen atom in the o-phen. The enthalpy change of liquid-phase reaction of formation of the complex, Δ_rH_m^Ө (l), was determined to be (-32.821 ± 0.147 ) kJ·mol^-1 at 298.15 K by an RD-496 Ⅲ type heat conduction microcalormeter. The enthalpy change of the solid-phase reaction of formation of the complex, Δ_rH_m^Ө (s), was calculated to be (104.160 ± 0.168) kJ · mol^-1 on the basis of an appropriate thermochemistry cycle. The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature of liquid-phase reaction. Fundamental parameters, such as the activation enthalpy (ΔH_≠^Ө), the activation entropy (ΔS_≠^Ө), the activation free energy (ΔG_≠^Ө), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained by combination the reaction thermodynamic and kinetic equations with the data of thermokinetic experiments. The molar heat capacity of the complex, c_m, was determined to be (82.23 ± 1.47) J·mol^-1·K^-1 by the same microcalormeter. The constant-volume combustion energy of the complex, Δ_cU, was determined as (-17 898.228 ± 8.59) kJ·mol^-1 by an RBC-Ⅱtype rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δ_cH_m^Ө, and standard enthalpy of formation, Δ_fH_m^Ө, were calculated to be (-17 917.43 ± 8.11) kJ·mol^-1 and (-859.95 ±10.12) kJ·mol^-1, respectively.     

配合物[Sm(o-MOBA)3(phen)·H2O]2·4H2O的合成与晶体结构

The title complex [Sm(o-MOBA)₃(phen)·H₂O]₂·4H₂O has been synthesized by the reaction of SmCl₃·6H₂O with o-methoxybenzoic acid and 1,10-phenanthroline in 1∶3∶1 molar ratio. The crystal structure was determined by X-ray single crystal diffraction. The crystal belongs to triclinic system, space group P1 with a=1.203(10) nm, b=1.293(10) nm, c=1.306(11) nm, α=64.50(10)°, β=81.93(10)°, γ=74.81(10)°. The molecular structure shows that the Sm³⁺ ion coordinates to nine atoms. The carboxylate groups are bonded to the samarium ion in three modes: monodentate, bidentate chelating, tridentate chelating-bridging. CCDC: 603740.     

MgFe2O4纳米粉体的水热合成及其表征(英)

MgFe₂O₄ nanoparticles were hydrothermally synthesized at 150 ℃ using iron nitrate [Fe(NO₃)₃·9H₂O], magnesium nitrate [Mg(NO₃)₂·6H₂O] and sodium hydroxide (NaOH) as starting materials by carefully controlling the reaction conditions. The influences of several factors such as presence or absence of Na⁺, molar ratio of Fe³⁺ / Mg²⁺, concentration of mental ions, temperature and reaction time on resultant products were investigated in the hydrothermal process. The sample was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and its magnetic properties were measured using vibrating sample magnetometer (VSM).     

三元体系YCl3-CdCl2-H2O和四元体系YCl3-CdCl2-HCl(～8.8%)-H2O (25 ℃)的相平衡及其固相新化合物的研究

The equilibrium solubilities of the ternary system YCl₃-CdCl₂-H₂O, the quaternary system YCl₃-CdCl₂-HCl(～8.8%)-H₂O were determined at 25 ℃ and the phase diagrams were constructed. The results show that the ternary system was complicated with six equilibrim solid phases CdCl₂·2.5H₂O, CdCl₂·H₂O, 8CdCl₂·YCl₃·15H₂O (8∶1 type), 4CdCl₂·YCl₃·13H₂O(4∶1 type), 5CdCl₂·2YCl₃·26H₂O (5∶2 type) and YCl₃·6H₂O. The quaternary system was also complicated with four equilibrim solid phase CdCl₂·H₂O, 4CdCl₂·YCl₃·13H₂O (4∶1 type), 5CdCl₂·2YCl₃·26H₂O(5∶2 type) and YCl₃·6H₂O. Among the three new compounds 8CdCl₂·YCl₃·15H₂O, 4CdCl₂·YCl₃·13H₂O and 5CdCl₂·2YCl₃·26H₂O, 8CdCl₂·YCl₃·15H₂O was a kind of metastable compound only in ternary system, and it was changed into 4CdCl₂·YCl₃·13H₂O with time. Both 4∶1 type and 5∶2 type existed in ternary and quaternary system, but they were also congruently soluble compounds in quaternary system. They have been prepared from the system and have been characterized by XRD, TC-DTG and DSC.     

四元体系CdCl2-LaCl3-(9.7%)HCl-H2O在298K的相平衡及其固相化合物的研究

The equilibrium solubility of the LaCl₃-CdCl₂-(9.7%)HCl-H₂O quaternary system at 298K was determined and the phase diagram was constructed. The results show that the system is complicated with four equilibrium solid- phases CdCl₂·H₂O， 8CdCl₂·LaCl₃·16H₂O(8∶1 type)， 4CdCl₂·LaCl₃·12H₂O(4∶1 type) and LaCl₃·7H₂O， respectively. The two new compounds 8CdCl₂·LaCl₃·16H₂O(8∶1 type) and 4CdCl₂·LaCl₃·12H₂O(4∶1 type) are congruently soluble in ～9.7% HCl-H₂O medium and have not yet been reported in literatures. Both com-pounds have been prepared from the system and have been characterized by XRD， TG-DTG and DSC.     

新型三维间排层状钴磷酸盐配合物Co3(PO4)2·6H2O的合成与晶体结构

A new three dimensional layered cobalt phosphate complex Co₃(PO₄)₂·6H₂O, was prepared by hydro-thermal reaction of Co(CH₃COO)₂·4H₂O and H₃PO₄, NH₄VO₃. The crystal structure of the complex was deter-mined by single-crystal X-ray diffraction. The result indicates that it crystallizes in the tetragonal space group I4/m. It rarely occurs in cobalt phosphate complex to form two kinds of coordinate geometry of Co(Ⅱ), six water molecular oxygen atoms surround Co(Ⅰ) and form an octahedron geometry, Co(2) bond to four oxygen atoms from 4PO₄^3- and one water molecular oxygen and build a tetragonal pyramid. The kinetic study shows that the first decomposition stage is governed by A(?)B(?)C mode. CSD: 414600.     

Yb(Cl4)3·3H2O-18C6-C2H5OH体系(25℃)的相化学研究及固态配合物的合成与性质

The solubilities of Yb(ClO₄)₃·3H₂O-18C6-C₂H₅OH ternary system at 25 were invstigated by a semimicro method for study of phase equilibrium.and the refractive indexes of saturated solutions were determined.The behavior of water in this system during the equilibrium was examined.The results indicate that there are two kinds of complexes formed in the system, their chemical compositions are: Yb(ClO₄)₃·18C6·3H₂O·2C₂H₅OH (I) and Yb(ClO₄)₃ 18C6·3H₂O·C₂H₅OH.Both are incongruently soluble in EtOH.The influences of rare earth ions and salt anions on formation of complexes were discussed.The two solid complexes have been prepared, and their composihons and properties have been investigated by chemical analysis, IR, DTG and DSC.According to the DSC, the enthalpies of some steps during the decomposition have been obtained for complexes (Ⅲ)and (Ⅳ).     

氰基桥联双核镝(Ⅲ)-铁(Ⅲ)配合物[DyFe(CN)6(DMF)4(H2O)3]·1.25H2O的合成与结构表征

A dinuclear complex [DyFe(CN)₆(DMF)₄(H₂O)₃]·1.25H₂O(DMF=N， N-dimethylformamide) 1 based on the cyanide as linkage was prepared and structurally characterized by X-ray single-crystal structure analysis. The Dy(Ⅲ) ion is eight coordinations in a square-antiprism arrangement and the Fe(Ⅲ) ion is six coordinations oriented octahedrally. The neutral units [DyFe(CN)₆(DMF)₄(H₂O)₃] are held together by hydrogen bonds formed by lattice water molecules， coordinated water molecules and nitrogen atoms of cyanide coming from other distinct complex units to afford a three-dimensional framework. CCDC： 192314.     

N2O活化的Fe/ZSM-5表面活性氧的表征(英)

Temperature-programmed reduction (H₂-TPR) was employed to quantitatively characterize the active oxygen species generated from a high Fe-loading Fe/ZSM-5 catalyst exposed to N₂O at 250 ℃. [Fe-O-Fe]²⁺ dimer was determined as the active iron complex for N₂O decomposition to produce the active oxygen. Reduction of Fe³⁺ to Fe²⁺ by H₂ in the dimer and removal of OH^- groups from Fe²⁺ dimer by heating Fe/ZSM-5 to 700 ℃ were the prerequisites for the formation of this active Fe complex. A linear correlation with a slope of 1.0 between the amount of [Fe-O-Fe]²⁺ and that of active oxygen species was observed. Maximum amount of active oxygen species can be generated by reducing Fe/ZSM-5 catalyst with H₂ at the temperatures over 500 ℃ and then heating the resulting product in Ar to 700 ℃, followed by N₂O exposure at 250 ℃. The ratio of the total number of oxygen atoms (Ode) deposited by interaction of [Fe-O-Fe]²⁺ with N₂O to the amount of [Fe-O-Fe]²⁺ was 2. However, not all the deposited oxygen atoms were active oxygen (O_a); the ratio of O_a and O_de was 0.5. The iron dimer complex composing active oxygen is a five-atom ion [Fe₂O₃]²⁺; the most probable structure is as follows:     

自旋交叉配合物[Fe(ttd)2(NCS)2]·H2O的合成和磁性研究

The ligand ttd(ttd=1,4,8,9-Tetraaza-triphenylene-2,3-dicarbonitrile) and a novel spin crossover complex [Fe(ttd)₂(NCS)₂]·H₂O were synthesized, and characterized by elemental analysis, IR, MS, and UV-vis spec-troscopy. The temperature dependence of magnetic susceptibility shows that there are a little break between 150～190K and an unusual step transition with a 50K width between 190～240K. Compared with the other complexes with the resemble structure, it can be found that the influence of ligand is very notable.     

锂离子电池正极材料LiNi1-xCoxO2的合成及电化学性能研究

LiNi_1-xCo_xO₂ cathode materials for lithium ion batteries were synthesized by the co-precipitation and solid-state reaction methods with LiOH·H₂O, Ni(NO₃)₂·6H₂O and Co(NO₃)₂·6H₂O as raw materials. The materials were characterized by XRD, SEM and electrochemical tests. The results showed that synthesized cathode materials were with layered structure similar to α-NaFeO₂ and uniform morphology and nearly normal grain size distribution and better electrochemical performance when x was 0.18. The first charge and discharge capacity of the cathode material was 224.3 mAh·g^-1 and 194.2 mAh·g^-1, respectively. 88.5% of the first discharge capacity remained at the 20th cycle.     

γ-Fe2O3纳米粉的低热固相制备及其电磁损耗特性(英)

The Fe(OH)₃ precursor was prepared by solid -state reaction with Fe(NO₃)₃·9H₂O, NaOH and dispersed poly-ethylene glycol at low heating temperature(25 ℃). Synthesis of iron oxide (γ-Fe₂O₃) nanoparticle was achieved by thermal decomposition of Fe(OH)₃·xH₂O precursor. The nanoparticle was characterized by TG-DTA, X-ray diffra-ction, TEM etc. The results showed that the nanoparticle was composed of γ-Fe₂O₃ and was a better absorber for electromagnetic wave within the low frequency band.     

二{桥-2，4，6-三[二(2-吡啶基)胺]-1，3，5-三嗪-N，N′，N ″，N′′′}·四氯合二锌(Ⅱ)的合成与晶体结构(英)

A dinuclear Zn(Ⅱ) complex C₆₆H₄₈Cl₄N₂₄Zn₂·2CH₃OH·2H₂O (1) was synthesized and characterized by X-ray crystallography. In the complex, two 2,4,6-tris[bis(2-pyridyl)amino]-1,3,5-triazine ligands are bridged together by two zinc(Ⅱ) ions and stacked in a parallel manner. CCDC: 267649.     

三元体系LiCl-LiNO3-H2O 273.15 K和323.15 K等温溶解度的测定

Solubility of the ternary system LiCl-LiNO₃-H₂O was measured at 273.15 K and 323.15 K by analyzing the equilibrated phase composition. Experimental result shows that there are three solubility branches at 273.15 K, corresponding to the solid phases LiCl·2H₂O，LiNO₃ and LiNO₃·3H₂O, respectively, while there are two solubility branches at 323.15 K, corresponding to the solid phase LiCl·H₂O and LiNO₃. The invariant point compositions are (1) 33.68wt% LiCl, 14.32wt% LiNO₃ and (2) 27.70wt% LiCl, 20.60wt% LiNO₃ at 273.15 K and (3) 39.07wt% LiCl, 16.89wt% LiNO₃ at 323.15 K. Also, the experimental results show that the solid phases in equilibrium with the solution {x(2.8LiCl+LiNO₃)-(1-x)H₂O} are LiNO₃·3H₂O or LiNO₃ at 273.15 K and LiNO₃ at 323.15 K.     

邻苯二甲酸Pb(Ⅱ)配合物纳米颗粒的合成及其燃烧催化性能研究

The nanoparticle Pb(Ⅱ)-Phtalate complex was synthesized by liquid dispersion deposition method using Pb(Ac)₂·3H₂O and potassium acid phthalate as the reactant. The nanoparticle complexes were characterized with TEM, XRD, TG, DSC and IR. The composition of the nanoparticle PbPht complex was determined by chemical and elemental analysis. The catalytic performance of nanoparticle complex on the combustion of RDX-CMDB propellant was investigated. The results showed the average particle size of complex were about 50 nm. The nanoparticle Pb(Ⅱ)-Phtalate complex can enhance burning-rate of propellant by 135%, and lower the pressure exponent by 74%.     

[Co(HOC10H6COO)2(H2O)4]配合物的合成、晶体结构和性质研究

Complex [Co(HOC₁₀H₆COO)₂(H₂O)₄] was synthesized by reaction of hydroxy-2-naphthoic acid with CoCl₂·6H₂O. The compound was characterized by elemental analysis, IR and the structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P2₁/n with a=0.675 8(2) nm, b=0.518 15(14) nm, c=2.962 9(9) nm, β=94.925(8)°. V=1.033 6(5) nm³, Z=2, D=1.624 Mg·m^-3, F(000)=522. The Co atom has an octahedron coordination geometry and was six-coordinated with two oxygen atoms from two carboxylate ligands and four oxygen atoms from four water molecules. The complex molecules were linked by different hydrogen bonds to form a 2D network. The complex has thermal stability and shows a strong fluorescent emission at 421 nm (λ_ex=342 nm). CCDC: 250903.     

[Sr(CHZ)(TNR)(H2O)(OH)]2·2H2O的晶体结构和热分解机理

The coordination compound of [Sr(CHZ)(TNR)(H₂O)(OH)]₂·2H₂O (TNR: 2,4,6-trinitroesorcinol, CHZ: carbohydrazide) was prepared by reacting CHZ solution and strontium styphnate solution (obtained through the reaction of strontium carbonate and styphnic acid). The molecular structure was characterized by using X-ray diffraction analysis, element analysis and FTIR analysis. The crystal belongs to triclinic with space group P1. The unit cell parameters were as follows: a=0.725 2(2) nm, b=1.021 2(2) nm, c=1.144 0(2) nm, α=69.50(3)°, β=78.82(3)°, γ=84.64(3)° and Z=2. The thermal decomposition of the compound is studied using differential scanning calorimetry (DSC) and thermogravimetry thermogravimetry-derivative (TG-DTG) techniques. CCDC: 269310.     

配位聚合物{[Co(4,4′-bpy)(H2O)4](Fum)·4H2O}n的合成和晶体结构

The complex {[Co(4,4′-bpy)(H₂O)₄](Fum)·4H₂O}_n(where 4,4′-bpy = 4,4′-bipyridine and Fum = fumarate) was synthesized and characterized by X-ray diffraction. The complex consists of one-dimensional chains containing cobalt(Ⅱ) ions bridged by 4,4′-bpy molecules. The six-coordination of Co²⁺ is achieved by means of four water molecules. The fumarate is not coordinated to cobalt ion while it forms hydrogen bonds with coordinated and non-coordinated water molecules and extends the structure into three-dimensional hydrogen bonding network. CCDC: 190488.