L-苏糖酸锰的制备及标准生成焓

The pink powder of manganese L-threonate was obtained by extracting with alcohol the concentrated solution derived from the reaction between L-threonic acid solution prepared by double decomposition reaction of calcium L-threonate with oxalic acid and superfluous manganese oxide at 80℃ for certain time. The composition of the new compound was determined by chemical and elemental analyses and its formula fits Mn(C₄H₇O₅)₂·H₂O, the IR spectra indicated that Mn²⁺ in the compound coordinates to oxygen atom of the carboxyl group, while the proton of the carboxyl group is dissociated, it was assumed that the coordination number of Mn²⁺ was 4. The results of TG-DTG showed that the compound have fairish stability, the intermediate and final product of the thermal de-composition of the compound are Mn(C₄H₇O₅)₂ and MnO₂, respectively. The constant volume combustion energy of the compound, Δ_cE, were determined by a precise rotating-bomb calorimeter at 298.15K, it was (-3384.30±1.21)kJ·mol^-1, its standard enthalpy of Combustion,Δ_cH_m^?,and standard enthalpy of formation,Δ_fH_m^? , were calculated. They are (-3383.07±1.21)kJ·mol^-1 and (-2 571.68±1.63)kJ·mol^-1, respectively.     

ZrWO4F2的前驱物法合成和表征

Zirconium tungsten oxyfluoride, ZrWO₄F₂, was firstly synthesized with the precursor route. The composition of the compound was determined by combining the results of ICP and XPS. The indexed powder X-ray diffraction pattern of this compound indicates that it is a pure phase, orthorhombic crystal system, space group D₂²=P2₁22 and a=15.32(2)?,b=13.877(7)?,c=8.42(2)?.Combining the results of the DTA-TGA curves from room temperature to 700℃ and XRD patterns in different temperatures the mechanism was revealed during the solid precursor (1) been heated to 700℃. The zirconium tungsten oxyfluoride was considered to be a metastable com-pound. The ascertaining of annealing time and temperature is the key of handling.     

正烷基单胺对层状甘氨酸-N，N-双甲基膦酸锆的插层

The layered zirconium glycine-N,N-dimethylphosphonate (ZGDMP) was prepared and the intercalation behavior of n-alkylmonoamines was investigated. The X-ray diffraction powder patterns demonstrated that the n-alkylmonoamines were taken up in one step and there were no other intermediate phases. The interlayer distance correlated with the number of carbon atoms of the n-alkylmonoamine chains. The n-alkylmonoamines were intercalated into ZGDMP in such a way that the protons of the interlayer -CO₂H groups were replaced by the terminal -NH₃⁺ of the protonated n-alkylmonoamines. The intercalated n-alkylmonoamines were released from the lamellar ZGDMP at temperature of 150 to 250 ℃.     

单分散超细ZnO粉体的制备与表征

Monodispersed superfine ZnO powders with particle size of about 200～400nm were successfully prepared by the decompressed distillation process with n-butyl alcohol as the solvent. The starting materials were Zn(NO₃)2·6H₂O and NH₃·H₂O. TG-DSC， XRD， TEM and BET surface areas techniques were used to characterize the precursor and as-prepared superfine ZnO powders. In the preparation process of superfine ZnO powders， two techniques including the decompressed distillation with n-butyl alcohol and washing with absolute ethanol were used to avoid agglomeration. It is showed that the decompressed distillation process has a better effect in avoiding ag-glomeration than washing with absolute ethanol. The precursor obtained by the decompressed distillation technique has a lower calcination temperature than the one obtained by washing with absolute ethanol. Zincite phase of ZnO with some impurities was obtained when the precursor was calcined at 200℃ for 2h. After it was calcined at 300℃ for 2h， pure superfine ZnO powder was obtained.     

新型超分子复合发光材料——联吡啶氮氧化物铕配合物-蒙脱土的室温固相插层组装及发光性能

Eu(Ⅲ) complexes with bipyO₂ ligand were intercalated into the interlayer spacing of montmorillonite (MMT) by solid-solid ion exchanging and coordination reaction of bipyO₂ with the Eu³⁺ ion existing in the interlayer spacing of Eu-MMT at room temperature, respectively. The obtained luminescent supramolecular composite materials, [Eu(bipyO₂)₄Cl₂]⁺-MMT and [Eu(bipyO₂)₄]³⁺-MMT were characterized by elemental analysis, XRD and FTIR spectroscopy. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalation assembly materials have regular layered structures and good luminescent properties. They emit characteristic red emissions of Eu³⁺ strongly under ultraviolet light excitation. The relative luminescence intensities of the unit mass of Eu³⁺ of intercalation assemblies are much better than that of the corresponding pure Eu³⁺ complex possibly due to the rigid layered structures of the materials and the supramolecular interaction between the host layers and the guest complex ions.     

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.     

超细掺锑SnO2制备工艺中前驱体洗涤分离的研究

Sb-doped SnO₂ ultrafine powders were prepared via oxidation-coprecipitation. Also the relation between surface characteristic (i.e. charged status and solvation) and precursor separation was studied. The results showed that the filter washing speed of precursor can be improved by reduced Precursor |ζ| values or lessen Precursor solvation. For example, adding to little organic solvents (such as ethanol )in Washing liquid morely accelerates to separation speed of precursor. This method and principle of washing and separation precursor can be used by other nona powders preparation with precipitation method, also sb doped SnO₂ ultrafine powders will be prepared easily in industry with it.     

[Ru(bpy)2tpphz]2+与Zn2+形成的双核配合物的荧光性质研究

The formation of heterobimetallic ruthenium(Ⅱ) complex was investigated by absorption and emission spectra. As an intercalator of DNA， the luminescent monometallic ruthenium(Ⅱ) complex [Ru(bpy)₂tpphz]²⁺ could coor-dinate with Zn²⁺ to form the nonluminescent heterobimetallic complex [Ru(bpy)₂(tpphz)Zn]⁴⁺. The emission in-tensity of complex decreased as increasing the amounts of Zn²⁺ and the luminescence was almost lost at the ratio of [Zn]/[Ru] of 1. After binding to DNA， the peripheral coordination site on the tpphz ligand remained accessible for Zn²⁺， the coordination occurred from the oppsite side of helix with respect to intercalated [Ru(bpy)₂tpphz]²⁺ and the nonluminescent heterobimetallic complex was formed. On the other hand， the [Ru(bpy)₂(tpphz)Zn]⁴⁺ also bound to DNA by intercalation and situated the region of the intercalated [Ru(bpy)₂tpphz]²⁺ between the base pairs of DNA. The complex looked like a molecular nut (the Zn²⁺) and bolt (the [Ru(bpy)₂tpphz]²⁺).     

高岭石结构缺陷的 1H MAS NMR和Raman研究

The structure default of kaolinites was characterized with ¹H MAS NMR and Raman spectra. Although the HI indexes of Suzhou and Maoming kaolinite are similar, their ¹H MAS NMR and Raman spectra are very different. ¹H MAS NMR showed that the hydroxyl proton chemical shifts of Suzhou kaolinite are in the higher field and with larger different between the inner surface hydroxyls protons and inner hydroxyls proton chemical shifts than Maoming kaolinite. Raman spectra showed that the surface hydroxyls stretching vibration bands of Suzhou kaolinite are in the high frequency region, and the half height widths of the bands are 7.0～14 cm^-1. The area ratio S_z/(S_z+S_A), where S_Z and S_A are the areas of bands 3685 cm^-1 and 3695 cm^-1 respectively, is 0.23. But the surface hydroxyls stretching vibration bands of Maoming kaolinite are in the low frequency region, and the half height widths of the bands are 8.9～15.1 cm^-1. The area ratio S_z/(S_z+S_A) is 0.77. Those data proved that Suzhou kaolinite has lower structure default than Maoming kaolinite and ¹H MAS NMR and Raman spectra are effective method for study of kaolinite structure default.     

用于制备聚氨酯纳米复合物的高岭石粒子的表征

Clay such as kaolinite， is commonly used as an additive to modify the thermal properties of polymer. In this paper， the morphology， composition， shape and structure of kaolinite was characterized by various advanced techniques. The TEM/ EDX data showed that the kaolinite had a larger particle size and a Si/Al ratio of 1.8. The individual particle of kaolinite was a single crystalline. TEM also showed that these particles were always stacked together due to the presence of electrostatic cohesive energy and hydrogen bond between plaletes. The PAS-FTIR spectra showed that no absorbance of hydroxyl group for hydration water in hydrogen bond region or at 1650cm^-1 was observed at room temperature. It meant a little ability to adsorb water for kaolinite particle. Kaolinite clay also showed no change for its PAS-FTIR spectra with increasing temperature. The TGA results revealed that kaolinite almost doesn′t lose weight at 60℃ due to loss of dehydration of absorbed water， however， it will decomposed around 510℃ and lose its hydroxyl functional group in the form of water (dehydroxylation). The result is consistent with that of PAS-FTIR analysis. This suggests that the structural hydroxyl group on the surface of individual kaolinite clay particle is very stable below 500℃， and the kaolinite composed polymer could be got by the reaction of its stable structural hydroxyl group with isocynate group of polyurethane prepolymer.