三缺位杂多化合物K_8［P_2W_（18）Mo_2Co_2（H_2O）_2O_（68）］·MoO_6·15H_2O的合成、结构及催化H_2O_2分解研究

合成了杂多化合物Ｋ８［Ｐ２Ｗ（１８）Ｍｏ２Ｃｏ２（Ｈ_２Ｏ）２Ｏ（６８）］·ＭｏＯ６·１５Ｈ２Ｏ，依据ＸＲＤ、ＩＲ、ＵＶ－Ｖｉｓ及ＸＰＳ确定了其晶体结构和配位原子价态，考察了该化合物催化Ｈ２Ｏ２分解的动力学行为。     

反相微乳液法制备纳米Al2O3颗粒及其形成反应机理的研究

通过聚乙二醇辛基苯基醚(曲拉通X-100)/正丁醇/环己烷/水溶液形成的体系, 采用反相微乳液法合成了Al₂O₃纳米粒子. 对前驱体进行热分析(TG-DTG-DTA), 确定了合适的煅烧温度为1150 ℃. 采用X射线衍射(XRD)、透射电镜(TEM)、紫外可见分光光度法(UV-vis)分别对产物的结构、粒度和形貌进行了表征, 考察了微乳液中水与表面活性剂的物质的量之比(ω_o)、煅烧温度和煅烧时升温速率等关键因素对产物形貌和晶相的影响, 并通过分析进一步揭示了Al₂O₃纳米粒子的形成机理. 结果表明, 控制ω_o为10、煅烧温度为1150 ℃可得到分散性好、粒径分布均匀的Al₂O₃纳米粒子, 且2 ℃/min的升温速率更有利于产物向稳定的α晶相转变.     

Quantum chemical studies on the structures, properties and decomposition of the azido derivatives of trinitrobenzenes

The geometries,heats of formation and electronic structures of 15 azido-derivatives of 1,2,3-TNB (Ⅰ),1,2,4-TNB (Ⅱ) and 1,3,5-TNB (Ⅲ) have been studied using quantum chemical AMI method at HF level.The effect of azido substitution on the structures and properties of TNBs has been discussed and the relative stability of the title compounds has been established.The processes of the decomposition of the title compounds by breaking C-NO2,C-N3 and CN-N2 bonds are investigated at UHF-AM1 level.It is shown that the decomposition of the title compounds may be initiated by the cleavage of both C-NO2 and N-N2 bonds.     

A spectroscopic study on the 12-heteropolyacids of molybdenum and tungsten (H3PMo12−nWnO40) combined with cetylpyridinium bromide in the epoxidation of cyclopentene

The epoxidation of cyclopentene with hydrogen peroxide catalyzed by 12-heteropolyacids of molybdenum and tungsten (H₃PMo_12−nW_nO₄₀, n = 1–11), 12-tungstophosphoric acid and 12-molybdophosphoric acid combined with cetylpyridinium bromide as a phase transfer reagent was carried out in acetonitrile. Among 13 heteropolyacids investigated, catalyst of H₃PMo₆W₆O₄₀ showed the highest activity, giving a conversion of 60% and a selectivity of 95% in the epoxidation of cyclopentene. The fresh catalysts and the catalysts under reaction condition were characterized by UV–vis, FT-IR and ³¹P NMR spectroscopy, which has revealed that all of the molybdotungstophosphoric acids were degraded in the presence of hydrogen peroxide to form a considerable amount of phosphorus-containing species. The active species resulted from H₃PMo₆W₆O₄₀ are new kinds of phosphorus-containing species, which is different from {PO₄[WO(O₂)₂]₄}³⁻.     

Thermal and structure analysis of FeSO4·H2O-BaO2 mixtures

Investigations on the thermal decomposition of FeSO₄·H₂O-BaO₂ mixtures were carried out under isothermal conditions by using simultaneously solid electrolyte cell (EMF-method). Evoked interactions producing oxygen in the temperature range 553-673 K were established by means of a solid electrolyte oxygen analyzer. Based on Mössbauer spectroscopy data and X-ray analysis it was proved that these reactions were associated with the release of oxygen from barium peroxide, oxidation of ferrosulphate-monohydrate to FeOHSO₄, and formation of barium ferrites such as BaFe₂O₄ and BaFe₁₂O₁₉.     

机械球磨与反应烧结合成Sr2CeO4发光体的研究

Sr₂CeO₄ phosphor was synthesized by mechanical milling and reactive sintering in this work. The solid state reaction of SrCO₃and CeO₂ (2∶1) started at about 850 ℃ and completed at 1 000 ℃ for about 4 h. Two types of formation mechanism of Sr₂CeO₄ were proposed. When the starting powder mixture was fired above 1 000 ℃, the unstable intermediate phase SrCeO₃was developed, which then reacted with SrCO₃to form the final product Sr₂CeO₄, however, SrCO₃and CeO₂ converted directly to Sr₂CeO₄ at a lower temperature. The XRD results showed the crystal structure of Sr₂CeO₄ was orthorhombic. The emission spectra displayed a broad band with maximum at about 465 nm. The mechanical milling of starting power mixture and the sintering temperature had no effect on this emission spectra.     

Temperature Development of Homo- and Hetero-Clustering in Saturated Vapors

Computational findings of temperature increase of clustering degree in saturated vapors are analyzed. A thermodynamic proof is presented and a simple criterion derived. Illustrations are based on saturated steam, magnesium and carbon vapor. The results are applicable to synthesis of fullerenes, metallofullerenes, and heterofullerenes, chemical vapor deposition technique, or atmospheric chemistry.     

Adducts of Rh2[MTPA]4 with some phosphine chalcogenides: nature of binding and ligand exchange

Adducts of four phosphine chalcogenides with the chiral dirhodium complex ([Rh-Rh]) were investigated by variable-temperature 1H and 31P NMR spectroscopy in order to compare their properties as axial ligands. Whereas the selenide (1) and the sulfide (2) are strong ligands with electrostatic attraction and, in addition, a significant orbital (HOMO-LUMO) interaction, the phosphine oxide compounds (P=O) bind primarily via electrostatic attraction and are relatively weak donors. Moreover, the overall bond strength in these adducts depends on steric congestion around the P=O group.     

Chemihiminescence by the interaction of XeO3 and the products of photolysis of uranyl solutions in sulfuric acid

Using the chemiluminescence oxidation of U(IV) and H₂O₂ with xenon trioxide as a model, it has been found that during the photolysis of solutions of UO₂SO₄ in sulfuric acid in the absence of any organic compounds, the accumulation of U(SO₄)₂ and H₂O₂ takes place as a result of the reaction of the primary products of the photoreduction of uranyl ion,i.e., UO₂ ⁺ and the OH radical.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 751–754, April, 1994.The work was financially supported by the Russian Foundation for Basic Research, Project 93-03-12291.     

Preparation of flame retardant polyamide 6 composite with melamine cyanurate nanoparticles in situ formed in extrusion process

This paper is focused on in situ preparation of melamine cyanurate (MCA) nanoparticles from reaction of melamine (MEL) and cyanuric acid (CA) and their flame retardant polyamide 6 (PA6) composite in the extrusion process through a novel reactive processing method. Fourier transform infrared (FT-IR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) were utilized to characterize the in situ formed MCA nanoparticles and their blends with PA6. Introduction of pentaerythritol (LTP) and water-bound plasticizer dioctyl phthalate (DPT) into the extrusion reaction system greatly inhibits the evaporation of water required for melamine and cyanuric acid reaction at high temperature (higher than 180 °C), laying a foundation for successful in situ preparation of MCA through reactive processing. XRD and FT-IR measurements indicate that under the effect of pentaerythritol, dioctyl phthalate and water, melamine really reacts with cyanuric acid to in situ form MCA in extrusion process. The reaction degree is close to 100%. A very important finding through SEM is that the in situ formed MCA particles, which were found to have aspect ratio of about 7.5, radial size in the range of 70-300 nm (mostly 70-90 nm) and crystallite size of less than 22 nm, are uniformly dispersed in the matrix PA6 at nanoscale. The in situ formed MCA nanoparticles greatly improve the flame retardancy and the mechanical properties of flame-retarded PA6 materials, and the introduced plasticizer dioctyl phthalate also ameliorates the related impact property. The obtained flame-retarded PA6 materials have good comprehensive performance with flame retardancy UL-94 V-0 rating at 1.6 and 3.2 mm thickness, tensile strength 48.0 MPa, elongation at break 106.3% and Izod notched impact strength 8.92 kJ/m². Compared with flame-retarded PA6 material with in situ formed MCA, the one prepared through conventional blending of PA6 with commercial MCA product has improved tensile strength but deteriorated impact strength and flame retardancy.