钼锑磷杂多酸铵的合成和性质研究

以简单酸铵盐为原料，采用不同的磷钼锑比，在控制反应温度７０～８０℃，溶液酸度２．５～３．０Ｎ的条件下，进行分步反应的方法，首次合成了以锑原子取代的钼锑磷杂多酸铵。通过元素分析，确定了它们的组成，用ｐＨ滴定曲线，电子吸收光谱和Ｘ射线等方法研究了它们的性质。     

钼钒磷杂多酸铵蓝的合成和性质研究

本实验采用分步加原料的方法，以不同的磷钼钒比，直接合成了三种１：１２系列的钼钒磷杂多酸铵蓝，即（ＮＨ４）４Ｈ２·１５Ｈ２Ｏ（ｂｌｕｃ—１），（ＮＨ４）５Ｈ２·和（ＮＨ４）６Ｈ２·３０Ｈ２Ｏ（ｂｌｕｃ－３），并研究了反应条件对这些钼钒磷杂多酸铵蓝形成的影响．通过元素分析、电位滴定、电子光谱和Ｘ射线衍射等测试手段研究了配合物的性质，并确定了配合物的组成．     

钼钨铌磷杂多化合物的研究（Ⅰ）：杂多酸的合成和表征

提出了分步酸化一分步加料合成[PNb_2Mo_xW_(10-x)O_(40)]~(5-)(x=0,2,4,6)系列杂多酸的方法,给出了最佳配料比和生成反应的pH值,并进行了红外、紫外、极谱、电位滴定及热稳定性研究。     

Photochemical Synthesis,Properties and X—Ray Crystal Structure of Tetrabutylammonium Dodecamolybdophosphate Heteropoly Blue

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Anodic Synthesis and Characterization of Na-Pb-O, Na-Pb-Bi-O Crystals

Crystals of Na-Pb-O and Na-Pb-Bi-O were electrosynthesized on the anode from molten salts. The resulting crystals have a hexagonal structure, in which the base ions (Pb and Bi) are in high oxidation states. By using KOH/NaOH (atomic ratio K:Na=I:I) mixture as a flux,incorporation of K ions into the lattice is inhibited while incorporation of Bi ions is enhanced. The magnetic measurement shows that the Na-Pb-Bi-O crystals are dominated by diamagnetism.     

杂多化合物催化性能的研究——第四周期过渡金属钼磷三元杂多化合物的合成及表征

本文用改进的方法成功地合成了以第四周期二价过渡金属离子取代12-钼磷杂多酸中的一个钼,并保持Keggin结构的五个新化合物:Na₅[PZ(H₂O)Mo₁₁O₃₉·5H₂O,其中Z分别为Mn、Co、Ni、Cu、Zn,并利用红外光谱及热分析等手段对合成产物的结构及热稳定性作了系统的研究,结果表明,合成产物与12-钼磷杂多化合物具有类似的结构,但合成产物的热稳定性明显低于12-钼磷杂多化合物。     

Synthesis and Characterization of a One- dimensional Molybdenum Oxide （H2enMe）[Mo3O10]

A hybrid organic-inorganic material (H2enMe)[Mo3O10] (C3H12Mo3N2O10, Mr = 523.97) has been synthesized under hydrothermal conditions and its crystal structure was determined by X-ray diffraction. It crystallizes in the orthorhombic system, space group Pnma with a = 12.430(2), b = 7.6089(12), c = 11.9553(19) , V = 1130.7(3) 3, Dc = 3.078 g/cm3, Z = 4, μ(MoKa) = 3.328 mm1, F(000) = 1000, the final R = 0.0256 and wR = 0.0716 for 1314 observed reflections with I > 2σ(I). A total of 11780 reflections were measured and 1325 were unique (Rint = 0.0244). It consists of infinite one-dimensional edge-sharing MoO6 octahedral chains with [Mo3O10]2 moieties. The protonated diaminopropane cations are located between the chains and linked to the oxygen atoms of the inorganic skeletal backbones by hydrogen bonds. It is indicated that the as-synthesized compound displays photochromic property in the solid state.     

高含量钒的钼钒磷杂多化合物的合成和性质研究

本工作改进了文献[4]报导的几种原料同时混合、加热煮沸合成的方法采用分步加入原料,控制反应温度、多次重结晶的方法合成了6、7、8个钒原子取代的钼钒磷杂多酸铵;并以铵盐为原料,用离子交换、冷冻分离和真空抽吸相结合的提纯方法制备了未见文献报导的相应的固体杂多酸;H₅[PMo₅V₇O_37.5]·xH₂O,H₆[PMo₄V₈O_37.5]·xH₂O。通过元素组成分析确定了它们的组成。这些杂多酸在水溶液、非水溶液中的电位滴定表明,杂多阴离子在分解前没有发生自电离、水解等情况,它们在水溶液中是稳定的。酸的碱度分别为5、5、6。通过纸上色谱实验,讨论了杂多酸的分解过程。由热重分析和溶解性实验得到它们的分解温度,本文还讨论了这些化合物的红外、紫外光谱,x光粉末衍射及极谱性质。光谱结果表明,它们可能具有Keggin结构,由导数脉冲极谱得到它们的峰电位。     

Synthesis and Characterization of Ion-exchange Copolyimide

A new diamine, disodium 4, 4‘-di(4-aminophenoxy)-3, 3‘-disulfonate-1, 1‘-diphenylketone, was prepared from the nucleophilic substitution of disodium 4, 4‘-difluoro-3, Y-disulfonate-1, l‘-diphenylketone and p-aminophenol. Polymerization of this diamine and 4,4‘-diamino-1, 1‘-diphenyl ether with 3, 3‘, 4, 4‘-tetracarboxyl dianhydride-1, 1‘- diphenyl ketone gave ion-exchange copolyimide. The new diamine and its polyimide were characterized with ^1H-NMR and FT-IR.     

杂多化合物催化性能的研究——第四周期过渡金属钼磷三元杂多化合物的合成及表征

本文用改进的方法成功地合成了以第四周期二价过渡金属离子取代12-钼磷杂多酸中的一个钼,并保持Keggin结构的五个新化合物:Na_5[PZ(H_2O)Mo_(11)O_(39)·5H_2O,其中Z分别为Mn、Co、Ni、Cu、Zn,并利用红外光谱及热分析等手段对合成产物的结构及热稳定性作了系统的研究,结果表明,合成产物与12-钼磷杂多化合物具有类似的结构,但合成产物的热稳定性明显低于12-钼磷杂多化合物。     

9—钼—3钒硅酸钾的合成与表征

钼钒硅杂多化合物作为氧化还原型催化剂应用于某些有机合成反应已引起化学工作者的关注,其合成与分离均有一定的难度,一钒及二钒取代的钼钒硅杂多化合物已有文献报道,但三钒取代的钼钒硅杂多化合物尚未见报道,本文采用正交设计方法,成功地合成了标题杂多化合物,并通过IR、UV、TG-DTA、~(51)V NMR和ESR等测试手段进行了表征。     

Synthesis and CD Spectra of Chiral Molybdenum-fullerenyl Complexes with Pineno-bipyridine Ligands

The synthesis and characterization of two chiral fullerene complexes( )4in^CD-[Mo(η^2-C60)(CO)3(L^RR)]1 and (-)430^CD-[Mo(η^2-C60)(CO3)(L^SS)2 were described,the CD spectra of 1 and 2 in the visible range show Cotton effects,which are approximately of mirror image,indicating that the appended pineno-groups with opposite chirality in bipyridines can perturb the fullcrene chromophores through the molybdenum centers and lead to induced CD effects.     

Synthesis and Characterization of PE-g-MA／MgAI-LDH Exfoliation Nanocomposite via Solution Intercalation

An organo‐modified MgAl‐layered double hydroxide (OMgAl‐LDH) was successfully exfoliated in the xylene solution of polyethylene‐grafted‐maleic anhydride (PE‐g‐MA) under re‐fluxing condition. A PE‐g‐MA/MgAl‐LDH exfoliation nanocomposite was formed after the precipitation of PE‐g‐MA from the dispersion system. The structure and thermal property of the PE‐g‐MA/MgAl‐LDH exfoliation nanocomposite were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetry analysis (TGA). The disappearance of d₀₀₁ XRD peak of OMgAl‐LDH at 20 = 3.2° suggests that the MgAl hydroxide sheets are exfoliated in the nanocomposite. The TEM image shows that the MgAl hydroxide sheets of less than 70 nm in length or width are exfoliated and dispersed disorderly in PE‐g‐MA matrix. TGA profiles indicate that the PE‐g‐MA/MgAl‐LDH nanocomposite with 5 wt% OMgAl‐LDH loading shows a faster charring process in temperature range from 210 to 390 °C and a greater thermal stability beyond 390 °C than PE‐g‐MA does. The decomposition temperature of the nanocomposite is 25 °C higher than that of PE‐g‐MA as measured at 50% weight loss. The PE‐g‐MA/MgAl‐LDH nanocomposite is promising for application of flame‐retardant polymeric materials.     

Synthesis, Characterization and Thermal Decomposition Mechanism of Cetyltrimethyl Ammonium Tetrathiotungstate

The synthesis, characterization and thermal decomposition mechanism of cetyltrimethyl ammonium tetrathiotungstate （CTriMATT） were studied herein. The as-synthesized CTriMATT was characterized by Elemental analysis, X-ray diffraction （XRD）, Fourier transform infrared （FT-IR）, Ultraviolet visible （UV-Vis） spectra. The results showed that the as-synthesized CTriMATT had high purity and good crystallinity. The introduction of alkyl groups induced a shift of the stretching vibration band of W-S bond to lower wavenumber, while it had no influence on the position of WS4^2-. Thermogravimetric analysis （TG）, differential thermal analysis （DTA） and in situ XRD characterizations revealed that CTriMATT began to decompose at 423 K in nitrogen and was converted to WS2 eventually. In addition, the decomposition product of CTriMATT at 673 K in nitrogen was characterized by N2 adsorption （BET） and scanning electron microscopy （SEM）. The results demonstrated that WS2 with higher specific surface area, and pore volume could be obtained from the thermal decomposition of CTriMATT in nitrogen.     

Synthesis and Structural Characterization of Three New Inorganic ＂Host-gues＂ Polyoxomolybdates

Since two interesting inorganic “host‐guest” polyoxomolybdates 1 and 2 have been reported previously, we have now succeeded in selectively isolating three new acetated “host‐guest” polyoxomolybdates 3–5, which considerably extend the range of structures in the cyclic polyoxomolybdate catalogue. 3 crystallizes in the triclinic space group P‐1 with a = 1.22235(1) nm, b = 1.52977(2) nm, c = 1.54022(1) nm, a = 113.746(1)°, β = 96.742(1)°, γ = 101.564(1)°, V = 2.51892(4) nm³, Z =1, D_c = 2.568 g. cm^?3. 4 and 5 crystallize in the monoclinic system: P2(1)/n, a = 1.08298(2) nm, b = 1.54029(1) nm, c = 2.78893(5) nm, β =94.2730(10)°, V = 4.63929(12) nm³, Z = 2 and D_c = 2.671 g. cm^?3 for 4, and C2/c, a =2.59907(8) nm, b = 1.65992(3) nm, c = 2.28473(7) nm, β‐93.4370(10)°, V = 9.8392(5) nm³, Z = 4 and D_c = 2.556 g. cm^?3 for 5. The structures of 3, 4 and 5 consist of 18‐membered “host‐guest” polyoxoanions [ Na (X)₂| ∈ |(μ_3‐OH)₄Mo^y₈Mo^VI₁₀52(μ₂‐CH₃COO)₂]^?(R+9 (X = CH₃COO^?for 3, DMF for 4 and H₂O for 5), which are connected via Na* ions or hydrogen bonds into infinite extended frameworks.     

Synthesis and Characterization of Copolymercore-Silvershell Composite Microspheres

Composite microspheres composed of monodispersed poly（St-co-MAA） latices with diameter about 260 nm as core and Ag nanocrystals as shell were prepared by an in situ reduction method. The shell thickness could be controlled in the range of 15--45 nm by this coating process. The structure and the composition of the core-shell microspheres were characterized by transmission electron microscopy （TEM）, X-ray diffractometry （XRD）, X-ray photoelectron spectroscopy （XPS）, and thermogravimetric analysis （TG）. The formation of the composite microspheres is explained by the nucleation of silver on the surface of the latices followed by growth of the silver shell.     

Synthesis and Characterization of Dual Acidic Ionic Liquids

Novel ionic liquids with dual acidity, of which the cation contains Brφnsted acidity and anions contain Lewis acidity were synthesized. These ionic liquids obtained were identified by NMR, FF-IR, SDT and FAB-MS. Their acidities were determined by pyridine probe on IR spectrography.