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101.
Sulfur diisocyanate is generated from a heterogeneous reaction of gaseous sulfur dichloride with silver cyanate and studied for the first time in the gas phase. Combined with quantum chemical calculations, the electronic structure is characterized by photoelectron spectroscopy (PES). Simultaneously, an investigation of the possible ionization and dissociation processes for the molecular cation is presented based on experimental soft ionization mass spectrometry. From the calculated bond-dissociation energies, the dissociation pathway is determined. S(NCO)2+ undergoes 1,3-sigmatropic rearrangement with a smaller barrier height (9.9 kcal mol(-1)) than the neutral counterpart. Thus, the 1,3-sigmatropic rearrangement is preferred for the molecular cation, and OCNCO+ and NS+ is produced by subsequent dissociation of the rearrangement product. The analysis agrees very well with the experimental mass spectrum. 相似文献
102.
Assembly of well-aligned multiwalled carbon nanotubes in confined polyacrylonitrile environments: electrospun composite nanofiber sheets 总被引:5,自引:0,他引:5
Ge JJ Hou H Li Q Graham MJ Greiner A Reneker DH Harris FW Cheng SZ 《Journal of the American Chemical Society》2004,126(48):15754-15761
Highly oriented, large area continuous composite nanofiber sheets made from surface-oxidized multiwalled carbon nanotubes (MWNTs) and polyacrylonitrile (PAN) were successfully developed using electrospinning. The preferred orientation of surface-oxidized MWNTs along the fiber axis was determined with transmission electron microscopy and electron diffraction. The surface morphology and height profile of the composite nanofibers were also investigated using an atomic force microscope in tapping mode. For the first time, it was observed that the orientation of the carbon nanotubes within the nanofibers was much higher than that of the PAN polymer crystal matrix as detected by two-dimensional wide-angle X-ray diffraction experiments. This suggests that not only surface tension and jet elongation but also the slow relaxation of the carbon nanotubes in the nanofibers are determining factors in the orientation of carbon nanotubes. The extensive fine absorption structure detected via UV/vis spectroscopy indicated that charge-transfer complexes formed between the surface-oxidized nanotubes and negatively charged (-CN[triple bond]N:) functional groups in PAN during electrospinning, leading to a strong interfacial bonding between the nanotubes and surrounding polymer chains. As a result of the highly anisotropic orientation and the formation of complexes, the composite nanofiber sheets possessed enhanced electrical conductivity, mechanical properties, thermal deformation temperature, thermal stability, and dimensional stability. The electrical conductivity of the PAN/MWNT composite nanofibers containing 20 wt % nanotubes was enhanced to approximately 1 S/cm. The tensile modulus values of the compressed composite nanofiber sheets were improved significantly to 10.9 and 14.5 GPa along the fiber winding direction at the MWNT loading of 10 and 20 wt %, respectively. The thermal deformation temperature increased with increased MWNT loading. The thermal expansion coefficient of the composite nanofiber sheets was also reduced by more than an order of magnitude to 13 x 10(-6)/ degrees C along the axis of aligned nanofibers containing 20 wt % MWNTs. 相似文献
103.
Fang Q Zhu G Xue M Sun J Tian G Wu G Qiu S 《Dalton transactions (Cambridge, England : 2003)》2004,(14):2202-2207
Four three-dimensional non-interpenetrating open coordination frameworks constructed from the CTC ligand (CTC =cis,cis-1,3,5-cyclohexanetricarboxylate) coordinated to metal ions (Mn(II) and Cd(II)): Mn(3)(CTC)(2)(DMF)(2)(1); Cd(3)(CTC)(2)(H(2)O)(3).H(2)O (2); Cd(3)(CTC)(2)(4,4'-bpy)(2)(EG)(2)(3); Cd(3)(CTC)(2)(mu(2)-hmt)(DMF)(C(2)H(5)OH)(H(2)O).2H(2)O (4)(DMF = dimethylformamide and EG = ethylene glycol) have been synthesized by slow evaporation of DMF-C(2)H(5)OH-H(2)O solutions of M(II)(Mn(II) or Cd(II)) and CTC in the presence of the organic bases TEA (triethylamine), TEA, 4,4'-bpy (4,4'-bipyridine) and hmt (hexamethylenetetramine), respectively, and structurally characterized by X-ray crystallography. The polymer constructed by CTC and Mn(II) exhibits a 3-D architecture with 5 x 9 A channels; the polymer formed by CTC and Cd(II) exists a 3-D extended framework with 9 x 9 A channels; wave-like sheet subunits of the polymer are upheld by 4,4'-bpy ligands resulting in a 3-D framework with 4 x 10 A channels; two-fold alternate sheet subunits of the polymer are interlinked by mu(2)-hmt ligands to form a novel 3-D architecture with 7 x 8 A channels. Polymers exhibit their strongest excitation peaks at 391, 390 and 394 nm, respectively, and their main strong emission peaks are at 543, 460 (with a shoulder peak at about 570 nm) and 557 nm, respectively. 相似文献
104.
Yueping?Fang Xiaogang?Wen Shihe?YangEmail author Qi?Pang Lu?Ding Jiannong?Wang Weikun?Ge 《Journal of Sol-Gel Science and Technology》2005,36(2):227-234
Uniform ZnO nanorods arrays are grown directly from and on Zn foils in pure water under hydrothermal conditions at a relatively
low temperature. The nanorods are 80–200 nm in diameter and ∼ 1 μm in length, which grow on the Zn foil along the [001] direction.
By changing the pure water to a urea solution, a Zn compound ([Zn5(OH)6(CO3)2], a precursor of ZnO nanoflowers film, is created by self-assembly. The ZnO nanoflowers film can be easily obtained by heating
the [Zn5(OH)6(CO3)2] compound in N2 at 350∘C for 5–6 hours. Possible growth processes of the ZnO nanorods arrays and the [Zn5(OH)6(CO3)2] nanoflowers are discussed. Photoluminescence properties of the as-prepared ZnO nanostructures have been measured. The ZnO
nanorods array synthesized using our method has minimal defects so that only band-gap emission is observed. However, the ZnO
nanoflowers film, obtained by heating the [Zn5(OH)6(CO3)2] nanoflower precursor in N2, is polycrystalline and displays strong defect-related emission. 相似文献
105.
Xiaoqing Zeng Maofa Ge Zheng Sun Jiang Bian Dianxun Wang 《Journal of Molecular Structure》2007,840(1-3):59-65
Gaseous nitryl azide N4O2 is generated by the heterogeneous reaction of gaseous ClNO2 with freshly prepared AgN3 at −50 °C. The geometric and electronic structure of the molecule in the gas phase has been characterized by in situ photoelectron spectroscopy (PES) and quantum chemical calculations. The experimental first vertical ionization energy of N4O2 is 11.39 eV, corresponding to the ionization of an electron on the highest occupied molecular orbital (HOMO) {4a″(πnb(N4–N5–N6))}−1. An apparent vibrational spacing of 1600 ± 60 cm−1 (νasO1N2O3) on the second band at 12.52 eV (πnb(O1–N2–O3)) further confirms the preference of energetically stable chain structure in the gas phase. To complement the experimental results, the potential-energy surface of this structurally novel transient molecule is discussed. Both calculations and spectroscopic results suggest that the molecule adopts a trans-planar chain structure, and a five-membered ring decomposition pathway is more favorable. 相似文献
106.
In this paper, we used bond-length equalization, aromatic stabilization energies (ASE) and nucleus-independent chemical shifts
(NICS), calculated with (density functional theory) B3LYP levels at the 6-311+G** basis set, to evaluate the aromaticity of a set of 38 five-member planar π-electron aromatic systems: sila-, aza- and phospha-
derivatives and their parent systems. The result revealed statistically significant correlations among the above three criteria,
and the order of aromaticity of the whole set was: Aza- derivatives rings > Phospha- derivatives rings > Sila- derivatives
rings > Carbon-containing rings; NICS(0.6) and NICS(0.8) had the same results in evaluating the order of aromaticity in our
case. 相似文献
107.
The crystallization processes of hydrated Mg-borates, boric, magnesium hydroxide and Mg-oxychloride from MgO-B2O3-18%MgCl2-H2O supersaturated solution at 20°C have been studied by kinetic method. The crystallization solid phases were characterized
by X-ray powder diffraction, IR spectra, thermal analysis and chemical analysis. The liquid-solid phase diagram of thermodynamic
nonequilibrium state has been given. In this phase diagram, there exist eight crystallization fields, boric acid(H3BO3), trigomagneborite(MgO · 3B2O3 · 7.5H2O, MgO · 3B2O3 · 7H2O), hungchaoite(MgO · 2B2O3 · 9H2O), inderite(2MgO · 3B2O3 · 15H2O), chloropinnoite(2MgO · 2B2O3 · MgCl2 · 14H2O), magnesium hydroxide(Mg(OH)2) and magnesium oxychloride (5Mg(OH)2 · MgCl2 · 8H2O). 相似文献
108.
The rheological behavior and the morphology in blends of polyethylene terephthalate (PET) with ionomeric polyester were investigated over a wide range of different blending ratios. The ionomeric polyester is derived from PET modified through copolycondensation with sulfonate moiety, sodiosulfo isophthalate (Na-SIP), iso-phthalic acid (IPA) and polyethylene glycol (PEG). The results showed that the apparent viscosity and non-Newtonian index of the PET/ionomeric polyester blend system had a nonlinearity change with the change of the blend ratio of PET/ionomeric polyester. The anomaly of the viscous flow activation energy change was found as the content of ionomeric polyester was about 40% (w/w) in the blend system, suggesting the presence of physical cross-linked structure formed by strong polar tangling points and the phase separation owing to poor compatibility between the PET and ionomeric polyester. The morphology and thermal behavior of the blends were observed, respectively, with differential scanning calorimetry (DSC) and atomic force microscopy (AMF). 相似文献
109.
110.
用EXAFS研究NiO在γ-Al2O3表面上的分散 总被引:1,自引:0,他引:1
本文使用EXAFS方法研究NiO在γ-Al_2O_3的表面上的分散情况。文章讨论了Ni含量为7%、13%、18%、26%、35%的NiO/γ-Al_2O_3体系的径向结构函数图以及Ni含量为13%、26%的NiO/α-Al_2O_3样品的径向结构函数图,认为NiO能在γ-Al_2O_3表面上成单层分散。分散后的Ni-O距离接近NiO晶体的Ni-O距离,表明Ni离子和γ-Al_2O_3表面上的氧有很强的相互作用。 相似文献