A new class of epoxy nanocomposites with completely defined organic/inorganic phases was prepared by reacting octakis(glycidyldimethylsiloxy)octasilsesquioxane [(glydicylMe(2)SiOSiO(1.5))(8)] (OG) with diaminodiphenylmethane (DDM) at various compositional ratios. The effects of reaction curing conditions on nanostructural organization and mechanical properties were explored. A commercial epoxy resin based on the diglycidyl ether of bisphenol A (DGEBA) was used as a reference material throughout these studies. FTIR was used to follow the curing process and to demonstrate that the silsesquioxane structure is preserved during processing. OG/DDM composites possess comparable tensile moduli (E) and fracture toughness (K(IC)) to, and better thermal stabilities than, DGEBA/DDM cured under similar conditions. Dynamic mechanical analysis and model reaction studies suggest that the maximum cross-link density is obtained at N = 0.5 (NH(2):epoxy groups = 0.5) whereas the mechanical properties are maximized at N = 1.0. Digestion of the inorganic core with HF followed by GPC analysis of the resulting organic tether fragments when combined with the model reaction studies confirms that, at N = 0.5, each organic tether connects four cubes, while, at N = 1.0, linear tethers connecting two cubes dominate the network structure. Thus, well-defined nanocomposites with controlled variation of the organic tether architecture can be made and their properties assessed.
The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn0.5Ce0.5Ox solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). The high activity can be attributed to the formation of a Mn0.5Ce0.5Ox solid solution with an ultrahigh manganese doping concentration in the CeO2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface.
This paper explores the size effect of zirconia particles on the catalysis of Ni metal for CO2 re-forming of
methane. It is revealed for the first time that when the sizes of zirconia particles become samller than 25 nm,
the oxide forms nanocomposite catalysts with size-comparable Ni-metal nanocrystals (10−15 nm). The
nanocomposite catalysts show extremely stable catalysis, which is in strong contrast with the deactivating Ni
catalyst supported on bigger zirconia particles (>25 nm). This raises the possibility of tailoring the catalytic
behavior of oxide-supported metal catalysts by reducing the particle size of oxide to make high-performance
nanocomposite catalysts.
Inner-shell electronic structures, properties and ionization spectra of DNA/RNA bases are studied with respect to their parent pyrimidine and purine species. Density functional theory B3LYP/aug-cc-pVTZ has been employed to produce the geometries of the bases, whereas LB94/et-pVQZ//B3LYP/aug-cc-pVTZ is used to calculate site-related Hirshfeld charges and core (vertical) ionization energies, as well as inner-shell spectra of C1s, N1s and O1s for DNA/RNA bases and their parent pyrimidine and purine species. The site-dependent variations of properties indicate the changes and inheritance of chemical environment when pyrimidine and purine become substituted. In general, although the changes are site-dependent, they are also ring-dependent. Pyrimidine bases change less significantly with respect to their parent pyrimidine than the purine bases with respect to their parent purine. Pyrimidine bases such as uracil, thymine and cytosine inherit certain properties from their parent pyrimidine, such as the Hirshfeld charge distributions and the order of core ionization energy level etc. No particular sites in the pyrimidine derivatives are engaged with a dramatic chemical shift nor with energy crossings to other sites. For the core shell spectra, the purine bases inherit very little from their parent purine, and guanine exhibits the least similarities to the parent among all the DNA/RNA bases.
V 2 O 5 xerogel films modified by poly(ethylene oxide) (PEO) were obtained via the sol-gel method. Investigations were conducted by X-ray diffractometry (XRD), Fourier transformation infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry. The results show that when the V 2 O 5 xerogel is modified by the intercalation of PEO, the H atoms in PEO are hydrogen-bonded with the O atoms of the VLO bonds of the V 2 O 5 xerogel, which effectively shielded against electrostatic interactions between the V 2 O 5 interlayer and Li 1 ions. The reversibility of insertion/extraction of Li 1 ions is greatly improved by modification of the V 2 O 5 xerogel with PEO.
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