ZrO2/PMMA Nanocomposites： Preparation and Its Dispersion in Polymer Matrix

ZrO2/PMMA nanocomposite particles are synthesized through an in-situ free radical emulsion polymerization based on the silane coupling agent （Z-6030） modified ZrO2 nanoparticles, and the morphology, size and its distribution of nanocomposite particles are investigated. Scanning electron microscopy （SEM） images demonstrate that the methyl methacrylate （MMA） feeding rate has a significant effect on the particle size and morphology. When the MMA feeding rate decreases from 0.42 ml-min-1 to 0.08 ml. min-1, large particles （about 200-550.nm） will not form, and the size distribution become narrow （36-54 nm）. The average nanocomposite particles size increases from 34 nm to 55 nm, as the MMA/ZrO2 nanoparticles mass ratio increased from 4 ： 1 to 16 ： 1. Regular spherical ZrO2/PMMA nanocomposite particles are synthesized when the emulsifier OP-10 concentration is 2 mg.m1-1. The nanocomposite particles could be mixed with VAc-VeoVa10 polymer matrix just by magnetic stirring to prepare the ZrOE/PMMA/VAc-VeoVal0 hybrid coatings. SEM and atomic force microscopy （AFM） photos reveal that the distribution of the ZrO2/PMMA nanocomposite particles in the VAc-VeoVal0 polymer matrix is homogenous and stable. Here, the grafted-PMMA polymer on ZrO2 nanoparticles plays as a bridge which effectively connects the ZrO2 nanoparticles and the VAc-VeoVal0 polymer matrix with improved comparability. In consequence, the hybrid coating with good dispersion stability is obtained.

Preparation and Characterization of ZrO_2 Nanoparticles Capped by Trioctylphosphine Oxide (TOPO)

Monodisperse ZrO2 nanoparticles capped by trioctylphosphine oxide （TOPO） were prepared in non-aqueous solvent using in-situ synthesis method. Transmission electron microscopy（TEM）, X-ray diffraction（XRD）, X-ray photoelectron spectrometer（XPS）, Fourier transformation infrared spectroscopy （FTIR）, and thermogravimetric analysis（TGA） were adopted to characterize and investigate the size, structure, composition, and the binding manners between organic capping agent TOPO and inorganic ZrO2 nanocores of the as-prepared nanoparticles. In addition, the nanoparticles were also studied to determine their solubility and relative stability. The experimental results show that the prepared nanoparticles contain about 25% organic capping shell TOPO, 75% inorganic ZrO2 nanocores, and can be easily dissolved and be stably disersed in non-polar organic solvents.

Synthesis, Characterization and Thermal Stability of CeO_2 Stabilized ZrO_2 Ultra Fine Nanoparticles Via a Sol-gel Route

CeO_2 stabilized ZrO_2 ultra fine nanoparticles were successfully synthesized via a simple and effective sol-gel synthetic approach by using zirconylchloride octahydrate, cerium nitrate hexahydrate, and citric acid as starting materials. A series of techniques, including X-ray diffraction（XRD）, thermogravimetry（TG）, differential scanning calorimetry（DSC）, Fourier transform infrared spectroscopy（FTIR）, transmission electron microscopy（TEM）, and N_2-sorption analysis, were used to characterize the structure and morphology of the asprepared samples. XRD studies indicate that the as-synthesized sample is of well crystallized tetragonal phase of CeO_2 stabilized ZrO_2 with high purity. TEM images show that the as-synthesized sample is composed of a large number of fine dispersive nanoparticles with an average size about 10 nm. The as-synthesized tetragonal CeO_2 stabilized ZrO_2 sample was heated at different temperatures in order to evaluate its thermal stability. The exprimental results reveal that the as-synthesized tetragonal CeO_2 stabilized ZrO_2 sample exhibits excellent stability without the occurrence of phase transformation.

Zr（Ⅳ） surface sites determine CH3OH formation rate on Cu/ZrO2/SiO2-CO2 hydrogenation catalysts

Cu/ZrO2/SiO2 are efficient catalysts for the selective hydrogenation of CO2 to CH3OH. In order to understand the role of ZrO2 in these mixed-oxides based catalysts, in situ X-ray absorption spectroscopy has been carried out on the Cu and Zr K-edge. Under reaction conditions, Cu remains metallic, while Zr is present in three types of coordination environment associated with 1) bulk ZrO2, 2) coordinatively saturated and 3) unsaturated Zr(Ⅳ) surface sites. The amount of coordinatively unsaturated Zr surface sites can be quantified by linear combination fit of reference X-Ray absorption near edge structure (XANES) spectra and its amount correlates with CH3OH formation rates, thus indicating the importance of Zr(Ⅳ) Lewis acid surface sites in driving the selectivity toward CH3OH. This finding is consistent with the proposed mechanism, where CO2 is hydrogenated at the interface between the Cu nanoparticles that split H2 and Zr(Ⅳ) surface sites that stabilizes reaction intermediates.