Polymer-hematite nanocomposites: templating effect of commercial ion-exchangers in the growth of size-controlled iron oxide nanoparticles.

The commercially available ion-exchange resin Amberlite IR120 has been used as the stabilizing agent for the preparation of a size controlled nanostructured hematite phase. The employed synthetic approach, based on the loading of Fe3+ by ion exchange and the subsequent treatment with an aqueous base solution, produces a nanocomposite material with a remarkably high content of oxide nanoparticles (iron content = 18.8% w/w, corresponding to 24.9% w/w of Fe2O3). Scanning electron microscopy and energy dispersive X-ray spectroscopy investigation show that the iron distribution is egg-like and parallels the distribution of the sulfonic groups of the ion-exchanger. Transmission electron microscopy characterization reveals that the size of the ferric oxide nanoparticles in the nanocomposites is narrowly distributed in the 4-6 nm range and that it is the same after the first and the fifth ion-exchange-precipitation cycle. Selected area Electron Diffraction (SAED) analysis of the nanostructured oxide after five ion-exchange-precipitation cycles indicates that it is hematite with a distorted structure.

Versatile plug flow catalytic cell for in situ transmission/fluorescence x-ray absorption fine structure measurements.

A novel flow-through catalytic cell has been developed for in situ x-ray absorption spectroscopy (XAS) experiments on heterogeneous catalysts under working conditions and in the presence of a liquid and a gas phase. The apparatus allows to carry out XAS measurements in both the transmission and fluorescence modes, at moderate temperature (from RT to 50-80 °C) and low-medium gas pressure (up to 7-8 bars). The materials employed are compatible with several chemicals such as those involved in the direct synthesis of hydrogen peroxide (O2, H2, H2O2, methanol). The versatile design of the cell allows to fit it to different experimental setups in synchrotron radiation beamlines. It was used successfully for the first time to test nanostructured Pd catalysts during the direct synthesis of hydrogen peroxide (H2O2) in methanol solution from dihydrogen and dioxygen.

Cross-linked polyvinyl polymers versus polyureas as designed supports for catalytically active M(0) nanoclusters. Part III. Nanometer scale structure of the cross-linked polyurea support EnCat 30 and of the Pd(II)/EnCat 30 and Pd(0)/EnCat 30NP catalysts.

The cross-linked polyurea support EnCat 30, its related macromolecular complex Pd(II)/EnCat 30 and its related Pd(0)/EnCat 30NP nanocomposite are thoroughly investigated with SEM, TEM, ISEC and ESR in the solid state (SEM and TEM) and swollen state in THF (ISEC and ESR). Pd(II)/EnCat 30 and its related Pd(0)/EnCat 30NP are obtained by microencapsulation of palladium acetate in a polyurea framework, which is formed upon hydrolysis/condensation of mixtures of multi-functional oligo-arylisocyanates in dichloroethane. Most remarkably, both Pd(II)/EnCat and Pd(0)/EnCat 30NP turn out to be far more (nano)porous and swellable materials than the blank polyurea matrix (EnCat 30). It is proposed that there is a strong nanostructural effect exerted by Pd(II) species due to its interaction with functional groups (amines stemming from the hydrolysis of the isocyanato groups or ureido groups belonging to the polymer chains) during the growth of the cross-linked polymer framework. As a consequence, the catalytic species in both Pd(II)/EnCat 30 and Pd(0)/EnCat 30NP are much more accessible to molecules diffusing from liquid phases in contact with the materials and, hence, are better catalysts than expected from the morphology of blank polyurea EnCat 30.