Using Prussian blue analogue nanoparticles confined into ordered mesoporous silica monoliths as precursors of oxides

Powdered Prussian blue analogues (PBAs) and PBAs confined in ordered mesoporous silica monoliths were used as oxide precursors through thermal treatment under an oxidizing atmosphere. The study focuses on the transformation of the alkali cation-free CoCo PBA of chemical formula K_0.1Co^II₄[Co^III(CN)₆]_2.7·20 H₂O. The compounds were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), IR spectroscopy and small-angle X-ray scattering (SAXS), and the magnetic properties of the calcined samples were investigated. In both cases, powdered and confined PBAs, the coordination polymers are transformed into well-crystallized Co₃O₄ spinel oxide. In the case of the confined PBA, isolated Co₃O₄ single crystals confined within the ordered mesoporosity of the monoliths were evidenced by HRTEM. A preliminary study shows an effect of particle size and confinement on the magnetic properties of the confined oxide particles.     

First nanoparticles of Bechgaard salts

Well-dispersed nanoparticles of the superconducting Bechgaard salts, namely (TMTSF)₂PF₆ and (TMTSF)₂ClO₄, have been electrochemically grown in organic solution in the presence of a supporting electrolyte either being an ionic liquid or a long alkyl-chains quaternary ammonium salt. Nanoparticles exhibit sizes in the 20–75 nm range. Nanoparticle powders have been characterized by infrared, Raman, visible absorption spectroscopy, and by preliminary transport measurements at room temperature.     

Toluene total oxidation over Pd and Au nanoparticles supported on hydroxyapatite

The total oxidation of toluene was carried out in a series of catalytic systems composed of either palladium or gold, as active phase, with hydroxyapatite as supports. The influence of different parameters on the catalytic reactivity was investigated: the type of support, the active phase content, the preparation method, and the nature of the active phase. Hydroxyapatite supports, impregnated by the active phase, showed better reactivities than that of the classical alumina one. Moreover, low palladium content (0.25 wt%) is enough to get high toluene conversions at low temperatures. Two preparation methods were used to introduce the active phase on the support: the conventional wet impregnation and the nanoparticle deposition achieved by impregnation of a colloidal suspension of the noble metal using the surfactant HEA16Cl. Introducing palladium by either of these methods leads to similar catalytic efficiencies. In addition to this, palladium is much more active than gold, gold was not probably present under the form of highly dispersed nanoparticles. X-ray Photoelectron Spectroscopy (XPS) evidenced PdO presence on the surface of all our catalysts. Palladium impregnated on apatite by conventional method showed an improvement of catalytic reactivity after 13 h under reacting mixture, probably because of Pd(0) formation besides PdO. As a result and after a literature survey, our catalysts could be classified among the most reactive systems towards total oxidation of toluene.     

Elaboration of thin colloidal silica films with controlled thickness and wettability

Silica films with controlled thickness and wettability have been formed by sequential adsorption of colloidal silica nanoparticles and a cationic polyelectrolyte (poly(allylamine hydrochloride) or poly(diallyldimethylammonium chloride)) was used as the binding agent. Whatever be the conditions used, the structure of films appeared dense and non-porous. Thicknesses varying from 12 to 430 nm and wettability varying from 5 to 60° were obtained when the pH or concentration of the silica solution was varied. Quartz crystal microbalance measurements evidenced the formation of regular and reproducible thin films mainly composed of silica nanoparticles. These films contained few polycations due to the formation of long-distance charge pairs between silica nanoparticles and polycations.     

Spin-crossover nanoparticles and nanocomposite materials

This contribution reports on the state of the art of the elaboration and the application of nanoparticles (NPs) and nanohybrid/nanocomposite materials based on spin-crossover (SCO) complexes. The first part of this review concerns the syntheses and the characterizations of the physical properties of SCO NPs. All of the methods including homogeneous and heterogeneous media syntheses developed for the elaboration of such NPs and the associated methods used for their morphological characterization are presented. A particular attention is paid on the effects of the size reduction and the influence of the environment on the SCO properties and to specific and recent remarkable advanced physical measurements realized on a batch of NPs or on an isolated object. The second part presents the elaboration of various nanocomposite or nanohybrid materials for which SCO NPs have been associated with magnetic entities, noble metals, different fluorescent dyes, and different active polymers with the objectives to go toward specific applications based on synergistic effects between the two components.     

Self-aggregation of poly(butadiene)-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) triblock copolymers in heptane studied by viscometry and dynamic light scattering

Poly(butadiene)-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PBP2VPPEO) triblock copolymers of various compositions and molecular weights were prepared by sequential anionic polymerization. Their micellization behavior was examined in heptane, which is a selective solvent for PB whereas P2VP and PEO are insoluble. Dynamic light scattering and viscometry were used to determine the basic micellar characteristics, such as aggregation number, micellar sizes, and polydispersity, which were correlated to the molecular characteristics of the copolymers. Such ABC triblock copolymers form structured micelle-like nanoparticles having a core–shell morphology with hydrodynamic diameters in the range of 45–75 nm.     

Oxidation of carbon black,propene and toluene on highly reducible Co/SBA-15 catalysts

Different cobalt loadings (3, 6, 12, 24 wt%) were impregnated using the double-solvent technique on SBA-15 calcined at 500 °C presenting a high specific surface area. The impregnated solids were stabilized at 450 °C in the air. The impregnation of cobalt led to the incorporation of cobalt oxide nanoparticles in the mesoporosity of the SBA-15. The cobalt nanoparticles were easily reducible compared to similar solids prepared by different methods. The presence of these nanoparticles enhanced significantly the reactivity of the catalysts in the considered reaction. The addition of more than 12 wt% of cobalt did not enhance the catalytic reactivity due to the deposition of cobalt oxide species on the surface of the support. The cobalt-impregnated solids are efficient in decreasing the oxidation temperature of different probe molecules and are totally selective towards the formation of CO₂ and H₂O.