No abstract

A new method was employed for the preparation of a set of lanthanum cobaltites of general formula La1-xMxCoO3+ with M=Ce, Eu and x=0, 0.05, 0.1, 0.2. All the samples so prepared showed nanostructured, thermally very stable and characterised by highly crystalline perovskite-like structure and high surface area. Their activity as catalysts for the catalytic flameless combustion of methane was by ca. one order of magnitude higher than that of their analogues, prepared through the usual calcination-milling procedure.Adsorption of oxygen was accompanied by formation of paramagnetic species. Desorption of preadsorbed oxygen was dependent on the nature of the doping element and on the value of the stoichiometric coefficient x of their formula. A correlation between the temperature of the maximal rate of oxygen release and catalytic activity was found. The following scale of activity for the title reaction vs. x values could be set up: 0.1 Ce > 0.05 Ce > 0 > 0.05 Eu > 0.1 Eu  0.2 Ce. The higher activity of Ce-doped catalysts as compared to those doped with Eu was found to be related to the strength of the bond between oxygen and Co ions.

A flame pyrolysis (FP) procedure has been set up for the preparation of V/Al/O catalysts to be employed for the oxidative dehydrogenation of propane to propylene. The samples have been characterised by means of various techniques (FT-IR, Raman, EPR, ICP-MS, TGA, XRD, SEM) and their catalytic activity has been evaluated in two different operating modes, i.e. under anaerobic conditions and by co-feeding oxygen. The particle size distribution became progressively more homogeneous with increasing V concentration, due to the catalytic effect of the V ions during the FP synthesis. Some V2O5 segregation was observed even at low V loading. However, higher V dispersion was attained with respect to a reference sample prepared by impregnation of the FP-prepared alumina support. 2The increase of V concentration always led to an improvement of propane conversion, though selectivity showed different trends depending on the operating conditions. The comparison with the sample prepared by impregnation showed similar catalytic activity, with a bit higher selectivity for the FP-prepared sample under anaerobic conditions.

A set of LaMnO3 and LaCoO3 catalysts was prepared through different synthesis procedures. The selected techniques included the sol-gel method, flame hydrolysis from aqueous solution, complexation through EDTA and solid-state reaction. The last was accomplished through reactive grinding by ball milling either in a vibration mill or in a planetary mill. EDTA complexation was applied for LaCoO3 only and did not improve significantly catalyst activity or stability, with respect to other techniques. Ball milling never allowed obtaining a pure perovskitic phase, at least under the most energetic grinding conditions permitted by our apparatus. The highest activity for the catalytic flameless combustion of methane was obtained with the sol-gel prepared samples, though thermal resistance revealed insufficient for high temperature applications. A bit lower activity, but coupled with good thermal stability was obtained with the samples prepared through flame hydrolysis.

The amount of the trace elements As, Ba, Cd, Cr, Cu, Hg, Li, Mn, Ni, Pb, Rb, Se, Sr, and Zn was measured in top soils and edible mushrooms, Boletus edulis, Macrolepiota procera, collected at five distinct green microhabitats inside the Lucca province, North-Central Italy (years 2008-2009). Results showed a top soil element content within the Italian statutory limits. Concerning the amount of mushroom elements, we observed significant species-differences obtaining higher levels of Ni, Rb, and Se in B. edulis or As, Pb, Cu in M. procera. Bioaccumulation factors (BCFs: element in mushroom/element in soil) resulted species-dependent and element-selective: in particular, B. edulis preferentially accumulated Se (BCFs varying from 14 to 153), while M. procera mainly concentrated Cu (BCFs varying from 5 to 15). As well, both species displayed between-site BCF differences. By a multivariate principal component approach, cluster analysis (CA), we could resolve two main clusters of soil element composition, corresponding to the most ecologically divergent sites. Besides, CA showed no cluster relating to element contents of B. edulis at the different collection sites, while a separation in groups was found for M. procera composition with respect to harvesting locations, suggesting uptake systems, in this saprotrophic species, sensitive to microhabitat. Regarding consumer safety, Cd, Hg, Pb levels resulted sometime relevant in present samples, never reaching values from current literature on mushrooms collected in urban-polluted areas. Our findings encourage a deeper assessment of the molecular mechanisms of metal intake by edible mushrooms, encompassing genetic biochemical and geo-ecological variables, with particular awareness to element bioavailability in soils and fungi.