Danilo Loche

An X-ray absorption spectroscopy study of the inversion degree in zinc ferrite nanocrystals dispersed on a highly porous silica aerogel matrix

The structural properties of zinc ferrite nanoparticles with spinel structure dispersed in a highly porous SiO(2) aerogel matrix were compared with a bulk zinc ferrite sample. In particular, the details of the cation distribution between the octahedral (B) and tetrahedral (A) sites of the spinel structure were determined using X-ray absorption spectroscopy. The analysis of both the X-ray absorption near edge structure and the extended X-ray absorption fine structure indicates that the degree of inversion of the zinc ferrite spinel structures varies with particle size. In particular, in the bulk microcrystalline sample, Zn(2+) ions are at the tetrahedral sites and trivalent Fe(3+) ions occupy octahedral sites (normal spinel). When particle size decreases, Zn(2+) ions are transferred to octahedral sites and the degree of inversion is found to increase as the nanoparticle size decreases. This is the first time that a variation of the degree of inversion with particle size is observed in ferrite nanoparticles grown within an aerogel matrix.

ZnFe2O4 nanoparticles dispersed in a highly porous silica aerogel matrix: a magnetic study

We report the detailed structural characterization and magnetic investigation of nanocrystalline zinc ferrite nanoparticles supported on a silica aerogel porous matrix which differ in size (in the range 4-11 nm) and the inversion degree (from 0.4 to 0.2) as compared to bulk zinc ferrite which has a normal spinel structure. The samples were investigated by zero-field-cooling-field-cooling, thermo-remnant DC magnetization measurements, AC magnetization investigation and Mössbauer spectroscopy. The nanocomposites are superparamagnetic at room temperature; the temperature of the superparamagnetic transition in the samples decreases with the particle size and therefore it is mainly determined by the inversion degree rather than by the particle size, which would give an opposite effect on the blocking temperature. The contribution of particle interaction to the magnetic behavior of the nanocomposites decreases significantly in the sample with the largest particle size. The values of the anisotropy constant give evidence that the anisotropy constant decreases upon increasing the particle size of the samples. All these results clearly indicate that, even when dispersed with low concentration in a non-magnetic and highly porous and insulating matrix, the zinc ferrite nanoparticles show a magnetic behavior similar to that displayed when they are unsupported or dispersed in a similar but denser matrix, and with higher loading. The effective anisotropy measured for our samples appears to be systematically higher than that measured for supported zinc ferrite nanoparticles of similar size, indicating that this effect probably occurs as a consequence of the high inversion degree.

Halogen-bonding in a new family of tris(haloanilato)metallate(III) magnetic molecular building blocks

Here we report on new tris(haloanilato)metallate(III) complexes with general formula [A]3[M(X2An)3] (A = (n-Bu)4N(+), (Ph)4P(+); M = Cr(III), Fe(III); X2An = 3,6-dihalo derivatives of 2,5-dihydroxybenzoquinone (H4C6O4), chloranilate (Cl2An(2-)), bromanilate (Br2An(2-)) and iodanilate (I2An(2-))), obtained by a general synthetic strategy, and their full characterization. The crystal structures of these Fe(III) and Cr(III) haloanilate complexes consist of anions formed by homoleptic complexes formulated as [M(X2An)3](3-) and (Et)3NH(+), (n-Bu)4N(+), or (Ph4)P(+) cations. All complexes exhibit octahedral coordination geometry with metal ions surrounded by six oxygen atoms from three chelate ligands. These complexes are chiral according to the metal coordination of three bidentate ligands, and both Λ and Δ enantiomers are present in their crystal lattice. The packing of [(n-Bu)4N]3[Cr(I2An)3] (5a) shows that the complexes form supramolecular dimers that are held together by two symmetry related I···O interactions (3.092(8) Å), considerably shorter than the sum of iodine and oxygen van der Waals radii (3.50 Å). The I···O interaction can be regarded as a halogen bond (XB), where the iodine behaves as the XB donor and the oxygen atom as the XB acceptor. This is in agreement with the properties of the electrostatic potential for [Cr(I2An)3](3-) that predicts a negative charge accumulation on the peripheral oxygen atoms and a positive charge accumulation on the iodine. The magnetic behaviour of all complexes, except 5a, may be explained by considering a set of paramagnetic non-interacting Fe(III) or Cr(III) ions, taking into account the zero-field splitting effect. The presence of strong XB interactions in 5a are able, instead, to promote antiferromagnetic interactions among paramagnetic centers at low temperature, as shown by the fit with the Curie-Weiss law, in agreement with the formation of halogen-bonded supramolecular dimers.

Exfoliated Graphene into Highly Ordered Mesoporous Titania Films: Highly Performing Nanocomposites from Integrated Processing

To fully exploit the potential of self-assembly in a single step, we have designed an integrated process to obtain mesoporous graphene nanocomposite films. The synthesis allows incorporating graphene sheets with a small number of defects into highly ordered and transparent mesoporous titania films. The careful design of the porous matrix at the mesoscale ensures the highest diffusivity in the films. These exhibit an enhanced photocatalytic efficiency, while the high order of the mesoporosity is not affected by the insertion of the graphene sheets and is well-preserved after a controlled thermal treatment. In addition, we have proven that the nanocomposite films can be easily processed by deep X-ray lithography to produce functional arrays.

The influence of composition and porosity on the magnetic properties of FeCo-SiO2 nanocomposite aerogels.

FeCo-SiO2 aerogel nanocomposites with different porosity were obtained using two different sol-gel procedures: the first involves a single acidic step and gives rise to relatively dense aerogels while the second procedure allows one to obtain highly porous aerogels using urea in the second step to promote fast gelation. Samples with different loading of FeCo equimolar alloy and with different Fe : Co ratios were prepared. The magnetic properties of all the nanocomposite aerogels were extensively studied as a function of porosity and composition. Particular attention was paid to the role played by the interparticle interactions, which are mediated by the silica matrix, in determining the collective magnetic behaviour. The kind and strength of magnetic interactions are affected by both the composition and the porosity of the matrix.

Charge separation in Pt-decorated CdSe@CdS octapod nanocrystals

We synthesize colloidal CdSe@CdS octapod nanocrystals decorated with Pt domains, resulting in a metal-semiconductor heterostructure. We devise a protocol to control the growth of Pt on the CdS surface, realizing both a selective tipping and a non-selective coverage. Ultrafast optical spectroscopy, particularly femtosecond transient absorption, is employed to correlate the dynamics of optical excitations with the nanocrystal morphology. We find two regimes for capture of photoexcited electrons by Pt domains: a slow capture after energy relaxation in the semiconductor, occurring in tipped nanocrystals and resulting in large spatial separation of charges, and an ultrafast capture of hot electrons occurring in nanocrystals covered in Pt, where charge separation happens faster than energy relaxation and Auger recombination. Besides the relevance for fundamental materials science and control at the nanoscale, our nanocrystals may be employed in solar photocatalysis.

From: Trash to resource: Recovered-Pd from spent three-way catalysts as a precursor of an effective photo-catalyst for H2 production

The successful production of a nanostructured and highly dispersed Pd-TiO2 photo-catalyst, using [Pd(Me2dazdt)2](I3)2 (Me2dazdt = N,N′-dimethyl-perhydrodiazepine-2,3-dithione) salt, obtained through the selective and safe recovery of palladium from model exhaust three-way catalysts (TWCs), is reported here. The photo-catalyst prepared by the impregnation/photo-reduction of palladium on the support showed improved performance in H2 production from methanol and in glycerol photo-reforming compared to reference photo-catalysts obtained from conventional Pd-salts. The reported results represent a case of successful palladium “recovery and re-employment” and thus constitute an example of green chemistry by providing, in one route, the environmentally friendly recovery of a critical metal and its employment in the renewable energy field.

Sol–gel chemistry for graphene–silica nanocomposite films

Fabrication of graphene nanocomposite films via sol–gel chemistry is still a challenging task because of the low solubility of graphene in common solvents. In the present work we have successfully developed a suitable synthesis method employing a solution of exfoliated graphene in 1-vinyl-2-pyrrolidone that is added to an anhydrous sol of silicon tetrachloride in ethanol. Thin graphene–silica films with high optical transparency have been obtained; the graphene sheets are composed of two layers and do not aggregate at a large range of concentrations upon incorporation into the matrix. Thermal processing of the silica films allows complete removal of 1-vinyl-2-pyrrolidone without oxidation or degradation of the graphene sheets which are embedded in the oxide.

Euphorbia characias latex: micromorphology of rubber particles and rubber transferase activity.

We have recently characterized a natural rubber in the latex of Euphorbia characias. Following that study, we here investigated the rubber particles and rubber transferase in that Mediterranean shrub. Rubber particles, observed by scanning electron microscopy, are spherical in shape with diameter ranging from 0.02 to 1.2 μm. Washed rubber particles exhibit rubber transferase activity with a rate of radiolabeled [(14)C]IPP incorporation of 4.5 pmol min(-1)mg(-1). Denaturing electrophoresis profile of washed rubber particles reveals a single protein band of 37 kDa that is recognized in western blot analysis by antibodies raised against the synthetic peptide whose sequence, DVVIRTSGETRLSNF, is included in one of the five regions conserved among cis-prenyl chain elongation enzymes. The cDNA nucleotide sequence of E. characias rubber transferase (GenBank JX564541) and the deduced amino acid sequence appear to be highly homologous to the sequence of several plant cis-prenyltransferases.

Incorporation of graphene into silica-based aerogels and application for water remediation

Graphene/silica nanocomposites in the form of highly porous aerogels are obtained for the first time by integrating a novel approach for the production of low defectivity graphene with a two-step route for the synthesis of a silica-based monolith. Different from the other synthetic methods, the use of co-gelation of a dispersed phase and matrix followed by high temperature supercritical drying leads to well dispersed bilayered graphene inside a high surface area silica matrix with an open texture porosity. Physico-chemical characterization provides evidence that the developed graphene/SiO2 bulk aerogel nanocomposites combine the distinct features of both the dispersed graphene sheets and the porous silica aerogel matrix. It was found that incorporation of graphene in the aerogel, even at low loading, increases significantly the hydrophobic behaviour of the materials. This, combined with the high surface/volume ratio of the aerogel, makes the resulting nanocomposite a suitable candidate as a novel oil sorbent for water remediation. In particular, the developed graphene/silica aerogels selectively and quickly uptake oil, up to more than 7 times the aerogel sorbent mass, from oil–water mixtures, and keeps floating on water after absorbing the oil phase. The suitability of the developed composites as a class of novel sorbents for environmental remediation in the occurrence of flammable liquid spills, where burning represents a major threat, is supported by the specific features of silica aerogels such as a relative fire-resistance, in addition to the high porosity and hydrophobic nature.