Enrico Maccallini

Electronic and vibrational excitations in carbon nanotubes

We investigated the electronic and vibrational properties of single wall carbon nanotubes by reflection electron energy loss and X-ray absorption spectroscopies. We report on single particle excitations measured at the C-1s edge and on collective excitations of the valence band region. The comparison between the two techniques allows us to locate empty electronic states of the carbonaceous sample. Loss spectra taken in the infrared region reveal two loss features at 90 and 170 meV assigned to the excitation of optical phonon modes.

Island organization of TiO2 hierarchical nanostructures induced by surface wetting and drying.

We report on the reorganization and bundling of titanium oxide nanostructured layers, induced by wetting with different solvents and subsequent drying. TiO(2) layers are deposited by pulsed laser deposition and are characterized by vertically oriented, columnar-like structures resulting from assembling of nanosized particles; capillary forces acting during evaporation induce bundling of these structures and lead to a micrometer-size patterning with statistically uniform islands separated by channels. The resulting surface is characterized by a hierarchical, multiscale morphology over the nanometer-micrometer length range. The structural features of the pattern, i.e., characteristic length, island size, and channel width, are shown to depend on properties of the liquid (i.e., surface tension) and thickness and density of the TiO(2) layers. The studied phenomenon permits the controlled production of multiscale hierarchically patterned surfaces of nanostructured TiO(2) with large porosity and large surface area, characterized by superhydrophilic wetting behavior without need for UV irradiation.

A two-dimensional magnetic hybrid material based on intercalation of a cationic Prussian blue analog in montmorillonite nanoclay

A highly ordered two-dimensional hybrid magnetic nanocomposite has been prepared by synthesizing and intercalating a new cationic aluminum-hydroxy ferric ferrocyanide compound into a cation-adsorbing nanoclay (montmorillonite). Chemical and structural properties were investigated by X-ray diffraction, transmission electron microscopy, thermogravimetric and differential thermal analyses, Fourier transform infrared, X-ray photoemission, and Mössbauer spectroscopies. Elemental analysis was based on proton-induced gamma ray emission and X-ray fluorescence spectroscopy data, N/C elemental ratios, and cation-exchange capacity measurements. Magnetic properties were studied by SQUID magnetometry. The results suggest: (i) that the cationic Prussian blue analog comprises Al-hydroxy cations embedded into a monolayer thick two-dimensional ferric ferrocyanide array; and (ii) that the clay-Prussian blue nanohybrid consists of such arrays stacked between the clay layers. The latter material orders ferromagnetically at approximately 5K showing a hundred times higher remanence than that of the starting material, soluble Prussian blue (ammonium ferric ferrocyanide).

Metallic Tin-Filling Effects on Carbon Nanotubes Revealed by Atomically Resolved Spectro-Microscopies

The identification of features in the Local Density of States (LDOS) of carbon nanotubes (CNTs) obtained by Scanning Tunneling Spectroscopy (STS) is of great importance in order to understand their properties. In this work, Single- and Multi-Wall Carbon Nanotubes are compared with Multi-Wall CNTs filled with tin nanowires (Sn@CNTs) in order to investigate the effect on morphological and electronic properties of the CNTs metallic filling. The LDOS of CNTs, together with topology changes, is investigated by using spatially resolved STM/STS at room temperature and in air and compared to the LDOS of highly oriented pyrolitic graphite (HOPG). The LDOS of CNTs is dominated from different electronic states filling the C 2pσ-2pσ* band gap. The appearance of those states is linked to the diameter and the defects of the CNTs. In fact, Snnanowires encapsulation induces changes in the structure of the CNTs and the appearance of electronic states in the LDOS inside the band gap. A more extensive description of the samples is obtained depicting the morphological features and the vibrational structure on wider areas using Scanning Electron Microscopy (SEM) and Raman spectroscopy, respectively.

Enhanced hydrogen and methane storage of hybrid mesoporous organosilicas

In this study, hybrid mesoporous organosilicas (HMOs) were synthesized by using tetraethyl orthosilicate (TEOS) as the silica source and 1,4-bis(triethoxysilyl)benzene (BTB) in various ratios of BTB to TEOS. The two extreme cases of 0 and 100 mol% BTB were compared with the partial addition of BTB (25 mol%) and the partial absence of TEOS (75 mol% BTB). The synthesized mesoporous materials were characterized by means of powder X-ray diffraction (PXD), scanning electron microscopy (SEM) and helium pycnometry for the determination of skeletal density. The Brunauer–Emmett–Teller (BET) method was used for the determination of the specific surface area (SSA) and non-local density functional theory (NLDFT) calculations were employed for the determination of the pore size distribution (PSD). The hydrogen and methane sorption properties were investigated using a Sieverts apparatus under isothermal sorption equilibrium conditions at cryogenic and close to ambient temperatures, respectively. For hydrogen, the combination of phenyl rings with pores at the micro/mesopore border resulted in an increase in sorption capacity. The simultaneous presence of two different precursors increased the surface inhomogeneity, which led to a wider distribution of adsorption sites close to the micro/mesopore border, which favored the hydrogen sorption properties. The presence of the phenyl rings doubled the number of methane molecules that the material surface could accommodate. The partial substitution of TEOS by BTB (25 mol%) gave the same density of adsorbed methane as the non-hybrid material, which consisted of 100% BTB. The materials exhibited excellent reversibility and sorption stability upon aging. Their sorption performance was evaluated using the Toth model and was correlated with their structural characteristics. The fraction of micropores among the total number of pores was quantitatively correlated with the maximum storage capacity and the adsorbate–adsorbent interaction strength. Finally, for a low coverage of methane the enthalpy of adsorption was calculated by the Clausius–Clapeyron equation.