Reutilization of silicon- and aluminum- containing wastes in the perspective of the preparation of SiO2-Al2O3 based porous materials for adsorbents and catalysts.

The waste materials available as sources of silicon and aluminum for producing porous materials like amorphous silicas, aluminas, amorphous silica-aluminas, and zeolites, to be used as catalyst and adsorbents, are briefly summarized. The procedures for preparing these materials from wastes are also taken into account. The limits of this approach in terms of economy and environmental protection are also briefly considered. It is concluded that mesoporous materials can be prepared from wastes, but care to product quality and to overall process efficiency is needed.

Surface Characterization of Mesoporous CoOx/SBA-15 Catalyst upon 1,2-Dichloropropane Oxidation.

The active combustion catalyst that is based on 30 wt % cobalt oxide on mesoporous SBA-15 has been tested in 1,2-dichloropropane oxidation and is characterized by means of FT-IR (Fourier transform infrared spectroscopy) and ammonia-TPD (temperature-programmed desorption). In this work, we report the spectroscopic evidence for the role of surface acidity in chloroalkane conversion. Both Lewis acidity and weakly acidic silanol groups from SBA support are involved in the adsorption and initial conversion steps. Moreover, total oxidation reaction results in the formation of new Bronsted acidic sites, which are likely associated with the generation of HCl at high temperature and its adsorption at the catalyst surface. Highly dispersed Co oxide on the mesoporous support and Co-chloride or oxychloride particles, together with the presence of several families of acidic sites originated from the conditioning effect of reaction products may explain the good activity of this catalyst in the oxidation of Chlorinated Volatile Organic Compounds.

Innovative Mesoporous Nanosilicas: SBR Nanocomposite for Low Environmental Impact Tread Tyre.

Silica nanoparticles with different aspect ratios (A.R.) were tested as reinforcing fillers of styrenebutadiene copolymer (s-SBR) for "green tyres," i.e., tires with lower rolling resistance. A commercial nanosilica with A.R. = 1 (Aerosil® 200) was compared with two nanosilica samples with A.R. = 2 and 4, synthesized by means of an innovative process, to ascertain if the filler shape was significant to improve the composite properties. In addition, bis-triethoxysilylpropyltetrasulfide was grafted onto the particles surface, in order to obtain more hydrophobic materials and to enhance their dispersion in the elastomeric composites: pristine and modified silicas were then compared. Grafting extent was evaluated by thermogravimetric analysis. The surface properties of silicas were investigated by Fourier transform infrared spectroscopy and inverse gas chromatography. s-SBR/silica nanocomposites were then prepared and characterized assessing their dynamic-mechanical properties and carrying out morphological observations by transmission electron microscopy.

Exploring, tuning, and exploiting the basicity of hydrotalcites for applications in heterogeneous catalysis.

Basic catalysis! The basic properties of hydrotalcites (see picture) make them attractive for numerous catalytic applications. Probing the basicity of the catalysts is crucial to understand the base-catalysed processes and to optimise the catalyst preparation. Various parameters can be employed to tune the basic properties of hydrotalcite-based catalysts towards the basicity demanded by each target chemical reaction.Hydrotalcites offer unique basic properties that make them very attractive for catalytic applications. It is of primary interest to make use of accurate tools for probing the basicity of hydrotalcite-based catalysts for the purpose of 1) fundamental understanding of base-catalysed processes with hydrotalcites and 2) optimisation of the catalytic performance achieved in reactions of industrial interest. Techniques based on probe molecules, titration techniques and test reactions along with physicochemical characterisation are overviewed in the first part of this review. The aim is to provide the tools for understanding how series of parameters involved in the preparation of hydrotalcite-based catalytic materials can be employed to control and adapt the basic properties of the catalyst towards the basicity demanded by each target chemical reaction. An overview of recent and significant achievements in that perspective is presented in the second part of the paper.

Decomposition of hexamethylcyclotrisiloxane over solid oxides.

The decomposition of hexamethylcyclotrisiloxane (HMCTS) has been studied at room temperature and in the range 473-673 K over the surface of basic (CaO, MgO) and acidic oxides (Al(2)O(3), SiO(2)). Alumina allows the complete removal of HMCTS from synthetic biogases at 673 K. A reactive adsorption occurs with surface silication and release of methane. The adsorption capacity of our alumina adsorbent (180 m(2) g(-1)), until saturation, at 673 K, is 0.31 g((HMCTS))g((Al2O3))(-1), which corresponds to one silicon atom per 9 A(2), i.e. the silication monolayer capacity. On the contrary, silica, which is an excellent adsorbent for siloxanes at room temperature, looses its adsorption ability at high temperature as it is typical of a molecular adsorption behavior. Basic oxides such as MgO and CaO have strong reactivity in decomposing siloxanes in the absence of CO(2), but loose reactivity when in contact with carbon dioxide because of surface carbonation.

Technologies for the removal of phenol from fluid streams: a short review of recent developments.

The available technologies for the abatement of phenol from water and gaseous streams are briefly reviewed, and the recent advancements summarized. Separation technologies such as distillation, liquid-liquid extraction with different solvents, adsorption over activated carbons and polymeric and inorganic adsorbents, membrane pervaporation and membrane-solvent extraction, have been discussed. Destruction technologies such as non-catalytic, supercritical and catalytic wet air oxidation, ozonation, non-catalytic, catalytic and enzymatic peroxide wet oxidation, electrochemical and photocatalytic oxidation, supercritical wet gasification, destruction with electron discharges as well as biochemical treatments have been considered. As for the abatement of phenol from gases, condensation, absorption in liquids, adsorption on solids, membrane separation, thermal, catalytic, photocatalytic and biological oxidation have also been considered. The experimental conditions and the performances of the different techniques have been compared.

State of supported rhodium nanoparticles for methane catalytic partial oxidation (CPO): FT-IR studies.

The effect of pretreatments as well as of rhodium precursor and of the support over the morphology of Rh nanoparticles were investigated by Fourier transform infrared (FT-IR) spectroscopy of adsorbed CO. Over a Rh/alumina catalyst, both metallic Rh particles, characterized by IR bands in the range 2070-2060 cm-1 and 1820-1850 cm-1, and highly dispersed rhodium species, characterized by symmetric and asymmetric stretching bands of RhI(CO)2 gem-dicarbonyl species, are present. Their relative amount changes following pretreatments with gaseous mixtures, representative of the catalytic partial oxidation (CPO) reaction process. The Rh metal particle fraction decreases with respect to the Rh highly dispersed fraction in the order CO approximately CO/H2 > CH4/H2O, CH4/O2 > CH4 > H2. The metal particle dimensions decrease in the order CH4/O2 > H2 > CH4/H2O > CO > CO/H2. Grafting from a carbonyl rhodium complex also increases the amount and the dimensions of Rh0 particles at the catalyst surface. Increasing the ratio (extended rhodium metal particles/highly dispersed Rh species) allows a shorter conditioning process. The surface reconstruction phenomena going on during catalytic activity are related to this effect.

Influence of the silane modifiers on the surface thermodynamic characteristics and dispersion of the silica into elastomer compounds.

A good dispersion of silica into elastomers, typically used in tire tread production, is obtained by grafting of the silica with multifunctional organosilanes. In this study, the influence of the chemical structure of a triethoxysilane (TES), octadecyltriethoxysilane (ODTES), and ODTES/bistriethoxysilylpropyltetrasulfane (TESPT) mixture was investigated by inverse gas chromatography (IGC) at infinite dilution. Thermodynamic results indicate a higher polarity of the silica surface modified with TES as compared to that of the unmodified silica due to new OH groups deriving from the hydrolysis of ethoxy groups of the silane; the long hydrocarbon substituent of the ODTES lies on the surface of silica and reduces the dispersive component of the silica surface tension. A comparison with silica modified with TESPT is discussed. An accurate morphological investigation by transmission electron microscopy (TEM) and automated image analysis (AIA) was carried out on aggregates of silica dispersed into a SBR compound loaded with 35 phr (per hundred rubber) of untreated and TESPT-treated silica. Morphological descriptors such as the projected area/perimeter ratio (A/P) and roundness (P2/4piA) provided direct and quantitative indications about the distribution of the filler into the rubber matrix.

Characterization of Pd-Cu alloy nanoparticles on gamma-Al2O3-supported catalysts.

Cu-Pd/Al2O3 bimetallic catalysts have been characterized by XRD, TEM, and EDX techniques. The surface structure has been investigated by FT-IR spectroscopy of low-temperature adsorbed CO in the reduced and in the oxidized state. Evidence has been provided of the formation of Cu-Pd alloy nanoparticles, both of the alpha-phase (disordered fcc) and of the beta-phase (ordered CsCl-type). IR spectra suggest that Cu likely decorates the edges while Pd mostly stays at the main faces. Part of copper disperses as Cu+ on the support even after reduction. The presence of copper seems to modify strongly the sate of oxidized Pd centers in oxidized high-Pd content materials. The redox chemistry of the system, where Pd is reduced more easily than Cu, appears to be very complex.

A reexamination of the adsorption of CO and nitriles on alkali-metal mordenites: characterization of multiple interactions.

The low temperature adsorption of CO and the room temperature adsorption of propionitrile and ortho-toluonitrile on LiMOR, NaMOR, KMOR and CsMOR zeolites have been investigated by FT-IR spectroscopy. Two different CO species, both most probably located in the main channels coordinated on Na ions at IV and VI sites, have been observed. They are associated to a shift of the CO stretching to higher frequencies, as usual. However, together, more strongly bonded species associated to a slight shift of the CO stretching to a lower frequency are also observed. Similar species, with the CN stretching shifted upwards (weaker adsorption) and with the CN stretching shifted downwards (stronger adsorption) are also observed in the case of the interaction of propionitrile (PrN), a molecule that should enter the main channels, and in the case of the interaction of ortho-toluonitrile (o-TN), whose access to the main channels should be highly hindered. The data show that the species characterized by a stronger adsorption but a lower stretching frequency may form both in the main channels and at the external surface. Their formation is easier with the larger cations. These species are identified as "multiply bonded", possibly to two cations. The evidence for this new interaction, stronger than the usual one site-one molecule species, may change considerably the view of the adsorption chemistry of cationic zeolites, from localized simple sites to cooperative complex interactions.

Surface modification of H-ferrierite by reaction with triethoxysilane.

The interaction of triethoxysilane (TES) with H-ferrierite (H-FER) and its effects on acidity have been investigated by infrared spectroscopy. TES adsorbs only on the external surface of H-FER and allows the almost complete disappearance of the external silanol groups. New SiH groups are formed which appear to be inactive in acid-base interactions. The adsorption of propionitrile, which diffuses into the zeolitic channels, provides evidence for the lack of substantial perturbation of the strongly acidic internal bridging OH groups. On the contrary, the adsorption of the hindered basic probe molecule o-toluonitrile, which cannot penetrate the FER channels, shows that not only terminal silanols but also Al3+ Lewis acid sites present on the external surface of H-FER almost totally disappear after TES treatment. Treatment with TES seems to allow virtually the total deactivation of the H-FER external surface.

Fourier transform infrared spectroscopic study of the adsorption of CO and nitriles on Na-mordenite: evidence of a new interaction.

The low temperature adsorption of CO and the room temperature adsorption of acetonitrile, propionitrile, isobutyronitrile, pivalonitrile, benzonitrile, and o-toluonitrile on Na-mordenite (NaMOR) have been investigated by Fourier transform infrared (FT-IR) spectroscopy. The results have been compared with analogous experiments performed on H-mordenite, Na-X zeolite, and Na-silica-alumina. The Na distribution in NaMOR has also been investigated by X-ray diffraction and far-IR spectroscopy. The conclusions are that Na+ ion distribution is essentially random and that, together with the well-known interaction of the probes with Na+ ions in the side pockets and the main channels, a stronger additional interaction occurs in all cases. This new interaction is likely multiple, involving either more Na+ ions or Na and oxygen species. This interaction is more pronounced with the hindered nitriles, whose access at the main channels is likely forbidden. This suggests that this interaction, which is also observed on Na-X zeolites but not with Na-silica-alumina, occurs at the external mouths of the mordenite channels.