Dehydration of Fructose to 5-HMF over Acidic TiO2 Catalysts

Different solid sulfonic titania-based catalysts were investigated for the hydrothermal dehydration of fructose to 5-hydroxymethylfurfural (5-HMF). The catalytic behavior of the materials was evaluated in terms of fructose conversion and selectivity to 5-HMF. The surface and structural properties of the catalysts were investigated by means of X-ray diffraction (XRD), N2 adsorption isotherms, thermo-gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and acid capacity measurements. Special attention was focused on the reaction conditions, both in terms of 5-HMF selectivity and the sustainability of the process, choosing water as the solvent. Among the various process condition…

Interaction of Gold with Co-Condensed and Grafted HMS-SH Silica: A 29Si {1H} CP-MAS NMR Spectroscopy, XRD, XPS and Au LIII EXAFS Study

Hexagonal mesoporous silica (HMS) is functionalised with mercaptopropyl groups by adopting two different procedures ; co-condensation and grafting. In both cases tetraethylorthosilicate (TEOS) and 3-mercaptopropyltriethoxysilane (3-MPTES) are used as the silicon and sulfur precursors, respectively. The obtained materials are analysed by several techniques such as N 2 sorption, TG-DTA, XRD, SAXS and-solid state 29 Si { 1 H} CP-MAS NMR spectroscopy. By taking advantage of the chemical interaction between gold and the -SH groups, the effect of the thiol addition procedure on the supporting capability of the functionalised silica is evaluated by depositing gold through the incipient wet impregn…

Ni-Based Catalysts for Low Temperature Methane Steam Reforming: Recent Results on Ni-Au and Comparison with Other Bi-Metallic Systems

Steam reforming of light hydrocarbons provides a promising method for hydrogen production. Ni-based catalysts are so far the best and the most commonly used catalysts for steam reforming because of their acceptably high activity and significantly lower cost in comparison with alternative precious metal-based catalysts. However, nickel catalysts are susceptible to deactivation from the deposition of carbon, even when operating at steam-to-carbon ratios predicted to be thermodynamically outside of the carbon-forming regime. Reactivity and deactivation by carbon formation can be tuned by modifying Ni surfaces with a second metal, such as Au through alloy formation. In the present review, we su…

Green and Direct Synthesis of Benzaldehyde and Benzyl Benzoate in One Pot

High yields of valued benzaldehyde and benzyl benzoate are obtained in one pot starting from benzyl alcohol using oxygen as only oxidant under mild conditions (2 bar O2, 100 °C) along with an ultralow amount (0.02 mol %) of Au nanoparticles heterogenized over a spherical ORMOSIL mesoporous support. The process is remarkably selective and the catalyst is stable.

Heterogenizing palladium tetraiodide catalyst for carbonylation reactions

We report the first example of successful heterogenization of the classical PdI42- carbonylation catalyst, achieved in two simple steps from ionic liquid-functionalized multi-walled carbon nanotubes (MWCNTs). The newly developed materials (PdI4@MWCNT-imi-X, X = Br, I) present the PdI42- anion supported on an imidazolium network (imi) grown on MWCNTs and have been fully characterized. The activity of PdI4@MWCNT-imi-X has been successfully tested in a paradigmatic carbonylation reaction, the oxidative monoaminocarbonylation of 1-alkynes with amines to give high value added 2-ynamides (obtained in good yields, 50–84%, starting from various substrates). The heterogeneous catalyst could be easil…

Correction: Supported C60-IL-PdNPs as extremely active nanocatalysts for C–C cross-coupling reactions

Correction for ‘Supported C60-IL-PdNPs as extremely active nanocatalysts for C–C cross-coupling reactions’ by Francesco Giacalone et al., J. Mater. Chem. A, 2016, 4, 17193–17206.

Coupling chemical reaction to electrospray: a novel preparation of gold nanostructures

The simultaneous reduction of Au(III) to Au(0), synthesis of gold nanoparticles and their deposition onto boron-doped silicon target have been attained by the electrospray technique. In this way the overall process can be considered as a novel chemical/physical hybrid method which synergically exploits the merits of both approaches. Various experimental conditions have been explored to optimize the process: it has been found that, by applying a negative high voltage to the boron-doped silicon target and with the presence of the surfactant Bis(2-ethylhexyl)sulfosuccinate sodium salt in the solution, a quantitative transformation of Au(III) to Au(0) nanoparticles has been obtained. The deposi…

An Atom-Economical Approach to Functionalized Single-Walled Carbon Nanotubes: Reaction with Disulfides

Owing to their unique structure, thermal stability, and mechanical and electronic properties, single-walled carbon nanotubes (SWCNTs) have been a subject of continuous and intense interest. However, various applications in many fields, such as molecular electronics, solar cells, and nanomedicine, often require the development of reproducible protocols for the chemical modification of SWCNTs. In fact, one of the main drawbacks of the use of SWCNTs is their tendency to aggregate and intrinsic poor solubility, which prevent their manipulation and limit their potential. To date, several methods have been described for the chemical functionalization of SWCNTs; however, new versatile and reliable…

New biocides based on imidazolinium-functionalised hybrid mesoporous silica nanoparticles

Here, we report the development of a new biocide based on hybrid mesoporous silica nanoparticles (MSN). The MSN was synthesized by condensation method in emulsion followed by grafting with two different silylated ionic liquid moieties, namely butyl imidazolinium bromide and imidazolinium propansulfonate betaine. Features of nanoparticles were characterized by Thermogravimetry, Infrared and ss-NMR Spectroscopy, and Transmission Electron Microscopy. The antibacterial properties were tested against a Gram-positive bacterial strain previously isolated from artefacts of interest in the field of Cultural Heritage. Interestingly, the hybrid material presents an antibacterial activity higher than i…

Paper-TiO2 composite: An effective photocatalyst for 2-propanol degradation in gas phase

Two simple routes for the synthesis of a paper-TiO2 composite were tuned up and the efficiency of the resulting paper-TiO2 photocatalyst was investigated in the 2-propanol oxidation in gas phase. The first route involved the in-situ generation over the sheet of paper of a TiO2 layer starting from a solution of Ti (OBu)4 in tert-butanoliacetic acid, followed by hydrothermal treatment at 120 degrees C for 3 h. The sample was labelled as paper-TiO2 (H). The second approach was based on the adsorption on the paper of a ready-made suspension of titania nanoparticles (TiO2 sol), generated in autoclave at 140 degrees C and stable in acid medium at pH <3. The sample was labelled as paper-TiO2 (S). …

Single-Walled Carbon Nanotube–Polyamidoamine Dendrimer Hybrids for Heterogeneous Catalysis

We report the synthesis and catalytic properties of single-walled carbon nanotube-polyamidoamine dendrimers hybrids (SWCNT-PAMAM), prepared via a convergent strategy. The direct reaction of cystamine-based PAMAM dendrimers (generations 2.5 and 3.0) with pristine SWCNTs in refluxing toluene, followed by immobilization and reduction of [PdCl4](2-), led to the formation of highly dispersed small palladium nanoparticles homogeneously confined throughout the nanotube length. One of these functional materials proved to be an efficient catalyst in Suzuki and Heck reactions, able to promote the above processes down to 0.002 mol % showing a turnover number (TON) of 48 000 and a turnover frequency (T…

Salmeterol Xinafoate (SX) loaded into mucoadhesive solid lipid microparticles for COPD treatment

Chronic obstructive pulmonary disease (COPD) is one of the main health problems worldwide. It is characterised by chronic inflammation in the lungs that leads to progressive, chronic, largely irreversible airflow obstruction. The use of long-acting β agonists remain today the frontline treatment for COPD with the aim of minimizing side effects and enhancing therapeutic usefulness. To this purpose, in this paper, mucoadhesive solid lipid microparticles (SLMs) containing a long-acting β-2 agonist, Salmeterol Xinafoate (SX) were prepared, characterised (size, z-potential, aerodynamic diameter, turbidimetric evaluations, drug loading and entrapping efficiency) and tested in a model of bronchial…

Catechol-Functionalized Carbon Nanotubes as Support for Pd Nanoparticles

Carbon nanotubes have been covalently functionalized with catechol moieties through the formation of the corresponding aryl radicals obtained by reacting 4-aminocatechol with isoamyl nitrite. The functionalized multiwalled carbon nanotubes have been in turn used to immobilize Pd(II) ions on its surface forming catechol-Pd complexes, which were reduced to Pd nanoparticles (NPs). The so-obtained hybrid material has been characterized by means of thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). This latter technique allowed to estimate the nanoparticle size (5.7 +/- 2.8 nm) wh…

The Effect of Ni Doping on the Performance and Electronic Structure of LSCF Cathodes Used for IT-SOFCs

We investigated the effect of nickel doping on the electronic structure and performance of nanostructured La0.6Sr0.4Co0.2Fe0.8-0.03Ni0.03O3-delta prepared by the one-pot sol gel method. The commercial undoped La0.6Sr0.4Co0.2Fe0.8O3-delta (ISCF0.8) was used as reference. Moreover, for comparison, Ni (3 mol %) was deposited by wetness impregnation over the La0.6Sr0.4Co0.2Fe0.8O3-delta. We show by in situ X-ray absorption spectroscopy at 900 degrees C under air flow that nickel enters the B perovskite site of the material and favors the stabilization of the cobalt oxidation state, as evidenced by the delay in the decrease of the average Co valence with respect to undoped samples. Our results a…

Multi-layered, covalently supported ionic liquid phase (mlc-SILP) as highly cross-linked support for recyclable palladium catalysts for the suzuki reaction in aqueous medium

The reaction between an excess of 1,4-bis(3-vinylimidazolium-1-yl) bromide and a mercaptopropyl-modified amorphous silica gel or ordered mesoporous silica SBA-15 in the presence of azobisisobutyronitrile (AIBN) afforded new materials, which have a high loading of imidazolium moieties. These materials, which contain a highly cross-linked polymeric network, have been denoted as multi-layered, covalently supported ionic liquid phase (mlc-SILP) and have been used as support for palladium catalysts containing a high loading of the metal (10 wt%). Such materials were characterized by several techniques (13C magic angle spinning nuclear magnetic resonance, the Brunauer–Emmett–Teller technique, sma…

Templating effect of carbon nanoforms on highly cross-linked imidazolium network: Catalytic activity of the resulting hybrids with Pd nanoparticles

Two different carbon nanoforms (CNFs), namely multi-walled carbon nanotubes (MWCNTs) and carbon nanohorns (CNHs), have been chosen as support for the direct polymerization of a bis-vinylimidazolium salt. Transmission electron microscopy analyses revealed a templating effect of the CNFs on the growth of the polymeric network, which perfectly covers their whole surfaces creating a cylindrical or spherical coating for MWCNTs and CNHs, respectively. Subsequently, the CNFs-polyimidazolium have been used as stabilizers for Pd nanoparticles (Pd NPs), and the obtained materials have been characterized by means of analytical and spectroscopic techniques and then employed as easily recoverable and re…

Composite Nanoparticles

International audience; Composite nanoparticles are advanced materials having recently gained increasing attention due to their scientific and technological importance.They find awide variety of applications such as catalysts with huge activity and specificity,metal semiconductor junctions, optical sensors, and modifiers of polymeric films for packaging.

Supported C60-IL-PdNPs as extremely active nanocatalysts for C-C cross-coupling reactions

A C60-ionic liquid hybrid has been covalently linked to three different solid supports, namely amorphous silica, SBA-15 and Fe2O3@SiO2, and the resulting materials have been employed as covalently supported ionic liquid phases (cSILP) in order to immobilize and stabilize palladium nanoparticles (PdNPs). These novel hybrid materials are based on a sort of "matryoshka" system (PdNPs@imidazolium-salt@C60@support) in which the imidazolium-based moieties have not been directly linked to the surface of the support, but they are present in an octopus-like spatial arrangement on the uniformly surface-distributed fullerenes. These materials have been fully characterized and successfully employed as …

Hybrid paper–TiO2 coupled with a Cu2O heterojunction: an efficient photocatalyst under sun-light irradiation

Hybrid paper-TiO2, paper-Cu2O-TiO2 and paper-TiO2-Cu2O photocatalysts were prepared via a non-hydrolytic sol-gel process followed by mild hydrothermal treatment to generate the TiO2 layer, and a reduction process to form the Cu2O nanoparticles. The hybrid photocatalysts have been characterized by Raman, TGA, FE-SEM, UV-Vis and XPS. The immobilized TiO2 was found to form a homogeneous thin layer composed of nanoparticles with a size smaller than 10 nm. The Cu2O nanoparticles with sizes of 30-100 nm were generated either on the top of the TiO2 layer or by reduction of Cu2+ ions. All the prepared hybrid catalysts showed efficient photocatalytic properties for the degradation of toluidine when …

Geochemistry of phosphatic nodules as a tool for understanding depositional and taphonomical settings in a paleolithic cave site (San teodoro, Sicily)

Interpreting depositional settings of cave sites is generally problematic, especially in absence of palaeontological/archaeological evidence. This is the case of some deposits at San Teodoro Cave (Sicily), a key site for the Mediterranean Palaeolithic. In a stratigraphic level interrupted by a carbonatic concretion, phosphatic nodules are present only in the part enclosed between the concretion and the cave wall. The discovery of these nodules combined with the punctual lack of fossils had initially suggested an erosion phenomenon and subsequent formation of nodules at a vadose level. Here we show the usefulness of an integrated, geochemical-palaeoecological approach in defining stratigraph…

Fullerene-ionic-liquid conjugates: a new class of hybrid materials with unprecedented properties.

A modular approach has been followed for the synthesis of a series of fullerene-ionic-liquid (IL) hybrids in which the number of IL moieties (two or twelve), anion, and cation have been varied. The combination of C60 and IL give rise to new unique properties in the conjugates such as solubility in water, which was higher than 800 mg mL(-1) in several cases. In addition, one of the C60 -IL hybrids has been employed for the immobilization of palladium nanoparticles through ion exchange followed by reduction with sodium borohydride. Surprisingly, during the reduction several carbon nanostructures were formed that comprised nano-onions and nanocages with few-layer graphene sidewalls, which have…

First evidence of Pleistocene ochre production from bacteriogenic iron oxides. A case study of the Upper Palaeolithic site at the San Teodoro Cave (Sicily, Italy)

Abstract The use of iron pigments is well documented in the archaeological horizons of the different parts of the world since the Middle Pleistocene. The mineralogical and chemical composition of the pigments allowed defining, in most cases, their inorganic origin, which were then used after a limited transformation and manipulation. The use of a biogenic ochraceous pigment and its manipulation has recently been described in a late Holocene archaeological horizon of the American continent. Here we describe the earliest case of archaeological use of ferrous pigment produced by iron-oxidising bacteria (FeOB), the first identified in a European Epigravettian (late Upper Palaeolithic) layer, at…

Gold nanoparticles stabilized by modified halloysite nanotubes for catalytic applications

Chemical Modification of Carbon Nanotubes with Sulfonylamides

Iron and lithium-iron alkyl phosphates as nanostructured material for rechargeable batteries

Abstract Inorganic/organic hybrid materials composed by iron atoms bonded to an alkyl phosphate can be easily synthesized by mixing at 110 °C iron chlorides with tri-alkyl phosphates. Since structural information on these products are lacking and taking into account that lithium/iron organic hybrid materials are important in lithium ion battery technology we report here the physico-chemical characterization of different hybrid lithium/iron butylphosphates. These materials are characterized by the presence of elongated hexagonal crystals stable up to 315 °C. The insertion of lithium does not affect the local structure. Thanks to such structures the material can be electrochemically-cycled an…

Au/CeO2 Photocatalyst for the Selective Oxidation of Aromatic Alcohols in Water under UV, Visible and Solar Irradiation

Au nanoparticles supported on CeO2 have been prepared and investigated as photocatalysts for the photocatalytic selective oxidation of benzyl alcohol and 4-methoxybenzyl alcohol to the correspondent benzaldehydes, in aqueous suspensions and room conditions under UV, visible and natural solar light irradiation. Au nanoparticles have been supported by impregnation (1 and 3 wt.%) on two types of CeO2 (i.e., a commercial one and a home prepared oxide obtained in the presence of NaOH as precipitation agent). The Au impregnated samples showed strong visible radiation absorption at 565–570 nm associated to localized surface plasmon resonance (LSPR). The bare CeO2 samples are activated by UV light …

TiO2/Ag2O immobilized on cellulose paper: A new floating system for enhanced photocatalytic and antibacterial activities

Paper-TiO2-Ag2O floating photocatalysts were produced under mild condition and their photocatalytic activity for the degradation of aromatic amine under sunlight stimulant was investigated. Characterizations by Raman, XRD, XPS, DRS and PL confirmed the presence of TiO2 and Ag2O, and the morphology of the appended TiO2/Ag2O layer was probed by FE-SEM. The photocatalytic activity of the prepared samples was investigated by the degradation of aniline (AN) in water under simulated sun-light illumination and constrained conditions, i.e. non-stirring and non-oxygenation. The presence of Ag2O combined with TiO2 was shown to improve the resistance of paper to bacteria attack, thus increasing the du…

Sustainable Recycling of Insoluble Rust Waste for the Synthesis of Iron-Containing Perovskite-Type Catalysts

Insoluble rust waste from the scraping of rusted iron-containing materials represents a cheap, eco-friendly, and available source of iron. LaFeO3 perovskite-type powders were successfully prepared by solution combustion synthesis using rust waste from an electricity transmission tower manufacturer. Solution combustion synthesis enabled introduction of this insoluble iron precursor directly into the final product, bypassing complex extraction procedures. Catalytic activity in the propylene oxidation of the waste-derived LaFeO3 with stoichiometric Fe/La ratio was almost identical to the commercial iron nitrate-derived LaFeO3 , thus demonstrating the viability of this recycling solution. The a…

Highly Loaded Multi-Walled Carbon Nanotubes Non-Covalently Modified with a Bis-Imidazolium Salt and their Use as Catalyst Supports

The surfaces of multi-walled carbon nanotubes (MWCNTs) were non-covalently modified using two bis-imidazolium dibromide derivatives having phenyl or pyrene groups. Due to the presence of the two pyrene groups the bis(pyren-1-ylmethylimidazolium) dibromide derivative was immobilised at a loading of about 15-16 wt %, whereas only <3 wt % of the phenyl derivative was immobilised. The presence of the two imidazolium cations helped the immobilisation of tetrachloropalladate ions after exchange with bromide ions. Tetrachloropalladate was used as pre-catalyst in several Suzuki-Miyaura carbon-carbon cross-coupling reactions in water or water/ethanol at 50 °C in only 0.1 mol % and compared with the …

Palladium local structure of La1-xSrxCo1-yFey-0.03Pd0.03O3-δperovskites synthesized using a one pot citrate method

Nanostructured La1-xSrxCo1-yFey-0.03Pd0.03O3-δ(LSCF-Pd) perovskites with fixed La-Sr composition (x = 0.4) and two different Fe contents (y = 0.2 and 0.8) were successfully synthesized using a one pot citrate method starting from nitrates of the metal cations. Pd-free La1-xSrxCo1-yFeyO3-δ(LSCF) systems were prepared for comparison. LSCF powders were calcined at 1300 °C and characterized by XRD and Rietveld refinement, EXAFS, XPS, TPR analyses. Promotion of La0.6Sr0.4Co0.8Fe0.2O3-δand of La0.6Sr0.4Co0.2Fe0.8O3-δby incorporation of palladium was evidenced by solving the local environment of Pd using EXAFS spectroscopy. XPS analyses, in agreement with TPR measurements, demonstrated an inc…

Gold nanoparticles stabilized by modified halloysite nanotubes for catalytic applications

A highly sustainable prototype of a flow system based on gold nanoparticles (4.2 nm) supported on thiol-functionalized halloysite nanotubes (HNTs) was developed for catalytic applications. The catalytic performances were evaluated using the reduction of 4-nitrophenol to 4-aminophenol as a model system. Under the best experimental conditions (0.0001 mol%, 1.97 × 10−8 mg of Au nanoparticles), an impressive apparent turnover frequency value up to 2 204 530 h−1 was achieved and the halloysite-based catalyst showed full recyclability even after ten cycles. The high catalytic activity confirms the importance of the use of HNTs as support for Au nanoparticles that can exert a synergistic effect bo…