On the thermal stabilization of carbon-supported SiO2 catalysts by phosphorus:evaluation in the oxidative dehydrogenation of ethylbenzene to styrene and a comparison with relevant catalysts

A strategy to enhance the thermal stability of C/SiO2 hybrids for the O2-based oxidative dehydrogenation of ethylbenzene to styrene (ST) by P addition is proposed. The preparation consists of the polymerization of furfuryl alcohol (FA) on a mesoporous precipitated SiO2. The polymerization is catalyzed by oxalic acid (OA) at 160 °C (FA:OA = 250). Phosphorous was added as H3PO4 after the polymerization and before the pyrolysis that was carried out at 700 °C and will extend the overall activation procedure. Estimation of the apparent activation energies reveals that P enhances the thermal stability under air oxidation, which is a good indication for the ODH tests. Catalytic tests show that the P/C/SiO2 hybrids are readily active, selective and indeed stable in the applied reactions conditions for 60 h time on stream. Coke build-up during the reaction attributed to the P-based acidity is substantial, leading to a reduction of the surface area and pore volume. The comparison with a conventional MWCNT evidences that the P/C/SiO2 hybrids are more active and selective at high temperatures (450–475 °C) while the difference becomes negligible at lower temperature. However, the comparison with reference P/SiO2 counterparts shows a very similar yield than the hybrids but more selective to ST. The benefit of the P/C/SiO2 hybrid is the lack of stabilization period, which is observed for the P/SiO2 to create an active coke overlayer. For long term operation, P/SiO2 appears to be a better choice in terms of selectivity, which is crucial for commercialization.

Cu and Fe oxides dispersed on SBA-15:a Fenton type bimetallic catalyst for N,N-diethyl-p-phenyl diamine degradation

A bimetallic oxidation catalyst has been synthesized via wet impregnation of copper and iron over a mesoporous SBA-15 silica support. Physicochemical properties of the resulting material were characterized by XRD, N2 physisorption, DRUVS, FTIR, Raman, SEM and HRTEM, revealing the structural integrity of the parent SBA-15, and presence of highly dispersed Cu and Fe species present as CuO and Fe2O3. The CuFe/SBA-15 bimetallic catalyst was subsequently utilized for the oxidative degradation of N,N-diethyl-p-phenyl diamine (DPD) employing a H2O2 oxidant in aqueous solution.

Fast pyrolysis of cassava rhizome in the presence of catalysts

Cassava rhizome was catalytically pyrolysed at 500 °C using analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) in order to investigate the effect of catalysts on bio-oil properties. The catalysts studied were zeolite ZSM-5, two aluminosilicate mesoporous materials Al-MCM-41 and Al-MSU-F, and a proprietary commercial catalyst alumina-stabilised ceria MI-575. The influence of catalysts on pyrolysis products was observed through the yields of aromatic hydrocarbons, phenols, lignin-derived compounds, carbonyls, methanol and acetic acid. Results showed that all the catalysts produced aromatic hydrocarbons and reduced oxygenated lignin derivatives, thus indicating an improvement of bio-oil heating value and viscosity. Among the catalysts, ZSM-5 was the most active to all the changes in pyrolysis products. In addition, all the catalysts with the exception of MI-575 enhanced the formation of acetic acid. This is clearly a disadvantage with respect to the level of pH in the liquid bio-fuel.

A structural investigation of the alkali metal site distribution within bioactive glass using neutron diffraction and multinuclear solid state NMR

The atomic-scale structure of Bioglass and the effect of substituting lithium for sodium within these glasses have been investigated using neutron diffraction and solid state magic angle spinning (MAS) NMR. Applying an effective isomorphic substitution difference function to the neutron diffraction data has enabled the Na-O and Li-O nearest-neighbour correlations to be isolated from the overlapping Ca-O, O-(P)-O and O-(Si)-O correlations. These results reveal that Na and Li behave in a similar manner within the glassy matrix and do not disrupt the short range order of the network former. Residual differences are attributed solely to the variation in ionic radius between the two species. Successful simplification of the 2

Structural characterisation of hypoxia-mimicking bioactive glasses

Nickel and cobalt are both known to stimulate the hypoxia-inducible factor-1 (HIF-1a), thus significantly improving blood vessel formation in tissue engineering applications. We have manufactured nickel and cobalt doped bioactive glasses to act as a controlled delivery mechanism of these ions. The resultant structural consequences have been investigated using the methods of isotopic and isomorphic substitution applied to neutron diffraction. The structural sites present will be intimately related to their release properties in physiological fluids such as plasma and saliva, and hence the bioactivity of the material. Detailed structural knowledge is therefore a prerequisite for optimising material design. Results show that nickel and cobalt adopt a mixed structural role within these bioactive glasses occupying both network-forming (tetrahedral) and network-modifying (5-fold) geometries. Two thirds of the Ni (or Co) occupies a five-fold geometry with the remaining third in a tetrahedral environment. A direct comparison of the primary structural correlations (e.g. Si-O, Ca-O, Na-O and O-Si-O) between the archetypal 45S5 Bioglass® and the Ni and Co glasses studied here reveal no significant differences. This indicates that the addition of Ni (or Co) will have no adverse effects on the existing structure, and thus on in vitro/in vivo dissolution rates and therefore bioactivity of these glasses.

Multifunctional bioactive glass scaffolds coated with layers of poly(d,l-lactide-co-glycolide) and poly(n-isopropylacrylamide-co-acrylic acid) microgels loaded with vancomycin

A new family of multifunctional scaffolds, incorporating selected biopolymer coatings on basic Bioglass® derived foams has been developed. The polymer coatings were investigated as carrier of vancomycin which is a suitable drug to impart antibiotic function to the scaffolds. It has been proved that coating with PLGA (poly(lactic-co-glycolic acid)) with dispersed vancomycin-loaded microgels provides a rapid delivery of drug to give antibacterial effects at the wound site and a further sustained release to aid mid to long-term healing. Furthermore, the microgels also improved the bioactivity of the scaffolds by acting as nucleation sites for the formation of HA crystals in simulated body fluid. © 2013 Elsevier B.V. All rights reserved.

Facile route to conformal hydrotalcite coatings over complex architectures:a hierarchically ordered nanoporous base catalyst for FAME production

An alkali- and nitrate-free hydrotalcite coating has been grafted onto the surface of a hierarchically ordered macroporous-mesoporous SBA-15 template via stepwise growth of conformal alumina adlayers and their subsequent reaction with magnesium methoxide. The resulting low dimensional hydrotalcite crystallites exhibit excellent per site activity for the base catalysed transesterification of glyceryl triolein with methanol for FAME production.

Molecular dynamics simulations of the adsorption and diffusion behavior of pure and mixed alkanes in silicalite

The adsorption and diffusion of mixed hydrocarbon components in silicalite have been studied using molecular dynamic simulation methods. We have investigated the effect of molecular loadings and temperature on the diffusional behavior of both pure and mixed alkane components. For binary mixtures with components of similar sizes, molecular diffusional behavior in the channels was noticed to be reversed as loading is increased. This behavior was noticeably absent for components of different sizes in the mixture. Methane molecules in the methane/propane mixture have the highest diffusion coefficients across the entire loading range. Binary mixtures containing ethane molecules prove more difficult to separate compared to other binary components. In the ternary mixture, however, ethane molecules diffuse much faster at 400 K in the channel with a tendency to separate out quickly from other components. © 2005 Elsevier Inc. All rights reserved.

Alumina-grafted SBA-15 as a high performance support for Pd-catalysed cinnamyl alcohol selective oxidation

Ultrathin alumina monolayers grafted onto an ordered mesoporous SBA-15 silica framework afford a composite catalyst support with unique structural properties and surface chemistry. Palladium nanoparticles deposited onto Al-SBA-15 via wet impregnation exhibit the high dispersion and surface oxidation characteristic of pure aluminas, in conjunction with the high active site densities characteristic of thermally stable, high-area mesoporous silicas. This combination confers significant rate enhancements in the aerobic selective oxidation (selox) of cinnamyl alcohol over Pd/Al-SBA-15 compared to mesoporous alumina or silica supports. Operando, liquid-phase XAS highlights the interplay between dissolved oxygen and the oxidation state of palladium nanoparticles dispersed over Al-SBA-15 towards on-stream reduction: ambient pressures of flowing oxygen are sufficient to hinder palladium oxide reduction to metal, enabling a high selox activity to be maintained, whereas rapid PdO reduction and concomitant catalyst deactivation occurs under static oxygen. Selectivity to the desired cinnamaldehyde product mirrors these trends in activity, with flowing oxygen minimising CO cleavage of the cinnamyl alcohol reactant to trans-β-methylstyrene, and of cinnamaldehyde decarbonylation to styrene. © 2013 Elsevier B.V.

An energy-efficient route to the rapid synthesis of organically-modified SBA-15 via ultrasonic template removal

A low energy route for the removal of Pluronic P123 surfactant template during the synthesis of SBA-15 mesoporous silicas is explored. The conventional reflux of the hybrid inorganic-organic intermediate formed during co-condensation routes to Pr-SOH-SBA-15 is slow, utilises large solvent volumes, and requires 24 h to remove ∼90% of the organic template. In contrast, room temperature ultrasonication in a small methanol volume achieves the same degree of template extraction in only 5 min, with a 99.9% energy saving and 90% solvent reduction, without compromising the textural, acidic or catalytic properties of the resultant Pr-SOH-SBA-15. © 2014 The Royal Society of Chemistry.

Selective oxidation of allylic alcohols over highly ordered Pd/meso-Al2 O3 catalysts

Highly ordered mesoporous alumina was prepared via evaporation induced self assembly and was impregnated to afford a family of Pd/meso-Al2O3 catalysts for the aerobic selective oxidation (selox) of allylic alcohols under mild reaction conditions. CO chemisorption and XPS identify the presence of highly dispersed (0.9–2 nm) nanoparticles comprising heavily oxidised PdO surfaces, evidencing a strong palladium-alumina interaction. Surface PdO is confirmed as the catalytically active phase responsible for allylic alcohol selox, with initial rates for Pd/meso-Al2O3 far exceeding those achievable for palladium over either amorphous alumina or mesoporous silica supports. Pd/meso-Al2O3 is exceptionally active for the atom efficient selox of diverse allylic alcohols, with activity inversely proportional to alcohol mass.

Enhanced selective aerobic alcohol oxidation through nanoengineered catalyst supports

The selective conversion of alcohols to their carbonyl derivatives is a critical step towards a sustainable chemical industry. Heterogeneous Pd catalysts represent some of the most active systems known, even so further studies into the active species and role of support are required. Through controlling support mesostructure, using non-interconnected SBA-15 and interlinked SBA-16 and KIT-6, we have evaluated the role of pore architecture on supported Pd nanoparticles and their subsequent activity for liquid phase aerobic allylic alcohol selective oxidation.[1,2] These synthesised silica supports exhibit high surface areas (>800 m2g-1), and similar mesopore diameters (3.5 to 5 nm), but differ in their pore connectivity and arrangement; p6mm (SBA-15), I3mm (SBA-16) and I3ad (KIT-6). When evaluated alongside commercial non-mesoporous silica (200 m2 g-1) they promote enhanced Pd dispersion with interpenetrating assemblies providing further elevation. Macropore introduction into SBA-15, producing a hierarchical macro-mesoporous silica (MM-SBA-15), allows control over mesopore length and accessibility which escalates Pd distribution to levels akin to KIT-6 and SBA-16. Controlling dispersion, and likewise nanoparticle size, is thus facilitated through the choice of support and additionally Pd loading, with cluster sizes spanning 3.2 to 0.8 nm. X-ray spectroscopies indicate nanoparticles are PdO terminated with the oxide content a function of dispersion. Kinetic studies allude to surface PdO being the active site responsible, with a constant TOF observed, independent of loading and support. This confirms activity is governed by PdO density, whilst also overruling internal mass diffusion constraints. MM-SBA-15 facilitates superior activity and TOFs for long chain acyclic terpene alcohols due to reduced internal mass transport constraints.

Hierarchically ordered nanoporous Pd/SBA-15 catalyst for the aerobic selective oxidation of sterically challenging allylic alcohols

The utility of a hierarchically ordered nanoporous SBA-15 architecture, comprising 270 nm macropores and 5 nm mesopores (MM-SBA-15), for the catalytic aerobic selective oxidation of sterically challenging allylic alcohols is shown. Detailed bulk and surface characterization reveals that incorporation of complementary macropores into mesoporous SBA-15 enhances the dispersion of sub 2 nm Pd nanoparticles and thus their degree of surface oxidation. Kinetic profiling reveals a relationship between nanoparticle dispersion and oxidation rate, identifying surface PdO as the catalytically active phase. Hierarchical nanoporous Pd/MM-SBA-15 outperforms mesoporous analogues in allylic alcohol selective oxidation by (i) stabilizing PdO nanoparticles and (ii) dramatically improving in-pore diffusion and access to active sites by sesquiterpenoid substrates such as farnesol and phytol. © 2013 American Chemical Society.

True liquid crystal templating of SBA-15 with reduced microporosity

Mesoporous silica SBA-15 was synthesised by the true liquid crystal templating method, yielding a material with reduced microporosity compared with that produced by the more conventional liquid crystal templating route. Further advancements allow the generation of metal nanoparticle-doped SBA-15 materials with well-defined metal particle sizes, which posses potential as catalytic systems. © 2013 Elsevier Inc. All rights reserved.