Dry gel conversion of organosilane templated mesoporous silica: from amorphous to crystalline catalysts for benzene oxidation

Mesoporous silica grown using [3-(trimethoxysilyl)propyl]octadecyldimethylammonium chloride as the mesoporogen in the presence of Fe and Al is X-ray amorphous, but contains very small domains with features of MFI zeolite as evidenced by IR and Raman spectroscopy. When applied as a catalyst, this amorphous sample shows good performance in the selective oxidation of benzene using nitrous oxide. Addition of tetrapropylammonium as structure directing agent to the as-synthesized mesoporous silica and subsequent dry gel conversion results in the formation of hierarchical Fe/ZSM-5 zeolite. During dry gel conversion the wormhole mesostructure of the initial material is completely lost. A dominant feature of the texture after crystallization is the high interconnectivity of micropores and mesopores. Substantial redistribution of low-dispersed Fe takes place during dry gel conversion towards highly dispersed isolated Fe species outside the zeolite framework. The catalytic performance in the oxidation of benzene to phenol of these highly mesoporous zeolites is appreciably higher than that of the parent material.

Isomorphism between ice and silica

Both ice and silica crystallize into solid-state structures composed of tetrahedral building units that are joined together to form an infinite four-connected net. Mathematical considerations suggest that there is a vast number of such nets and thus potential crystal structures. It is therefore perhaps surprising to discover that, despite the differences in the nature of interatomic interactions in these materials, a fair number of commonly observed ice and silica phases are based on common nets. Here we use computer simulation to investigate the origin of this symmetry between the structures formed for ice and silica and to attempt to understand why it is not complete. We start from a comparison of the dense phases and then move to the relationship between the different open (zeolitic and clathratic) structures formed for both materials. We show that there is a remarkably strong correlation between the energetics of isomorphic silica and water ice structures and that this correlation arises because of the strong link between the total energy of a material and its local geometric features. Finally, we discuss a number of as yet unsynthesized low-energy structures which include a phase of ice based on quartz, a silica based on the structure of ice VI, and an ice clathrate that is isomorphic to the silicate structure nonasil.

DRIFTS/MS/Isotopic Labeling Study on the NO-Moderated Decomposition of a Silica-Supported Nickel Nitrate Catalyst Precursor

In the preparation of silica-supported nickel oxide from nickel nitrate impregnation and drying, the replacement of the traditional air calcination step by a thermal treatment in 1% NO/Ar prevents agglomeration, resulting in highly dispersed NiO. The mechanism by which NO prevents agglomeration was investigated by using combined in situ diffuse reflectance infrared fourier transform (DRIFT) spectroscopy and mass spectrometry (MS). After impregnation and drying, a supported nickel hydroxynitrate phase with composition Ni(3)(NO(3))(2)(OH)(4) had been formed. Comparison of the evolution of the decomposition gases during the thermal decomposition of Ni(3)(NO(3))(2)(OH)(4) in labeled and unlabeled NO and O(2) revealed that NO scavenges oxygen radicals, forming NO(2). The DRIFT spectra revealed that the surface speciation evolved differently in the presence of NO as compared with in O(2) or Ar. It is proposed that oxygen scavenging by NO depletes the Ni(3)(NO(3))(2)(OH)(4) phase of nitrate groups, creating nucleation sites for the formation of NiO, which leads to very small (similar to 4 nm) NiO particles and prevents agglomeration.

Development of a heterogeneous catalyst for lignocellulosic biomass conversion:Glucose dehydration by metal chlorides in a silica-supported ionic liquid layer

An attempt is made to immobilize the homogeneous metal chloride/EMIMCl catalyst for glucose dehydration to 5-hydroxymethylfurfural. To this end, ionic liquid fragments were grafted to the surface of SBA-15 to generate a heterogenized mimick of the homogeneous reaction medium. Despite a decrease in the surface area, the ordered mesoporous structure of SBA-15 was largely retained. Metal chlorides dispersed in such ionic liquid film are able to convert glucose to HMF with much higher yields as is possible in the aqueous phase. The reactivity order CrCl > AlCl > CuCl > FeCl is similar to the order in the ionic liquid solvent, yet the selectivity are lower. The HMF yield of the most promising CrCl-Im-SBA-15 can be improved by using a HO:DMSO mixture as the reaction medium and a 2-butanol/MIBK extraction layer. Different attempts to decrease metal chloride leaching by using different solvents are described. © 2013 American Institute of Chemical Engineers Environ Prog.

Adsorption Study using Optimised 3D Organised Mesoporous Silica Coated with Fe and Al Oxides for Specific As(III) and As(V) Removal from Contaminated Synthetic Groundwater

This work presents the possibility of optimising 3D Organised Mesoporous Silica (OMS) coated with both iron and aluminium oxides for the optimal removal of As(III) and As(V) from synthetic contaminated water. The materials developed were fully characterised and were tested for removing arsenic in batch experiments. The effect of total Al to Fe oxides coating on the selective removal of As(III) and As(V) was studied. It was shown that 8% metal coating was the optimal configuration for the coated OMS materials in removing arsenic. The effect of arsenic initial concentration and pH, kinetics and diffusion mechanisms was studied, modelled and discussed. It was shown that the advantage of an organised material over an un-structured sorbent was very limited in terms of kinetic and diffusion under the experimental conditions. It was shown that physisorption was the main adsorption process involved in As removal by the coated OMS. Maximum adsorption capacity of 55 mg As(V).g-1 was noticed at pH 5 for material coated with 8% Al oxides while 35 mg As(V).g-1 was removed at pH 4 for equivalent material coated with Fe oxides.

Marine Biosilica as a Tool to Understand the Therapeutic Benefit of Silica in Bone Repair

It is widely accepted that silicon-substituted materials enhance bone formation, yet the mechanism by which this occurs is poorly understood. This work investigates the potential of using diatom frustules to answer on fundamental questions surrounding the role of silica in bone healing. Biosilica with frustules 20m were isolated from Cyclotella meneghiniana a unicellular microalgae that was sourced from the Mississippi River, USA. Silanisation chemistry was used to modify the surface of C. meneghiniana with amine (–NH2) and thiol (–SH) terminated silanes. Untreated frustules and both functionalised groups were soaked in culture medium for 24hrs. Following the culture period, frustules were separated from the conditioned medium by centrifugation and both were tested separately in vitro for cytotoxicity using murine-monocyte macrophage (J774) cell line. Cytotoxicity was measured using LDH release to measure damage to cell membrane, MTS to measure cell viability and live-dead staining. The expression and release of pro-inflammatory cytokines (IL-6 and TNF) were measured using ELISA. Our results found that diatom frustules and those functionalised with amino groups showed no cytotoxicity or elevated cytokine release. Diatom frustules functionalised with thiol groups showed higher levels of cytotoxicity. Diatom frustules and those functionalised with amino groups were taken forward to an in vivo mouse toxicity model, whereby the immunological response, organ toxicity and route of metabolism/excretion of silica were investigated. Histological results showed no organ toxicity in any of the groups relative to control. Analysis of blood Si levels suggests that modified frustules are metabolised quicker than functionalised frustules, suggesting that physiochemical attributes influence their biodistribution. Our results show that diatom frustules are non cytotoxic and are promising materials to better understand the role of silica in bone healing.