Organometallic precursors for pillared clay synthesis

The synthetic hectorite, laponite has been used within the paper industry to produce mildly conducting paper for use in electrographic printing. The aim of this research was to modify laponite in order to improve the electrical conductivity. In a continuation of a previous investigation involving organotin intercalation of laponite, the organotin precursor (p-CH3,OC6H4)4Sn was synthesised and characterised using Mass Spectroscopy, Infrared Spectroscopy and elemental analysis. Results of intercalation with this compound and a range of organobismuth and organoantimony compounds suggested that a halide content within the precursor was necessary for improvement in conductivity to be observed. Organometallic intercalation of a range of organotellurium compounds with laponite provided evidence that a hydrolysis reaction on the clay surface followed by the release of hydrochloric acid was an important first step if a reaction was to occur with the clay. Atomic Absorption Spectroscopy studies have shown that the acid protons underwent exchange with the interlayer sodium ions in the clay to varying degrees. Gas-liquid Chromatography and Infrared Spectroscopy revealed that the carbon-tellurium bond remained intact. Powder X-ray diffraction revealed that there had been no increase in the basal spacing. The a.c. conductivity of the modified clays in the form of pressed discs was studied over a frequency range of 12Hz - 100kHz using two electrode systems, silver paste and stainless steel. The a.c. conductivity consists of two components, ionic and reactive. The conductivity of laponite was increased by intercalation with organometallic compounds. The most impressive increase was gained using the organotellurium precursor (p-CH3OC6H4)2TeCl2. Conductivity investigations using the stainless steel electrode where measurements are made under pressure showed that in the case of laponite, where poor particle-particle contact exists at ambient pressure, there is a two order of magnitude increase in the measured a.c. conductivity. This significant increase was not seen in modified laponites where the particle-particle contact had already been improved upon. Investigations of the clay surface using Scanning Electron Microscopy suggested that the improvement in particle-particle contact is the largest factor in the determination of the conductivity. The other important factor is the nature and the concentration of the interlayer cations. A range of clays were synthesised in order to increase the concentration of sodium interlayer cations. A sol-gel method was employed to carry out these syntheses. A conductivity evaluation showed that increasing the concentration of the sodium cations within the clay led to an increase in the conductivity.

Polymer-peptide conjugate hydrogels:towards controlled drug delivery

Peptide-based materials exhibit remarkable supramolecular self-assembling behavior, owing to their overwhelming propensity to from hierarchical structures from a-helices and ß-sheets. Coupling a peptide sequence to a synthetic polymer chain allows greater control over the final physical properties of the supermolecular material. So-called ‘polymer-peptide conjugates’ can be used to create biocompatible hydrogels which are held together by reversible physical interactions. Potentially, the hydrogels can be loaded with aqueous-based drug molecules, which can be injected into targeted sites in the body if they can exhibit a gel-sol-gel transition under application and removal of a shear force. In this review, we introduce this topic to readers new to the field of polymer-peptide conjugates, discussing common synthetic strategies and their self-assembling behavior. The lack of examples of actual drug delivery applications from polymer-peptide conjugates is highlighted in an attempt to incite progress in this area.

Cobalt promoted TiO2/GO for the photocatalytic degradation of oxytetracycline and Congo Red

A family of titania derived nanocomposites synthesized via sol-gel and hydrothermal routes exhibit excellent performance for the photocatalytic degradation of two important exemplar water pollutants, oxytetracycline and Congo Red. Low loadings of Co3O4 nanoparticles dispersed over the surfaces of anatase TiO2 confer visible light photoactivity for the aqueous phase decomposition of organics through the resulting heterojunction and reduced band gap. Subsequent modification of these Co3O4/TiO2 composites by trace amounts of graphene oxide nanosheets in the presence of a diamine linker further promotes both oxytetracycline and Congo Red photodegradation under simulated solar and visible irradiation, through a combination of enhanced photoresponse and consequent radical generation. Radical quenching and fluorescence experiments implicate holes and hydroxyl radicals as the respective primary and secondary active species responsible for oxidative photodegradation of pollutants.

Identifying the active phase in Cs-promoted MgO nanocatalysts for triglyceride transesterification

Background: Biodiesel is a clean-burning, renewable and biodegradable diesel fuel substitute derived from animal fats and plant oils, which may play an important role in replacing diminishing fossil fuel reserves and combating climate change. Conventional biodiesel production uses soluble base catalysts, such as Na or K alkoxides, to convert oils into fuel, and as a result requires energy intensive aqueous quench cycles to isolate the biodiesel product. Results: Cs-doping nanoparticulate MgO, prepared via a novel, supercritical sol-gel method, yields a solid base catalyst with improved activity for the transesterification of pure triacylglycerides (TAGs) and olive oil. Conclusion: Here, X-ray absorption spectroscopy (XAS) is used to probe the local chemical environment of Cs atoms in order to identify the nature of the catalytically active species as CsMg(CO)(HO). © 2013 Society of Chemical Industry.

Structure-sensitive biodiesel synthesis over MgO nanocrystals

Size-controlled MgO nanocrystals were synthesised via a simple sol-gel method and their bulk and surface properties characterised by powder XRD, HRTEM and XPS. Small, cubic MgO single crystals, generated by low temperature processing, expose weakly basic (100) surfaces. High temperature annealing transforms these into large, stepped cuboidal nanoparticles of periclase MgO which terminate in more basic (110) and (111) surfaces. The size dependent evolution of surface electronic structure correlates directly with the associated catalytic activity of these MgO nanocrystals towards glyceryl tributyrate transesterification, revealing a pronounced structural preference for (110) and (111) facets. © 2009 The Royal Society of Chemistry.

Size-controlled TiO2 nanoparticles on porous hosts for enhanced photocatalytic hydrogen production

Nanocystalline TiO2 particles were successfully synthesized on porous hosts (SBA-15 and ZSM-15) via a sol-gel impregnation method. Resulting nanocomposites were characterized by XRD, TEM, BET surface analysis, Raman and UV-vis diffuse reflectance spectroscopy, and their photocatalytic activity for H2 production evaluated. XRD evidences the formation of anatase nanoparticles over both ZSM-5 and SBA-15 porous supports, with TEM highlighting a strong particle size dependence on titania precursor concentration. Photocatalytic activities of TiO2/ZSM-5 and TiO2/SBA-15 composites were significantly enhanced compared to pure TiO2, owing to the smaller TiO2 particle size and higher surface area of the former. TiO2 loadings over the porous supports and concomitant photocatalytic hydrogen production were optimized with respect to light absorption, available surface reaction sites and particle size. 10%TiO2/ZSM-5 and 20%TiO2/SBA-15 proved the most active photocatalysts, exhibiting extraordinary hydrogen evolution rates of 10,000 and 8800μmolgTiO2 -1 h-1 under full arc, associated with high external quantum efficiencies of 12.6% and 5.4% respectively under 365nm irradiation.

Optimising catalytic properties of supported sulfonic acid catalysts

Siliceous mesoporous molecular sieves (SBA-15) have been functionalised with propylsulfonic acid groups by both co-condensing 3-mercaptopropyltrimethoxysilane with the solid at the synthesis (sol-gel) stage and by grafting the same compound to pre-prepared SBA-15, followed, in both cases, by oxidation to sulfonic acid. The acidic and catalytic properties of the supported sulfonic acids prepared in the two ways have been compared, using ammonia adsorption calorimetry and the benzylation reaction between benzyl alcohol and toluene. Using a combination of X-ray photoelectron spectroscopy and other analytical techniques, the level of functionalisation and the extent of subsequent oxidation of tethered thiol to sulfonic acid, both in the bulk and close to the surface of SBA-15 particles, have been assessed. The research shows that the co-condensing route leads to higher levels of functionalisation than the grafting route. The extent of oxidation of added thiol to acid groups is similar using the two routes, about 70% near the surface and only 50% in the bulk. Comparison is made with polymer supported sulfonic acid catalysts, Amberlysts 15 and 35, and Nafion. Nafion shows the highest acid strength and the highest specific catalytic activity of all materials studied. Amongst the other materials, average acid strengths are broadly similar but there appears to be a relationship between the concentration of acid sites on the catalysts and their specific activity in the benzylation reaction. A model is proposed to explain this, in which clustering of sulfonic acid groups, even to a small extent, leads to disproportionately enhanced catalytic activity. © 2009 Elsevier B.V. All rights reserved.

Novel sol–gel preparation of (P2O5)0.4–(CaO)0.25–(Na2O)X–(TiO2)(0.35−X) bioresorbable glasses (X = 0.05, 0.1, and 0.15)

Quaternary phosphate-based glasses in the P2O5–CaO–Na2O–TiO2 system with a fixed P2O5 and CaO content of 40 and 25 mol% respectively have been successfully synthesised via sol–gel method and bulk, transparent samples were obtained. The structure, elemental proportion, and thermal properties of stabilised sol–gel glasses have been characterised using X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), 31P nuclear magnetic resonance (31P NMR), titanium K-edge X-ray absorption near-edge structure (XANES), fourier transform infrared (FTIR) spectroscopy, and differential thermal analysis (DTA). The XRD results confirmed the amorphous nature for all stabilized sol–gel derived glasses. The EDX result shows the relatively low loss of phosphorus during the sol–gel process and Ti K-edge XANES confirmed titanium in the glass structure is in mainly six-fold coordination environment. The 31P NMR and FTIR results revealed that the glass structure consist of mainly Q1 and Q2 phosphate units and the Ti4+ cation was acting as a cross-linking between phosphate units. In addition DTA results confirmed a decrease in the glass transition and crystallisation temperature with increasing Na2O content. Ion release studies also demonstrated a decrease in degradation rates with increasing TiO2 content therefore supporting the use of these glasses for biomedical applications that require a degree of control over glass degradation. These sol–gel glasses also offer the potential to incorporate proactive molecules for drug delivery application due to the low synthesis temperature employed.

Bioactive organic/inorganic hybrids with improved mechanical performance

New sol-gel functionalized poly-ethylene glycol (PEGM)/SiO2-CaO hybrids were prepared with interpenetrating networks of silica and PEGM through the formation of Si-O-Si bonds. Bioactive and mechanical properties were investigated for a series of hybrids containing varying organic/inorganic ratios and PEG molecular weights. In contrast to the unmodified PEG/SiO2-CaO hybrids, which rapidly dissolved and crumbled, the epoxy modified hybrids exhibited good mechanical properties and bioactivity. The compressive strength and Young's modulus were greater for higher molecular weight PEGM hybrids (PEGM600 compared to PEGM300). Compressive strengths of 138 MPa and 81 MPa were found for the 50: 50 and 60: 40 organic/inorganic hybrid samples respectively, which are comparable with cortical bone. Young's modulus values of ∼800 MPa were obtained for the 50 : 50 and 60 : 40 organic/inorganic hybrids. Bioactivity tests were conducted by immersing the hybrids into simulated body fluid and observing the formation of apatite. Apatite formation was observed within 24 hours of immersion. PEGM600 hybrids showed enhanced apatite formation compared to PEGM300 hybrids. Increased apatite formation was observed with increasing organic/inorganic ratio. 70 : 30 and 60 : 40 hybrids exhibited the greatest apatite formation. All PEGM hybrids samples had good cell viability and proliferation. The 60 : 40 PEGM600 hybrids displayed the optimal combination of bioactivity and mechanical strength. The bioactivity of these hybrids, combined with the enhanced mechanical properties, demonstrate that these materials have significant potential for bone regeneration applications.

A hydrothermally stable transition alumina by condensation-enhanced self-assembly and pyrolysis crystallization:application in the steam reforming of methane

The preparation of a steam-based hydrothermally stable transition alumina is reported. The gel was derived from a synthetic sol-gel route where Al-tri-sec-butoxide is hydrolysed in the presence of a non-ionic surfactant (EO20PO70EO20), HCl as the catalyst and water (H2O/Al = 6); the condensation was enhanced by treating the hydrolysed gel with tetrabutylammonium hydroxide (TBAOH), after which it was dried at 60 °C by solvent evaporation. The so-obtained mesophase was crystallized under argon at 1200 °C (1 h) producing a transition alumina containing δ/α, and possibly θ, alumina phases. Due to its surface acidity, the pyrolysis conditions transform the block copolymer into a cross-linked char structure that embeds the alumina crystallites. Calcination at 650 °C generates a fully porous material by burning the char; a residual carbon of 0.2 wt.% was found, attributed to the formation of surface (oxy)carbides. As a result, this route produces a transition alumina formed by nanoparticles of about 30 nm in size on average, having surface areas in the range of 59-76 m2 g-1 with well-defined mesopores centered at 14 nm. The material withstands steam at 900 °C with a relative surface area rate loss lower than those reported for δ-aluminas, the state-of-the-art MSU-X γ-alumina and other pure γ-aluminas. The hydrothermal stability was confirmed under relevant CH4 steam reforming conditions after adding Ni; a much lower surface area decay and higher CH4 conversion compared to a state-of-the-art MSU-X based Ni catalyst were observed. Two effects are important in explaining the properties of such an alumina: the char protects the particles against sintering, however, the dominant effect is provided by the TBAOH treatment that makes the mesophase more resistant to coarsening and sintering. This journal is © the Partner Organisations 2014.

Condensation-enhanced self-assembly as a route to high surface area α-aluminas

High surface area nanosized α-alumina has been obtained by thermally treating a sol-gel-derived mesophase at 1200 C; the mesophase was synthesized by a sol-gel route involving evaporation induced self-assembly (EISA) of a hydrolyzed gel from Al-tri-sec-butoxide in s-BuOH in the presence of a nonionic surfactant (EO20PO70EO20), HCl as catalyst, and water (H2O/Al = 6). The activated material renders moderate surface areas of about 8.4-10 m2 g-1, associated with significant crystallite coarsening. The key aspect to produce smaller crystallites is making the mesophase more resistant to coarsening. This was achieved by enhancing the condensation step by treating the hydrolyzed gel with tetrabutyl ammonium hydroxide (TBAOH) before evaporation. The characteristics of the mesophase indicate condensation of the primary particles with less AlO5 unsaturated sites, at the expense of a lower solid yield due to small crystallites dissolution. The activated TBAOH condensed EISA material is composed of α-alumina aggregated crystallites of about 60-100 nm, and the material possesses surface areas ranging from 16 to 24 m2 g -1 due to the improved resistance to coarsening. At least two aspects are suggested to play a role in this. The worm-hole morphology of the mesophase aggregates yields high particle coordination, which favors densification rather than coarsening. Furthermore, the decrease of the AlO5 defect sites by the TBAOH condensation makes the mesophase less reactive and consequently more resistant to coarsening. © 2013 American Chemical Society.

Low temperature sintering semiconducting barium strontium titanate

Low temperature sintering has become a very important research area in ceramics processing and sintering as a promising process to obtain grain size below 100nm. For electronic ceramics, low temperature sintering is particularly difficult, because not only the required microstructure but also the desired electronic properties should be obtained. In this dissertation, the effect of liquid sintering aids and particle size (micrometer and nanometer) on sintering temperature and Positive Temperature Coefficient Resistivity (PTCR) property are investigated for Ba1-xSrxTiO3 (BST) doped with 0.2-0.3mol% Sb3+ (x = 0.1, 0.2, 0.3, 0.4 and 0.5). Different sintering aids with low melting point are used as sintering aids to decrease the sintering temperature for micrometer size BST particles. Micrometer size and nanometer size Ba1-xSrxTiO 3 (BST) particles are used to demonstrate the particle size effect on the sintering temperature for semiconducting BST. To reduce the sintering temperature, three processes are developed, i.e. 1 using sol-gel nanometer size Sb3+ doped powders with a sintering aid; 2 using micrometer size powders plus a sintering aid; and 3 using nanometer size Sb3+ doped powders with sintering aids. Grain size effect on PTCR characteristics is investigated through comparison between micrometer size powder sintered pellets and nanometer size powder sintered pellets. The former has lower resistivity at temperatures below the Curie temperature (Tc) and high resistivity at temperatures above the Curie temperature (Tc) along with higher ρ max/ρmin ratio (ρmax is the highest resistivity at temperatures above Tc, ρmin is the lowest resistivity at temperatures below Tc), whereas the latter has both higher ρ max and ρmin. Also, ρmax/ρmin is smaller than that of pellets with larger grain size. The reason is that the solid with small grain size has more grain boundaries than the solid with large grain size. The contribution z at room temperature and high temperature and a lower ρmax/ρmin ratio value.

Improved sampling, pre-concentration, and detection of hidden explosives and illicit drugs by a novel solid phase microextraction geometry coupled to ion mobility spectrometry

The 9/11 Act mandates the inspection of 100% of cargo shipments entering the U.S. by 2012 and 100% inspection of air cargo by March 2010. So far, only 5% of inbound shipping containers are inspected thoroughly while air cargo inspections have fared better at 50%. Government officials have admitted that these milestones cannot be met since the appropriate technology does not exist. This research presents a novel planar solid phase microextraction (PSPME) device with enhanced surface area and capacity for collection of the volatile chemical signatures in air that are emitted from illicit compounds for direct introduction into ion mobility spectrometers (IMS) for detection. These IMS detectors are widely used to detect particles of illicit substances and do not have to be adapted specifically to this technology. For static extractions, PDMS and sol-gel PDMS PSPME devices provide significant increases in sensitivity over conventional fiber SPME. Results show a 50–400 times increase in mass detected of piperonal and a 2–4 times increase for TNT. In a blind study of 6 cases suspected to contain varying amounts of MDMA, PSPME-IMS correctly detected 5 positive cases with no false positives or negatives. One of these cases had minimal amounts of MDMA resulting in a false negative response for fiber SPME-IMS. A La (dihed) phase chemistry has shown an increase in the extraction efficiency of TNT and 2,4-DNT and enhanced retention over time. An alternative PSPME device was also developed for the rapid (seconds) dynamic sampling and preconcentration of large volumes of air for direct thermal desorption into an IMS. This device affords high extraction efficiencies due to strong retention properties under ambient conditions resulting in ppt detection limits when 3.5 L of air are sampled over the course of 10 seconds. Dynamic PSPME was used to sample the headspace over the following: MDMA tablets (12–40 ng detected of piperonal), high explosives (Pentolite) (0.6 ng detected of TNT), and several smokeless powders (26–35 ng of 2,4-DNT and 11–74 ng DPA detected). PSPME-IMS technology is flexible to end-user needs, is low-cost, rapid, sensitive, easy to use, easy to implement, and effective. ^

Improved dynamic headspace sampling and detection using capillary microextraction of volatiles coupled to gas chromatography mass spectrometry

Sampling and preconcentration techniques play a critical role in headspace analysis in analytical chemistry. My dissertation presents a novel sampling design, capillary microextraction of volatiles (CMV), that improves the preconcentration of volatiles and semivolatiles in a headspace with high throughput, near quantitative analysis, high recovery and unambiguous identification of compounds when coupled to mass spectrometry. The CMV devices use sol-gel polydimethylsiloxane (PDMS) coated microglass fibers as the sampling/preconcentration sorbent when these fibers are stacked into open-ended capillary tubes. The design allows for dynamic headspace sampling by connecting the device to a hand-held vacuum pump. The inexpensive device can be fitted into a thermal desorption probe for thermal desorption of the extracted volatile compounds into a gas chromatography-mass spectrometer (GC-MS). The performance of the CMV devices was compared with two other existing preconcentration techniques, solid phase microextraction (SPME) and planar solid phase microextraction (PSPME). Compared to SPME fibers, the CMV devices have an improved surface area and phase volume of 5000 times and 80 times, respectively. One (1) minute dynamic CMV air sampling resulted in similar performance as a 30 min static extraction using a SPME fiber. The PSPME devices have been fashioned to easily interface with ion mobility spectrometers (IMS) for explosives or drugs detection. The CMV devices are shown to offer dynamic sampling and can now be coupled to COTS GC-MS instruments. Several compound classes representing explosives have been analyzed with minimum breakthrough even after a 60 min. sampling time. The extracted volatile compounds were retained in the CMV devices when preserved in aluminum foils after sampling. Finally, the CMV sampling device were used for several different headspace profiling applications which involved sampling a shipping facility, six illicit drugs, seven military explosives and eighteen different bacteria strains. Successful detection of the target analytes at ng levels of the target signature volatile compounds in these applications suggests that the CMV devices can provide high throughput qualitative and quantitative analysis with high recovery and unambiguous identification of analytes.

Low Temperature Sintering Semiconductive Barium Strontium Titanate

Low temperature sintering has become a very important research area in ceramics processing and sintering as a promising process to obtain grain size below 100nm. For electronic ceramics, low temperature sintering is particularly difficult, because not only the required microstructure but also the desired electronic properties should be obtained. In this dissertation, the effect of liquid sintering aids and particle size (micrometer and nanometer) on sintering temperature and Positive Temperature Coefficient Resistivity (PTCR) property are investigated for Ba1-xSrxTiO3 (BST) doped with 0.2-0.3mol% Sb3+ (x = 0.1,0.2,0.3,0.4 and 0.5). Different sintering aids with low melting point are used as sintering aids to decrease the sintering temperature for micrometer size BST particles. Micrometer size and nanometer size Ba1-xSrxTiO3 (BST) particles are used to demonstrate the particle size effect on the sintering temperature for semiconducting BST. To reduce the sintering temperature, three processes are developed, i.e. 1 using sol-gel nanometer size Sb3+ doped powders with a sintering aid; 2 using micrometer size powders plus a sintering aid; and 3 using nanometer size Sb3+ doped powders with sintering aids. Grain size effect on PTCR characteristics is investigated through comparison between micrometer size powder sintered pellets and nanometer size powder sintered pellets. The former has lower resistivity at temperatures below the Curie temperature (Tc) and high resistivity at temperatures above the Curie temperature (Tc) along with higher ñmax/ñmin ratio (ñmax is the highest resistivity at temperatures above Tc, ñmin is the lowest resistivity at temperatures below Tc), whereas the latter has both higher ñmax and ñmin. Also, ñmax/ñmin is smaller than that of pellets with larger grain size. The reason is that the solid with small grain size has more grain boundaries than the solid with large grain size. The contribution z at room temperature and high temperature and a lower ñmax/ñmin ratio value.