Structural and Catalytic Studies of a Trimethyltin Vanadate Coordination Polymer

The organotin vanadate [Me₃SnVO₃] (1) has been prepared and characterised in the solid state by powder X-ray diffraction (XRD), thermogravimetric analysis, multinuclear magic-angle spinning (MAS) NMR, IR and Raman spectroscopy. The phase purity and structure of microcrystalline 1 were confirmed by carrying out a full Rietveld structural refinement at ambient temperature and from conventional powder XRD. ⁵¹V and ¹¹⁹Sn MAS NMR data for compound 1 were in agreement with the predicted structure, showing two equally-abundant, nonequivalent Me₃Sn groups and two equally-abundant, nonequivalent vanadium atoms. The compound was applied as a catalyst for the liquid-phase epoxidation of olefins at 55 °C using tert-butyl hydroperoxide (tBuOOH) as the oxidant. The reaction rate for the different substrates followed the order cis-cyclooctene > (R)-(+)-limonene ≅ trans-2-octene > cyclododecene > styrene > 1-octene; the corresponding epoxides were the only observed products. Leaching tests indicated that the catalytic epoxidation of cyclooctene was mainly heterogeneous in nature. This paper is dedicated to Professor Ian Manners and his scientific accomplishments.     

A simple but sound approach for processing crystal growth kinetic data

The effects of common data smoothing techniques, on the estimating of the kinetic and thermodynamic parameters of the crystal growth process, were discussed in the light of birth and spread model. Adoption of the moving average, and filtration caused a noticeable misunderstanding of the real ruling growth mechanism, especially, during the early period of the crystal growth.In this work, a MATLAB routine was developed with standard, and reliable method to treat the prolonged concentration-time data sets, as obtained from continuous recording of refractometric °Brix readings of pure sucrose solutions in laboratory batch crystallization process. The method consists of finding the median of the residence time for every °Brix concentration, with and without interference of previous and post readings. In addition to 30% reduction in the evaluated interfacial free energies, up to 5-folds of increase in the estimates of the overall kinetic coefficients were reported using the common smoothing techniques instead of the proposed routine.     

Catalytic conversion ofHevea brasiliensis andVirola sebifera oils to hydrocarbon fuels

Catalytic hydrocracking ofHevea brasiliensis (Seringa) andVirola sebifera (Ucuuba) oils was carried out in the presence of a NiMo/Al₂O₃ catalyst sulfidizedin situ with elemental sulfur at 360°C. The initial pressure of hydrogen was 140 bars. Conversions of nearly 100% of the vegetable oils were achieved. The compositions of the liquid fuels were studied in detail by gas chromatography/mass spectrometry. The main products were found to be alkanes, cycloalkanes, aromatics and carboxylic acids.     

Ethanol oxidation on a high temperature PBI-based DEFC using Pt/C, PtRu/C and Pt3Sn/C as catalysts

A high temperature ethanol-fed polymer electrolyte membrane fuel cell has been implemented by using H₃PO₄-doped m-polybenzimidazole as polymeric electrolyte. Commercial Pt/C, PtRu/C and Pt₃Sn/C catalysts are used in the anode. The performance was assessed in terms of polarization curves at different temperatures, feeding the cell with a high concentration ethanol solution (water/ethanol mass ratio of 2). The product distribution was measured with the support of a gas chromatograph. The use of bimetallic catalysts increased the current density. PtRu/C showed the best performance up to 175 °C, but it is outperformed by Pt₃Sn/C at 200 °C. In terms of oxidation products, higher temperatures and current densities favour the oxidation of ethanol. However, Pt₃Sn/C promoted the generation of more oxidized products compared to PtRu/C (in which most of the ethanol is oxidized to acetaldehyde), especially at high temperature. This accounts for the large current density. In terms of complete oxidation of ethanol to CO₂, Pt/C was by far the most efficient catalyst for C–C scission, achieving percentages of 56 % of CO₂, although operating above 175 °C dramatically boosted an undesirable methanation process that slashed the efficiency. The combination of fuel cell results and product distribution helped to suggest the different oxidation routes on the surface of the different catalysts.     

Effects of different surface treatments of zirconia on the bond strength of self-adhesive resinous cement

Purpose: The aim of this study was to evaluate the effects of different zirconia surface treatments on the bond strength of two self-adhesive resinous cements (SARC).

Methods: Two hundred and eight cylindrical specimens were obtained from Y-TZP zirconia (half with diameter 3.2 mm and half with 4.8 mm). After sintering and polishing, specimens were divided into four groups (n = 26), according to surface treatment: Control (no treatment); Sandblasting (Al₂O₃ particles); Rocatec (Al₂O₃ particles, tribochemical silica coating and silane application); Laser (Nd: YAG laser: 20 Hz, 100 mJ, 0.2 J/cm²). The surface roughness (Ra) was evaluated after the surface treatments, and the groups were divided into two subgroups (n = 13), according to the SARC tested: RelyX U200 and Bifix SE. The 2.2-mm cylinders were bonded to 4.8-mm cylinders and stressed until failure under shear using a universal testing machine. Bond strength and Ra were analyzed using ANOVA, and Tukey’s test (α = 0.05).

Results: Surface treatment was significant (p < 0.0001), but cement type (p = 0.73) was not. Related to roughness, significant differences were found for the treatment type (p < 0.0001), with laser being the treatment with higher Ra values.

Conclusions: Nd:YAG laser produced a rougher surface and a higher bond strength compared with sandblasting, silicatization, and control groups.     

Graphene for tough and electroconductive alumina ceramics

A simple, fast and upscalable method is described to produce graphene/alumina (G/Al₂O₃) composites by spark plasma sintering (SPS) with a significant improvement on both mechanical and electrical properties of monolithic Al₂O₃. Graphene oxide (GO) was mixed with Al₂O₃ using a colloidal method obtaining an excellent dispersion of GO in the alumina matrix. The material was consolidated by SPS that allowed, in one-step, the in situ reduction of the GO during the sintering process. A detailed Raman analysis was found to be very useful to study the orientation of the graphene in the composite and to evaluate and optimise its thermal reduction. Graphene platelets acted as elastic bridges avoiding crack propagation and providing this material with a crack bridging reinforcement mechanism. A very low graphene loading (0.22 wt%) led to a 50% improvement on the mechanical properties of the alumina and to an increase of the electrical conductivity up to eight orders of magnitude.     

Chlorinated Polycyclic Aromatic Hydrocarbons Associated with Drinking Water Disinfection: Synthesis,Formation under Aqueous Chlorination Conditions and Genotoxic Effects

Polycyclic aromatic hydrocarbons (PAHs) are among the most persistent and toxic organic micropollutants present in water and several of them are mutagenic and carcinogenic. Although it has been shown that chlorinated derivatives of PAHs (Cl-PAHs) may be formed during the water chlorination procedure, little is known about their potential genotoxic and carcinogenic effects. The objectives of the present work were to prepare and characterize the major chlorinated derivatives of benzo[a]pyrene (BaP) and fluoranthene (Fluo), to develop an analytical methodology for their quantification in water samples and to analyse their potential genotoxicity. Chlorinated standards were prepared by a newly developed two phase method (water/n-hexane) using sodium hypochlorite. 6-Chloro-benzo[a]pyrene was selectively obtained from BaP, while 1,3-dichloro-fluoranthene and 3-chloro-fluoranthene were obtained from Fluo. All products were isolated and characterized by nuclear magnetic resonance and mass spectrometry. The formation of BaP- and Fluo-chlorinated derivatives under aqueous chlorination conditions was observed using a SPE-HPLC-FLD methodology. In addition, the cytotoxic and genotoxic activities of the three chlorinated derivatives were analyzed in comparison to their parent compounds, in a human-derived hepatoma cell line using the neutral red uptake and comet assays, respectively. The results showed that, at the equimolar doses of 100 and 125 μM, 6-Cl-BaP was able to induce a significantly higher level of DNA damage than BaP, suggesting a more potent genotoxic effect. In contrast, neither Fluo nor its chlorinated derivatives were genotoxic in the same cell line. The identification of new and possibly hazardous water chlorination by-product from PAHs emphasizes the need to minimize total organic carbon content of raw water and the implementation of safer water disinfection methods.     

Infrared and ultraviolet–visible spectroscopic studies of silica, [(Cp)2ZrCl2] and trimethylaluminum interactions

Infrared and UV–vis studies of metallocene immobilization on silica are reported here. The results have indicated changes in the Zr coordination sphere of metallocene depending on the immobilization route used. The reaction of [(Cp)₂ZrCl₂] with silica formed [(Cp)₂ZrCl]⁺[SiO]⁻ species. The same metallocene, reacting with TMA modified silica, formed monomethylated and dimethylated species by the substitution of chloro for methyl ligands, stabilized on the surface by interaction with “MAO-like” species (methylaluminoxane, MAO). These monomethylated and dimethylated cationic zirconium species are the active centers for the polymerization reaction. Different order of TMA addition in the silica modification step generated surface species of a similar nature, differing in their relative quantities. The highest amount of these active species was obtained when the support was added to the TMA solution rather than adding the TMA solution to the silica support. This was the most significant parameter affecting catalytic activity in ethylene polymerization.