Electrochemical generation of oxygen-containing groups in an ordered microporous zeolite-templated carbon

Zeolite templated carbon (ZTC) was electrochemically oxidized under various conditions, and its chemistry and structural evolution were compared to those produced by conventional chemical oxidation. In both oxidation methods, a general loss of the original structure regularity and high surface area was observed with increasing amount of oxidation. However, the electrochemical method showed much better controllability and enabled the generation of a large number of oxygen functional groups while retaining the original structure of the ZTC. Unlike chemical treatments, highly microporous carbons with an ordered 3-D structure, high surface area (ranging between 1900 and 3500 m2/g) and a large number of oxygen groups (O = 11,000–3300 μmol/g), have been prepared by the electrochemical method. Some insights into the electrooxidation mechanism of carbon materials are proposed from the obtained polarization curves, using ZTC as a model carbon material.

Methoxylation of α-pinene over mesoporous carbons and microporous carbons: A comparative study

A biomass derived carbon, a commercial microporous carbon and a xerogel mesoporous carbon catalysts were used in the study of α-pinene methoxilation reaction and the influence of textural and physical–chemical properties of the carbons was evaluated. Biomass carbon presented the higher activity, whereas the commercial one is the less active in the conditions studied. The main product of the reaction was α-terpinyl methyl ether and good values of selectivity were obtained over all the catalysts. A kinetic model was developed assuming that the α-pinene is consumed according to the parallel reaction network. The kinetic model presents high quality fittings to the experimental concentration profiles. These results show that it is possible to activate a waste residue using H3PO4 and convert it to high added value product such as acid catalyst.

Quantum effect induced reverse kinetic molecular sieving in microporous materials

We report kinetic molecular sieving of hydrogen and deuterium in zeolite rho at low temperatures, using atomistic molecular dynamics simulations incorporating quantum effects via the Feynman-Hibbs approach. We find that diffusivities of confined molecules decrease when quantum effects are considered, in contrast with bulk fluids which show an increase. Indeed, at low temperatures, a reverse kinetic sieving effect is demonstrated in which the heavier isotope, deuterium, diffuses faster than hydrogen. At 65 K, the flux selectivity is as high as 46, indicating a good potential for isotope separation.

Quantum effects on adsorption and diffusion of hydrogen and deuterium in microporous materials

Monte Carlo and molecular dynamics simulations and neutron scattering experiments are used to study the adsorption and diffusion of hydrogen and deuterium in zeolite Rho in the temperature range of 30-150 K. In the molecular simulations, quantum effects are incorporated via the Feynman-Hibbs variational approach. We suggest a new set of potential parameters for hydrogen, which can be used when Feynman-Hibbs variational approach is used for quantum corrections. The dynamic properties obtained from molecular dynamics simulations are in excellent agreement with the experimental results and show significant quantum effects on the transport at very low temperature. The molecular dynamics simulation results show that the quantum effect is very sensitive to pore dimensions and under suitable conditions can lead to a reverse kinetic molecular sieving with deuterium diffusing faster than hydrogen.

Structural evolution in a hydrothermal reaction between Nb2O5 and NaOH solution: From Nb2O5 grains to microporous Na2Nb2O6 center dot(2)/3H2O fibers and NaNbO3 cubes

Niobium pentoxide reacts actively with concentrate NaOH solution under hydrothermal conditions at as low as 120 degrees C. The reaction ruptures the corner-sharing of NbO7 decahedra and NbO6 octahedra in the reactant Nb2O5, yielding various niobates, and the structure and composition of the niobates depend on the reaction temperature and time. The morphological evolution of the solid products in the reaction at 180 degrees C is monitored via SEM: the fine Nb2O5 powder aggregates first to irregular bars, and then niobate fibers with an aspect ratio of hundreds form. The fibers are microporous molecular sieve with a monoclinic lattice, Na2Nb2O6 center dot(2)/3H2O. The fibers are a metastable intermediate of this reaction, and they completely convert to the final product NaNbO3 Cubes in the prolonged reaction of 1 h. This study demonstrates that by carefully optimizing the reaction condition, we can selectively fabricate niobate structures of high purity, including the delicate microporous fibers, through a direct reaction between concentrated NaOH solution and Nb2O5. This synthesis route is simple and suitable for the large-scale production of the fibers. The reaction first yields poorly crystallized niobates consisting of edge-sharing NbO6 octahedra, and then the microporous fibers crystallize and grow by assembling NbO6 octahedra or clusters of NbO6 octahedra and NaO6 units. Thus, the selection of the fibril or cubic product is achieved by control of reaction kinetics. Finally, niobates with different structures exhibit remarkable differences in light absorption and photoluminescence properties. Therefore, this study is of importance for developing new functional materials by the wet-chemistry process.

Systematic selection of solvents for the fabrication of 3D combined macro- and microporous polymeric scaffolds for soft tissue engineering

In this study, we investigate the fabrication of 3D porous poly(lactic-co-glycolic acid) (PLGA) scaffolds using the thermally-induced phase separation technique. The current study focuses on the selection of alternative solvents for this process using a number of criteria, including predicted solubility. toxicity, removability and processability. Solvents were removed via either vacuum freeze-drying or leaching, depending on their physical properties. The residual solvent was tested using gas chromatography-mass spectrometry. A large range of porous, highly interconnected scaffold architectures with tunable pore size and alignment was obtained, including combined macro- and microporous structures and an entirely novel 'porous-fibre' structure. The morphological features of the most promising poly(lactic-co-glycolic acid) scaffolds were analysed via scanning electron microscopy and X-ray micro-computed tomography in both two and three dimensions. The Young's moduli of the scaffolds under conditions of temperature, pH and ionic strength similar to those found in the body were tested and were found to be highly dependent on the architectures.

Precipitation casting of drug-loaded microporous PCL matrices:incorporation of progesterone by co-dissolution

Microporous, poly(ε-caprolactone) (PCL) matrices were loaded with progesterone by precipitation casting using co-solutions of PCL and progesterone in acetone. Progesterone loadings up to 32% w/w were readily achieved by increasing the drug content of the starting PCL solution. The kinetics of steroid release in PBS at 37°C over 10 days could be described effectively by a diffusional release model although the Korsmeyer-Peppas model indicated the involvement of multiple release phenomena. The diffusion rate constant (D) increased from 8 to 24 μg/mg matrix/day0.5 as the drug loading increased from 3.6 to 12.4% w/w. A total cumulative release of 75%-95% indicates the high efficiency of steroid delivery. Increasing the matrix density from 0.22 to 0.39 g/cm3, by increasing the starting PCL solution concentration, was less effective in changing drug release kinetics. Retention of anti-proliferative activity of released steroid was confirmed using cultures of breast cancer epithelial (MCF-7) cells. Progesterone released from PCL matrices into PBS at 37°C over 14 days retarded the growth of MCF-7 cells by a factor of at least 3.5 compared with progesterone-free controls. These findings recommend further investigation of precipitation-cast PCL matrices for delivery of bioactive molecules such as anti-proliferative agents from implanted, inserted or topical devices.

Preparation of a microporous silicon oximide gel from the reaction of tris(dimethylamino)silylamine with formamide and its pyrolytic conversion into a silicon oxynitride based glass

A high-surface-area silicon oximide-based gel [SiOC(H)=NSi]m[Si2N-C(H)=O]n[SiN(H)-C(H)=O]p[SiOC(H)=NH]q[SiNH]r[SiNH2]s[SiNMe2]t was prepared via a formamide-based aminolysis of tris(dimethylamino)silylamine, (Me2N)3SiNH2. The structure of the gel and the mechanism of formation are elucidated. Pyrolysis of the gel at 1000 °C under N2 flow gave an amorphous microporous oxynitride-based glass with a BET surface area of 195 m2 g−1. © The Royal Society of Chemistry 2005.

Microporous polycaprolactone matrices for drug delivery and tissue engineering:the release behaviour of bioactives having extremes of aqueous solubility

Microporous polycaprolactone (PCL) matrices loaded with hydrophobic steroidal drugs or a hydrophilic drug - pilocarpine hydrochloride - were produced by precipitation casting using solutions of PCL in acetone. The efficiency of steroid incorporation in the final matrix (progesterone (56 %) testosterone (46 %) dexamethasone (80 %)) depended on the nature of the drug initially co-dissolved in the PCL solution. Approximately 90 % w/w of the initial load of progesterone, 85 % testosterone and 50 % dexamethasone was released from the matrices in PBS at 37°C over 8 days. Pilocarpine hydrochloride (PH)-loaded PCL matrices, prepared by dispersion of powder in PCL solution, released 70-90 % of the PH content over 12 days in PBS. Application of the Higuchi model revealed that the kinetics of steroid and PH release were consistent with a Fickian diffusion mechanism with corresponding diffusion coefficients of 5.8 × 10-9 (progesterone), 3.9 × 10 -9 (testosterone), 7.1 × 10-10 (dexamethasone) and 22 × 10-8 cm2/s (pilocarpine hydrochloride). The formulation techniques described are expected to be useful for production of implantable, insertable and topical devices for sustained delivery of a range of bioactive molecules of interest in drug delivery and tissue engineering.

Síntese, caracterização e estudo da regeneração do silicoaluminofosfato-11 (SAPO-11)

heterogeneous catalyst such as a silicoaluminophosphate, molecular sieve with AEL (Aluminophosphate eleven) structure such as SAPO-11, was synthesized through the hydrothermal method starting from silica, pseudoboehmite, orthophosphoric acid (85%) and water, in the presence of a di-isopropylamine organic template. For the preparation of SAPO-11 in a dry basis it was used as reactants: DIPA; H3PO4; SiO4; Pseudoboehmite and distilled water. The crystallization process occurred when the reactive hydrogel was charged into a vessel and autoclaved at 200ºC for a period of 72 hours under autogeneous pressure. The obtained material was washed, dried and calcined to remove the molecular sieves of DIPA. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), nitrogen adsorption (BET) and thermal analysis (TG/DTG). The acidic properties were determined using adsorption of nbutylamine followed by programmed thermodessorption. This method revealed that SAPO-11 shows an acidity that ranges from weak to moderate. However, a small quantity of strong acid sites could be detected there. The deactivation of the catalysts was conducted by artificial coking followed by the cracking of the n-hexane in a fixed bed with a continuous flow micro-reactor coupled on line to a gas chromatograph. The main products obtained were: ethane, propane, isobutene, n-butane, n-pentane and isopentane. The Vyazovkin (model-free) kinetics method was used to determine the regeneration and removal of the coke

ENGINEERING HIERARCHICAL MESO-/MICROPOROUS LAMELLAR ZEOLITES WITH VARIABLE TEXTURAL AND CATALYTIC PROPERTIES

Meso-/microporous zeolites combine the charactersitics of well-defined micropores of zeolite with efficient mass transfer consequences of mesopores to increase the efficiency of the catalysts in reactions involving bulky molecules. Different methods such as demetallation and templating have been explored for the synthesis of meso-/microporous zeolites. However, they all have limitations in production of meso-/microporous zeolites with tunable textural and catalytic properties using few synthesis steps. To address this challenge, a simple one-step dual template synthesis approach has been developed in this work to engineer lamellar meso-/microporous zeolites structures with tunable textural and catalytic properties. First, one-step dual template synthesis of meso-/microporous mordenite framework inverted (MFI) zeolite structures was investigated. Tetrapropyl ammonium hydroxide (TPAOH) and diquaternary ammonium surfactant ([C22H45-N+(CH3)2-C6H12-N+(CH3)2-C6H13]Br2, C22-6-6) were used as templates to produce micropores and mesopores, respectively. The variation in concentration ratios of dual templates and hydrothermal synthesis conditions resulted in production of multi-lamellar MFI and the hybrid lamellar-bulk MFI (HLBM) zeolite structures. The relationship between the morphology, porosity, acidity, and catalytic properties of these catalysts was systematically studied. Then, the validity of the proposed synthesis approach for production of other types of zeolites composites was examined by creating a meso-/microporous bulk polymorph A (BEA)-lamellar MFI (BBLM) composite. The resulted composite samples showed higher catalytic stability compared to their single component zeolites. The studies demonstrated the high potential of the one-step dual template synthesis procedure for engineering the textural and catalytic properties of the synthesized zeolites.

Microporous organic polymers based on hexaphenylbiadamantane:synthesis, ultra-high stability and gas capture

Hexaphenylbiadamantane-based microporous organic polymers (MOPs) were successfully synthesized by Suzuki coupling under mild conditions. The obtained MOPs show high surface area (891 m2 g−1), ultra-high thermal (less than 40% mass loss at temperatures up to 1000 °C) and chemical (no apparent decomposition in organic solvents for more than 7 days) stability, gas (H2, CO2, CH4) capture capabilities and vapor (benzene, hexane) adsorption. These combined abilities render the synthesized MOPs an attractive candidate as thermo-chemically stable adsorbents for practical use in gas storage and pollutant vapor adsorption.

Primary alkaline battery cathodes a three-scale model

A mathematical model for the galvanostatic discharge and recovery of porous, electrolytic manganese dioxide cathodes, similar to those found within primary alkaline batteries is presented. The phenomena associated with discharge are modeled over three distinct size scales, a cathodic (or macroscopic) scale, a porous manganese oxide particle (or microscopic) scale, and a manganese oxide crystal (or submicroscopic) scale. The physical and chemical coupling between these size scales is included in the model. In addition, the model explicitly accounts for the graphite phase within the cathode. The effects that manganese oxide particle size and proton diffusion have on cathodic discharge and the effects of intraparticle voids and microporous electrode structure are predicted using the model.

Synthesis and characterization of sodalite–polyimide nanocomposite membranes

Nanocomposite membranes are fabricated from sodalite nanocrystals (Sod-N) dispersed in BTDA-MDA polyimide matrices and then characterized structurally and for gas separation. No voids are found upon investigation of the interfacial contact between the inorganic and organic phases, even at a Sod-N loading of up to 35 wt.%. This is due to the functionalization of the zeolite nanocrystals with amino groups (==Si_(CH3)(CH2)3NH2), which covalently link the particles to the polyimide chains in the matrices. The addition of Sod-N increases the hydrogen-gas permeability of the membranes, while nitrogen permeability decreases. Overall, these nanocomposite membranes display substantial selectivity improvements. The sodalite–polyimide membrane containing 35 wt.% Sod-N has a hydrogen permeability of 8.0 Barrers and a H2/N2 ideal selectivity of 281 at 25 C whereas the plain polyimide membrane exhibits a hydrogen permeability of 7.0 Barrers and a H2/N2 ideal selectivity of 198 at the same testing temperature.