Effect of sintering atmosphere on the pore-structure stability of cerium-doped nanostructured alumina

Pore-structure stability of pure and Ce-doped alumina in air and argon atmospheres was studied using DTA, TGA, N2 ads./des. and XRD with a view to understand the importance of the ionic size of the dopant cation on the pore-structure stability of alumina. The ionic size effect was studied by heat treating the Ce-alumina system in both oxidizing and reducing atmospheres to have Ce4+ (87 pm) and Ce3+ (106 pm) respectively. No compound formation between Ce and alumina was observed. In the case of pure alumina there is a drastic reduction in porosity during the transformation to α-alumina. Ce-doped alumina has a higher DSC transformation temperature corresponding to the α-alumina transformation compared to pure alumina. Ce-doped alumina showed higher pore-structure stability compared with pure alumina and the stability was relatively higher in reducing atmosphere (higher Ce3+/Ce4+ ratio, higher effective ionic size) compared with oxidizing conditions (lower Ce3+/Ce4+ ratio, lower effective ionic size)

Preparation and structure of microporous silica membranes

Silica sols have been prepared in an alcoholic solution by hydrolysis and condensation of TEOS (tetra-ethyl-ortho-silicate) molecules as a function of water and nitric acid concentration. The polymers are intended as precursors for ceramic, gas separation membranes. These molecules show fractal behavior as determined by SAXS (Small Angle X-ray Scattering). Microporosity of dried and calcined silica polymers is determined by N2-adsorption at 77 K. Fractal dimension and porosity increase with increasing acid concentration. Both the sol structure and the drying kinetics determine the porosity values. N2-adsorption isotherms are not very suitable for the determination of pore size distributions of microporous silica

Amine impregnated porous silica gel sorbents synthesized from water-glass precursors for CO2 capturing

In this work, porous silica gel-solid beads have been made from economically affordable water-glass precursors via sol-gel nano casting technique. A stable nanometric silica sol was prepared first from water glass and studied for surface potential and sol to gel transition. A free-flow, injectable gel was obtained upon aging the sol which was then assembled into spherical silica beads in a chemical bath. A surface area of 304.7m2g-1 was obtained for water glass derived silica gel beads. These gel beads were impregnated with 3-aminopropyltrimethoxysilane (APTMS) and polyethylenimine (PEI) active functional groups at different percentages for turning the gel beads as sorbents for CO2 gas adsorption. The effect of amine loading on the thermal stability, morphology as well as porosity was studied and was correlated with CO2 adsorption values. Depending upon the amount of amine loaded in the gel support CO2 uptake was found varied. These amine modified silica gel porous adsorbents showed CO2 adsorption capacity at temperatures as low as 100°C; samples modified with 15wt% PEI had CO2 adsorption capacity of 1.16mmolg-1 at 50°C. © 2015 Elsevier B.V

Evolution of pore structure in microporous silica membranes:sol-gel procedures and strategies

Silica membranes exhibiting excellent molecular sieving capability, which would find applications in fuel‐cell electric vehicles with on‐board hydrogen generation, for example, are the aim of the sol‐gel strategies outlined here. It is shown that optimization of the sol‐gel synthesis parameters is important in order to achieve membranes with minimum defects and hence high selectivity. The preparation of the supported membranes is described and the gas permeation behavior of membranes made from different sol compositions reported

Synthesis, characterisation and gas permeation studies on microporous silica and alumina-silica membranes for separation of propane and propylene

Microporous silica membranes are known to exhibit molecular sieving effects. However, separation of nearly equal sized molecules is difficult to carry out by size exclusion. Introducing sorption selectivity and keeping the kinetics favourable to facilitate a good contribution of permeation from sorption is a possible solution to enhance selectivity of adsorbing molecules. Results are presented in this paper on the synthesis of a microporous silica membrane with commendable permselectivity between helium and propylene. Modifications are performed on the membrane to improve its almost non-selective nature to propylene/propane mixtures to give practical separation values. Gas separation results on the modified membranes are presented. Surface selectivity on the newly added alumina surface layer is identified as the helping mechanism in realising this separation

Sol-gel synthesis of molecular sieving silica membranes

Polymeric silica sol was synthesized by the acid catalyzed hydrolysis and condensation of tetra-ethyl-ortho-silicate. Calcined unsupported membranes made from this sol showed microporous nature. Supported membranes on alumina were prepared by dipping and calcining. Helium showed activated diffusion with an apparent activation energy of 17 kJ mol−1. H2 permeation was comparable to that of helium under identical conditions. N2, Ar, O2, C3H6, C3H8, n-C4H10 and i-C4H10 permeation values were extremely small and therefore difficult to fit appropriate diffusion models. At 303 K hydrocarbon permeation was about 2 times higher than that of N2, Ar or O2. permselectivity around 1000 and helium permeation in the order of 10−7–10−8 mol m−2 s−1 Pa−1 were measured in the temperature range of 303–460 K. Comparison of Eact, selectivity and He and N2 permeation of different samples evidenced the dependence of nitrogen flux on processing defects. Obviously permeation rate of nitrogen molecule was insignificant through majority pores of the membrane

Synthesis of gas and vapor molecular sieving silica membranes and analysis of pore size and connectivity

Pervaporation and gas permeation properties of microporous silica membranes made by a sol−gel method are discussed. Defect free molecular sieving membranes are prepared by a dip coating process. The molecular sieving performance was measured and controlled based on gas permeation behavior of the membranes. The apparent activation energy for helium permeation and He/N2 perm-selectivity values were used as the parameters for optimization of the membrane performance. The membranes with very high activation energy for He diffusion were used for pervaporation studies with a methanol/MTBE mixture at 323 K. Separation factor values as high as 260 were measured at a total liquid flux of 0.3 kg/m2 hr. Sorption studies performed on corresponding silica gels revealed a separation mechanism based on diffusion of vapor molecules. Permeation of the vapor molecules through the micropores followed an activated diffusion mechanism. The gas permeation data could provide an understanding of the pore size distribution of the membrane, and the vapor sorption and diffusion data on the size and connectivity of the membrane pores

A facile one pot synthetic approach for C3N4-ZnS composite interfaces as heterojunctions for sunlight-induced multifunctional photocatalytic applications

Herein, we report a facile one pot synthetic protocol for the creation of C3N4-ZnS composite interfaces by the co-pyrolysis of a precursor mix containing zinc nitrate, melamine, and thiourea at 550°C in air. The organic-inorganic semiconductor heterojunctions thus formed displayed increased absorbance in the longer wavelength region and facilitated broad absorption of visible light compared to pure ZnS, C3N4 and conventionally synthesized hybrid samples. The decreased emission intensity, increased photocurrent generation and decreased fluorescence lifetime revealed reduced exciton recombinations in the co-pyrolysed sample containing C3N4-ZnS heterostructures. The samples displayed sunlight driven photocatalytic reduction of nitrophenol as well as hydrogen generation (4 mmol g-1 h-1) by water splitting. © The Royal Society of Chemistry 2016

Reactive oxygen species (ROS) mediated enhanced anti-candidal activity of ZnS-ZnO nanocomposites with low inhibitory concentrations

Enhanced antifungal activity against the yeast species Candida albicans, Candida tropicalis and Saccharomyces cerevisiae was displayed by ZnS-ZnO nanocomposites prepared by a simple precipitation technique. The antifungal activity was significantly more in the presence of indoor light than under dark conditions and was a clear confirmation of the inhibitory role of reactive oxygen species (ROS) generated in situ by the photocatalytic nanocomposites. The generation of ROS was further evidenced by flow cytometry results and membrane permeabilisation studies. Time kill assay and growth curve analysis indicated diminished antifungal activity under dark conditions due primarily to Zn2+ efflux in solution. © 2015 The Royal Society of Chemistry

Melamine formaldehyde-metal organic gel interpenetrating polymer network derived intrinsic Fe-N-doped porous graphitic carbon electrocatalysts for oxygen reduction reaction

Fe, N doped porous graphitic carbon electrocatalyst (Fe-MOG-MF-C), obtained by pyrolysis of an Interpenetrating Polymer Network (IPN) comprised of melamine formaldehyde (MF as hard segment) and Metal-Organic Gel (MOG as soft segment), exhibited significant Oxygen Reduction Reaction (ORR) activity in alkaline medium. BET surface area analysis of Fe-MOG-MF-C showed high surface area (821 m2 g-1), while TEM, Raman and XPS results confirmed Fe and N co-doping. Furthermore, a modulated porous morphology with a higher degree of surface area (950 m2 g-1) has been accomplished for the system (Fe-MOG-MFN-C) when aided by a sublimable porogen, such as naphthalene. XPS results further demonstrated that these systems exhibited a better degree of distribution of graphitic N and an onset potential value of 0.91 V vs. RHE in 0.1 M KOH solution following an efficient four-electron ORR pathway. The electrocatalytic activity of Fe-MOG-MFN-C is superior to that of Fe-MOG-MF-C by virtue of its higher graphitic N content and surface area. Thus, the study presents a new class of IPN derived MF-MOG nanocomposites with the potential to generate extended versions of in situ Fe-N doped porous graphitic carbon structures with superior ORR activity