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Sample records for porous silica supporter

  1. Porous Silica-Supported Solid Lipid Particles for Enhanced Solubilization of Poorly Soluble Drugs.

    PubMed

    Yasmin, Rokhsana; Rao, Shasha; Bremmell, Kristen E; Prestidge, Clive A

    2016-07-01

    Low dissolution of drugs in the intestinal fluid can limit their effectiveness in oral therapies. Here, a novel porous silica-supported solid lipid system was developed to optimize the oral delivery of drugs with limited aqueous solubility. Using lovastatin (LOV) as the model poorly water-soluble drug, two porous silica-supported solid lipid systems (SSL-A and SSL-S) were fabricated from solid lipid (glyceryl monostearate, GMS) and nanoporous silica particles Aerosil 380 (silica-A) and Syloid 244FP (silica-S) via immersion/solvent evaporation. SSL particles demonstrated significantly higher rate and extent of lipolysis in comparison with the pure solid lipid, depending on the lipid loading levels and the morphology. The highest lipid digestion was observed when silica-S was loaded with 34% (w/w) solid lipid, and differential scanning calorimeter (DSC) analysis confirmed the encapsulation of up to 2% (w/w) non-crystalline LOV in this optimal SSL-S formulation. Drug dissolution under non-digesting intestinal conditions revealed a three- to sixfold increase in dissolution efficiencies when compared to the unformulated drug and a LOV-lipid suspension. Furthermore, the SSL-S provided superior drug solubilization under simulated intestinal digesting condition in comparison with the drug-lipid suspension and drug-loaded silica. Therefore, solid lipid and nanoporous silica provides a synergistic effect on optimizing the solubilization of poorly water-soluble compound and the solid lipid-based porous carrier system provides a promising delivery approach to overcome the oral delivery challenges of poorly water-soluble drugs.

  2. Porous Silica-Supported Solid Lipid Particles for Enhanced Solubilization of Poorly Soluble Drugs.

    PubMed

    Yasmin, Rokhsana; Rao, Shasha; Bremmell, Kristen E; Prestidge, Clive A

    2016-07-01

    Low dissolution of drugs in the intestinal fluid can limit their effectiveness in oral therapies. Here, a novel porous silica-supported solid lipid system was developed to optimize the oral delivery of drugs with limited aqueous solubility. Using lovastatin (LOV) as the model poorly water-soluble drug, two porous silica-supported solid lipid systems (SSL-A and SSL-S) were fabricated from solid lipid (glyceryl monostearate, GMS) and nanoporous silica particles Aerosil 380 (silica-A) and Syloid 244FP (silica-S) via immersion/solvent evaporation. SSL particles demonstrated significantly higher rate and extent of lipolysis in comparison with the pure solid lipid, depending on the lipid loading levels and the morphology. The highest lipid digestion was observed when silica-S was loaded with 34% (w/w) solid lipid, and differential scanning calorimeter (DSC) analysis confirmed the encapsulation of up to 2% (w/w) non-crystalline LOV in this optimal SSL-S formulation. Drug dissolution under non-digesting intestinal conditions revealed a three- to sixfold increase in dissolution efficiencies when compared to the unformulated drug and a LOV-lipid suspension. Furthermore, the SSL-S provided superior drug solubilization under simulated intestinal digesting condition in comparison with the drug-lipid suspension and drug-loaded silica. Therefore, solid lipid and nanoporous silica provides a synergistic effect on optimizing the solubilization of poorly water-soluble compound and the solid lipid-based porous carrier system provides a promising delivery approach to overcome the oral delivery challenges of poorly water-soluble drugs. PMID:27048207

  3. Porous silica supports for micro-Raman spectroscopic studies of individual living cells

    NASA Astrophysics Data System (ADS)

    Cristini-Robbe, O.; Raulin, K.; Dubart, F.; Bernard, R.; Kinowski, C.; Damene, N.; El Yazidi, I.; Boed, A.; Turrell, S.

    2013-10-01

    A work was undertaken to explore the possibility of using porous silica gels as support materials for in vitro studies of individual living cells. Accordingly, tetra methyl orthosilicate-derived silica xerogels were prepared and tested as substrates for human breast adenocarcinoma MCF-7 cells. Micro-Raman spectra and BET measurements were used to determine the effect of sol-pH and autoclave sterilization on the substrate. MCF-7 cells were then seeded and grown on the resulting silica gels. Combined techniques show that (a) sol-pH affects substrate porosity and (b) autoclave conditions affect only the substrate surface thus increasing the surface porosity. Micro-Raman spectra of in situ grown MCF-7 cells indicate that they proliferate well on these xerogel surfaces with a preference for base-catalyzed substrates and that the surface morphology of supports can have a definite effect on the adherence and on the life time of human cells. Spectral evolutions observed for cells over a period of 48 h have made it possible to show that these substrates enable the easy maintenance of cell viability for over 36 h and that micro-Raman techniques make it possible to study individual cells and to characterize evolutional changes at different stages of their life-times. Results point to these new porous silica supports as promising substrates for rapid screening of drug toxicity.

  4. Comparison of superficially porous and fully porous silica supports used for a cyclofructan 6 hydrophilic interaction liquid chromatographic stationary phase.

    PubMed

    Dolzan, Maressa D; Spudeit, Daniel A; Breitbach, Zachary S; Barber, William E; Micke, Gustavo A; Armstrong, Daniel W

    2014-10-24

    A new HILIC stationary phase comprised of native cyclofructan-6 (CF6) bonded to superficially porous silica particles (2.7μm) was developed. Its performance was evaluated and compared to fully porous silica particles with 5μm (commercially available as FRULIC-N) and 3μm diameters. Faster and more efficient chromatography was achieved with the superficially porous particles (SPPs). The columns were also evaluated in the normal phase mode. The peak efficiency, analysis time, resolution, and overall separation capabilities in both HILIC and normal phase modes were compared. The analysis times using the superficially porous based column in HILIC mode were shorter and the theoretical plates/min were higher over the entire range of flow rates studied. The column containing the superficially porous particles demonstrated higher optimum flow rates than the fully porous particle packed columns. At higher flow rates, the advantages of the superficially porous particles was more pronounced in normal phase separations than in HILIC, clearly demonstrating the influence that the mode of chromatography has on band broadening. However, the minimum reduced plate heights (hmin) were typically lower in HILIC than in the normal phase mode. Overall, the superficially porous particle based CF6 column showed clear advantages over the fully porous particle columns, in terms of high throughput and efficient separations of polar compounds in the HILIC mode.

  5. Transport of nano zero-valent iron supported by mesoporous silica microspheres in porous media.

    PubMed

    Yang, Zhangmei; Qiu, Xinhong; Fang, Zhanqiang; Pokeung, Tsang

    2015-01-01

    Effective in situ remediation of groundwater requires the successful delivery of reactive iron particles through sand. However, the agglomeration of nano zero-valent iron (NZVI) particles limits the migration distance, which inhibits their usefulness. In the study described herein, NZVI supported by mesoporous silica microspheres covered with FeOOH (SiO2@FeOOH@Fe) was synthesized, and its mobility was demonstrated on the basis of transport in porous media. Degradation of decabromodiphenyl ether (BDE209) was more efficient by SiO2@FeOOH@Fe than by 'bare' NZVI. Breakthrough curves and mass recovery showed the mobility of SiO2@FeOOH@Fe in granular media was better than that of bare NZVI. It increased greatly in the presence of natural organic matter (NOM) and decreased when high Ca2+ and Mg2+ concentrations were encountered. Analysis of the transport data on the basis of filtration theory showed diffusion to be the main mechanism for particle removal in silicon sand. Increasing the NOM may decrease agglomeration of the grains of sand, which has a positive effect on the mobility of SiO2@FeOOH@Fe. Presumably, increasing the concentrations of Ca2+ and Mg2+ compresses the diffuse double layer of SiO2@FeOOH@Fe, resulting in a reduction of mobility.

  6. Design of porous silica supported tantalum oxide hollow spheres showing enhanced photocatalytic activity.

    PubMed

    Sharma, Manu; Das, Debashree; Baruah, Arabinda; Jain, Archana; Ganguli, Ashok K

    2014-03-25

    Silica-supported tantalum oxide (ST) hollow spheres were designed for photocatalytic applications in the UV range of 4.1 to 4.8 eV. These nanostructures with a variable diameter of 100-250 nm and shell thickness of 24-58 nm were obtained by the hydrothermal treatment of tantalum isopropoxide and tetraethylorthosilicate at 120 °C for 48 h in the presence of cetyl trimethyl ammonium bromide, which was used as a capping agent. The maximum observed surface area was found to be 610 m(2)/g and pore size distribution of ST hollow spheres varied from 13.4 to 19.0 nm. Lewis acidity of silica and the contact area between SiO2 and Ta2O5 plays a crucial role in controlling the photocatalytic properties of the ST hollow spheres. We observe a remarkable 6× enhancement in the photoactivity of silica-supported tantalum oxide hollow spheres compared to pure Ta2O5.

  7. Encapsulation of folic acid in different silica porous supports: A comparative study.

    PubMed

    Pérez-Esteve, Édgar; Ruiz-Rico, María; de la Torre, Cristina; Villaescusa, Luis A; Sancenón, Felix; Marcos, María D; Amorós, Pedro; Martínez-Máñez, Ramón; Barat, José Manuel

    2016-04-01

    Although folic acid is essential to numerous bodily functions, recent research indicates that a massive exposition to the vitamin could be a double-edged sword. In this study, the capacity of different caped mesoporous silica particles (i.e. Hollow Silica Shells, MCM-41, SBA-15 and UVM-7) to dose FA during its passage through the gastrointestinal tract has been evaluated. Results confirmed that the four capped materials were capable to hinder the delivery of FA at low pH (i.e. stomach) as well as able to deliver great amounts of the vitamin at neutral pH (i.e. intestine). Nevertheless, the encapsulation efficiency and the deliver kinetics differed among supports. While supports with large pore entrance exhibited an initial fast release, MCM-41, showed a sustained release along the time. This correlation between textural properties and release kinetics for each of the supports reveals the importance of a proper support selection as a strategy to control the delivery of active molecules. PMID:26593466

  8. Encapsulation of folic acid in different silica porous supports: A comparative study.

    PubMed

    Pérez-Esteve, Édgar; Ruiz-Rico, María; de la Torre, Cristina; Villaescusa, Luis A; Sancenón, Felix; Marcos, María D; Amorós, Pedro; Martínez-Máñez, Ramón; Barat, José Manuel

    2016-04-01

    Although folic acid is essential to numerous bodily functions, recent research indicates that a massive exposition to the vitamin could be a double-edged sword. In this study, the capacity of different caped mesoporous silica particles (i.e. Hollow Silica Shells, MCM-41, SBA-15 and UVM-7) to dose FA during its passage through the gastrointestinal tract has been evaluated. Results confirmed that the four capped materials were capable to hinder the delivery of FA at low pH (i.e. stomach) as well as able to deliver great amounts of the vitamin at neutral pH (i.e. intestine). Nevertheless, the encapsulation efficiency and the deliver kinetics differed among supports. While supports with large pore entrance exhibited an initial fast release, MCM-41, showed a sustained release along the time. This correlation between textural properties and release kinetics for each of the supports reveals the importance of a proper support selection as a strategy to control the delivery of active molecules.

  9. Heterofunctional hydrophilic-hydrophobic porous silica as support for multipoint covalent immobilization of lipases: application to lactulose palmitate synthesis.

    PubMed

    Bernal, Claudia; Illanes, Andres; Wilson, Lorena

    2014-04-01

    Lipase-catalyzed synthesis of sugar esters, as lactulose palmitate, requires harsh conditions, making it necessary to immobilize the enzyme. Therefore, a study was conducted to evaluate the effect of different chemical surfaces of hierarchical meso-macroporous silica in the immobilization of two lipases from Pseudomonas stutzeri (PsL) and Alcaligenes sp. (AsL), which exhibit esterase activity. Porosity and chemical surface of silica supports, before and after functionalization and after immobilization, were characterized by gas adsorption and Fourier transform infrared (FTIR) spectroscopy. PsL and AsL were immobilized in octyl (OS), glyoxyl (GS), and octyl-glyoxyl silica (OGS). Hydrolytic activity, thermal and solvent stability, and sugar ester synthesis were evaluated with those catalysts. The best support in terms of expressed activity was OS in the case of PsL (100 IU g(-1)), while OS and OGS were the best for AsL with quite similar expressed activities (60 and 58 IU g(-1), respectively). At 60 °C in aqueous media the more stable biocatalysts were GS-PsL and OGS-AsL (half-lives of 566 and 248 h, respectively), showing the advantage of a heterofunctional support in the latter case. Lactulose palmitate synthesis was carried out in acetone medium (with 4% of equilibrium moisture) at 40 °C obtaining palmitic acid conversions higher than 20% for all biocatalysts, being the highest of those obtained with OGS-AsL and OS-PsL. Therefore, screening of different chemical surfaces on porous silica used as supports for lipase immobilization allowed obtaining active and stable biocatalyst to be employed in the novel synthesis of lactulose palmitate.

  10. Preparation and SO{sub 2} sorption/desorption behavior of an Ionic liquid supported on porous silica particles

    SciTech Connect

    Zhang, Z.M.; Wu, L.B.; Dong, J.; Li, B.G.; Zhu, S.P.

    2009-02-15

    The ionic liquid 1,1,3,3-tetramethylguanidinium lactate (TMGL) was supported onto porous silica particles via a facile impregnation-vaporization method. The TMGL-supported particles gave high porosity and large specific surface area. The SO{sub 2} sorption/desorption properties of the silica-supported TMGL (TMGL-SiO{sub 2}) were evaluated, and high SO{sub 2} sorption capacity and rate were achieved. Its capacity reached 0.6 g SO{sub 2}/g TMGL in 15-30 min with pure SO{sub 2} gas and 0.15 g SO{sub 2}/g TMGL in 17 h with a N{sub 2}/SO{sub 2} mixture gas that contained 2160 ppm SO{sub 2}. The SO{sub 2} concentration was reduced to 12.6 ppm after sorption. The TMGL-SiO{sub 2} system could be reused for many sorption/desorption cycles without change in its capacity. It was also characterized by good mechanical strength and thermal stability at temperature up to 130{sup o}C. The SO{sub 2} sorbent system appears to be useful in gas desulfurization.

  11. Neutron scattering studies of structure, hydrothermal stability and transport in porous silica catalyst supports

    NASA Astrophysics Data System (ADS)

    Pollock, Rachel A.

    Mesoporous materials are interesting as catalyst supports, because molecules can move efficiently in and out of the pore network, but they must be stable in water if they are to be used for the production of biofuels. Before investigating hydrothermal stability and transport properties, the pore structure of SBA-15 was characterized using small angle neutron scattering (SANS) and non-local density functional theory (NLDFT) analysis of nitrogen sorption isotherms. A new Contrast Matching SANS method, using a range of probe molecules to directly probe the micropore size, gave a pore size distribution onset of 6 ± 0.2 Å, consistent with cylindrical pores formed from polymer template strands that unravel into the silica matrix. Diffraction intensity analysis of SANS measurements, combined with pore size distributions calculated from NLDFT, showed that the secondary pores are distributed relatively uniformly throughout the silica framework. The hydrothermal stability of SBA-15 was evaluated using a post-calcination hydrothermal treatment in both liquid and vapor phase water. The results were consistent with a degradation mechanism in which silica dissolves from regions of small positive curvature, e.g. near the entrance to the secondary pores, and is re-deposited deeper into the framework. Under water treatment at 115 °C, the mesopore diameter increases and the intra-wall void fraction decreases significantly. The behavior is similar for steam treatment, but occurs more slowly, suggesting that transport is faster when condensation occurs in the pores. Quasielastic neutron scattering (QENS) measurements of methane in SBA-15 probed the rotational and translational motion as a function of temperature and loading. A qualitative analysis of the QENS data suggested that for the initial dose of methane at 100 K, the self diffusion constant is similar in magnitude to literature values for methane in ZSM-5 and Y-zeolite, showing that the secondary pores trap methane and limit

  12. Stabilization of Metal-Loaded Ion-Exchange Resin with a Porous Silica Supporter Through Thermal Treatment

    SciTech Connect

    Kim, I-T. Park, H-S.; Yoo, J-H.; Kim, J-H.

    2003-02-25

    A new ion exchanger with porous silica as a supporting material and diphosphonic acid as a functional chelating group has been developed at ANL for the effective removal of transition metals and actinide ions from very acidic radioactive liquid wastes. The applicability of this resin for the treatment of low- and/or intermediate-level aqueous waste from nuclear power plants (NPP) has not been reported in scientific literature, but is under study now in Korea. The major radioisotopes in NPP radioactive liquid waste are Cs and Co in neutral pH ranges. This study on the thermal stabilization of metal-loaded waste resin has been carried out in parallel with the sorption experiment. Thermal treatment of metal (Co, Cs or U) loaded resin was accomplished to see the possibility of enhancing the safety and stability of the final product during transportation and disposal. In this paper, characteristics of the metal-loaded resins before and after heat treatment at three different thermal conditions were investigated and compared with each other to see the effectiveness of the thermal treatment method.

  13. Dynamic Compaction Modeling of Porous Silica Powder

    NASA Astrophysics Data System (ADS)

    Borg, John P.; Schwalbe, Larry; Cogar, John; Chapman, D. J.; Tsembelis, K.; Ward, Aaron; Lloyd, Andrew

    2006-07-01

    A computational analysis of the dynamic compaction of porous silica is presented and compared with experimental measurements. The experiments were conducted at Cambridge University's one-dimensional flyer plate facility. The experiments shock loaded samples of silica dust of various initial porous densities up to a pressure of 2.25 GPa. The computational simulations utilized a linear Us-Up Hugoniot. The compaction events were modeled with CTH, a 3D Eulerian hydrocode developed at Sandia National Laboratory. Simulated pressures at two test locations are presented and compared with measurements.

  14. Synthesis of silica based porous nanomaterials

    NASA Astrophysics Data System (ADS)

    Mueller, Paul S.

    Silica is one of the most abundant elements on the planet, has flexible bonding properties and generally excellent stability. Because of these properties, silica has been a vital component in technologies ranging from ancient glassware to modern supercomputers. Silica is able to form a wide range of materials both alone and as a component of larger material frameworks. Porous silica based nanomaterials are rapidly growing in importance because of their many applications in a wide variety of fields. This thesis focuses on the synthesis of silica based porous nanomaterials: nanocrystalline zeolites, mesoporous silica nanoparticles, and iron oxide core/shell nanocomposites. The synthetic conditions of these materials were varied in order to maximize efficiency, minimize environmental impact, and produce high quality material with far reaching potential applications. The materials were characterized by physicochemical techniques including Transmission Electron Microscopy, Dynamic Light Scattering, Powder X-Ray Diffraction, Solid State NMR, and Nitrogen Adsorption Isotherms. The materials were evaluated and conditions were controlled to produce high yields of quality nanomaterials and hypothesize methods for further synthetic control. The products will be used in studies involving nanoparticle toxicity, environmental remediation, and drug delivery.

  15. Chitosan-silica hybrid porous membranes.

    PubMed

    Pandis, Christos; Madeira, Sara; Matos, Joana; Kyritsis, Apostolos; Mano, João F; Ribelles, José Luis Gómez

    2014-09-01

    Chitosan-silica porous hybrids were prepared by a novel strategy in order to improve the mechanical properties of chitosan (CHT) in the hydrogel state. The inorganic silica phase was introduced by sol-gel reactions in acidic medium inside the pores of already prepared porous scaffolds. In order to make the scaffolds insoluble in acidic media chitosan was cross-linked by genipin (GEN) with an optimum GEN concentration of 3.2 wt.%. Sol-gel reactions took place with Tetraethylorthosilicate (TEOS) and 3-glycidoxypropyltrimethoxysilane (GPTMS) acting as silica precursors. GPTMS served also as a coupling agent between the free amino groups of chitosan and the silica network. The morphology study of the composite revealed that the silica phase appears as a layer covering the chitosan membrane pore walls. The mechanical properties of the hybrids were characterized by means of compressive stress-strain measurements. By immersion in water the hybrids exhibit an increase in elastic modulus up to two orders of magnitude. PMID:25063153

  16. Influence of mechanochemical activation in various media on structure of porous and non-porous silicas

    NASA Astrophysics Data System (ADS)

    Sydorchuk, V.; Khalameida, S.; Zazhigalov, V.; Skubiszewska-Zięba, J.; Leboda, R.; Wieczorek-Ciurowa, K.

    2010-11-01

    Influence of mechanochemical activation on porous structure and surface properties of porous and non-porous silicas in air, water and ethanol has been studied. Milled samples have been investigated with help of nitrogen adsorption-desorption, mercury porometry, thermogravimetric analysis, FTIR and ESR spectroscopy. It has been revealed that destruction of porous structure of silicagel at dry milling and, on the contrary, formation of porous silica from non-porous powders (aerosils) during treatment in liquid media occurs.

  17. Preparation of silica-supported porous sorbent for heavy metal ions removal in wastewater treatment by organic-inorganic hybridization combined with sucrose and polyethylene glycol imprinting.

    PubMed

    Li, Feng; Du, Ping; Chen, Wei; Zhang, Shusheng

    2007-03-01

    A new porous sorbent for wastewater treatment of metal ions was synthesized by covalent grafting of molecularly imprinted organic-inorganic hybrid on silica gel. With sucrose and polyethylene glycol 4000 (PEG 4000) being synergic imprinting molecules, covalent surface coating on silica gel was achieved by using polysaccharide-incorporated sol-gel process starting from the functional biopolymer, chitosan and an inorganic epoxy-precursor, gamma-glycidoxypropyltrimethoxysiloxane (GPTMS) at room temperature. The prepared porous sorbent was characterized by using simultaneous thermogravimetry and differential scanning calorimeter (TG/DSC), scanning electron microscopy (SEM), nitrogen adsorption porosimetry measurement and X-ray diffraction (XRD). Copper ion, Cu(2+), was chosen as the model metal ion to evaluate the effectiveness of the new biosorbent in wastewater treatment. The influence of epoxy-siloxane dose, buffer pH and co-existed ions on Cu(2+) adsorption was assessed through batch experiments. The imprinted composite sorbent offered a fast kinetics for the adsorption of Cu(2+). The uptake capacity of the sorbent imprinted by two pore-building components was higher than those imprinted with only a single component. The dynamic adsorption in column underwent a good elimination of Cu(2+) in treating electric plating wastewater. The prepared composite sorbent exhibited high reusability. Easy preparation of the described porous composite sorbent, absence of organic solvents, cost-effectiveness and high stability make this approach attractive in biosorption. PMID:17386667

  18. Porous thin films of functionalized mesoporous silica nanoparticles.

    PubMed

    Kobler, Johannes; Bein, Thomas

    2008-11-25

    The synthesis of extremely small mesoporous silica nanoparticles via a specific co-condensation process with phenyl groups is demonstrated. The suspensions are ideally suited for the production of nanoscale thin films by spin-coating. Thanks to the small particle size and the resulting low surface roughness, the films show excellent optical qualities and exhibit good diffusion properties and a highly accessible pore system. The availability of such homogeneous porous thin films made it possible to use ellipsometric porosimetry (EP) as a convenient method to determine the effective porosity of the films on their original support without destroying it. It was possible to record sorption isotherms of the thin films with ellipsometry and to correlate the data with nitrogen sorption data of dried powders of the same material. The thin films showed very low refractive indices of around 1.2. PMID:19206399

  19. Synthesis design of polar polymers and nanostructured porous silica

    NASA Astrophysics Data System (ADS)

    Schmidt-Winkel, Patrick Niels

    Nanostructured and functional materials have attracted a great deal of attention because of their importance for scientific and technological progress in our society. We have proposed a novel concept for functional, polar organic polymers that is based on the ferrielectric ordering of electric dipoles along the polymer backbone. In this context, a polar odd-numbered aliphatic polysulfone and low-molecular weight model compounds possessing remarkable thermal stability, degrading at 100°C above previously prepared polysulfones, have been synthesized and characterized. Mesoporous molecular sieves with uniform pores ranging from 2--50 nm in size are promising materials for catalysis, host-guest chemistry, separation, immobilization, encapsulation, insulation, etc. We have described a novel synthesis method to produce hierarchically ordered mesoporous silica in which the ordering on meso- to macroscopic length scales is controlled and significantly improved in one step. In search of a simple, efficient procedure to synthesize porous materials with ultralarge mesopores (30--50 nm), we have discovered microemulsions as novel colloidal templates for mesostructured cellular foams (MCFs). MCFs represent a new class of materials with well-defined, adjustable, and continuous ultralarge mesopores (9--42 nm). The microemulsion templating route has opened up new possibilities to engineer mesoporous systems for applications such as catalyst supports where mass transport is often limited by narrow pore openings. The microemulsion templates used to prepare MCF materials have been characterized by small-angle neutron scattering (SANS) studies. The microemulsion droplet size increases linearly with the cube root of the oil concentration, ethanol is required as cosurfactant, and the temperature behavior of the microemulsions is similar to the pure surfactant solution. In situ SANS studies of acid-synthesized SBA-15- and MCF-type silica have shown that silica condensation is fast early

  20. New porous polycaprolactone-silica composites for bone regeneration.

    PubMed

    Plazas Bonilla, Clara E; Trujillo, Sara; Demirdögen, Bermali; Perilla, Jairo E; Murat Elcin, Y; Gómez Ribelles, José L

    2014-07-01

    Polycaprolactone porous membranes were obtained by freeze extraction of dioxane from polycaprolactone-dioxane solid solutions. Porosities as high as 90% with interconnected structures were obtained by this technique. A silica phase was synthesized inside the pores of the polymer membrane by sol-gel reaction using tetraethylorthosilicate (TEOS) as a silica precursor and catalyzed in acidic and basic conditions. Two different morphologies of the inorganic phase were obtained depending on the type of catalyst. In acid catalyzed sol-gel reaction, a homogeneous layer of silica was deposited on the pores, and discrete microspheres were synthesized on the pore walls when a basic catalyst was used. The morphology of the inorganic phase influenced the mechanical and thermal behavior, as well as the hydrophilic character of the composites. Bioactivity of the porous materials was tested in vitro by measuring the deposition of hydroxyapatite on the surfaces of the porous composite membranes. Polycaprolactone/silica composites revealed a superior bioactivity performance compared with that of the pure polymer; evidenced by the characteristic cauliflower structures on the material surface, increase in weight and Ca/P ratio of the hydroxyapatite layer. Also, the acid catalyzed composites presented better bioactivity than the base catalyzed composites, evidencing the importance in the morphology of the silica phase.

  1. Nucleic acid separations using superficially porous silica particles

    PubMed Central

    Close, Elizabeth D.; Nwokeoji, Alison O.; Milton, Dafydd; Cook, Ken; Hindocha, Darsha M.; Hook, Elliot C.; Wood, Helen; Dickman, Mark J.

    2016-01-01

    Ion pair reverse-phase liquid chromatography has been widely employed for nucleic acid separations. A wide range of alternative stationary phases have been utilised in conjunction with ion pair reverse-phase chromatography, including totally porous particles, non-porous particles, macroporous particles and monolithic stationary phases. In this study we have utilised superficially porous silica particles in conjunction with ion pair reverse-phase liquid chromatography for the analysis of nucleic acids. We have investigated a range of different pore-sizes and phases for the analysis of a diverse range of nucleic acids including oligonucleotides, oligoribonucleotides, phosphorothioate oligonucleotides and high molecular weight dsDNA and RNA. The pore size of the superficially porous silica particles was shown to significantly affect the resolution of the nucleic acids. Optimum separations of small oligonucleotides such as those generated in RNase mapping experiments were obtained with 80 Å pore sizes and can readily be interfaced with mass spectrometry analysis. Improved resolution of larger oligonucleotides (>19 mers) was observed with pore sizes of 150 Å. The optimum resolution for larger dsDNA/RNA molecules was achieved using superficially porous silica particles with pore sizes of 400 Å. Furthermore, we have utilised 150 Å pore size solid-core particles to separate typical impurities of a fully phosphorothioated oligonucleotide, which are often generated in the synthesis of this important class of therapeutic oligonucleotide. PMID:26948761

  2. Dynamic Compaction Modeling Comparison for Porous Silica Powder

    NASA Astrophysics Data System (ADS)

    Borg, John; Schwalbe, Larry; Chapman, D. J.; Lloyd, Andrew; Ward, Aaron

    2005-07-01

    A computational analysis of the dynamic compaction of porous silica is presented and compared with experimental measurements. The experiments were conducted at Cambridge University's one-dimensional flyer plate facility. The experiments shock loaded samples of silica dust of various initial porous densities up to a pressure of 2.25 GPa. The computational simulations utilized porous material models, P-lambda and P-alpha, in conjunction with a linear Us-up Hugoniot. Two hydrocodes were used to simulate the compaction event: CTH and KO. CTH is a three-dimensional Eulerian hydrocode developed at Sandia National Laboratory and KO is a one-dimensional Lagrangian hydrocode developed at Lawrence Livermore National Laboratory. A comparison of the advantages and disadvantages, along with a discussion of the salient features, of the two models are presented.

  3. Zinc oxide nanostructures confined in porous silicas.

    PubMed

    Coasne, Benoit; Mezy, Aude; Pellenq, R J M; Ravot, D; Tedenac, J C

    2009-02-18

    We report on molecular simulations of zinc oxide nanostructures obtained within silica nanopores of diameter D = 1.6 nm and D = 3.2 nm. Both the effects of confinement (by varying the pore size) and degree of pore filling on the structure of the nanomaterial are addressed. Two complementary approaches are adopted: 1) the stability of the three crystalline phases of ZnO (wurtzite, rocksalt, and blende) in the silica nanopores is studied, and 2) ZnO nanostructures are obtained by slowly cooling down a homogeneous liquid phase confined in the silica pores. None of the ideal nanostructures (wurtzite, rocksalt, blende) retains the ideal structure of the initial crystal when confined within the silica pores. Only the structure starting from the ideal wurtzite nanocrystal remains significantly crystalline after relaxation, as revealed by the marked peaks in the pair correlation functions for this system. The morphology and degree of cristallinity of the structures are found to depend on the parameters involved in the synthesis (pore size, filling density). Nanograin boundaries are observed between domains of different crystal structures. Reminiscent features of the bulk behavior, such as faceting of the nanostructures, are also observed when the system size becomes large. We show that the use of nanopores as a template imposes that the confined particles exhibit neutral (basal) surfaces. These predictions provide a guide to experiments on semiconductor nanoparticles.

  4. Porous polylactic acid-silica hybrids: preparation, characterization, and study of mesenchymal stem cell osteogenic differentiation.

    PubMed

    Pandis, Christos; Trujillo, Sara; Matos, Joana; Madeira, Sara; Ródenas-Rochina, Joaquín; Kripotou, Sotiria; Kyritsis, Apostolos; Mano, João F; Gómez Ribelles, José Luis

    2015-02-01

    A novel approach to reinforce polymer porous membranes is presented. In the prepared hybrid materials, the inorganic phase of silica is synthesized in-situ and inside the pores of aminolyzed polylactic acid (PLA) membranes by sol-gel reactions using tetraethylorthosilicate (TEOS) and glycidoxypropyltrimethoxysilane (GPTMS) as precursors. The hybrid materials present a porous structure with a silica layer covering the walls of the pores while GPTMS serves also as coupling agent between the organic and inorganic phase. The adjustment of silica precursors ratio allows the modulation of the thermomechanical properties. Culture of mesenchymal stem cells on these supports in osteogenic medium shows the expression of characteristic osteoblastic markers and the mineralization of the extracellular matrix. PMID:25303745

  5. Porous polylactic acid-silica hybrids: preparation, characterization, and study of mesenchymal stem cell osteogenic differentiation.

    PubMed

    Pandis, Christos; Trujillo, Sara; Matos, Joana; Madeira, Sara; Ródenas-Rochina, Joaquín; Kripotou, Sotiria; Kyritsis, Apostolos; Mano, João F; Gómez Ribelles, José Luis

    2015-02-01

    A novel approach to reinforce polymer porous membranes is presented. In the prepared hybrid materials, the inorganic phase of silica is synthesized in-situ and inside the pores of aminolyzed polylactic acid (PLA) membranes by sol-gel reactions using tetraethylorthosilicate (TEOS) and glycidoxypropyltrimethoxysilane (GPTMS) as precursors. The hybrid materials present a porous structure with a silica layer covering the walls of the pores while GPTMS serves also as coupling agent between the organic and inorganic phase. The adjustment of silica precursors ratio allows the modulation of the thermomechanical properties. Culture of mesenchymal stem cells on these supports in osteogenic medium shows the expression of characteristic osteoblastic markers and the mineralization of the extracellular matrix.

  6. Preparation of monodisperse porous silica particles using poly(glycidyl methacrylate) microspheres as a template.

    PubMed

    Grama, S; Horák, D

    2015-01-01

    Monodisperse macroporous poly(glycidyl methacrylate) (PGMA) microspheres were used as a template for preparing porous silica particles. The starting polymer microspheres that were 9.3 microm in size were synthesized by multistep swelling polymerization using a modified Ugelstad technique. Subsequently, silica (SiO2) was deposited on the surface and inside the PGMA microspheres to produce poly(glycidyl methacrylate)-silica hybrid particles (PGMA-SiO2). Upon calcination of the PGMA-SiO2 microspheres, porous silica particles were formed. The morphology, particle size, polydispersity and inner structure of the silica microspheres were investigated by scanning and transmission electron microscopy. Thermogravimetric analysis and dynamic adsorption of nitrogen determined the amount of silica formed and its specific surface area. Compared with the starting PGMA microspheres, the size of the porous silica particles decreased by up to 30%. These porous silica microspheres are promising for chromatography and biomedical applications. PMID:26447591

  7. Preparation of monodisperse porous silica particles using poly(glycidyl methacrylate) microspheres as a template.

    PubMed

    Grama, S; Horák, D

    2015-01-01

    Monodisperse macroporous poly(glycidyl methacrylate) (PGMA) microspheres were used as a template for preparing porous silica particles. The starting polymer microspheres that were 9.3 microm in size were synthesized by multistep swelling polymerization using a modified Ugelstad technique. Subsequently, silica (SiO2) was deposited on the surface and inside the PGMA microspheres to produce poly(glycidyl methacrylate)-silica hybrid particles (PGMA-SiO2). Upon calcination of the PGMA-SiO2 microspheres, porous silica particles were formed. The morphology, particle size, polydispersity and inner structure of the silica microspheres were investigated by scanning and transmission electron microscopy. Thermogravimetric analysis and dynamic adsorption of nitrogen determined the amount of silica formed and its specific surface area. Compared with the starting PGMA microspheres, the size of the porous silica particles decreased by up to 30%. These porous silica microspheres are promising for chromatography and biomedical applications.

  8. Temperature dependence of porous silica antireflective (AR) coating

    NASA Astrophysics Data System (ADS)

    Tang, Yongxing; Le, Yueqin; Zhang, Weiqing; Jiang, Minhua; Sun, Jinren; Liu, Xiaolin

    1998-02-01

    In this paper, the antireflective coatings consisting of porous silica particles from a silica sol are applied by dip method. The relationships among composition, viscosity and temperature have been studied. The coating homogeneity is opium for the laser wavelengths of 1064 nm, 532 nm and 355 nm. The peak transmission of coated BK-7 glass substrate is higher than 99.5%. The laser induced damage thresholds of the antireflective coatings were range of 7 - 10 J/cm2, for 1 ns pulse width and 1064 nm wavelength. These damage thresholds were suitable for our national ICF program. It is noted that the optical homogeneity of coating and the viscosity of coating sol were strongly influenced by the temperatures in the duration of sol ripening.

  9. A Compaction Model for Highly Porous Silica Powder.

    NASA Astrophysics Data System (ADS)

    Church, P. D.; Tsembelis, K.

    2005-07-01

    This paper describes research to develop an equation of state to describe the behaviour of a highly porous silica powder. It shows that whilst molecular modelling techniques can be readily applied to develop a description of a compact material the description of the compaction process is more problematic. An empirical model, based upon the Lennard-Jones potential, has been shown to be capable of describing the compaction process observed in simple experiments. This development and application of the model in the Eulerian hydrocode GRIM to reproduce experimental plate impact data over a wide range of impact velocities is described and the results compared with experimental data.

  10. Chemisorption of chromium acetylacetonate on porous high surface area silica

    NASA Astrophysics Data System (ADS)

    Haukka, Suvi; Lakomaa, Eeva-Liisa; Suntola, Tuomo

    1994-01-01

    Atomic layer epitaxy (ALE) reactions (i.e. saturating gas-solid reactions) of chromium acetylacetonate (Cr(acac) 3) at 200-280°C with silica preheated at 200-820°C were studied by determining chromium and carbon concentrations, recording FTIR spectra, and reacting Cr(acac) 3 with the silylated silica surface. Cr(acac) 3 was found to be selectively chemisorbed to silica through reaction with the isolated OH groups, leading to release of one acac ligand. The relatively large size of the supported chromium complex that formed had a highly controlling effect on the amount of chromium atoms bound. In addition to this steric hindrance, the saturation density of chromium could be further regulated by the preheat temperature of the silica, which determines the number of OH groups, and by the reaction temperature. The reaction with the silylated silica surface provided a means for achieving an even lower saturation density of chromium and confirmed that the strongly H-bonded OH groups present on silica preheated at 200°C were only partly reactive. The ligands of the surface complex could be removed by water vapor and air treatment.

  11. Porous silicon nanocrystals in a silica aerogel matrix

    PubMed Central

    2012-01-01

    Silicon nanoparticles of three types (oxide-terminated silicon nanospheres, micron-sized hydrogen-terminated porous silicon grains and micron-size oxide-terminated porous silicon grains) were incorporated into silica aerogels at the gel preparation stage. Samples with a wide range of concentrations were prepared, resulting in aerogels that were translucent (but weakly coloured) through to completely opaque for visible light over sample thicknesses of several millimetres. The photoluminescence of these composite materials and of silica aerogel without silicon inclusions was studied in vacuum and in the presence of molecular oxygen in order to determine whether there is any evidence for non-radiative energy transfer from the silicon triplet exciton state to molecular oxygen adsorbed at the silicon surface. No sensitivity to oxygen was observed from the nanoparticles which had partially H-terminated surfaces before incorporation, and so we conclude that the silicon surface has become substantially oxidised. Finally, the FTIR and Raman scattering spectra of the composites were studied in order to establish the presence of crystalline silicon; by taking the ratio of intensities of the silicon and aerogel Raman bands, we were able to obtain a quantitative measure of the silicon nanoparticle concentration independent of the degree of optical attenuation. PMID:22805684

  12. Porous silicon nanocrystals in a silica aerogel matrix

    NASA Astrophysics Data System (ADS)

    Amonkosolpan, Jamaree; Wolverson, Daniel; Goller, Bernhard; Polisski, Sergej; Kovalev, Dmitry; Rollings, Matthew; Grogan, Michael D. W.; Birks, Timothy A.

    2012-07-01

    Silicon nanoparticles of three types (oxide-terminated silicon nanospheres, micron-sized hydrogen-terminated porous silicon grains and micron-size oxide-terminated porous silicon grains) were incorporated into silica aerogels at the gel preparation stage. Samples with a wide range of concentrations were prepared, resulting in aerogels that were translucent (but weakly coloured) through to completely opaque for visible light over sample thicknesses of several millimetres. The photoluminescence of these composite materials and of silica aerogel without silicon inclusions was studied in vacuum and in the presence of molecular oxygen in order to determine whether there is any evidence for non-radiative energy transfer from the silicon triplet exciton state to molecular oxygen adsorbed at the silicon surface. No sensitivity to oxygen was observed from the nanoparticles which had partially H-terminated surfaces before incorporation, and so we conclude that the silicon surface has become substantially oxidised. Finally, the FTIR and Raman scattering spectra of the composites were studied in order to establish the presence of crystalline silicon; by taking the ratio of intensities of the silicon and aerogel Raman bands, we were able to obtain a quantitative measure of the silicon nanoparticle concentration independent of the degree of optical attenuation.

  13. Positronium cooling in porous silica measured via Doppler spectroscopy

    SciTech Connect

    Cassidy, D. B.; Hisakado, T. H.; Meligne, V. E.; Tom, H. W. K.; Mills, A. P. Jr.; Crivelli, P.; Liszkay, L.; Perez, P.

    2010-01-15

    We have measured the kinetic energy of positronium (Ps) atoms emitted into a vacuum from a porous silica film subsequent to positron bombardment, via the Doppler spread of the linewidth of the Ps 1{sup 3}S-2{sup 3}P transition. We find that the deeper in the target film that positrons are implanted the colder is the emitted Ps, an effect we attribute to cooling via collisions in the pores as the atoms diffuse back to the film surface. We observed a lower limit to the mean Ps kinetic energy associated with motion in the direction of the laser, E{sub x}=42+-3 meV, that is consistent with conversion of the confinement energy of Ps in the 2.7-nm-diameter pores to kinetic energy in vacuum. An implication is that a porous sample would need to be composed of pores greater than around 10 nm in diameter in order to produce thermal Ps in vacuum with temperatures of less than 100 K. By performing Doppler spectroscopy on intense pulses of Ps we have experimentally demonstrated the production of many excited-state Ps atoms simultaneously, which could have numerous applications, including laser cooling and fundamental spectroscopic studies of Ps and the production of antihydrogen.

  14. NMR and SIP properties of partially saturated porous silica glasses

    NASA Astrophysics Data System (ADS)

    Wiens, E.; Klitzsch, N.; Mohnke, O.; Clauser, C.

    2009-04-01

    The signal responses of both, spectral induced polarization (SIP) and nuclear magnetic resonance (NMR) are sensitive to the inner surfaces of the water filled porous media. Therefore both methods are well suited to noninvasively determine hydrological relevant parameters such as the pore radii distributions or hydraulic permeability of fully and partially saturated rocks and soils. NMR exploits the relaxation of the magnetization of fluids in the pore space of porous medium. In SIP the frequency dependence of the complex resistivity is determined, which mainly arises from the polarization of charges at the fluid matrix interface. In this work we study the dependence of NMR and SIP signals on the inner structure of fully and partially saturated artificial porous silica glasses (VitraPOR). The samples are characterized by an accurately defined pore space with well known pore radii distributions and surface properties. The mean pore sizes of the investigated samples range from 1.0µm to 250µm. Laboratory NMR saturation recovery (T1) and CPMG (T2) measurements have been carried out using a 3.91 MHz NMR spectrometer. SIP measurements were conducted in an extended frequency range from 1mHz - 1MHz using four point and two point configurations for low and high frequencies ranges, respectively. A homogeneous partial saturation down to 1 vol. % has been realized by applying a uniform negative pressure gradient to the samples at each desaturation step. Additionally the corresponding pf curves have been recorded and evaluated. On the basis of the results from these experiments and corresponding numerical pore scale simulations of NMR relaxation (Nuclear Magnetic Resonance; see also Mohnke et al SSS23) and SIP (see also Volkmann et al MPRG7) we aim at an interpretation scheme for combined NMR and SIP measurements in order to assess structure, state and thus transport properties of fully and partially saturated soils.

  15. Molecular engineering of porous silica using aryl templates

    DOEpatents

    Loy, D.A.; Shea, K.J.

    1994-06-14

    A process is described for manipulating the porosity of silica using a series of organic template groups covalently incorporated into the silicate matrix. The templates in the bridged polysilsesquioxanes are selectively removed from the material by oxidation with oxygen plasma or other means, leaving engineered voids or pores. The size of these pores is dependent upon the length or size of the template or spacer. The size of the templates is measured in terms of Si-Si distances which range from about 0.67 nm to 1.08 nm. Changes introduced by the loss of the templates result in a narrow range of micropores (i.e. <2 nm). Both aryl and alkyl template groups are used as spacers. Novel microporous silica materials useful as molecular sieves, desiccants, and catalyst supports are produced. 3 figs.

  16. Molecular engineering of porous silica using aryl templates

    DOEpatents

    Loy, Douglas A.; Shea, Kenneth J.

    1994-01-01

    A process for manipulating the porosity of silica using a series of organic template groups covalently incorporated into the silicate matrix. The templates in the bridged polysilsesquioxanes are selectively removed from the material by oxidation with oxygen plasma or other means, leaving engineered voids or pores. The size of these pores is dependent upon the length or size of the template or spacer. The size of the templates is measured in terms of Si-Si distances which range from about 0.67 nm to 1.08 nm. Changes introduced by the loss of the templates result in a narrow range of micropores (i.e. <2 nm). Both aryl and alkyl template groups are used as spacers. Novel microporous silica materials useful as molecular seives, dessicants, and catalyst supports are produced.

  17. Preparation and characterization of silica nanoparticulate polyacrylonitrile composite and porous nanofibers

    NASA Astrophysics Data System (ADS)

    Ji, Liwen; Saquing, Carl; Khan, Saad A.; Zhang, Xiangwu

    2008-02-01

    In this study, polyacrylonitrile (PAN) composite nanofibers containing different amounts of silica nanoparticulates have been obtained via electrospinning. The surface morphology, thermal properties and crystal structure of PAN/silica nanofibers are characterized using attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, wide-angle x-ray diffraction (WAXD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results indicate that the addition of silica nanoparticulates affects the structure and properties of the nanofibers. In addition to PAN/silica composite nanofibers, porous PAN nanofibers have been prepared by selective removal of the silica component from PAN/silica composite nanofibers using hydrofluoric (HF) acid. ATR-FTIR and thermal gravimetric analysis (TGA) experiments validate the removal of silica nanoparticulates by HF acid, whereas SEM and TEM results reveal that the porous nanofibers obtained from composite fibers with higher silica contents exhibited more nonuniform surface morphology. The Brunauer-Emmett-Teller (BET) surface area of porous PAN nanofibers made from PAN/silica (5 wt%) composite precursors is higher than that of pure nonporous PAN nanofibers.

  18. Silica decorated on porous activated carbon nanofiber composites for high-performance supercapacitors

    NASA Astrophysics Data System (ADS)

    Kim, So Yeun; Kim, Bo-Hye

    2016-10-01

    A hybrid of silica decorated on porous activated carbon nanofibers (ACNFs) is fabricated in the form of a web via electrospinning and an activation process as an electrode material for electrochemical capacitors in an organic electrolyte. The introduction of PhSiH3 (PS) into the polyacrylonitrile (PAN) solution induces a porous ACNF structure containing silica nanoparticles (NPs) via the spontaneous sol-gel process of PS by steam in the subsequent physical activation process. These inorganic-organic hybrid composites of porous ACNF containing silica NPs show superior specific capacitance and energy density in electrochemical tests, along with good rate capability and excellent cycle life in an organic electrolyte, which is attributed to the combination of ACNF's high surface area and silica's hydrophilicity. The electrochemical performance decreases with increasing PS concentration, and this trend is consistent with the specific surface area results, which reveal the rapid formation of a double layer.

  19. One-pot pseudomorphic crystallization of mesoporous porous silica to hierarchical porous zeolites

    SciTech Connect

    Xing, Jun-Ling; Jiang, Shu-Hua; Pang, Jun-Ling; Yuan, En-Hui; Ma, Xiao-Jing; Lam, Koon-Fung; Xue, Qing-Song; Zhang, Kun

    2015-09-15

    Hierarchically porous silica with mesopore and zeolitic micropore was synthesized via pseudomorphic crystallization under high-temperature hydrothermal treatment in the presence of cetyltrimethylammonium tosylate and tetrapropylammonium ions. A combined characterization using small-angle X-ray diffraction (XRD), nitrogen adsorption, high-resolution transmission electron microscopy (TEM), thermogravimetric analysis (TG), and elemental analysis showed that dual templates, CTA{sup +} and TPA{sup +} molecules, can work in a cooperative manner to synthesize mesoporous zeolite in a one-pot system by precisely tuning the reaction conditions, such as reaction time and temperature, and type and amount of heterometal atoms. It is found that the presence of Ti precursor is critical to the successful synthesis of such nanostructure. It not only retards the nucleation and growth of crystalline MFI domains, but also acts as nano-binder or nano-glue to favor the assembly of zeolite nanoblocks. - Graphical abstract: Display Omitted - Highlights: • A facile method to synthesize mesoporous zeolites with hierarchical porosity was presented. • It gives a new insight into keeping the balance between mesoscopic and molecular ordering in hierarchical porous materials. • A new understanding on the solid–solid transformation mechanism for the synthesis of titanosilicate zeolites was proposed.

  20. Formation of bimodal porous silica-titania monoliths by sol-gel route

    NASA Astrophysics Data System (ADS)

    Ruzimuradov, O. N.

    2011-10-01

    Silica-titania monoliths with micrometer-scale macroporous and nanometer-scale mesoporous structure and high titania contents are prepared by sol-gel process and phase separation. Titanium alkoxide precursor was not effective in the preparation of high titania content composites because of strong decrease in phase separation tendency. Bimodal porous gels with high titania content were obtained by using inorganic salt precursors such as titanium sulfate and titanium chloride. Various characterization techniques, including SEM, XRD, Hg porosimetry and N2 adsorption have been carried out to investigate the formation process and physical-chemical properties of silica-titania monoliths. The characterization results show that the silica-titania monoliths possess a bimodal porous structure with well-dispersed titania inside silica network. The addition of titania in silica improves the thermal stability of both macroporous and mesoporous structures.

  1. Dopamine/Silica Nanoparticle Assembled, Microscale Porous Structure for Versatile Superamphiphobic Coating.

    PubMed

    Li, Fang; Du, Miao; Zheng, Qiang

    2016-02-23

    Artificial superamphiphobic surfaces, which could repel both water and low surface tension organic liquids, have been limited to particular kinds of materials or surfaces thus far. In this work, a kind of microscale porous coating was developed. Taking dopamine and hydrophilic fumed silica nanoparticles as initial building blocks, microscale porous coating was constructed via ice templation. Polydopamine bound silica nanoparticles together to form a porous structure network and rendered the coating to have potential for further postfunctionalization. After two-step CVD, the microscale porous coating changes from superhydrophilic to superamphiphobic, exhibiting super-repellency to droplets with surface tension of 73-23 mN/m. The influences of concentration of initial dopamine, hydrophilic fumed silica nanoparticles, and dry conditions on the formation of the porous structure have been studied to optimize the conditions. Coatings with different pore sizes and pore heights have been fabricated to discover the relationship between the structure parameters and the repellency of the porous coatings. Only with optimal pore size and pore height can the porous coating display superamphiphobicity. Compared with nanoscale, the microscale structure favors the achievement of superamphiphobicity. Given the outstanding adhesive ability of polydopamine, the superamphiphobic coatings have been successfully applied to various materials including artificial materials and natural materials. PMID:26828414

  2. Dopamine/Silica Nanoparticle Assembled, Microscale Porous Structure for Versatile Superamphiphobic Coating.

    PubMed

    Li, Fang; Du, Miao; Zheng, Qiang

    2016-02-23

    Artificial superamphiphobic surfaces, which could repel both water and low surface tension organic liquids, have been limited to particular kinds of materials or surfaces thus far. In this work, a kind of microscale porous coating was developed. Taking dopamine and hydrophilic fumed silica nanoparticles as initial building blocks, microscale porous coating was constructed via ice templation. Polydopamine bound silica nanoparticles together to form a porous structure network and rendered the coating to have potential for further postfunctionalization. After two-step CVD, the microscale porous coating changes from superhydrophilic to superamphiphobic, exhibiting super-repellency to droplets with surface tension of 73-23 mN/m. The influences of concentration of initial dopamine, hydrophilic fumed silica nanoparticles, and dry conditions on the formation of the porous structure have been studied to optimize the conditions. Coatings with different pore sizes and pore heights have been fabricated to discover the relationship between the structure parameters and the repellency of the porous coatings. Only with optimal pore size and pore height can the porous coating display superamphiphobicity. Compared with nanoscale, the microscale structure favors the achievement of superamphiphobicity. Given the outstanding adhesive ability of polydopamine, the superamphiphobic coatings have been successfully applied to various materials including artificial materials and natural materials.

  3. Fabrication of autofluorescent porous silica nanoparticles for redox-responsive drug release.

    PubMed

    Cao, Na; Zhao, Yanbao; Sang, Bin; Wang, Zhihua; Cao, Liuqin; Sun, Lei; Zou, Xueyan

    2016-12-01

    Porous silica nanoparticles were prepared by emulsion-condensation route. The silica nanoparticles with diameter of 50nm have both accessible center-radial large pore channels (19.9nm) and small pore size of 3.5nm. The hierarchical porous structure endows them large pore volume for loading drugs and sustained release property. The silica nanoparticles were further modified with glucose-oxidized glutathione. The formulated Schiff base and disulfide bonds render the silica nanoparticles auto-fluorescent and redox-responsive properties. The cleavage of disulfide bonds caused by reactive thiols facilitates aminomethylbenzoic acid (AMA) release. The release of drug leads to the loss of fluorescence, which would be used to monitor the drug delivery and carrier distribution. PMID:27612720

  4. Enhancement of Li+ ion conductivity in solid polymer electrolytes using surface tailored porous silica nanofillers

    NASA Astrophysics Data System (ADS)

    Mohanta, Jagdeep; Singh, Udai P.; Panda, Subhendu K.; Si, Satyabrata

    2016-09-01

    The current study represents the design and synthesis of polyethylene oxide (PEO)-based solid polymer electrolytes by solvent casting approach using surface tailored porous silica as nanofillers. The surface tailoring of porous silica nanostructure is achieved through silanization chemistry using 3-glycidyloxypropyl trimethoxysilane in which silane part get anchored to the silica surface whereas epoxy group get stellated from the silica surface. Surface tailoring of silica with epoxy group increases the room temperature electrochemical performances of the resulting polymer electrolytes. Ammonical hydrolysis of organosilicate precursor is used for both silica preparation and their surface tailoring. The composite solid polymer electrolyte films are prepared by solution mixing of PEO with lithium salt in presence of silica nanofillers and cast into film by solvent drying, which are then characterized by impedance measurement for conductivity study and wide angle x-ray diffraction for change in polymer crystallinity. Room temperature impedance measurement reveals Li+ ion conductivity in the order of 10‑4 S cm‑1, which is correlated to the decrease in PEO crystallinity. The enhancement of conductivity is further observed to be dependent on the amount of silica as well as on their surface characteristics.

  5. Enhancement of Li+ ion conductivity in solid polymer electrolytes using surface tailored porous silica nanofillers

    NASA Astrophysics Data System (ADS)

    Mohanta, Jagdeep; Singh, Udai P.; Panda, Subhendu K.; Si, Satyabrata

    2016-09-01

    The current study represents the design and synthesis of polyethylene oxide (PEO)-based solid polymer electrolytes by solvent casting approach using surface tailored porous silica as nanofillers. The surface tailoring of porous silica nanostructure is achieved through silanization chemistry using 3-glycidyloxypropyl trimethoxysilane in which silane part get anchored to the silica surface whereas epoxy group get stellated from the silica surface. Surface tailoring of silica with epoxy group increases the room temperature electrochemical performances of the resulting polymer electrolytes. Ammonical hydrolysis of organosilicate precursor is used for both silica preparation and their surface tailoring. The composite solid polymer electrolyte films are prepared by solution mixing of PEO with lithium salt in presence of silica nanofillers and cast into film by solvent drying, which are then characterized by impedance measurement for conductivity study and wide angle x-ray diffraction for change in polymer crystallinity. Room temperature impedance measurement reveals Li+ ion conductivity in the order of 10-4 S cm-1, which is correlated to the decrease in PEO crystallinity. The enhancement of conductivity is further observed to be dependent on the amount of silica as well as on their surface characteristics.

  6. Racetrack micro-resonators based on ridge waveguides made of porous silica

    NASA Astrophysics Data System (ADS)

    Girault, P.; Lorrain, N.; Lemaitre, J.; Poffo, L.; Guendouz, M.; Hardy, I.; Gadonna, M.; Gutierrez, A.; Bodiou, L.; Charrier, J.

    2015-12-01

    The fabrication of micro-resonators, made from porous silica ridge waveguides by using an electrochemical etching method of silicon substrate followed by thermal oxidation and then by a standard photolithography process, is reported. The design and fabrication process are described including a study of waveguide dimensions that provide single mode propagation and calculation of the coupling ratio between a straight access waveguide and the racetrack resonator. Scanning electronic microscopy observations and optical characterizations clearly show that the micro-resonator based on porous silica ridge waveguides has been well implemented. This porous micro-resonator is destined to be used as an optical sensor. The porous nature of the ridge waveguide constitutes the detection medium which will enhance the sensor sensitivity compared to usual micro-resonators based on the evanescent wave detection. A theoretical sensitivity of 1170 nm per refractive index unit has been calculated, taking into consideration experimental data obtained from the optical characterizations.

  7. In situ synthesis of porous silica nanoparticles for covalent immobilization of enzymes

    NASA Astrophysics Data System (ADS)

    Yang, Xiaowei; Cai, Zhengwei; Ye, Zhangmei; Chen, Sheng; Yang, Yu; Wang, Haifang; Liu, Yuanfang; Cao, Aoneng

    2012-01-01

    A simple method is used to covalently encapsulate enzymes in silica nanoparticles. The encapsulation is highlighted by the high enzyme loading and porous channels that provide efficient diffusion for small substrate and product molecules while preventing protease degradation.A simple method is used to covalently encapsulate enzymes in silica nanoparticles. The encapsulation is highlighted by the high enzyme loading and porous channels that provide efficient diffusion for small substrate and product molecules while preventing protease degradation. Electronic supplementary information (ESI) available: Experimental procedures and the result of the surface-grafted catalase control experiment. See DOI: 10.1039/c1nr11153a

  8. Immobilization of pectinmethylesterase from acerola (Malpighia glabra L.) in porous silica.

    PubMed

    de Assis, Sandra Aparecida; Trevisan, Henrique Celso; Mascarenhas, Olga Maria; Oliveira, Faria

    2003-06-01

    The total and partially purified enzyme pectinmethylesterase from acerola fruit was covalently immobilized on porous silica particles. These efficiency values were 114% for the total PME and 351% for the partially purified PME. In both forms the immobilization resulted in compounds with high thermal stability.

  9. Superwetting hierarchical porous silica nanofibrous membranes for oil/water microemulsion separation.

    PubMed

    Yang, Shan; Si, Yang; Fu, Qiuxia; Hong, Feifei; Yu, Jianyong; Al-Deyab, Salem S; El-Newehy, Mohamed; Ding, Bin

    2014-11-01

    Novel flexible, thermally stable and hierarchical porous silica nanofibrous membranes with superhydrophilicity and underwater superoleophobicity were prepared by a facile in situ synthesis method, which can effectively separate oil-in-water microemulsions solely driven by gravity, with an extremely high flux of 2237 L m(-2) h(-1). PMID:25260122

  10. Electrode With Porous Three-Dimensional Support

    DOEpatents

    Bernard, Patrick; Dauchier, Jean-Michel; Simonneau, Olivier

    1999-07-27

    Electrode including a paste containing particles of electrochemically active material and a conductive support consisting of a three-dimensional porous material comprising strands delimiting contiguous pores communicating via passages, characterized in that the average width L in .mu.m of said passages is related to the average diameter .O slashed. in .mu.m of said particles by the following equation, in which W and Y are dimensionless coefficients: wherein W=0.16 Y=1.69 X=202.4 .mu.m and Z=80 .mu.m

  11. Moisture sensor based on evanescent wave light scattering by porous sol-gel silica coating

    DOEpatents

    Tao, Shiquan; Singh, Jagdish P.; Winstead, Christopher B.

    2006-05-02

    An optical fiber moisture sensor that can be used to sense moisture present in gas phase in a wide range of concentrations is provided, as well techniques for making the same. The present invention includes a method that utilizes the light scattering phenomenon which occurs in a porous sol-gel silica by coating an optical fiber core with such silica. Thus, a porous sol-gel silica polymer coated on an optical fiber core forms the transducer of an optical fiber moisture sensor according to an embodiment. The resulting optical fiber sensor of the present invention can be used in various applications, including to sense moisture content in indoor/outdoor air, soil, concrete, and low/high temperature gas streams.

  12. Combination of porous silica monolith and gold thin films for electrode material of supercapacitor

    NASA Astrophysics Data System (ADS)

    Pastre, A.; Cristini-Robbe, O.; Boé, A.; Raulin, K.; Branzea, D.; El Hamzaoui, H.; Kinowski, C.; Rolland, N.; Bernard, R.

    2015-12-01

    An all-solid electrical double layer supercapacitor was prepared, starting from a porous silica matrix coated with a gold thin-film. The metallization of the silica xerogel was performed by an original wet chemical process, based on the controlled growth of gold nanoparticles on two opposite faces of the silica monolith as a seed layer, followed by an electroless deposition of a continuous gold thin film. The thickness of the metallic thin film was assessed to be 700 nm. The silica plays two major roles: (1) it is used as a porous matrix for the gold electrode, creating a large specific surface area, and (2) it acts as a separator (non-metallized part of the silica). The silica monolith was soaked in a polyvinyl alcohol and phosphoric acid mixture which is used as polymer electrolyte. Capacitance effect was demonstrated by cyclic voltammetry experiments. The specific capacitance was found to be equal to 0.95 mF cm- 2 (9.5 F g-1). No major degradation occurs within more than 3000 cycles.

  13. Water repellent porous silica films by sol-gel dip coating method.

    PubMed

    Rao, A Venkateswara; Gurav, Annaso B; Latthe, Sanjay S; Vhatkar, Rajiv S; Imai, Hiroaki; Kappenstein, Charles; Wagh, P B; Gupta, Satish C

    2010-12-01

    The wetting of solid surfaces by water droplets is ubiquitous in our daily lives as well as in industrial processes. In the present research work, water repellent porous silica films are prepared on glass substrate at room temperature by sol-gel process. The coating sol was prepared by keeping the molar ratio of methyltriethoxysilane (MTES), methanol (MeOH), water (H(2)O) constant at 1:12.90:4.74, respectively, with 2M NH(4)OH throughout the experiments and the molar ratio (M) of MTES/Ph-TMS was varied from 0 to 0.22. A simple dip coating technique is adopted to coat silica films on the glass substrates. The static water contact angle as high as 164° and water sliding angle as low as 4° was obtained for silica film prepared from M=0.22. The surface morphological studies of the prepared silica film showed the porous structure with pore sizes typically ranging from 200nm to 1.3μm. The superhydrophobic silica films prepared from M=0.22 retained their superhydrophobicity up to a temperature of 285°C and above this temperature the films became superhydrophilic. The porous and water repellent silica films are prepared by proper alteration of the Ph-TMS in the coating solution. The prepared silica films were characterized by surface profilometer, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier Transform Infrared (FT-IR) spectroscopy, humidity tests, chemical aging tests, static and dynamic water contact angle measurements.

  14. Infrared investigations on metal-support interactions in Ni-SiO{sub 2} catalyst precursors: Role of silica

    SciTech Connect

    Ghuge, K.D.; Babu, G.P.

    1995-02-01

    In a Ni-silica catalyst system prepared by the precipitation/deposition method the silica is reported to play a role in forming the {open_quotes}support{close_quotes} to nickel carbonate (or hydroxide) species. The support formed is identified as various types of nickel silicate species and also as the species comprising -Ni-O-Si- linkages. Further, the support is shown to (i) provide the definite porous structure to the catalyst and (ii) influence the reducibility of nickel species. Also, in nickel catalyst system prepared by impregnation method, formation of silicate species on surface and its influence on reduction of nickel and restriction in metal sintering is well established. However, the mechanism of silica conversion to support species and influence on metal dispersion, the formation of a definite porous network and catalytic activity in Ni-silica catalyst system prepared by precipitation is not well established. In this paper Ni-silica catalyst precursors were prepared by adding separate solutions of nickel sulfate and sodium carbonate simultaneously to the precipitation vessel containing a silica slurry as described by Nitta et al. and maintaining a SiO{sub 2}/Ni ratio of 0.5, precipitation temperature = 92{degrees}C, and pH = 8.5. 15 refs., 1 fig., 1 tab.

  15. Porous Silica Sol-Gel Glasses Containing Reactive V2O5 Groups

    NASA Technical Reports Server (NTRS)

    Stiegman, Albert E.

    1995-01-01

    Porous silica sol-gel glasses into which reactive vanadium oxide functional groups incorporated exhibit number of unique characteristics. Because they bind molecules of some species both reversibly and selectively, useful as chemical sensors or indicators or as scrubbers to remove toxic or hazardous contaminants. Materials also oxidize methane gas photochemically: suggests they're useful as catalysts for conversion of methane to alcohol and for oxidation of hydrocarbons in general. By incorporating various amounts of other metals into silica sol-gel glasses, possible to synthesize new materials with broad range of new characteristics.

  16. Determination of Ro 48-3656 in rat plasma by reversed-phase high-performance liquid chromatography. Comparison of 1.5-microm nonporous silica to 3.5-microm porous silica analytical columns.

    PubMed

    Paasch, B D; Lin, Y S; Porter, S; Modi, N B; Barder, T J

    1997-12-19

    We describe a method for measuring Ro 48-3656 in EDTA rat plasma by neutral pH, reversed-phase high-performance liquid chromatography using a 1.5-microm nonporous silica, C18 analytical column and UV absorbance detection to support pharmacokinetic studies. We also describe a comparison of the 1.5-microm nonporous silica C18 column versus 3.5-microm porous silica C18 columns. The final method using the 1.5-microm nonporous silica column demonstrated good precision (of both quantification and retention time), accuracy and recovery, linearity of dilution and limit of quantification (40 ng/ml Ro 48-3656 using a 20 microl injection). Samples of neat EDTA rat plasma were prepared by ultrafiltration followed by direct injection onto the HPLC column. PMID:9518155

  17. Superwetting hierarchical porous silica nanofibrous membranes for oil/water microemulsion separation

    NASA Astrophysics Data System (ADS)

    Yang, Shan; Si, Yang; Fu, Qiuxia; Hong, Feifei; Yu, Jianyong; Al-Deyab, Salem S.; El-Newehy, Mohamed; Ding, Bin

    2014-10-01

    Novel flexible, thermally stable and hierarchical porous silica nanofibrous membranes with superhydrophilicity and underwater superoleophobicity were prepared by a facile in situ synthesis method, which can effectively separate oil-in-water microemulsions solely driven by gravity, with an extremely high flux of 2237 L m-2 h-1.Novel flexible, thermally stable and hierarchical porous silica nanofibrous membranes with superhydrophilicity and underwater superoleophobicity were prepared by a facile in situ synthesis method, which can effectively separate oil-in-water microemulsions solely driven by gravity, with an extremely high flux of 2237 L m-2 h-1. Electronic supplementary information (ESI) available: Detailed synthesis and structural confirmation of BA-CHO, FT-IR and EDX results, Movie S1-S3. See DOI: 10.1039/c4nr04668d

  18. Anisotropic magnetic porous assemblies of oxide nanoparticles interconnected via silica bridges for catalytic application.

    PubMed

    Wacker, Josias B; Parashar, Virendra K; Gijs, Martin A M

    2011-04-19

    We report the microfluidic chip-based assembly of colloidal silanol-functionalized silica nanoparticles using monodisperse water-in-oil droplets as templates. The nanoparticles are linked via silica bridges, thereby forming superstructures that range from doublets to porous spherical or rod-like micro-objects. Adding magnetite nanoparticles to the colloid generates micro-objects that can be magnetically manipulated. We functionalized such magnetic porous assemblies with horseradish peroxidase and demonstrate the catalytic binding of fluorescent dye-labeled tyramide over the complete effective surface of the superstructure. Such nanoparticle assemblies permit easy manipulation and recovery after a heterogeneous catalytic process while providing a large surface similar to that of the individual nanoparticles. PMID:21417232

  19. Nanoscale assembly of lanthanum silica with dense and porous interfacial structures

    NASA Astrophysics Data System (ADS)

    Ballinger, Benjamin; Motuzas, Julius; Miller, Christopher R.; Smart, Simon; Diniz da Costa, João C.

    2015-02-01

    This work reports on the nanoscale assembly of hybrid lanthanum oxide and silica structures, which form patterns of interfacial dense and porous networks. It was found that increasing the molar ratio of lanthanum nitrate to tetraethyl orthosilicate (TEOS) in an acid catalysed sol-gel process alters the expected microporous metal oxide silica structure to a predominantly mesoporous structure above a critical lanthanum concentration. This change manifests itself by the formation of a lanthanum silicate phase, which results from the reaction of lanthanum oxide nanoparticles with the silica matrix. This process converts the microporous silica into the denser silicate phase. Above a lanthanum to silica ratio of 0.15, the combination of growth and microporous silica consumption results in the formation of nanoscale hybrid lanthanum oxides, with the inter-nano-domain spacing forming mesoporous volume. As the size of these nano-domains increases with concentration, so does the mesoporous volume. The absence of lanthanum hydroxide (La(OH)3) suggests the formation of La2O3 surrounded by lanthanum silicate.

  20. Nanoscale assembly of lanthanum silica with dense and porous interfacial structures

    PubMed Central

    Ballinger, Benjamin; Motuzas, Julius; Miller, Christopher R.; Smart, Simon; Diniz da Costa, João C.

    2015-01-01

    This work reports on the nanoscale assembly of hybrid lanthanum oxide and silica structures, which form patterns of interfacial dense and porous networks. It was found that increasing the molar ratio of lanthanum nitrate to tetraethyl orthosilicate (TEOS) in an acid catalysed sol-gel process alters the expected microporous metal oxide silica structure to a predominantly mesoporous structure above a critical lanthanum concentration. This change manifests itself by the formation of a lanthanum silicate phase, which results from the reaction of lanthanum oxide nanoparticles with the silica matrix. This process converts the microporous silica into the denser silicate phase. Above a lanthanum to silica ratio of 0.15, the combination of growth and microporous silica consumption results in the formation of nanoscale hybrid lanthanum oxides, with the inter-nano-domain spacing forming mesoporous volume. As the size of these nano-domains increases with concentration, so does the mesoporous volume. The absence of lanthanum hydroxide (La(OH)3) suggests the formation of La2O3 surrounded by lanthanum silicate. PMID:25644988

  1. The effect of elevated temperature on the strength parameters of silica acid ester consolidated porous limestones

    NASA Astrophysics Data System (ADS)

    Pápay, Zita; Török, Ákos

    2013-04-01

    The porous limestone is one of the most widespread construction materials of the monuments in Central Europe, with emblematic buildings in Vienna, Bratislava, Budapest and many other cities of Austria, Slovakia, Czech Republic and Hungary. The restoration of these monuments very often requires the consolidation of the porous limestone material, where various types of consolidants are used to strengthen the highly weathered stone. Our research focused on the understanding of the behaviour of consolidated porous limestone when the material is subjected to higher temperatures. Test procedure included the preparation of cylindrical test specimens from the Miocene porous limestone which was followed by consolidation by four various types of silica acid ester. The samples after consolidation were heated to 300 and 600 °C in electric oven. The material properties such as ultrasonic pulse velocity, density were tested before and after the treatment. Indirect tensile strength (Brazilian test) was used to compare the strength parameters of non treated and consolidated samples. Silica acid ester treated samples after heating were also measured in terms of strength, density and ultrasonic pulse velocity. The results show that there are significant changes in strength of various pre-treated samples after heating indicating the sensitivity of the materials to temperature changes and accidental fire.

  2. Silica coated noble metal nanoparticle hydrosols as supported catalyst precursors.

    PubMed

    Kong, Tung Shing Adam; Yu, Kai Man Kerry; Tsang, Shik Chi

    2006-04-01

    Synthesis of well-defined nanoparticles has been intensively pursued not only for their fundamental scientific interest, but also for many technological applications. One important development of the nanomaterial is in the area of chemical catalysis. We have now developed a new aqueous-based method for the synthesis of silica encapsulated noble metal nanoparticles in controlled dimensions. Thus, colloid stable silica encapsulated approximately 5 nm platinum nanoparticle is synthesized by a multi-step method. The thickness of the silica coating could be controlled using a different amount of silica precursor. These particles supported on a high surface area alumina are also demonstrated to display a superior hydrogenation activity and stability against metal sintering after thermal activation.

  3. CO adsorption on a silica bilayer supported on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Schlexer, Philomena; Pacchioni, Gianfranco; Włodarczyk, Radosław; Sauer, Joachim

    2016-06-01

    Silica bilayers are built up of two layers of corner sharing SiO4-tetrahedra and constitute an inert ultra-thin membrane supported on the Ru(0001) surface. We have investigated the adsorption of CO on that system using DFT with inclusion of dispersion corrections. The molecules adsorb at the interface between the SiO2 film and Ru(0001) surface. The estimated barrier for diffusion of CO through the silica bilayer is around 0.5 eV. The CO bond length, the C-O stretching frequency and the silica-ruthenium distance depend strongly on the CO coverage. The band observed at 2051 cm- 1 in previous experiments can be assigned to a CO coverage of around 0.5 ML on Ru(0001), with the silica bilayer floating above the CO molecules.

  4. Hierarchical control of porous silica by pH adjustment: Alkyl polyamines as surfactants for bimodal silica synthesis and its carbon replica

    NASA Astrophysics Data System (ADS)

    Abellán, G.; Carrillo, A. I.; Linares, N.; Serrano, E.; García-Martínez, J.

    2009-08-01

    Bimodal macro-mesoporous silica networks have been prepared in a simple one-pot synthesis using an inexpensive tetramine surfactant and tetraethoxysilane as a silica precursor. These novel materials show high pore volumes and templated mesopores (average pore size 3.0 nm) embedded in 20 nm thick walls forming interparticle large meso/macropores. The judicious control of the pH during the silica formation allows for the precise control of the interparticle condensation, likely due to the change in the interaction between the tetramine surfactant and the silica precursors. Finally, a highly porous carbon replica with bimodal porosity was prepared by using the bimodal silica as a hard sacrificial template. The microstructure of the silica template was accurately transferred to the carbon material obtaining high surface areas (up to 1300 m 2 g -1) and total pore volumes ≥2 cm 3 g -1.

  5. Photocatalytic activity of erbium-doped TiO{sub 2} nanoparticles immobilized in macro-porous silica films

    SciTech Connect

    Castaneda-Contreras, J.; Maranon-Ruiz, V.F.; Chiu-Zarate, R.; Perez-Ladron de Guevara, H.; Rodriguez, R.; Michel-Uribe, C.

    2012-02-15

    Highlights: Black-Right-Pointing-Pointer Erbium-doped TiO{sub 2} nanoparticles were immobilized on macro-porous silica films. Black-Right-Pointing-Pointer The films were obtained by a phase separation process. Black-Right-Pointing-Pointer The samples exhibited photo-catalytic activity under visible light. Black-Right-Pointing-Pointer The sensitization of TiO{sub 2} was attributed to a red shift in the TiO{sub 2} band-gap. -- Abstract: A macro-porous silica film served as mechanical support to immobilize TiO{sub 2} nanoparticles, which were doped with erbium. The films and the nanoparticles were prepared by sol-gel route. The nanoparticles exhibited photocatalytic activity under visible light. We obtained a degradation rate of methylene blue that followed first order kinetics. The sensitization of the nanoparticles to visible light was attributed to a red shift in the band-gap of the TiO{sub 2} due to the addition of erbium ions.

  6. Porous silica coated spherical microresonator for vapor phase sensing of ammonia at a sub-ppm level

    NASA Astrophysics Data System (ADS)

    Mallik, Arun K.; Farrell, Gerald; Liu, Dejun; Kavungal, Vishnu; Wu, Qiang; Semenova, Yuliya

    2016-05-01

    A new type of fiber optic sensor for the detection and quantification of ammonia (NH3) vapor levels is proposed and experimentally demonstrated. This sensor is based on a spherical silica micro resonator coated with porous silica gel. Whispering gallery modes (WGMs) in the micro resonator are excited by evanescent coupling to a tapered fiber with a 3.3 μm waist diameter. The optical properties of the porous silica layer change when it is exposed to ammonia vapor, leading to a spectral shift of the WGM resonant wavelengths. The sensitivity of the proposed sensor has been tested by exposing it to different low level concentrations of ammonia: 4 ppm, 8 ppm, 12 ppm and 30 ppm at a constant relative humidity (50% RH) and constant temperature (23°C). The detection limit is calculated from experimental results as 57 ppb of ammonia for a 282 μm diameter porous silica coated microsphere.

  7. Electrostatic self-assembly of PEG copolymers onto porous silica nanoparticles.

    PubMed

    Thierry, Benjamin; Zimmer, Lucie; McNiven, Scott; Finnie, Kim; Barbé, Christophe; Griesser, Hans J

    2008-08-01

    A critical requirement toward the clinical use of nanocarriers in drug delivery applications is the development of optimal biointerfacial engineering procedures designed to resist biologically nonspecific adsorption events. Minimization of opsonization increases blood residence time and improves the ability to target solid tumors. We report the electrostatic self-assembly of polyethyleneimine-polyethylene glycol (PEI-PEG) copolymers onto porous silica nanoparticles. PEI-PEG copolymers were synthesized and their adsorption by self-assembly onto silica surfaces were investigated to achieve a better understanding of structure-activity relationships. Quartz-crystal microbalance (QCM) study confirmed the rapid and stable adsorption of the copolymers onto silica-coated QCM sensors driven by strong electrostatic interactions. XPS and FT-IR spectroscopy were used to analyze the coated surfaces, which indicated the presence of dense PEG layers on the silica nanoparticles. Dynamic light scattering was used to optimize the coating procedure. Monodisperse dispersions of the PEGylated nanoparticles were obtained in high yields and the thin PEG layers provided excellent colloidal stability. In vitro protein adsorption tests using 5% serum demonstrated the ability of the self-assembled copolymer layers to resist biologically nonspecific fouling and to prevent aggregation of the nanoparticles in physiological environments. These results demonstrate that the electrostatic self-assembly of PEG copolymers onto silica nanoparticles used as drug nanocarriers is a robust and efficient procedure, providing excellent control of their biointerfacial properties.

  8. Evaluation of the acid properties of porous zirconium-doped and undoped silica materials

    SciTech Connect

    Fuentes-Perujo, D.; Santamaria-Gonzalez, J.; Merida-Robles, J.; Rodriguez-Castellon, E.; Jimenez-Lopez, A.; Maireles-Torres, P. . E-mail: maireles@uma.es; Moreno-Tost, R.

    2006-07-15

    A series of porous silica and Zr-doped silica molecular sieves, belonging to the MCM-41 and MSU families, were prepared and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and N{sub 2} adsorption at 77 K. Their acid properties have been evaluated by NH{sub 3}-TPD, adsorption of pyridine and deuterated acetonitrile coupled to FT-IR spectroscopy and the catalytic tests of isopropanol decomposition and isomerization of 1-butene. The acidity of purely siliceous solids were, in all cases, very low, while the incorporation of Zr(IV) into the siliceous framework produced an enhancement of the acidity. The adsorption of basic probe molecules and the catalytic behaviour revealed that Zr-doped MSU-type silica was more acidic than the analogous Zr-MCM-41 solid, with a similar Zr content. This high acidity observed in the case of Zr-doped silica samples is due to the presence of surface zirconium atoms with a low coordination, mainly creating Lewis acid sites. - Graphical abstract: The adsorption of basic probe molecules and the catalytic behaviour have revealed that MSU-type materials are more acidic than the analogous MCM-41 solids, mainly after the incorporation of zirconium into the silica framework.

  9. Shape control of self-organized porous silica submicron particles and their strength evaluation

    NASA Astrophysics Data System (ADS)

    Kiyohara, Keita; Inoue, Keita; Inoue, Shozo; Namazu, Takahiro

    2016-06-01

    In this paper, precise control of the shape, size, and porosity of porous silica submicron particles and their strength evaluation are described. Self-organization phenomenon of silica nanopowders and submicron polystyrene latex (PSL) balls in an atomized mist is used for the fabrication of the particles. When temperatures of lower- and upper-zone heaters are 100 and 600 °C, and N2 gas flow rate is 0.4 l/min, spherical particles are produced. When PSL concentration increases, the number of pores increases. Particles with uniformly-arranged pores are produced at the PSL concentration of around 3 wt %. By using the PSL balls of different diameters, porous silica particles including different size pores are made. Also, compressive fracture test is conducted to check the effect of vacuum annealing on the strength of particles. The annealed particle shows higher fracture force than the unannealed particle, which indicates that the annealing would be effective for improving the mechanical reliability.

  10. Hierarchical control of porous silica by pH adjustment: Alkyl polyamines as surfactants for bimodal silica synthesis and its carbon replica

    SciTech Connect

    Abellan, G.; Carrillo, A.I.; Linares, N.; Serrano, E.

    2009-08-15

    Bimodal macro-mesoporous silica networks have been prepared in a simple one-pot synthesis using an inexpensive tetramine surfactant and tetraethoxysilane as a silica precursor. These novel materials show high pore volumes and templated mesopores (average pore size 3.0 nm) embedded in 20 nm thick walls forming interparticle large meso/macropores. The judicious control of the pH during the silica formation allows for the precise control of the interparticle condensation, likely due to the change in the interaction between the tetramine surfactant and the silica precursors. Finally, a highly porous carbon replica with bimodal porosity was prepared by using the bimodal silica as a hard sacrificial template. The microstructure of the silica template was accurately transferred to the carbon material obtaining high surface areas (up to 1300 m{sup 2} g{sup -1}) and total pore volumes >=2 cm{sup 3} g{sup -1}. - Graphical abstract: Hierarchical bimodal porous silica and its carbon replica prepared by nanocasting.

  11. Toward compositional design of reticular type porous films by mixing and coating titania-based frameworks with silica

    NASA Astrophysics Data System (ADS)

    Kimura, T.

    2015-12-01

    A recently developed reticular type porous structure, which can be fabricated as the film through the soft colloidal block copolymer (e.g., PS-b-PEO) templating, is very promising as the porous platform showing high-performance based on its high surface area as well as high diffusivity of targeted organic molecules and effective accommodation of bulky molecules, but the compositional design of oxide frameworks has not been developed so enough to date. Here, I report reliable synthetic methods of the reticular type porous structure toward simple compositional variations. Due to the reproducibility of reticular type porous titania films from titanium alkoxide (e.g., TTIP; titanium tetraisopropoxide), a titania-silica film having similar porous structure was obtained by mixing silicon alkoxide (e.g., tetraethoxysilane) and TTIP followed by their pre-hydrolysis, and the mixing ratio of Ti to Si composition was easily reached to 1.0. For further compositional design, a concept of surface coating was widely applicable; the reticular type porous titania surfaces can be coated with other oxides such as silica. Here, a silica coating was successfully achieved by the simple chemical vapor deposition of silicon alkoxide (e.g., tetramethoxysilane) without water (with water at the humidity level), which was also utilized for pore filling with silica by the similar process with water.

  12. Thermal pretreatments of superficially porous silica particles for high-performance liquid chromatography: Surface control, structural characterization and chromatographic evaluation.

    PubMed

    Mignot, Mélanie; Sebban, Muriel; Tchapla, Alain; Mercier, Olivier; Cardinael, Pascal; Peulon-Agasse, Valérie

    2015-11-01

    This study reports the impact of thermal pretreatment between 400 and 1100°C on superficially porous silica particles (e.g. core-shell, fused-core; here abbreviated as SPP silica). The different thermally pretreated SPP silica (400°C, 900°C and 1100°C) were chemically bonded with an octadecyl chain under microwave irradiation. The bare SPP silica, thermally untreated and pretreated, as well as the chemically bonded phases (CBPs) were fully characterized by elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), and solid state cross polarization magic angle spinning (CP-MAS) (29)Si NMR. The chromatographic properties of the overall set of C18-thermally pretreated SPP silica stationary phases were determined using the Tanaka test. Complementary, the simplified Veuthey test was used to deeply study the silanol activity, considering a set of 7 basic solutes with various physicochemical properties. Both tests were also performed on different commercial SPP silica columns and different types of bonding chemistry (C18, Phenyl-hexyl, RP-amide, C30, aQ). Multivariate data analyses (hierarchical cluster analysis and principal component analysis) were carried out to define groups of stationary phases with similar chromatographic properties and situate them in relation to those commercially available. These different C18-thermally pretreated SPP silicas represented a wide range of stationary phases as they were spread out along the score plot. Moreover, this study highlighted that the thermal pretreatment improved the chemical stability of the SPP silica compare to untreated SPP silica and untreated porous silica. Consequently, higher thermal pretreatment can be applied (up to 900°C) before functionalization without destruction of the silica matrix. Indeed, a significantly lower dissolution of the thermally pretreated SPP silica under aggressive conditions could allow the use of the corresponding functionalized stationary phases at high

  13. Microcalorimetric study of silica- and zeolite-supported platinum catalysts

    SciTech Connect

    Sharma, S.B.; Dumesic, J.A. ); Miller, J.T. )

    1994-07-01

    Microcalorimetric measurements of the differential heats of hydrogen and carbon monoxide adsorption versus adsorbate coverate were made at 403 K for platinum supported on silica, magnesia/alumina, L-zeolite, Y-zeolite, and ZSM-5. The differential heats at zero coverage for hydrogen and carbon monoxide adsorption were 90 and 140 kJ/mol, respectively, for platinum supported on silica and nonacidic zeolites. The differential heats were large by approximately 20 kJ/mol for hydrogen and carbon monoxide adsorption on platinum particles supported on basis supports such as potassium/silica, magnesia/alumina, and zeolites containing basic cations (K[sup +], Ba[sup 2+]) exchanged in excess of the zeolite framework aluminum content. The microcalorimetric results suggest that the high paraffin aromatization activity and selectivity observed for L-zeolite-supported platinum catalysts do not appear to be caused solely by changes in the adsorptive properties of the cluster-size platinum particles located within the zeolite. 35 refs., 10 figs., 2 tabs.

  14. Biodiesel production from transesterification of palm oil with methanol over CaO supported on bimodal meso-macroporous silica catalyst.

    PubMed

    Witoon, Thongthai; Bumrungsalee, Sittisut; Vathavanichkul, Peerawut; Palitsakun, Supaphorn; Saisriyoot, Maythee; Faungnawakij, Kajornsak

    2014-03-01

    Calcium oxide-loaded porous materials have shown promise as catalysts in transesterification. However, the slow diffusion of bulky triglycerides through the pores limited the activity of calcium oxide (CaO). In this work, bimodal meso-macroporous silica was used as a support to enhance the accessibility of the CaO dispersed inside the pores. Unimodal porous silica having the identical mesopore diameter was employed for the purpose of comparison. Effects of CaO content and catalyst pellet size on the yield of fatty acid methyl esters (FAME) were investigated. The basic strength was found to increase with increasing the CaO content. The CaO-loaded bimodal porous silica catalyst with the pellet size of 325μm achieved a high %FAME of 94.15 in the first cycle, and retained an excellent %FAME of 88.87 after five consecutive cycles.

  15. The role of porous nanostructure in controlling lipase-mediated digestion of lipid loaded into silica particles.

    PubMed

    Joyce, Paul; Tan, Angel; Whitby, Catherine P; Prestidge, Clive A

    2014-03-18

    The rate and extent of lipolysis, the breakdown of fat into molecules that can be absorbed into the bloodstream, depend on the interfacial composition and structure of lipid (fat) particles. A novel method for controlling the interfacial properties is to load the lipid into porous colloidal particles. We report on the role of pore nanostructure and surface coverage in controlling the digestion kinetics of medium-chain and long-chain triglycerides loaded into porous silica powders of different particle size, porosity, and hydrophobicity/hydrophilicity. An in vitro lipolysis model was used to measure digestion kinetics of lipid by pancreatic lipase, a digestive enzyme. The rate and extent of lipid digestion were significantly enhanced when a partial monolayer of lipid was loaded in porous hydrophilic silica particles compared to a submicrometer lipid-in-water emulsion or a coarse emulsion. The inhibitory effect of digestion products was clearly evident for digestion from a submicrometer emulsion and coarse emulsion. This effect was minimal, however, in the two silica-lipid systems. Lipase action was inhibited for lipid loaded in the hydrophobic silica and considered due to the orientation of lipase adsorption on the methylated silica surface. Thus, hydrophilic silica promotes enhanced digestion kinetics, whereas hydrophobic silica exerts an inhibitory effect on hydrolysis. Evaluation of digestion kinetics enabled the mechanism for enhanced rate of lipolysis in silica-lipid systems to be derived and detailed. These investigations provide valuable insights for the optimization of smart food microparticles and lipid-based drug delivery systems based on lipid excipients and porous nanoparticles. PMID:24552363

  16. Construction and evaluation of controlled-release delivery system of Abamectin using porous silica nanoparticles as carriers

    NASA Astrophysics Data System (ADS)

    Wang, Yan; Cui, Haixin; Sun, Changjiao; Zhao, Xiang; Cui, Bo

    2014-12-01

    Photolysis and poor solubility in water of Abamectin are key issues to be addressed, which causes low bioavailability and residual pollution. In this study, a novel hydrophilic delivery system through loading Abamectin with porous silica nanoparticles (Abam-PSNs) was developed in order to improve the chemical stability, dispersity, and the controlled release of Abamectin. These results suggest that Abam-PSNs can significantly improve the performance of controllable release, photostability, and water solubility of Abamectin by changing the porous structure of silica nanoparticles, which is favorable to improve the bioavailability and reduce the residues of pesticides.

  17. Method for preparing high activity silica supported hydrotreating catalysts

    SciTech Connect

    Thompson, M.S.

    1986-03-04

    A method is described for preparing a silica supported hydrotreating catalyst containing from about 10-25%w molybdenum and from about 1-5%w nickel and/or cobalt as hydrogenation metals. The method consists of: (a) reacting a mixture of MoCl/sub 5/ and a compound selected from the group consisting of Ni(H/sub 2/O)/sub 6/Cl/sub 2/, Co(H/sub 2/O)/sub 6/Cl/sub 2/ and mixutres in amounts to provide a desired catalytic metals concentration of the support in the presence of a solubilizing amount of acetonitrile; (b) heating the mixture to between about 25/sup 0/ and 80/sup 0/C until most of the metal compounds have reacted and/or dissolved; (c) removing any undissolved solids from the solution; (d) impregnating the dried silica support with the hydrogenation metals-containing solution in one or more steps; and (e) drying the impregnated silica support at elevated temperature.

  18. Characterization and structural investigation of fractal porous-silica over an extremely wide scale range of pore size.

    PubMed

    Ono, Yusuke; Mayama, Hiroyuki; Furó, István; Sagidullin, Alexander I; Matsushima, Keiichiro; Ura, Haruo; Uchiyama, Tomoyuki; Tsujii, Kaoru

    2009-08-01

    We have succeeded in creating Menger sponge-like fractal body, i.e., porous-silica samples with Menger sponge-like fractal geometries, by a novel template method utilizing template particles of alkylketene dimer (AKD) and a sol-gel synthesis of tetramethyl orthosilicate (TMOS). We report here the first experimental results on characterization and structural investigations of the fractal porous-silica samples prepared with various conditions such as calcination temperature and packing condition of the template particles. In order to characterize the fractal porous-silica samples, pore volume distribution, porosity and specific surface area were measured over an extremely wide scale from 1 nm to 100 microm by means of mercury porosimetry, (1)H NMR cryoporometry, nitrogen gas adsorption experiments together with direct evaluations of cross-sectional fractal dimension D(cs), and size limits of D(cs). We have found that the pore volume distribution and specific surface area of the fractal porous-silica samples can be discussed in terms of different fractal porous structures at different scale regions. PMID:19406424

  19. Guest–host interactions of a rigid organic molecule in porous silica frameworks

    PubMed Central

    Wu, Di; Hwang, Son-Jong; Zones, Stacey I.; Navrotsky, Alexandra

    2014-01-01

    Molecular-level interactions at organic–inorganic interfaces play crucial roles in many fields including catalysis, drug delivery, and geological mineral precipitation in the presence of organic matter. To seek insights into organic–inorganic interactions in porous framework materials, we investigated the phase evolution and energetics of confinement of a rigid organic guest, N,N,N-trimethyl-1-adamantammonium iodide (TMAAI), in inorganic porous silica frameworks (SSZ-24, MCM-41, and SBA-15) as a function of pore size (0.8 nm to 20.0 nm). We used hydrofluoric acid solution calorimetry to obtain the enthalpies of interaction between silica framework materials and TMAAI, and the values range from −56 to −177 kJ per mole of TMAAI. The phase evolution as a function of pore size was investigated by X-ray diffraction, IR, thermogravimetric differential scanning calorimetry, and solid-state NMR. The results suggest the existence of three types of inclusion depending on the pore size of the framework: single-molecule confinement in a small pore, multiple-molecule confinement/adsorption of an amorphous and possibly mobile assemblage of molecules near the pore walls, and nanocrystal confinement in the pore interior. These changes in structure probably represent equilibrium and minimize the free energy of the system for each pore size, as indicated by trends in the enthalpy of interaction and differential scanning calorimetry profiles, as well as the reversible changes in structure and mobility seen by variable temperature NMR. PMID:24449886

  20. Carbon loss induced by plasma beam irradiation in porous silica films

    SciTech Connect

    Kurihara, K.; Ono, T.; Kohmura, K.; Tanaka, H.; Fujii, N.; Hata, N.; Kikkawa, T.

    2007-06-01

    Plasma-induced damages of porous silica films during plasma processes were investigated by using a plasma beam irradiation apparatus. We used the porous silica films incorporated with methyl groups to achieve high hydrophobicity. The carbon (methyl group) reductions in the film as an index of the level of damages induced by Ar, He, O{sub 2}, H{sub 2}, and N{sub 2} plasma irradiations were examined by x-ray photoelectron spectroscopy and secondary ion mass spectroscopy. The damage due to Ar and He plasma bombardment increased with an increase in the ion dosage, although it was not strongly affected by the ion energy in the range higher than 130 eV. Furthermore, it was found that the damage near the film surface was influenced more by metastable He atoms than by metastable Ar atoms. Both O ions and O atoms caused severe damage. N atoms did not affect the decrease of carbon content but reacted with carbon to form CN bonds. H atoms decreased carbon content slightly, but the amount of decrease was saturated by the further irradiation of H atoms.

  1. Phase equilibria and thermodynamic modeling of ethane and propane hydrates in porous silica gels.

    PubMed

    Seo, Yongwon; Lee, Seungmin; Cha, Inuk; Lee, Ju Dong; Lee, Huen

    2009-04-23

    In the present study, we examined the active role of porous silica gels when used as natural gas storage and transportation media. We adopted the dispersed water in silica gel pores to substantially enhance active surface for contacting and encaging gas molecules. We measured the three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria of C(2)H(6) and C(3)H(8) hydrates in 6.0, 15.0, 30.0, and 100.0 nm silica gel pores to investigate the effect of geometrical constraints on gas hydrate phase equilibria. At specified temperatures, the hydrate stability region is shifted to a higher pressure region depending on pore size when compared with those of bulk hydrates. Through application of the Gibbs-Thomson relationship to the experimental data, we determined the values for the C(2)H(6) hydrate-water and C(3)H(8) hydrate-water interfacial tensions to be 39 +/- 2 and 45 +/- 1 mJ/m(2), respectively. By using these values, the calculation values were in good agreement with the experimental ones. The overall results given in this study could also be quite useful in various fields, such as exploitation of natural gas hydrate in marine sediments and sequestration of carbon dioxide into the deep ocean.

  2. Preparation of silica sphere with porous structure in supercritical carbon dioxide.

    PubMed

    Chatterjee, Maya; Chatterjee, Abhijit; Ikushima, Yutaka; Kawanami, Hajime; Ishizaka, Takayuki; Sato, Masahiro; Suzuki, Toshishige; Yokoyama, Toshirou

    2010-08-01

    Silica sphere with porous structure has been synthesized in supercritical carbon dioxide. The structure originates from a delicate CO(2) trapping phenomenon intended for void formation in the inorganic framework. Silicate polymerization and subsequent removal of CO(2) by depressurization leaves the porous architecture. The key factor to obtain stable porous spherical structure was CO(2) pressure. Different characterization techniques such as X-ray diffraction, scanning and transmission electron microscopy and N(2) adsorption-desorption isotherm were used to determine the framework structure, morphology and porosity of the material. Microscopic visualization of calcined material suggested that the spherical structure was consisted of macroporous windows of diameter approximately 100 nm and the space between macropores presents a wormhole like mesoporous/microporous structure. The pore diameter of the mesoporous structure has been calculated as approximately 3 nm. X-ray diffraction and N(2) adsorption isotherm analysis confirmed the presence of micropores and also the macropores. In addition, the resulting material possess high thermal and hydrothermal stability associated with fully SiO(4) cross-linking. The spherical structure with different types of porosity was successfully obtained without using any molding agent.

  3. Thermally modulated porous silica multispectral filters and their application in remote imaging.

    PubMed

    Garcia Sega, Adrian; King, Brian H; Lee, Jessica Y; Sailor, Michael J; Miskelly, Gordon M

    2013-09-24

    We report a thermally tunable multispectral imaging filter based on reversible condensation of volatile organic fluids within a nanoporous one-dimensional photonic crystal. The photonic crystal (optical rugate filter) comprises oxidized porous silicon, prepared by electrochemical etch of silicon and subsequent air oxidation (porous silica rugate filter, pSiF). The reflectance spectrum of the pSiF is designed and constructed to match two of the red emission bands of the luminescent complex europium(III) tris-dipicolinate, [Eu(dpa)3](3-), which has been used as an indicator for anthrax spores. When the pSiF is fitted with a thermoelectric Peltier cooler/heater and sealed in a container with 2-propanol vapor, microcapillary effects drive the temperature-dependent condensation/evaporation of 2-propanol into/out of the porous nanostructure. Thermal cycling experiments show that the wavelengths of the spectral bands of the pSiF are reversibly tuned by ±35 nm for a temperature change of ±40 °C. Difference images of a UV-illuminated scene containing the [Eu(dpa)3](3-) target, obtained by reflection from pSiF that is continuously thermally cycled through the emission bands of the dye, show that the target can be discriminated from the background or from control targets with overlapping but dissimilar luminescence spectra. PMID:23968219

  4. Montmorillonite-based porous clay heterostructures (PCHs) intercalated with silica-titania pillars—synthesis and characterization

    NASA Astrophysics Data System (ADS)

    Chmielarz, Lucjan; Gil, Barbara; Kuśtrowski, Piotr; Piwowarska, Zofia; Dudek, Barbara; Michalik, Marek

    2009-05-01

    Porous clay heterostructures (PCHs) were synthesized using natural montmorillonite as a raw material. Apart from pure silica pillars also silica-titania pillars were intercalated into the interlayer space of the parent clay. The detailed studies of the calcination process of the as-prepared PCH samples as well as thermal stability of the pillared structure of these materials were performed. The pillared structure of PCHs intercalated with both silica and silica-titania clusters was found to be thermally stable up to temperatures exceeding 600 °C. It was found that titanium incorporated into the silica pillars was present mainly in the form of separated tetracoordinated cations. For the samples with the higher Ti loading also small contribution of titanium in the form of the polymeric oxide species was detected. Titanium incorporated into the PCH materials significantly increased their surface acidity forming mainly Brønsted acid sites.

  5. Laser supported solid state absorption fronts in silica

    SciTech Connect

    Carr, C W; Bude, J D

    2010-02-09

    We develop a model based on simulation and experiment that explains the behavior of solid-state laser-supported absorption fronts generated in fused silica during high intensity (up to 5GW/cm{sup 2}) laser exposure. We find that the absorption front velocity is constant in time and is nearly linear in laser intensity. Further, this model can explain the dependence of laser damage site size on these parameters. This behavior is driven principally by the temperature-activated deep sub band-gap optical absorptivity, free electron transport and thermal diffusion in defect-free silica for temperatures up to 15,000K and pressures < 15GPa. The regime of parameter space critical to this problem spans and extends that measured by other means. It serves as a platform for understanding general laser-matter interactions in dielectrics under a variety of conditions.

  6. Laser-supported solid-state absorption fronts in silica

    NASA Astrophysics Data System (ADS)

    Carr, C. W.; Bude, J. D.; Demange, P.

    2010-11-01

    We develop a model based on simulation and extensive experimentation that explains the behavior of solid-state laser-supported absorption fronts generated in fused silica during high intensity (up to 5GW/cm2 ) laser exposure. Both experiments and simulations show that the absorption front velocity is constant in time and is nearly linear in laser intensity. Further, this model can explain the dependence of laser damage site size on these parameters. We show that these absorption fronts naturally result from the combination of high-temperature-activated deep subband-gap optical absorptivity, free-electron transport, and thermal diffusion in defect-free silica for temperatures up to 15000K and pressures <10GPa . The regime of parameter space critical to this problem spans and extends that measured by other means. It serves as a platform for understanding general laser-matter interactions in dielectrics under a variety of conditions.

  7. SEPARATION PROPERTIES OF SURFACE MODIFIED SILICA SUPPORTED LIQUID MEMBRANES FOR DIVALENT METAL REMOVAL/RECOVERY

    EPA Science Inventory

    The synthesis and separation properties of a mesoporous silica supported liquid membrane (SLM) were studied. The membranes consisted of a silica layer, from dip-coated colloidal silica, on a a-alumina support, modified with DCDMS (dichlorodimethyl silane) to add surface methyl g...

  8. Impact of carbon on the surface and activity of silica-carbon supported copper catalysts for reduction of nitrogen oxides

    NASA Astrophysics Data System (ADS)

    Spassova, I.; Stoeva, N.; Nickolov, R.; Atanasova, G.; Khristova, M.

    2016-04-01

    Composite catalysts, prepared by one or more active components supported on a support are of interest because of the possible interaction between the catalytic components and the support materials. The supports of combined hydrophilic-hydrophobic type may influence how these materials maintain an active phase and as a result a possible cooperation between active components and the support material could occur and affects the catalytic behavior. Silica-carbon nanocomposites were prepared by sol-gel, using different in specific surface areas and porous texture carbon materials. Catalysts were obtained after copper deposition on these composites. The nanocomposites and the catalysts were characterized by nitrogen adsorption, TG, XRD, TEM- HRTEM, H2-TPR, and XPS. The nature of the carbon predetermines the composite's texture. The IEPs of carbon materials and silica is a force of composites formation and determines the respective distribution of the silica and carbon components on the surface of the composites. Copper deposition over the investigated silica-carbon composites leads to formation of active phases in which copper is in different oxidation states. The reduction of NO with CO proceeds by different paths on different catalysts due to the textural differences of the composites, maintaining different surface composition and oxidation states of copper.

  9. Corrosion resistance characterization of porous alumina membrane supports

    SciTech Connect

    Dong Yingchao; Lin Bin; Zhou Jianer; Zhang Xiaozhen; Ling Yihan; Liu Xingqin; Meng Guangyao; Hampshire, Stuart

    2011-04-15

    Tubular porous alumina ceramic membrane supports were fabricated by an extrusion-drying-sintering process and then characterized in detail in terms of corrosion resistance in both H{sub 2}SO{sub 4} and NaOH aqueous solutions. Variations in the properties of the alumina supports such as mass loss percent, mechanical strength, open porosity and pore size distribution were studied before and after corrosion under different conditions. In addition, the microstructures were analyzed using scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction before and after corrosion. The fabricated porous alumina supports offer possibilities for some potential applications as micro-filtration or ultra-filtration membrane supports, as well as in the pre-treatment of strongly acidic industrial waste-liquids. - Research highlights: {yields} Porous alumina membrane supports fabricated by extrusion-drying-sintering process. {yields} Corrosion resistance in 20 wt.% H{sub 2}SO{sub 4} and 1, 5, 10 wt.% NaOH aqueous solutions. {yields} Rapid mass loss and loss of flexural strength occurred in hot NaOH solution. {yields} Resistant to strong acid corrosion with low mass loss, low flexural strength loss. {yields} Porous alumina supports have potential for treatment of strong acid waste liquids.

  10. Predicting catalyst-support interactions between metal nanoparticles and amorphous silica supports

    NASA Astrophysics Data System (ADS)

    Ewing, Christopher S.; Veser, Götz; McCarthy, Joseph J.; Lambrecht, Daniel S.; Johnson, J. Karl

    2016-10-01

    Metal-support interactions significantly affect the stability and activity of supported catalytic nanoparticles (NPs), yet there is no simple and reliable method for estimating NP-support interactions, especially for amorphous supports. We present an approach for rapid prediction of catalyst-support interactions between Pt NPs and amorphous silica supports for NPs of various sizes and shapes. We use density functional theory calculations of 13 atom Pt clusters on model amorphous silica supports to determine linear correlations relating catalyst properties to NP-support interactions. We show that these correlations can be combined with fast discrete element method simulations to predict adhesion energy and NP net charge for NPs of larger sizes and different shapes. Furthermore, we demonstrate that this approach can be successfully transferred to Pd, Au, Ni, and Fe NPs. This approach can be used to quickly screen stability and net charge transfer and leads to a better fundamental understanding of catalyst-support interactions.

  11. Montmorillonite-based porous clay heterostructures (PCHs) intercalated with silica-titania pillars-synthesis and characterization

    SciTech Connect

    Chmielarz, Lucjan; Gil, Barbara; Kustrowski, Piotr; Piwowarska, Zofia; Dudek, Barbara; Michalik, Marek

    2009-05-15

    Porous clay heterostructures (PCHs) were synthesized using natural montmorillonite as a raw material. Apart from pure silica pillars also silica-titania pillars were intercalated into the interlayer space of the parent clay. The detailed studies of the calcination process of the as-prepared PCH samples as well as thermal stability of the pillared structure of these materials were performed. The pillared structure of PCHs intercalated with both silica and silica-titania clusters was found to be thermally stable up to temperatures exceeding 600 deg. C. It was found that titanium incorporated into the silica pillars was present mainly in the form of separated tetracoordinated cations. For the samples with the higher Ti loading also small contribution of titanium in the form of the polymeric oxide species was detected. Titanium incorporated into the PCH materials significantly increased their surface acidity forming mainly Bronsted acid sites. - Graphical abstract: Synthesis of the montmorillonite based porous clay heterostructures (PCHs) intercalated with silica-titania pillars has been performed. The mechanism of the thermal degradation of organic templates in the pore system of PCHs was studied. PCHs were characterized with respect to structure, texture, composition, surface acidity, thermal stability and form of introduced titanium.

  12. Permeation flux of organic molecules through silica-surfactant nanochannels in a porous alumina membrane.

    PubMed

    Yamashita, Tomohisa; Kodama, Shuji; Ohto, Mikiya; Nakayama, Eriko; Hasegawa, Sumiyo; Takayanagi, Nobutaka; Kemmei, Tomoko; Yamaguchi, Akira; Teramae, Norio; Saito, Yukio

    2006-12-01

    The permeation fluxes of phenol, benzene sulfonate (BS) and benzene disulfonate (BDS) through a porous anodic alumina membrane with the perpendicularly oriented silica-surfactant nanochannel assembly membrane (NAM) were measured in water-ethanol mixture media. The permeation flux depended on solute charges and on solvent composition. As the ethanol ratio increased, the fluxes of BS and BDS increased and the flux of phenol decreased. The results of extraction/elution experiments also depended on the solute charges and the solvent composition. Chromatographic experiments in n-hexane showed that dipole and hydrophobic interactions affect the retention of solutes. Permeation of the solute across the NAM in water-ethanol mixture is likely to be determined by various factors such as dipole interaction, hydrophobic interaction, solvation, and anion-exchange efficiencies.

  13. Aging influence on sensing properties of porous silica films sensitized toward ammonia

    NASA Astrophysics Data System (ADS)

    Tyszkiewicz, Cuma; Rogoziński, Roman

    2015-12-01

    The sol-gel technology allows preparation of thin silica films ranging in porosity from dense to highly porous. These films can function as a matrix binding molecules of the pH-sensitive dyes and can be utilized as the sensitive films for intensity based planar evanescent wave chemical sensors. Sensitive properties of these dyes decreases in time due to aging processes. We report characterization of weakening of sensing properties of highly porous silica films doped with the bromocresole purple (BCP). In the presence of the gaseous ammonia, the absorption band (AB) of protonated BCP centered at λ=430 nm, is shifted toward λ=591 nm due to deprotonation, resulting in the increase of sensitive films absorption in the range of wavelengths of shifted AB. Two sets of films were investigated. Films from the first one were cyclically exposed to the ammonia and stored isolated from the daylight. Films from the second set weren't exposed to the ammonia and were stored in a staining jar exposed to the daylight. A depth of the AB at λ=430 nm was measured using a spectrophotometer. A sensitivity of the films toward ammonia was measured using LED emitting at center wavelength λ=610 nm. As was shown, the sensitivity of these films exposed to the ammonia diluted in dry air, and isolated from the daylight, decreases in time exponentially. The magnitude of that decrease monotonically depends on the ammonia concentration. It was also shown that the daylight causes quick aging of films not exposed to the ammonia. A depth of the AB centered at λ=430 nm relatively quickly decreased when compared with films isolated from the daylight and exposed to the ammonia.

  14. A silica-supported solid dispersion of bifendate using supercritical carbon dioxide method with enhanced dissolution rate and oral bioavailability.

    PubMed

    Cai, Cuifang; Liu, Muhua; Li, Yun; Guo, Bei; Chang, Hui; Zhang, Xiangrong; Yang, Xiaoxu; Zhang, Tianhong

    2016-01-01

    In this study, to enhance the dissolution rate and oral bioavailability of bifendate, a silica-supported solid dispersion (SD) of bifendate was prepared using supercritical carbon dioxide (ScCO2) technology. The properties of bifendate-silica SD were characterized by differential scanning calorimetry (DSC), X-ray diffraction (X-RD) and scanning electron microscopy. The pharmacokinetic study was carried out in beagle dogs using commercial bifendate dropping pills as a reference which is a conventional SD formulation of bifendate and PEG6000. A novel method of Ultra Performance Convergence Chromatography-tandem mass spectrometry (UPC(2)™-MS/MS) method was applied to determine bifendate concentration in plasma. The amorphous state of bifendate in bifendate-silica SD was revealed in X-RD and DSC when the ratios of bifendate and silica were 1:15 and 1:19, respectively. In vitro dissolution rate was significantly improved with cumulative release of 67% within 20 min relative to 8% for the physical mixture of bifendate and silica, and which was also higher than the commercial dropping pill of 52%. After storage at 75% relative humidity (RH) for 10 d, no recrystallization was found and reduced dissolution rate was obtained due to the absorption of moisture. In pharmacokinetic study, Cmax and AUC0-t for bifendate-silica SD were 153.1 ng/ml and 979.8 ng h/ml, respectively. AUC0-t of bifendate-silica SDs was ∼1.6-fold higher than that of the commercial dropping pills. These results suggest that adsorbing bifendate onto porous silica via ScCO2 technique could be a feasible method to enhance oral bioavailability together with a higher dissolution rate.

  15. Large magnetocaloric effect in fine Gd2O3 nanoparticles embedded in porous silica matrix

    NASA Astrophysics Data System (ADS)

    ZeleÅáková, A.; Hrubovčák, P.; Kapusta, O.; ZeleÅák, V.; Franco, V.

    2016-09-01

    The magnetocaloric properties of a composite material consisting of isolated Gd2O3 nanoparticles with a diameter of 6-8 nm embedded in the pores of a mesoporous silica matrix have been studied. The fascinating nanostructure and composition were properly characterized by small angle X-ray scattering, X-ray absorption near edge structure, and TEM. Almost ideal paramagnetic behavior of the material was observed in the temperature range of 1.8-300 K. When compared to various nanosystems, the presented composite exhibits an extraordinarily large magnetic entropy change of 40 J/kg K for a field variation of 0-5 T at cryogenic temperature (3 K). Considering only the mass of the Gd2O3 nanoparticle fraction, this corresponds to 120 J/kg K. Calculated refrigerant capacities are 100 J/kg and 400 J/kg for the composite and nanoparticles, respectively. Our findings suggest that the combination of the unique porous structure of amorphous silica with fine gadolinium oxide nanoparticles and high value of magnetic entropy change enables to extend the application of the Gd2O3@SiO2 composite, to cryomagnetic refrigeration. In addition, the characteristics of the thermomagnetic behavior have been studied using the scaling analysis of the magnetic entropy change.

  16. Biodegradation of 2,4-dinitrophenol with laccase immobilized on nano-porous silica beads

    PubMed Central

    2013-01-01

    Many organic hazardous pollutants, including 2,4-dinitrophenol (2,4-DNP), which are water soluble, toxic, and not easily biodegradable make concerns for environmental pollution worldwide. In the present study, degradation of nitrophenols-contained effluents by using laccase immobilized on the nano-porous silica beads was evaluated. 2,4-DNP was selected as the main constituent of industrial effluents containing nitrophenols. The performance of the system was characterized as a function of pH, contact time, temperature, pollutant, and mediator concentrations. The laccase-silica beads were employed in a mixed-batch reactor to determine the degradation efficiency after 12 h of enzyme treatment. The obtained data showed that the immobilized laccase degraded more than 90% of 2,4-DNP within 12 h treatment. The immobilization process improved the activity and sustainability of laccase for degradation of the pollutant. Temperatures more than 50°C reduced the enzyme activity to about 60%. However, pH and the mediator concentration could not affect the enzyme activity. The degradation kinetic was in accordance with a Michaelis–Menten equation with Vmax and Km obtained as 0.25–0.38 μmoles/min and 0.13–0.017 mM, respectively. The stability of the immobilized enzyme was maintained for more than 85% of its initial activity after 30 days. Based on the results, it can be concluded that high resistibility and reusability of immobilized laccase on CPC-silica beads make it considerable choice for wastewater treatment. PMID:23547870

  17. Electroassisted codeposition of sol-gel derived silica nanocomposite directs the fabrication of coral-like nanostructured porous gold.

    PubMed

    Farghaly, Ahmed A; Collinson, Maryanne M

    2014-05-13

    Herein, we report on a one-step coelectrodeposition method to form gold-silica nanocomposite materials from which high surface area nanostructured gold electrodes can be produced. The as-prepared Au-SiO2 films possess an interconnected three-dimensional porous framework with different silica-gold ratios depending on the deposition solutions and parameters. Chemical etching of the nanocomposite films using hydrofluoric acid resulted in the formation of nanostructured porous gold films with coral-like structures and pores in the nanometer range. The cross-linkage of the gold coral branches resulted in the generation of a porous framework. X-ray photoelectron spectroscopy confirms the complete removal of silica. Well-controlled surface area enhancement, film thickness, and morphology were achieved by manipulating the deposition parameters, such as potential, time, and gold ion and sol-gel monomer concentrations in the deposition solution. An enhancement in the surface area of the electrode up to 57 times relative to the geometric area has been achieved. The thickness of the as-prepared Au-SiO2 nanocomposite films is relatively high and varied from 8 to 15 μm by varying the applied deposition potential while the thickness of the coral-like nanostructured porous gold films ranged from 0.22 to 2.25 μm. A critical sol-gel monomer concentration (CSGC) was determined at which the deposited silica around the gold coral was able to stabilize the coral-like gold nanostructures, while below the CSGC, the coral-like gold nanostructures were unstable and the surface area of the nanostructured porous gold electrodes decreased. PMID:24766096

  18. Wrinkling of graphene membranes supported by silica nanoparticles on substrates

    NASA Astrophysics Data System (ADS)

    Yamamoto, Mahito; Cullen, William; Fuhrer, Michael; Einstein, Theodore; Department of Physics, University of Maryland Team

    2011-03-01

    The challenging endeavor of modulating the morphology of graphene via a patterned substrate to produce a controlled deformation has great potential importance for strain engineering the electronic properties of graphene. An essential step in this direction is to understand the response of graphene to substrate features of known geometry. Here we employ silica nanoparticles with a diameter of 10-100 nm to uniformly decorate Si O2 and mica substrates before depositing graphene, to promote nanoscale modulation of graphene geometry. The morphology of graphene on this modified substrate is then characterized by atomic force spectroscopy. We find that graphene on the substrate is locally raised by the supporting nanoparticles, and wrinkling propagates radially from the protrusions to form a ridge network which links the protrusions. We discuss the dependence of the wrinkled morphology on nanoparticle diameter and graphene thickness in terms of graphene elasticity and adhesion energy. Supported by NSF-MRSEC, Grant DMR 05-20471

  19. Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration

    DOE PAGES

    Eedugurala, Naresh; Wang, Zhuoran; Chaudhary, Umesh; Nelson, Nicholas; Kandel, Kapil; Kobayashi, Takeshi; Slowing, Igor I.; Pruski, Marek; Sadow, Aaron D.

    2015-11-04

    The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe2)4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe2)n@MSN. Exhaustive characterization of Zr(NMe2)n@MSN with solid-state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily ≡SiOZr(NMe2)3. The presence of these nitrogen-containing zirconium sites is supported by 15N NMR spectroscopy, including natural abundance 15N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr(NMe2)n@MSN material reacts with pinacolborane (HBpin) to provide Me2NBpin and the material ZrH/Bpin@MSN that is composed of interacting surface-bonded zirconium hydride and surface-bonded borane ≡SiOBpinmore » moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1H/2H and 11B SSNMR and infrared spectroscopy and through its reactivity with D2. The zirconium hydride material or the zirconium amide precursor Zr(NMe2)n@MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. These supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites.« less

  20. Investigating the mesostructure of ordered porous silica nanocomposites by transmission electron microscopy techniques

    SciTech Connect

    Bullita, S.; Casula, M. F.; Piludu, M.; Falqui, A.; Carta, D.; Corrias, A.

    2014-10-21

    Nanocomposites made out of FeCo alloy nanocrystals supported onto pre-formed mesoporous ordered silica which features a cubic arrangement of pores (SBA-16) were investigated. Information on the effect of the nanocrystals on the mesostructure (i.e. pore arrangement symmetry, pore size, and shape) were deduced by a multitechnique approach including N2 physisorption, low angle X-ray diffraction, and Transmission electron microscopy. It is shown that advanced transmission electron microscopy techniques are required, however, to gain direct evidence on key compositional and textural features of the nanocomposites. In particular, electron tomography and microtomy techniques make clear that the FeCo nanocrystals are located within the pores of the SBA-16 silica, and that the ordered mesostructure of the nanocomposite is retained throughout the observed specimen.

  1. Synthesis and Characterisation of Porous Titania-Silica Composite Aerogel for NO(x) and Acetaldehyde Removal.

    PubMed

    Lee, Kwang Young; Park, Se Min; Kim, Jong Beom; El Saliby, Ibrahim; Shahid, Mohammad; Kim, Geon-Joong; Shon, Ho Kyong; Kim, Jong-Ho

    2016-05-01

    In this study, the synthesis of porous titania-silica (TiO2-SiO2) composite aerogel at ambient pressure by using non-hazardous chemicals as a source of silica was investigated. TiO2-SiO2 composite aerogels were characterised and their photocatalytic performances were investigated for the removal efficiency of acetaldehyde and NO(x) under UV light. Results showed that porous composite aerogel with aggregated morphology, high surface area and an increased mesoporosity were formed. TiO2-SiO2(1.8) composite, with high Ti/Si ratio, showed the best results in terms of photocatalytic removal of acetaldehyde and nitrogen oxide. PMID:27483782

  2. Synthesis and Characterisation of Porous Titania-Silica Composite Aerogel for NO(x) and Acetaldehyde Removal.

    PubMed

    Lee, Kwang Young; Park, Se Min; Kim, Jong Beom; El Saliby, Ibrahim; Shahid, Mohammad; Kim, Geon-Joong; Shon, Ho Kyong; Kim, Jong-Ho

    2016-05-01

    In this study, the synthesis of porous titania-silica (TiO2-SiO2) composite aerogel at ambient pressure by using non-hazardous chemicals as a source of silica was investigated. TiO2-SiO2 composite aerogels were characterised and their photocatalytic performances were investigated for the removal efficiency of acetaldehyde and NO(x) under UV light. Results showed that porous composite aerogel with aggregated morphology, high surface area and an increased mesoporosity were formed. TiO2-SiO2(1.8) composite, with high Ti/Si ratio, showed the best results in terms of photocatalytic removal of acetaldehyde and nitrogen oxide.

  3. Fabrication of silica moth-eye structures by photo-nanoimprinting using ordered anodic porous alumina molds

    NASA Astrophysics Data System (ADS)

    Yanagishita, Takashi; Endo, Takahide; Nishio, Kazuyuki; Masuda, Hideki

    2014-01-01

    Moth-eye structures composed of an ordered array of tapered SiO2 pillars were fabricated by photo-nanoimprinting using anodic porous alumina as a mold. The formation of SiO2 moth-eye structures was carried out using a photosensitive polysilane solution as a precursor of silica. The SiO2 moth-eye structures formed on the surface of a glass plate effectively suppressed the reflection of incident light.

  4. Porous Carbon Supports: Recent Advances with Various Morphologies and Compositions

    DOE PAGES

    Zhang, Pengfei; Zhu, Huiyuan; Dai, Sheng

    2015-08-31

    The importance of porous carbon as the support material is well recognized in the catalysis community, and it would be even more attractive if several characteristics are considered, such as the stability in acidic and basic media or the ease of noble metal recovery through complete burn off. Because it is still difficult to obtain constant properties even from batch to batch, activated carbons are not popular in industrial catalysis now.

  5. Synthesis and Characterization of Silica Alumina Supported Heteropolyoxometallets

    NASA Astrophysics Data System (ADS)

    Dangwal, A.; Singhal, S.; Semwal, S.; Shukla, S.

    2014-04-01

    Novel acid catalysts for alkane isomerization were synthesized with silica alumina supported heteropolyoxometallets by wet incipient method. Two series of catalysts were prepared by dispersing TPA or MPA. Characterization of catalysts was done by BET and TPD methods. Objective was to find high surface and acidity catalysts and to see the effect of synthesis parameter as loading or impregnation time on catalyst physicochemical properties as surface area, pore size, pore volume and acidity of HPA based oxide Seralox-5. TPA or MPA loading affected acidity and pore volume of catalysts, however no effect of impregnation time has been revealed. Surface area of catalysts was found in the range of 154-198 m2/g and acidity 10.1-17.7 ml/g of NH3 at STP. Among all the catalysts optimum characteristic catalysts were found from both the series, selecting one from each. These two catalysts exhibit high surface area, mesopore structure and high acidity.

  6. In situ growth of hollow gold-silver nanoshells within porous silica offers tunable plasmonic extinctions and enhanced colloidal stability.

    PubMed

    Li, Chien-Hung; Jamison, Andrew C; Rittikulsittichai, Supparesk; Lee, Tai-Chou; Lee, T Randall

    2014-11-26

    Porous silica-coated hollow gold-silver nanoshells were successfully synthesized utilizing a procedure where the porous silica shell was produced prior to the transformation of the metallic core, providing enhanced control over the structure/composition of the bimetallic hollow core. By varying the reaction time and the precise amount of gold salt solution added to a porous silica-coated silver-core template solution, composite nanoparticles were tailored to reveal a readily tunable surface plasmon resonance that could be centered across the visible and near-IR spectral regions (∼445-800 nm). Characterization by X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, scanning electron microscopy, and transmission electron microscopy revealed that the synthetic methodology afforded particles having uniform composition, size, and shape. The optical properties were evaluated by absorption/extinction spectroscopy. The stability of colloidal solutions of our composite nanoparticles as a function of pH was also investigated, revealing that the nanoshells remain intact over a wide range of conditions (i.e., pH 2-10). The facile tunability, enhanced stability, and relatively small diameter of these composite particles (∼110 nm) makes them promising candidates for use in tumor ablation or as photothermal drug-delivery agents. PMID:25321928

  7. Multifunctional nanocomposites constructed from Fe3O4-Au nanoparticle cores and a porous silica shell in the solution phase.

    PubMed

    Chen, Fenghua; Chen, Qingtao; Fang, Shaoming; Sun, Yu'an; Chen, Zhijun; Xie, Gang; Du, Yaping

    2011-11-01

    This work is directed towards the synthesis of multifunctional nanoparticles composed of Fe(3)O(4)-Au nanocomposite cores and a porous silica shell (Fe(3)O(4)-Au/pSiO(2)), aimed at ensuring the stability, magnetic, and optical properties of magnetic-gold nanocomposite simultaneously. The prepared Fe(3)O(4)-Au/pSiO(2) core/shell nanoparticles are characterized by means of TEM, N(2) adsorption-desorption isotherms, FTIR, XRD, UV-vis, and VSM. Meanwhile, as an example of the applications, catalytic activity of the porous silica shell-encapsulated Fe(3)O(4)-Au nanoparticles is investigated by choosing a model reaction, reduction of o-nitroaniline to benzenediamine by NaBH(4). Due to the existence of porous silica shells, the reaction with Fe(3)O(4)-Au/pSiO(2) core/shell nanoparticles as a catalyst follows second-order kinetics with the rate constant (k) of about 0.0165 l mol(-1) s(-1), remarkably different from the first-order kinetics with the k of about 0.002 s(-1) for the reduction reaction with the core Fe(3)O(4)-Au nanoparticles as a catalyst. PMID:21637876

  8. Fabrication of SnO2/porous silica/polyethyleneimine nanoparticles for pH-responsive drug delivery.

    PubMed

    Cao, Na; Li, Miao; Zhao, Yanbao; Qiu, Li; Zou, Xueyan; Zhang, Yu; Sun, Lei

    2016-02-01

    To create novel nanocarriers for achieving excellent drug delivery performance, pH-responsive fluorescent porous silica (PS) nanocarriers were developed by encapsulating SnO2 nanoparticles and coating polyethyleneimine (PEI) layer. SnO2/porous silica (SnO2/PS) nanoparticles have an average diameter of 80nm and center-radial large pore channels. The large channels endow them high surface area with a Brunauer-Emmett-Teller (BET) area of 939m(2)g(-1). Aspirin was used as test drug to evaluate the releasing behavior of SnO2/porous silica/polyethyleneimine (SnO2/PS/PEI) nanoparticles. Results indicated that aspirin can be successfully incorporated into the SnO2/PS/PEI nanoparticles and the SnO2/PS/PEI nanoparticles displayed excellent pH-responsive release. The release rate in pH7.4 buffer is higher than that in pH5.5 buffer, which attributed to the PEI structure change in varied pH buffer. In addition, the SnO2/PS/PEI nanoparticles presented novel drug-dependent fluorescence, which could be used to trace the drug release.

  9. Influence of Environmental Factors on the Adsorption Capacity and Thermal Conductivity of Silica Nano-Porous Materials.

    PubMed

    Zhang, Hu; Gu, Wei; Li, Ming-Jia; Fang, Wen-Zhen; Li, Zeng-Yao; Tao, Wen-Quan

    2015-04-01

    In this work, the influence of temperature and humidity environment on the water vapor adsorption capacity and effective thermal conductivity of silica nano-porous material is conducted within a relative humidity range from 15% to 90% at 25 °C, 40 °C and 55 °C, respectively. The experiment results show that both the temperature and relative humidity have significant influence on the adsorption capacity and effective thermal conductivity of silica nano-porous materials. The adsorption capacity and effective thermal conductivity increase with humidity because of the increases of water vapor concentration. The effective thermal conductivity increases linearly with adsorption saturation capacity at constant temperature. Because adsorption process is exothermic reaction, the increasing temperature is not conducive to the adsorption. But the effective thermal conductivity increases with the increment of temperature at the same water uptake because of the increment of water thermal conductivity with temperature Geometric models and unit cell structure are adopted to predict the effective thermal conductivity and comparisons with the experimental result are made, and for the case of moist silica nano-porous materials with high porosity no quantitative agreement is found. It is believed that the adsorbed water will fill in the nano-pores and gap and form lots of short cuts, leading to a significant reduction of the thermal resistance.

  10. Bone Tissue Response to Porous and Functionalized Titanium and Silica Based Coatings

    PubMed Central

    Chaudhari, Amol; Braem, Annabel; Vleugels, Jozef; Martens, Johan A.; Naert, Ignace; Cardoso, Marcio Vivan; Duyck, Joke

    2011-01-01

    Background Topography and presence of bio-mimetic coatings are known to improve osseointegration. The objective of this study was to evaluate the bone regeneration potential of porous and osteogenic coatings. Methodology Six-implants [Control (CTR); porous titanium coatings (T1, T2); thickened titanium (Ti) dioxide layer (TiO2); Amorphous Microporous Silica (AMS) and Bio-active Glass (BAG)] were implanted randomly in tibiae of 20-New Zealand white rabbits. The animals were sacrificed after 2 or 4 weeks. The samples were analyzed histologically and histomorphometrically. In the initial bone-free areas (bone regeneration areas (BRAs)), the bone area fraction (BAF) was evaluated in the whole cavity (500 µm, BAF-500), in the implant vicinity (100 µm, BAF-100) and further away (100–500 µm, BAF-400) from the implant. Bone-to-implant contact (BIC-BAA) was measured in the areas where the implants were installed in contact to the host bone (bone adaptation areas (BAAs)) to understand and compare the bone adaptation. Mixed models were used for statistical analysis. Principal Findings After 2 weeks, the differences in BAF-500 for different surfaces were not significant (p>0.05). After 4 weeks, a higher BAF-500 was observed for BAG than CTR. BAF-100 for AMS was higher than BAG and BAF-400 for BAG was higher than CTR and AMS. For T1 and AMS, the bone regeneration was faster in the 100-µm compared to the 400-µm zone. BIC-BAA for AMS and BAG was lower after 4 than 2 weeks. After 4 weeks, BIC-BAA for BAG was lower than AMS and CTR. Conclusions BAG is highly osteogenic at a distance from the implant. The porous titanium coatings didn't stimulate bone regeneration but allowed bone growth into the pores. Although AMS didn't stimulate higher bone response, it has a potential of faster bone growth in the vicinity compared to further away from the surface. BIC-BAA data were inconclusive to understand the bone adaptation. PMID:21935382

  11. N2O decomposition by mesoporous silica supported Rh catalysts.

    PubMed

    Hussain, Murid; Fino, Debora; Russo, Nunzio

    2012-04-15

    Nitrous oxide (N(2)O), a greenhouse gas produced by nitric acid and adipic acid plants, damages the ozone layer and causes many environmental problems. The potential of MCM-41, SBA-15-Conventional (SBA-15-C), SBA-15-Spherical (SBA-15-S) and KIT-6 supported Rh catalysts has been explored at specific conditions for N(2)O decomposition in order to investigate the characteristics of new catalyst supports (SBA-15-S, KIT-6) for this application. A Rh metal loading of 1 wt% was impregnated to synthesize mesoporous silica supported Rh catalysts. The catalysts were characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), N(2) adsorption/desorption, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and CO-chemisorption techniques. Of all the catalysts, Rh/SBA-15-S not only showed the highest activity, but also the best strength against ageing impact, O(2) inhibiting effect and long-term stability. The higher metal dispersion due to the smaller Rh particle size and a greater formation of Rh(+1) than Rh(0) or Rh(+3) on SBA-15-S compared to the other supports, favoured a higher N(2)O decomposition. The larger pore size of SBA-15-S in Rh/SBA-15-S might favour a better Rh access, diffusion and dispersion and lead to higher activity. The higher long-term stability of Rh/SBA-15-S, with preserved support characteristics, than the other supports indicates its significance.

  12. Adsorption characteristics of haloacetonitriles on functionalized silica-based porous materials in aqueous solution.

    PubMed

    Prarat, Panida; Ngamcharussrivichai, Chawalit; Khaodhiar, Sutha; Punyapalakul, Patiparn

    2011-09-15

    The effect of the surface functional group on the removal and mechanism of dichloroacetonitrile (DCAN) adsorption over silica-based porous materials was evaluated in comparison with powdered activated carbon (PAC). Hexagonal mesoporous silicate (HMS) was synthesized and functionalized by three different types of organosilanes (3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and n-octyldimethysilane). Adsorption kinetics and isotherm models were used to determine the adsorption mechanism. The selective adsorption of five haloacetonitriles (HANs) in the single and mixed solute systems was also studied. The experiments revealed that the surface functional groups of the adsorbents largely affected the DCAN adsorption capacities. 3-Mercaptopropyl-grafted HMS had a high DCAN adsorption capacity compared to PAC. The adsorption mechanism is believed to occur via an ion-dipole electrostatic interaction in which water interference is inevitable at low concentrations of DCAN. In addition, the adsorption of DCAN strongly depended on the pH of the solution as this related to the charge density of the adsorbents. The selective adsorption of the five HANs over PAC was not observed, while the molecular structure of different HANs obviously influenced the adsorption capacity and selectivity over 3-mercaptopropyl-grafted HMS. PMID:21752539

  13. Optical properties of lanthanide dyes for spectral conversion encapsulated in porous silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Pizzol, Paolo; Marques-Hueso, Jose; Robertson, Neil; Freris, Isidora; Bellotto, Luca; Meyer, Thomas J. J.; Richards, Bryce S.

    2012-06-01

    Lanthanide based dyes belong to one of the most promising fields of photovoltaic research, combining high quantum yields and large spectral shift. However, many challenges are faced when working with lanthanide dyes for spectral conversion: their thermal and chemical stability, which can greatly influence the shelf-life of the dyes; the absorption band position, which depends on the organic part of the dye, the so called "antenna" self-quenching mechanisms, which lead to a photoluminescence emission loss. The chemical composition of the surrounding environment of the dyes has a fundamental role in their properties. In this paper, the optical and PLQY (photoluminescence quantum yield) properties of an europium-based dye embedded in a silica matrix are reported. The in-house synthesized dye consists of a bis(2- (diphenylphosphino)phenyl)ether oxide (DPEPO) ligand and three hexafluoroacetylacetonate (hfac) co-ligands coordinating a central europium ion. The dye has been included in porous core-shell particles, to study its optical properties once embedded in a solid dielectric matrix. The optical properties of the resulting samples have been characterized by photoluminescence emission and PLQY measurements. The results have been compared with data obtained from a commercially available dye (BASF Lumogen family) in similar conditions.

  14. Fabrication of porous hollow silica nanoparticles and their applications in drug release control.

    PubMed

    Li, Zhu-Zhu; Wen, Li-Xiong; Shao, Lei; Chen, Jian-Feng

    2004-08-11

    Preparation and characterization of porous hollow silica nanoparticles (PHSN) for controlled release applications were investigated. Through orthogonally designed experiments, the optimal synthesis conditions for the preparation of PHSN were obtained and the produced PHSN were characterized by BET, SEM, TEM and IR. Scanning and transmission electron microscopy images revealed their hollow shell-core structure and also demonstrated that the size and shape of PHSN are determined by the templating CaCO3 nanoparticles. The produced PHSN were applied as a carrier to study the controlled release behaviors of Brilliant Blue F (BB), which was used as a model drug. Being loaded into the inner core and on the surfaces of the nanoparticles, BB was released slowly into a bulk solution for about 1140 min as compared to only 10 min for the normal SiO2 nanoparticles, thus exhibited a typical sustained release pattern without any burst effect. In addition, higher BET of the carriers, lower pH value and lower temperature prolonged BB release from PHSN, while stirring speed showed little influence on the release behavior. It showed that PHSN have a promising future in controlled drug delivery applications.

  15. Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration

    SciTech Connect

    Eedugurala, Naresh; Wang, Zhuoran; Chaudhary, Umesh; Nelson, Nicholas; Kandel, Kapil; Kobayashi, Takeshi; Slowing, Igor I.; Pruski, Marek; Sadow, Aaron D.

    2015-11-04

    The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe2)4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe2)n@MSN. Exhaustive characterization of Zr(NMe2)n@MSN with solid-state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily ≡SiOZr(NMe2)3. The presence of these nitrogen-containing zirconium sites is supported by 15N NMR spectroscopy, including natural abundance 15N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr(NMe2)n@MSN material reacts with pinacolborane (HBpin) to provide Me2NBpin and the material ZrH/Bpin@MSN that is composed of interacting surface-bonded zirconium hydride and surface-bonded borane ≡SiOBpin moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1H/2H and 11B SSNMR and infrared spectroscopy and through its reactivity with D2. The zirconium hydride material or the zirconium amide precursor Zr(NMe2)n@MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. These supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites.

  16. Studies of Immobilized Homogeneous Metal Catalysts on Silica Supports

    SciTech Connect

    Keith James Stanger

    2003-05-31

    The tethered, chiral, chelating diphosphine rhodium complex, which catalyzes the enantioselective hydrogenation of methyl-{alpha}-acetamidocinnamate (MAC), has the illustrated structure as established by {sup 31}P NMR and IR studies. Spectral and catalytic investigations also suggest that the mechanism of action of the tethered complex is the same as that of the untethered complex in solution. The rhodium complexes, [Rh(COD)H]{sub 4}, [Rh(COD){sub 2}]{sup +}BF{sub 4}{sup -}, [Rh(COD)Cl]{sub 2}, and RhCl{sub 3} {center_dot} 3H{sub 2}O, adsorbed on SiO{sub 2} are optimally activated for toluene hydrogenation by pretreatment with H{sub 2} at 200 C. The same complexes on Pd-SiO{sub 2} are equally active without pretreatments. The active species in all cases is rhodium metal. The catalysts were characterized by XPS, TEM, DRIFTS, and mercury poisoning experiments. Rhodium on silica catalyzes the hydrogenation of fluorobenzene to produce predominantly fluorocyclohexane in heptane and 1,2-dichloroethane solvents. In heptane/methanol and heptane/water solvents, hydrodefluorination to benzene and subsequent hydrogenation to cyclohexane occurs exclusively. Benzene inhibits the hydrodefluorination of fluorobenzene. In DCE or heptane solvents, fluorocyclohexane reacts with hydrogen fluoride to form cyclohexene. Reaction conditions can be chosen to selectively yield fluorocyclohexane, cyclohexene, benzene, or cyclohexane. The oxorhenium(V) dithiolate catalyst [-S(CH{sub 2}){sub 3}s-]Re(O)(Me)(PPh{sub 3}) was modified by linking it to a tether that could be attached to a silica support. Spectroscopic investigation and catalytic oxidation reactivity showed the heterogenized catalyst's structure and reactivity to be similar to its homogeneous analog. However, the immobilized catalyst offered additional advantages of recyclability, extended stability, and increased resistance to deactivation.

  17. Experimental study on heat transfer of supercritical carbon dioxide in a long silica-based porous-media tube

    NASA Astrophysics Data System (ADS)

    Hsieh, Jui-Ching; Lin, David T. W.; Lee, Bo-Heng; Chung, Ming-Che

    2016-07-01

    The heat transfer phenomena of supercritical carbon dioxide were experimentally investigated in a vertical tube containing silica-based porous media. The experiment was conducted at various levels of static pressure, flow rates, and initial wall temperatures as well as with silica sand of porous media in a long test section to study the heat transfer characteristics of supercritical carbon dioxide (CO2). The results indicated that the average heat transfer coefficient and outlet temperature at an initial wall temperature of 150 °C were higher and lower than that of 200 °C. The heat transfer performance was significantly influenced by flow rate of supercritical CO2. The porous media was provided large heat exchange surface between particles and CO2 to increase the heat transfer coefficient, especially when small diameter of particles. When the inlet temperature was higher than the pseudocritical temperature, the heat transfer coefficient sharply dropped when x/L ≥ 0.5, because of the development of a thermal boundary and the decrease of CO2 thermophysical properties of CO2 in a far pseudocritical temperature. When the pseudocritical temperature was higher than the inlet temperature of the fluid, the local heat transfer coefficient was affected by a thermal boundary and thermophysical properties of CO2 in pseudocritical point at a higher initial wall temperature or lower supercritical pressure when x/L ≤ 0.75; only the thermophysical properties of supercritical CO2 in pseudocritical point played a pivotal role when x/L > 0.75 at a lower initial wall temperature or higher supercritical pressure. In the present study, the supercritical pressure of 10.5 MPa constituted an optimal operating condition for supercritical CO2 a long silica-based porous-media tube because of the high heat transfer performance at 150 and 200 °C.

  18. N-doped mesoporous carbons supported palladium catalysts prepared from chitosan/silica/palladium gel beads.

    PubMed

    Zeng, Minfeng; Wang, Yudong; Liu, Qi; Yuan, Xia; Feng, Ruokun; Yang, Zhen; Qi, Chenze

    2016-08-01

    In this study, a heterogeneous catalyst including palladium nanoparticles supported on nitrogen-doped mesoporous carbon (Pd@N-C) is synthesized from palladium salts as palladium precursor, colloidal silica as template, and chitosan as carbon source. N2 sorption isotherm results show that the prepared Pd@N-C had a high BET surface area (640m(2)g(-1)) with large porosity. The prepared Pd@N-C is high nitrogen-rich as characterized with element analysis. X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HR-TEM), and Raman spectroscopy characterization of the catalyst shows that the palladium species with different chemical states are well dispersed on the nitrogen-containing mesoporous carbon. The Pd@N-C is high active and shows excellent stability as applied in Heck coupling reactions. This work supplies a successful method to prepare Pd heterogeneous catalysts with high performance from bulk biopolymer/Pd to high porous nitrogen-doped carbon supported palladium catalytic materials. PMID:27155234

  19. XPS studies of Pt catalysts supported on porous carbon

    NASA Astrophysics Data System (ADS)

    Tyagi, Deepak; Varma, Salil; Bharadwaj, S. R.

    2016-05-01

    Pt catalysts supported on porous carbon were prepared by hard templating route and used for HI decomposition reaction of Sulfur Iodine thermochemical cycle. These catalysts were characterized by X-ray photoelectron spectroscopy for oxidation state of platinum as well as nature of carbon present in the catalysts. It was found that platinum is present in metallic state and carbon is present in both sp2 and sp3 hybridization states. The catalysts were evaluated for their activity and stability for liquid phase HI decomposition reaction and it was observed that mesoporous carbon based catalysts were more active and stable under the reaction conditions.

  20. Facile preparation of silica-supported Ti catalysts effective for the epoxidation of cyclooctene using Ti-bridged silsesquioxanes.

    PubMed

    Wada, Kenji; Sakugawa, Shuko; Inoue, Masashi

    2012-08-18

    When used as additives, silicas strongly promoted the epoxidation of cyclooctene by (t)BuOOH in the presence of Ti-silsesquioxane (Ti-POSS), where Ti species were found to be bound to the silica surface. Based on this observation, highly-active silica-supported Ti catalysts were prepared by the thermal treatment of mixtures of Ti-POSS and silica.

  1. Facile sol-gel synthesis of porous silicas using poly(propylene)imine dendrimers as templates

    SciTech Connect

    Larsen, Gustavo; Lotero, Edgar; Marquez, Manuel

    2000-08-01

    Commercially available poly(propylene)imine (DAB-Am-32 and DAB-Am-64) dendrimers were used as single-molecule templates to tailor the porosity of silicas via a nonacidic sol-gel method. X-ray diffraction on both the as-prepared (oven-dried at 373 K) and the calcined (833 K) materials revealed that modest contraction took place on template removal and that the cavities created did not achieve three-dimensional ordering under the current synthesis conditions. Transmission electron microscopy of ''Pt-stained'' samples supported this picture. A modified Horvath-Kawazoe analysis of the argon adsorption isotherms indicated that DAB-Am-64 is a much more effective template than DAB-Am-32. Pyrolysis and oxidation protocols for template removal are also presented. (c) 2000 Materials Research Society.

  2. Magnetic Silica Supported Copper: A Modular Approach to Aqueous Ullmann-type Amination of Aryl Halides

    EPA Science Inventory

    One-pot synthesis of magnetic silica supported copper catalyst has been described via in situ generated magnetic silica (Fe3O4@SiO2); the catalyst can be used for the efficacious amination of aryl halides in aqueous medium under microwave irradiation.

  3. Magnetic isotope effects in the photolysis of dibenzyl ketone on porous silica. /sup 13/C and /sup 17/O enrichments

    SciTech Connect

    Turro, N.J.; Cheng, C.C.; Wan, P.; Chung, C.; Mahler, W.

    1985-04-25

    The photolysis of dibenzyl ketone (DBK) on porous silica has been investigated. Both /sup 13/C and /sup 17/O isotopic enrichment in the ketone remaining after partial photolysis is demonstrated. The efficiency of /sup 13/C enrichment was found to be relatively insensitive to the average pore diameter of the silica host, to the percent coverage by DBK, and to the application of an external magnetic field. A significant dependence of /sup 13/C enrichment with temperature, with a maximum in the enrichment-temperature profile, was observed. The results are interpreted in terms of the competition between pathways available to the triplet C/sub 6/H/sub 5/CH/sub 2/COCH/sub 2/C/sub 6/H/sub 5/ radical pair produced by photolysis of DBK.

  4. Electrical characteristics of mammalian cells on porous supports

    NASA Astrophysics Data System (ADS)

    Chen, Guo

    2003-10-01

    The quantification of epithelial barrier functions by measuring the trans-epithelial electrical resistance (TER) and using the Electric Cell-substrate Impedance Sensing (ECIS) has been complicated by the current flowing inside the narrow space underneath cells. This thesis work, by examining the electrical characteristics of epithelial cells on porous supports, is aimed to tackle this problem. A mathematical model has been constructed to quantify the impedance from the various sources within a cell/electrode system. This model presents three cell-related parameters, alpha, Rb and Cm: alpha stands for the impedance contribution from the above-mentioned current underneath cells, Rb is an equivalent representation of epithelial barrier functions and Cm denotes the capacitive impedance of cell membranes. Analysis of the three parameters as well as the electrode impedance (Z e) has revealed two experimental approaches to reduce or eliminate the complication of alpha to the deduction of Rb: lowering alpha down to zero or lowering both Ze and alpha. The experimental realization of the first approach has been studied by examining the electrical characteristics of the African green monkey kidney (BS-C-1) and Madin-Darby canine kidney (MDCK-II) cells on porous filters of mixed esters of cellulose or nitrocellulose. A unique setup featuring a plastic/filter/plastic triple-layer structure was constructed to measure the impedance of cells on filters. With the extremely low alpha, all the electrical characteristics can be explained by using an equivalent circuit and Rb can be directly obtained from the resistance difference in the low frequency range. The second approach has been experimentally investigated by examining the electrical characteristics of BS-C-1 cells on porous/rough electrodes, i.e. the gold ECIS electrodes electrochemically coated with conducting polypyrrole/heparin composites or platinum black. Ze and alpha, especially the former, were found to be significantly

  5. Effect of content of chiral selector and pore size of core-shell type silica support on the performance of amylose tris(3,5-dimethylphenylcarbamate)-based chiral stationary phases in nano-liquid chromatography and capillary electrochromatography.

    PubMed

    Rocchi, Silvia; Fanali, Salvatore; Farkas, Tivadar; Chankvetadze, Bezhan

    2014-10-10

    In this study the separation performance of various chiral stationary phases (CSPs) made of polysaccharide-based chiral selectors coated onto superficially porous (core-shell or fused-core) silica supports were evaluated. The CSPs obtained by coating of various amounts of chiral selector (1-5%) onto supports of various pore size (100 and 300 Å) were studied. Their evaluation was pursued in both chiral nano-liquid chromatography (nano-LC) and chiral capillary electrochromatography (CEC). Among the goals of this study was to re-examine our previous unexpected finding of better performance of superficially porous CSP under CEC conditions compared to nano-LC conditions for a new set of chiral compounds, as well as to study the effect of varying the chiral selector content and nominal pore size of supporting silica on the performance of core-shell silica-based polysaccharide-type CSPs. Based on the results of this study it can be seen that CSPs based on superficially porous silica can successfully be used for the separation of enantiomers in both nano-LC and CEC mode. Only a slight advantage of CEC over nano-LC mode was observed in this study from the viewpoint of plate numbers, especially at higher mobile phase flow rates. It must also be noted that the optimal theoretical plate height is still too high and further optimization of superficially porous CSPs is necessary for both nano-LC and CEC applications.

  6. New support for high-performance liquid chromatography based on silica coated with alumina particles.

    PubMed

    Silveira, José Leandro R; Dib, Samia R; Faria, Anizio M

    2014-01-01

    A new material based on silica coated with alumina nanoparticles was proposed for use as a chromatographic support for reversed-phase high-performance liquid chromatography. Alumina nanoparticles were synthesized by a sol-gel process in reversed micelles composed of sodium bis(2-ethylhexyl)sulfosuccinate, and the support material was formed by the self-assembly of alumina layers on silica spheres. Spectroscopic and (29)Si nuclear magnetic resonance results showed evidence of chemical bonds between the alumina nanoparticles and the silica spheres, while morphological characterizations showed that the aluminized silica maintained the morphological properties of silica desired for chromatographic purposes after alumina incorporation. Stability studies indicated that bare silica showed high dissolution (~83%), while the aluminized silica remained practically unchanged (99%) after passing one liter of the alkaline mobile phase, indicating high stability under alkaline conditions. The C18 bonded aluminized silica phase showed great potential for use in high-performance liquid chromatography to separate basic molecules in the reversed-phase mode.

  7. Supported metal nanoparticles on porous materials. Methods and applications.

    PubMed

    White, Robin J; Luque, Rafael; Budarin, Vitaliy L; Clark, James H; Macquarrie, Duncan J

    2009-02-01

    Nanoparticles are regarded as a major step forward to achieving the miniaturisation and nanoscaling effects and properties that have been utilised by nature for millions of years. The chemist is no longer observing and describing the behaviour of matter but is now able to manipulate and produce new types of materials with specific desired physicochemical characteristics. Such materials are receiving extensive attention across a broad range of research disciplines. The fusion between nanoparticle and nanoporous materials technology represents one of the most interesting of these rapidly expanding areas. The harnessing of nanoscale activity and selectivity, potentially provides extremely efficient catalytic materials for the production of commodity chemicals, and energy needed for a future sustainable society. In this tutorial review, we present an introduction to the field of supported metal nanoparticles (SMNPs) on porous materials, focusing on their preparation and applications in different areas. PMID:19169462

  8. Bifunctionalized mesoporous silica-supported gold nanoparticles: intrinsic oxidase and peroxidase catalytic activities for antibacterial applications.

    PubMed

    Tao, Yu; Ju, Enguo; Ren, Jinsong; Qu, Xiaogang

    2015-02-11

    Bifunctionalized mesoporous silica-supported gold nanoparticles as oxidase and peroxidase mimics for antibacterial applications are demonstrated. For the first time, these mesoporous silica-supported gold nanoparticles are applied as oxidase and peroxidase mimics. Taking advantage of their prominent enzyme activities, the MSN-AuNPs show excellent antibacterial properties against both Gram-negative and Gram-positive bacteria. Furthermore, MSN-AuNPs also exhibit outstanding performance in biofilm elimination . PMID:25655182

  9. A new high-throughput method utilizing porous silica-based nano-composites for the determination of partition coefficients of drug candidates.

    PubMed

    Yu, Chih H; Tam, Kin; Tsang, Shik C

    2011-09-01

    We show that highly porous silica-based nanoparticles prepared via micro-emulsion and sol-gel techniques are stable colloids in aqueous solution. By incorporating a magnetic core into the porous silica nano-composite, it is found that the material can be rapidly separated (precipitated) upon exposure to an external magnetic field. Alternatively, the porous silica nanoparticles without magnetic cores can be equally separated from solution by applying a high-speed centrifugation. Using these silica-based nanostructures a new high-throughput method for the determination of partition coefficient for water/n-octanol is hereby described. First, a tiny quantity of n-octanol phase is pre-absorbed in the porous silica nano-composite colloids, which allows an establishment of interface at nano-scale between the adsorbed n-octanol with the bulk aqueous phase. Organic compounds added to the mixture can therefore undergo a rapid partition between the two phases. The concentration of drug compound in the supernatant in a small vial can be determined by UV-visible absorption spectroscopy. With the adaptation of a robotic liquid handler, a high-throughput technology for the determination of partition coefficients of drug candidates can be employed for drug screening in the industry based on these nano-separation skills. The experimental results clearly suggest that this new method can provide partition coefficient values of potential drug candidates comparable to the conventional shake-flask method but requires much shorter analytical time and lesser quantity of chemicals.

  10. Liquid chromatography of polyglycerol fatty esters and fatty ethers on porous graphitic carbon and octadecyl silica by using evaporative light scattering detection and mass spectrometry.

    PubMed

    Cassel, S; Chaimbault, P; Debaig, C; Benvegnu, T; Claude, S; Plusquellec, D; Rollin, P; Lafosse, M

    2001-06-01

    A liquid chromatographic method has been developed for the analysis of polyglycerol fatty esters and fatty ethers which are non-ionic surfactants. Two methods were compared using either octadecyl silica or porous graphitic carbon. The octadecyl silica system with a hydroorganic mobile phase enables to compare the hydrophobic behavior of the compounds. The porous graphitic carbon enables the separation of the diastereoisomers. Detection of these non-UV-absorbing compounds was achieved by evaporative light scattering detection. Identification of isomers was performed by mass spectrometry.

  11. Gated silica mesoporous supports for controlled release and signaling applications.

    PubMed

    Coll, Carmen; Bernardos, Andrea; Martínez-Máñez, Ramón; Sancenón, Félix

    2013-02-19

    Blending molecular and supramolecular advances with materials science has resulted in recent years in the development of new organic-inorganic hybrid materials displaying innovative functionalities. One appealing concept in this field is the development of gated nanodevices. These materials are prepared by grafting molecular or supramolecular caps onto the external surface of mesoporous inorganic scaffolds loaded with a particular cargo. The caps or "gates" can then be opened and the cargo delivered at will upon the application of a given stimulus. In this Account, we report some of the recent advances we have made in designing such materials for drug delivery and as new chromo-fluorogenic probes. For controlled release applications, we have prepared capped hybrid mesoporous supports capable of being selectively opened by applying certain physical and chemical stimuli. We report examples of gated materials opened by changes in pH (using polyamines as caps), light (employing spiropyran derivatives or gold nanoparticles), and temperature (using selected paraffins). We also report gated materials opened by enzymes that cleave capping molecules based on lactose, hydrolyzed starch, and peptides. The use of enzymes is especially appealing because molecular caps built of enzyme-specific sequences made of peptides or other cleavable molecules could allow on-command delivery of drugs and biomolecules in specialized contexts. In the second part of the manuscript, we revisit the possibility of using hybrid gated nanomaterials as sensory systems. In such systems, when target analytes interact with the cap, their presence triggers the transport of a dye from pores to the solution, resulting in a chromo-fluorogenic signal that allows their detection. Two approaches are possible. In the first one, pores remain open and the dye can diffuse into the solution, until the presence of a target analyte binds to receptors in the caps and closes the gate. In the second approach, the caps

  12. Characteristics of the hydration layer structure in porous titania-silica obtained by the chemical vapor deposition method

    SciTech Connect

    Leboda, R.; Turov, V.V.; Marciniak, M.; Malygin, A.A.; Malkov, A.A.

    1999-11-23

    The titania-silica samples prepared by means of the chemical vapor deposition technique on the basis of mesoporous silica with different contents of grafted TiO{sub 2} were investigated. For these samples, the chemical shifts of adsorbed water, the thickness of the hydrate shell, and the free surface energy of aqueous medium were measured using the {sup 1}H NMR method. It was estimated that the chemical shift ({delta}) of the absorbed water is between 2.6 and 3.8 ppm. For the sample with 7.7 wt % TiO{sub 2}, the signal of strongly bonded water with {delta} {equals} 1.3 ppm is present in the spectra of adsorbed water. Probably this signal is caused by the water molecules, which form the electron-donor complexes with Ti atoms. With increasing TiO{sub 2} concentration, the free surface energy ({Delta}G{sub {Sigma}}) at first decreases from 160mJ/m{sup 2}, for the initial silica gel, to 90mJ/m{sup 2} for the sample containing 4.5 wt % TiO{sub 2} and then increase up to 130 mJ/m{sup 2} for the sample with 7.7 wt % TiO{sub 2} concentration. The values of {Delta}G{sub {Sigma}} for porous and nonporous materials were compared.

  13. [Preparation of 1 µm non-porous C18 silica gel stationary phase for chiral-pressurized capillary electrochromatography].

    PubMed

    Lu, Yangfang; Wang, Hui; Wang, Guiming; Wang, Yan; Gu, Xue; Yan, Chao

    2015-03-01

    Non-porous C18 silica gel stationary phase (1 µm) was prepared and applied to chiral separation in pressurized capillary electrochromatography (pCEC) for the enantioseparation of various basic compounds. The non-porous silica particles (1 µm) were synthesized using modified St6ber method. C18 stationary phase (1 µm) was prepared by immobilization of chloro-dimethyl-octadecylsilane. Using carboxymethyl-β-cyclodextrin (CM-β-CD) as the chiral additive, the pCEC conditions including the content of acetonitrile (ACN), concentration of buffer, pH, the concentration of chiral additive and flow rate as well as applied voltage were investigated to obtain the optimal pCEC conditions for the separation of four basic chiral compounds. The column provided an efficiency of up to 190,000 plates/m. Bupropion hydrochloride, clenbuterol hydrochloride, metoprolol tartrate, and esmolol hydrochloride were baseline separated under the conditions of 5 mmol/L ammonium acetate buffer at pH 4. 0 with 20% (v/ v) acetonitrile, and 15 mmol/L CM-β-CD as the chiral additive. The applied voltage was 2 kV and flow rate was 0.03 mL/min with splitting ratio of 300:1. The resolution were 1.55, 2.82, 1. 69, 1. 70 for bupropion hydrochloride, clenbuterol hydrochloride, metoprolol tartrate, esmolol hydrochloride, respectively. The C18 coverage was improved by repeating silylation method. The synthesized 1 µm C18 packings have better mechanical strength and longer service life because of the special, non-porous structure. The column used in pCEC mode showed better separation of the racemates and a higher rate compared with those used in the capillary liquid chromatography (cLC) mode. This study provided an alternative way for the method of pCEC enantioseparation with chiral additives in the mobile phase and demonstrated the feasibility of micron particle stationary phase in chiral separation. PMID:26182460

  14. [Preparation of 1 µm non-porous C18 silica gel stationary phase for chiral-pressurized capillary electrochromatography].

    PubMed

    Lu, Yangfang; Wang, Hui; Wang, Guiming; Wang, Yan; Gu, Xue; Yan, Chao

    2015-03-01

    Non-porous C18 silica gel stationary phase (1 µm) was prepared and applied to chiral separation in pressurized capillary electrochromatography (pCEC) for the enantioseparation of various basic compounds. The non-porous silica particles (1 µm) were synthesized using modified St6ber method. C18 stationary phase (1 µm) was prepared by immobilization of chloro-dimethyl-octadecylsilane. Using carboxymethyl-β-cyclodextrin (CM-β-CD) as the chiral additive, the pCEC conditions including the content of acetonitrile (ACN), concentration of buffer, pH, the concentration of chiral additive and flow rate as well as applied voltage were investigated to obtain the optimal pCEC conditions for the separation of four basic chiral compounds. The column provided an efficiency of up to 190,000 plates/m. Bupropion hydrochloride, clenbuterol hydrochloride, metoprolol tartrate, and esmolol hydrochloride were baseline separated under the conditions of 5 mmol/L ammonium acetate buffer at pH 4. 0 with 20% (v/ v) acetonitrile, and 15 mmol/L CM-β-CD as the chiral additive. The applied voltage was 2 kV and flow rate was 0.03 mL/min with splitting ratio of 300:1. The resolution were 1.55, 2.82, 1. 69, 1. 70 for bupropion hydrochloride, clenbuterol hydrochloride, metoprolol tartrate, esmolol hydrochloride, respectively. The C18 coverage was improved by repeating silylation method. The synthesized 1 µm C18 packings have better mechanical strength and longer service life because of the special, non-porous structure. The column used in pCEC mode showed better separation of the racemates and a higher rate compared with those used in the capillary liquid chromatography (cLC) mode. This study provided an alternative way for the method of pCEC enantioseparation with chiral additives in the mobile phase and demonstrated the feasibility of micron particle stationary phase in chiral separation.

  15. Physical and chemical immobilization of choline oxidase onto different porous solid supports: Adsorption studies.

    PubMed

    Passos, Marieta L C; Ribeiro, David S M; Santos, João L M; Saraiva, M Lúcia M F S

    2016-08-01

    This work carries out for the first time the comparison between the physical and chemical immobilization of choline oxidase onto aminated silica-based porous supports. The influence on the immobilization efficiency of concentration, pH, temperature and contact time between the support and choline oxidase, was evaluated. The immobilization efficiency was estimated taking into consideration the choline oxidase activity, which was assessed by using cadmium telluride (CdTe) quantum dots (QDs), obtained by hydrothermal synthesis, as photoluminescent probes. Hydrogen peroxide produced by enzyme activity was capable of quenching CdTe QDs photoluminescence. The magnitude of the PL quenching process was directly related with the enzyme activity. By comparing the chemical process with the physical adsorption, it was observed that the latter provided the highest choline oxidase immobilization. The equilibrium data were analyzed using Langmuir and Freundlich isotherms and kinetic data were fitted to the pseudo-first-order and pseudo-second-order models. Thermodynamic parameters, such as Gibbs free energy and entropy were also calculated. These results will certainly contribute to the development of new sensing schemes for choline, taking into account the growing demand for its quantification in biological samples. PMID:27241295

  16. Removal of formaldehyde from air using functionalized silica supports.

    PubMed

    Ewlad-Ahmed, Abdunaser M; Morris, Michael A; Patwardhan, Siddharth V; Gibson, Lorraine T

    2012-12-18

    This paper demonstrates the use of functionalized meso-silica materials (MCM-41 or SBA-15) as adsorbents for formaldehyde (H₂CO) vapor from contaminated air. Additionally new green nanosilica (GNs) materials were prepared via a bioinspired synthesis route and were assessed for removal of H₂CO from contaminated indoor air. These exciting new materials were prepared via rapid, 15 min, environmentally friendly synthesis routes avoiding any secondary pollution. They provided an excellent platform for functionalization and extraction of H₂CO demonstrating similar performance to the conventional meso-silica materials. To the authors' knowledge this is the first reported practical application of this material type. Prior to trapping, all materials were functionalized with amino-propyl groups which led to chemisorption of H₂CO; removing it permanently from air. No retention of H₂CO was achieved with nonfunctionalized material and it was observed that best extraction performance required a dynamic adsorption setup when compared to passive application. These results demonstrate the first application of GNs as potential adsorbents and functionalized meso-silica for use in remediation of air pollution in indoor air.

  17. Removal of formaldehyde from air using functionalized silica supports.

    PubMed

    Ewlad-Ahmed, Abdunaser M; Morris, Michael A; Patwardhan, Siddharth V; Gibson, Lorraine T

    2012-12-18

    This paper demonstrates the use of functionalized meso-silica materials (MCM-41 or SBA-15) as adsorbents for formaldehyde (H₂CO) vapor from contaminated air. Additionally new green nanosilica (GNs) materials were prepared via a bioinspired synthesis route and were assessed for removal of H₂CO from contaminated indoor air. These exciting new materials were prepared via rapid, 15 min, environmentally friendly synthesis routes avoiding any secondary pollution. They provided an excellent platform for functionalization and extraction of H₂CO demonstrating similar performance to the conventional meso-silica materials. To the authors' knowledge this is the first reported practical application of this material type. Prior to trapping, all materials were functionalized with amino-propyl groups which led to chemisorption of H₂CO; removing it permanently from air. No retention of H₂CO was achieved with nonfunctionalized material and it was observed that best extraction performance required a dynamic adsorption setup when compared to passive application. These results demonstrate the first application of GNs as potential adsorbents and functionalized meso-silica for use in remediation of air pollution in indoor air. PMID:23181357

  18. Porous silica particles grafted with an amphiphilic side-chain polymer as a stationary phase in reversed-phase high-performance liquid chromatography.

    PubMed

    Shahruzzaman, Md; Takafuji, Makoto; Ihara, Hirotaka

    2015-07-01

    The amphiphilic polymer-grafted silica was newly prepared as a stationary phase in high-performance liquid chromatography. Poly(4-vinylpyridine) with a trimethoxysilyl group at one end was grafted onto porous silica particles and the pyridyl side chains were quaternized with 1-bromooctadecane. The obtained poly(octadecylpyridinium)-grafted silica was characterized by elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy and Brunauer-Emmett-Teller analysis. The degree of quaternization of the pyridyl groups on the obtained stationary phase was estimated to be 70%. The selective retention behaviors of polycyclic aromatic hydrocarbons including some positional isomers were investigated using poly(octadecylpyridinium)-grafted silica as an amphiphilic polymer stationary phase in high-performance liquid chromatography and results were compared with commercially available polymeric octadecylated silica and phenyl-bonded silica columns. The results indicate that the selectivity toward polycyclic aromatic hydrocarbons exhibited by the amphiphilic polymer stationary phase is higher than the corresponding selectivity exhibited by a conventional phenyl-bonded silica column. However, compared with the polymeric octadecylated silica phase, the new stationary phase presents similar retention behavior for polycyclic aromatic hydrocarbons but different retention behavior particularly for positional isomers of disubstituted benzenes as the aggregation structure of amphiphilic polymers on the surface of silica substrate has been altered during mobile phase variation.

  19. Reactions of methyl radicals with silica supported silver nanoparticles in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Zidki, Tomer; Hänel, Andreas; Bar-Ziv, Ronen

    2016-07-01

    Silica supported silver nanoparticles (Ag°-SiO2-NCs, NCs=nanocomposites) suspended in aqueous solutions are efficient catalysts for the dimerization of methyl radicals to produce ethane, while bare silica is quite inert towards the interaction with methyl radicals. In the presence of small amounts of ethanol adsorbed on the SiO2 surface, the reaction path with methyl radicals is changed and methane is formed as the major product.

  20. Covalent immobilization of glucose oxidase onto new modified acrylonitrile copolymer/silica gel hybrid supports.

    PubMed

    Godjevargova, Tzonka; Nenkova, Ruska; Dimova, Nedyalka

    2005-08-12

    New polymer/silica gel hybrid supports were prepared by coating high surface area of silica gel with modified acrylonitrile copolymer. The concentrations of the modifying agent (NaOH) and the modified polymer were varied. GOD was covalently immobilized on these hybrid supports and the relative activity and the amount of bound protein were determined. The highest relative activity and sufficient amount of bound protein of the immobilized GOD were achieved in 10% NaOH and 2% solution of modified acrylonitrile copolymer. The influence of glutaraldehyde concentration and the storage time on enzyme efficiency were examined. Glutaraldehyde concentration of 0.5% is optimal for the immobilized GOD. It was shown that the covalently bound enzyme (using 0.5% glutaraldehyde) had higher relative activity than the activity of the adsorbed enzyme. Covalently immobilized GOD with 0.5% glutaraldehyde was more stable for four months in comparison with the one immobilized on pure silica gel, hybrid support with 10% glutaraldehyde and the free enzyme. The effect of the pore size on the enzyme efficiency was studied on four types of silica gel with different pore size. Silica with large pores (CPC-Silica carrier, 375 A) presented higher relative activity than those with smaller pore size (Silica gel with 4, 40 and 100 A). The amount of bound protein was also reduced with decreasing the pore size. The effect of particle size was studied and it was found out that the smaller the particle size was, the greater the activity and the amount of immobilized enzyme were. The obtained results proved that these new polymer/silica gel hybrid supports were suitable for GOD immobilization. PMID:16080168

  1. Refractive index detection range adjustable liquid-core fiber optic sensor based on surface plasmon resonance and a nano-porous silica coating

    NASA Astrophysics Data System (ADS)

    Chen, Yuzhi; Li, Xuejin; Zhou, Huasheng; Hong, Xueming; Geng, Youfu

    2016-09-01

    A liquid-core fiber optic surface plasmon resonance sensor with an adjustable nano-porous silica coating is first presented in this paper. By adjusting the refractive index of the nano-porous silica coating, the sensor can be used in different refractive index detection ranges. A low refractive index interval of 1.33-1.34 and a high refractive index interval of 1.42-1.44 are taken as examples to be investigated. Results show that our sensor works well in these two intervals by using appropriate nano-porous silica coatings. The highest sensitivities of the low and high refractive index intervals are obtained to be 5840 nm/RIU and 5120 nm/RIU, respectively. In addition, the sensing performances and the working wavelengths can be adjusted to meet different working requirements by changing the refractive index of the nano-porous silica coating. We also take the single mode incidence cases to explain the effects of different single incident light modes on the sensing performances.

  2. Refractive index detection range adjustable liquid-core fiber optic sensor based on surface plasmon resonance and a nano-porous silica coating

    NASA Astrophysics Data System (ADS)

    Chen, Yuzhi; Li, Xuejin; Zhou, Huasheng; Hong, Xueming; Geng, Youfu

    2016-09-01

    A liquid-core fiber optic surface plasmon resonance sensor with an adjustable nano-porous silica coating is first presented in this paper. By adjusting the refractive index of the nano-porous silica coating, the sensor can be used in different refractive index detection ranges. A low refractive index interval of 1.33–1.34 and a high refractive index interval of 1.42–1.44 are taken as examples to be investigated. Results show that our sensor works well in these two intervals by using appropriate nano-porous silica coatings. The highest sensitivities of the low and high refractive index intervals are obtained to be 5840 nm/RIU and 5120 nm/RIU, respectively. In addition, the sensing performances and the working wavelengths can be adjusted to meet different working requirements by changing the refractive index of the nano-porous silica coating. We also take the single mode incidence cases to explain the effects of different single incident light modes on the sensing performances.

  3. Fabrication of Hollow Porous Silica Using a Combined Emulsion Sol-Gel Process and Amphiphilic Triblock Copolymer for Loading of Quercetin.

    PubMed

    Lee, Sang Gil; Kim, Young Ho; Bae, Jun Tae; Lee, Chung Hee; Pyo, Hyeong Bae; Kang, Kuk Hyoun; Lee, Dong Kyu

    2015-10-01

    Flavonoids have recently attracted significant interest as potential reducing agents, hydrogen-donating antioxidants, and singlet oxygen-quenchers. Quercetin, in particular, induces the expression of a gene, known to be associated with cell protection, in dose- and time-dependent manners. Therefore, quercetin may be used as an effective cosmeceutical material useful in the protection of dermal skin. In this study, hollow porous silica spheres used to load quercetin were prepared by using a combined emulsion sol-gel process and triblock copolymer as a template. Fabrication of hollow porous silica spheres was performed under various conditions such as the molar ratios of H2O/TEOS (Rw) and weight ratios of poloxamer 184/poloxamer 407. Loading of quercetin in hollow porous silica spheres was devised to improve the stability of quercetin and to consider the possibility as a raw cosmetic material. The surface of inclusion complexes of quercetin in hollow porous silicas was modified to enhance the stability of quercetin. The physicochemical properties of the samples were investigated using scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA)-differential thermal analysis (DTA) and Brunauer-Emmett-Teller (BET) surface area and porosity analysis. Determination of quercetin concentration was carried out by high-performance liquid chromatography (HPLC) analysis. PMID:26726443

  4. Solid Sulfonic Acid Catalysts Based on Porous Carbons and Carbon-Silica Composites

    NASA Astrophysics Data System (ADS)

    Tian, Xiao Ning; Luo, Lijuan; Jiang, Zhongqing; Zhao, X. S.

    Mesoporous carbons prepared using a templating method under different carbonization temperatures are sulfonated with concentrated H2SO4. Without the moving of silica template carbon-silica composites were prepared, which can maintain the pore structure well during sulfonation reaction process. The resultant samples are characterized using nitrogen adsorption, transmission electron microscope, field-emission scanning electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy, and elemental analysis techniques. The catalytic performances of the sulfonated carbons and composites are evaluated by esterification reaction of methanol with acetic acid. The results show that a low-temperature carbonization process is favorable for improving the reaction conversion of acetic acid. In addition, the sulfonated carbon-silica composites show a higher acetic acid conversion than the sulfonated mesoporous carbons.

  5. Preparation of magnetic nano-composite: barium hexaferrite loaded in the ordered meso-porous silica matrix (MCM-41).

    PubMed

    Emamian, H R; Honarbakhsh-Raouf, A; Ataie, A

    2010-04-01

    In this work a magnetic nano-composite was synthesized by modified incorporation of iron-barium complex into ordered meso-porous silica (MCM-41) as a matrix. The MCM-41 was synthesized by silylation treatment which was accompanied by pH adjusting. Low angle XRD patterns of both annealed MCM-41 and resulted composite exhibited the characteristic reflection of high quality hexagonal meso-structures. TEM image of the composite material revealed that the hexagonal ordered meso-structure host material was not affected by wet impregnation and subsequent calcination in order to incorporate with barium hexaferrite. Also, TEM images accompanied by EDS analysis confirmed the formation of second phase consists of barium and iron ions inside the MCM-41 channels. The resulted composite material showed a super-paramagnetic nature at room temperature.

  6. The effect of porous support composition and operating parameters on the performance of supported liquid membranes

    SciTech Connect

    Takigawa, D.Y.

    1991-02-01

    Factors, such as porous support composition and operating parameters, that influence the performance of supported liquid membranes (SLMs) were investigated. SLMs of varying porous support compositions and structures were studied for the transport of metal ions. A microporous polybenzimidazole support was synthesized and prepared in the form of an SLM. This SLM containing the selective extractant di-(2-ethylhexyl)phosphoric acid was evaluated for the transport of copper and neodymium. Dramatically improved performance over that of commercially available membranes was found in tests for removing the metal ions from solution. Metal ion transport reaches near completion in less than 3 hours, whereas Celgard-polypropylene and Nuclepore-polycarbonate reaches only 50% completion even after 15 hours. The transport driving force for acidic extractants is a pH gradient between the feed and strip solutions. Polybenzimidazole, an acid- and radiation-resistant polymer, has two protonatable tertiary nitrogens per repeat unit that may help sustain the pH driving force. Another factor may be the ability of the polybenzimidazole to hydrogen bond with the extractant. Transport through the flat-sheet SLMs were tested using a unique cell design. Countercurrent flow of the feed and strip solutions was established through machined channels in half-cell faceplates that are in a spiral, mirror-image pattern with respect to each other, with the flat-sheet SLM interposed between the two channeled solutions. 7 refs., 14 figs.

  7. Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

    SciTech Connect

    Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang Gao, Ziwei

    2015-01-15

    A successive anchoring of Ti(NMe{sub 2}){sub 4}, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, {sup 13}C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands. - Graphical abstract: The ligand-tailored silica supported “single site” titanium complexes were synthesized by SOMC strategy and fully characterized. Their catalytic activity were evaluated by benzaldehyde silylcyanation. - Highlights: • Single-site silica supported Ti active species was prepared by SOMC technique. • O-donor ligand tailored Ti surface species was synthesized. • The surface species was characterized by XPS, {sup 13}C CP-MAS NMR, XANES etc. • Catalytic activity of the Ti active species in silylcyanation reaction was evaluated.

  8. Hydrogen and oxygen adsorption stoichiometries on silica supported ruthenium nanoparticles

    SciTech Connect

    Berthoud, Romain; Delichere, Pierre; Gajan, David; Lukens, Wayne; Pelzer, Katrin; Basset, Jean-Marie; Candy, Jean-Pierre; Coperet, Christophe

    2008-12-01

    Treatment under H{sub 2} at 300 C of Ru(COD)(COT) dispersed on silica yields 2 nm ruthenium nanoparticles, [Ru{sub p}/SiO{sub 2}], according to EXAFS, HRTEM and XPS. H{sub 2} adsorption measurements on [Ru{sub p}/SiO{sub 2}] in the absence of O{sub 2} show that Ru particles adsorb up to ca. 2 H per surface ruthenium atoms (2H/Ru{sub s}) on various samples; this technique can therefore be used to measure the dispersion of Ru particles. In contrast, O{sub 2} adsorption on [Ru{sub p}/SiO{sub 2}] leads to a partial oxidation of the bulk at 25 C, to RuO{sub 2} at 200 C and to sintering upon further reduction under H{sub 2}, showing that O{sub 2} adsorption cannot be used to measure the dispersion of Ru particles.

  9. Encapsulation of protein molecules in transparent porous silica matrices via an aqueous colloidal sol-gel process

    SciTech Connect

    Liu, D.M.; Chen, I.W.

    1999-12-10

    Encapsulation of several biologically important proteins, cytochrome c, catalase, myoglobin, and hemoglobin, into transparent porous silica matrices by an aqueous colloidal sol-gel process that requires no alcohol is reported. Optical characterization indicates a successful retention of protein conformation after encapsulation. The conformation retention is strongly correlated to both the rate of gelation and the subsequent drying speed. Using hemoglobin as a model protein, a higher colloidal solid concentration and a lower synthesis pH were found, both causing faster gelation, resulting in a better retention of conformation. Hemoglobin encapsulated in a thin film, which dries faster, also showed a better retention than in the bulk. This is attributed to the fact that when a protein is isolated, and especially when it is confined to a space close to its own dimensions, conformational changes are sterically hindered, hence the structural stability. Enzymatic activity of bovine liver catalase was also monitored and showed a remarkable improvement when encapsulated using the aqueous colloidal process, compared to using the conventional alkoxide-based process. Thus, the aqueous colloidal sol-gel process offers a promising alternative to the conventional sol-gel process for encapsulating biomolecules into transparent, porous matrices.

  10. Porous carbon-coated silica macroparticles as anode materials for lithium ion batteries: Effect of boric acid

    NASA Astrophysics Data System (ADS)

    Kim, Young-Kuk; Moon, Jong-Woo; Lee, Jung-Goo; Baek, Youn-Kyung; Hong, Seong-Hyun

    2014-12-01

    We report carbon-coated porous silica macroparticles (SiO2@C) prepared using polymeric templates and subsequent carbonization with sucrose for improved electrochemical energy storage in lithium-ion batteries (LIBs). In addition, boron is introduced to improve the stability of electrochemical cells by pyrolyzing mixtures of sucrose and boric acid (SiO2@C + B) under inert atmosphere. The initially large surface area of porous SiO2 (SBET ∼ 658 m2 g-1) is reduced to 102 m2 g-1 after carbonization and introduction of boric acid. Surface of both SiO2@C and SiO2@C + B are covered with amorphous carbon. In particular, SiO2@C + B particles containing borosilicate (Si-O-B) phase and B-O bondings and Si-C-O bondings are also detected from the X-ray photoelectron spectra. The SiO2@C + B macroparticles shows high reversible charge capacity up to 503 mAh g-1 after 103 cycles of Li intercalation/de-intercalation although initial capacity was 200 mAh g-1. The improved charge capacity of SiO2@C + B is attributed to formation of advantageous microstructures induced from boric acid.

  11. Supported Intrinsically Porous Oligomers as Hybrid Materials for Separations, Storage, and Sensing

    NASA Astrophysics Data System (ADS)

    Thompson, Anthony Boone

    Adsorption-desorption phenomena are often difficult to study at the molecular level because the surfaces on which they occur can be heterogeneous, giving a wide distribution of adsorption sites and associated energies. Considering that these phenomena underlie an incredibly wide variety of industrially important processes, a better understanding could aid in the development of more efficient methods. In this work, we describe an approach to designing materials with well-defined adsorption sites by covalently attaching intrinsically porous molecules to solid surfaces by a rigid multidentate linker. These cup-shaped molecules are intended to act as adsorption sites on the material, whereas the rigid attachment to the solid support serves to prevent movement and conformational changes of the sites, leading to better understanding of adsorption phenomena. As a proof-of-concept application, materials were used for adsorption of n-butanol biofuel and related compounds from dilute aqueous solution. The materials were thermally and hydrolytically stable, and adsorption phenomena were reversible. Adsorption sites containing more hydrophobic molecular area led to stronger adsorption, suggesting that it is driven by weak van der Waals forces. Likewise, adsorption sites that were strongly polarized performed poorly, possibly reflecting a greater energy penalty of removing water molecules from the cavity. Upon placing a Lewis acidic metal at the bottom of the cavity, an enhancement was seen only with the most acidic metal, which may indicate weak guest coordination. Observing that hydrophobic interactions dominate adsorption on these materials, efforts were made to develop hybrid materials with large hydrophobic area for adsorption. Glaser coupling of diethynylbenzene was used to grow oligo(phenylene butadiynylene)s from the surface of silica, resulting in materials that were more than 25% organic by weight. In addition to their potential use as adsorbents, these materials may

  12. Particles of porous silicon formed from silica powders of plant origin and their structural properties

    NASA Astrophysics Data System (ADS)

    Kashko, I.; Girel, K.; Yanushkevich, K.; Bandarenka, H.

    2016-08-01

    In this paper, we present the results on study of formation regularities, morphology, composition and photoluminescence of porous silicon particles fabricated by the magnesiothermal reduction of different samples of biogenic silicon dioxide based on rice husk, bamboo husk and bamboo joints at 650 °C at argon atmosphere.

  13. Controllable synthesis of hollow mesoporous silica spheres and application as support of nano-gold

    SciTech Connect

    Wang, Tao; Ma, Weihua Shangguan, Junnan; Jiang, Wei; Zhong, Qin

    2014-07-01

    Hollow silica spheres with mesoporous structure were synthesized by sol–gel/emulsion method. In the process, the surfactant, cetyltrimethylammonium bromide (CTAB) was used to stabilize the oil droplet and also used as structure direct agent. The diameter of the hollow silica spheres, ranging from 895 nm to 157 nm, can be controlled by changing the ratio of ethanol to water and the concentration of the surfactant as well. The shell thickness of the spheres decreased when the ratio of ethanol to water decreased. The proposed mechanism of the formation of silica spheres could elucidate the experimental results well. Furthermore, the resultant hollow mesoporous silica spheres were then employed as support of nano-gold which was used to catalyze the isomerization reaction of propylene oxide to produce allyl alcohol. - Graphical abstract: It is the schematic mechanism for the formation of hollow mesoporous silica spheres. - Highlights: • The formation mechanism of the hollow spheres is proposed. • The isomerization of propylene oxide can be catalyzed by the nano-gold/SiO{sub 2}. • The hollow silica spheres can be prepared controllably.

  14. A new high-throughput method utilizing porous silica-based nano-composites for the determination of partition coefficients of drug candidates.

    PubMed

    Yu, Chih H; Tam, Kin; Tsang, Shik C

    2011-09-01

    We show that highly porous silica-based nanoparticles prepared via micro-emulsion and sol-gel techniques are stable colloids in aqueous solution. By incorporating a magnetic core into the porous silica nano-composite, it is found that the material can be rapidly separated (precipitated) upon exposure to an external magnetic field. Alternatively, the porous silica nanoparticles without magnetic cores can be equally separated from solution by applying a high-speed centrifugation. Using these silica-based nanostructures a new high-throughput method for the determination of partition coefficient for water/n-octanol is hereby described. First, a tiny quantity of n-octanol phase is pre-absorbed in the porous silica nano-composite colloids, which allows an establishment of interface at nano-scale between the adsorbed n-octanol with the bulk aqueous phase. Organic compounds added to the mixture can therefore undergo a rapid partition between the two phases. The concentration of drug compound in the supernatant in a small vial can be determined by UV-visible absorption spectroscopy. With the adaptation of a robotic liquid handler, a high-throughput technology for the determination of partition coefficients of drug candidates can be employed for drug screening in the industry based on these nano-separation skills. The experimental results clearly suggest that this new method can provide partition coefficient values of potential drug candidates comparable to the conventional shake-flask method but requires much shorter analytical time and lesser quantity of chemicals. PMID:21780284

  15. Structural and optical characteristics of fullerenes incorporated inside porous silica aerogel

    NASA Astrophysics Data System (ADS)

    Zhu, Lei; Li, Yufen; Wang, Jue; Shen, Jun

    1995-06-01

    The successful synthesis of fullerene-doped silica aerogel by the sol-gel process followed by the supercritical drying technique is reported. The fullerenes (C 60/C 70) can be embedded inside micropores linked by the silica skeleton and the fullerene structures were retained in the fabrication process as seen using mass spectroscopy, Fourier transform infrared spectroscopy and transmission electron microscopy. The fulleren-doped composites were found to be able to emit intense visible light (2.26 eV) under Ar + laser (488 nm) excitation at room temperature. The luminescent intensity increased strongly with low doping of fullerenes (0.05 mol%), then decreased while the peak was red-shifted and finally quenched upon heavy doping (2.5 mol%). This phenomenon is explained as a result of the quantum confinement effect for fullerenes which produces emissions far above the inter-band gap of C 60/C 70.

  16. The effect of porous support composition and operating parameters on the performance of supported liquid membranes

    SciTech Connect

    Takigawa, D.Y. )

    1992-03-01

    Supported liquid membranes (SLMs) of varying porous support compositions and structures were studied for the transport of metal ions. A microporous polybenzimidazole support was synthesized and prepared in the form of an SLM. This SLM, containing the selective extractant di-(2-ethylhexyl) phosphoric acid, was evaluated for the transport of copper and neodymium. Metal ion transport reaches near completion in less than 3 h, whereas Celgard-polypropylene and Nucleopore-polycarbonate reaches only 50% completion even after 15 h. The transport driving force for acidic extractants is a pH gradient between the feed and strip solutions. Polybenzimidazole, an acid-and radiation-resistant polymer, has two protonatable tertiary nitrogens per repeat unit that may help sustain the pH driving force. Another factor may be the ability of the polybenzimidazole to hydrogen bond with the extractant. Transport through the flat-sheet SLMs was tested by using a unique cell design. Countercurrent flow of the feed and strip solutions was established through machined channels in half-cell face plates that are in a spiral, mirror-image pattern with respect to each other, with the flat-sheet SLM interposed between the two channeled solutions. Advantages comprised in the design of the two clamped half-cells (tangential entry, zero primary pressure, zero pressure differential, controlled flow regimes, no sharp turns, and channeled flow) give operating parameters that will not physically dislodge the liquid membrane from the porous support; consequently, the lifetime of the support is increased. Permeability coefficients remained unchanged after a month of daily use versus 20 to 100% declines for membranes in other cell configurations.

  17. Switching on the Metathesis Activity of Re Oxo Alkylidene Surface Sites through a Tailor-Made Silica-Alumina Support.

    PubMed

    Valla, Maxence; Stadler, David; Mougel, Victor; Copéret, Christophe

    2016-01-18

    Re oxo alkylidene surface species are putative active sites in classical heterogeneous Re-based alkene-metathesis catalysts. However, the lack of evidence for such species questions their existence and/or relevance as reaction intermediates. Using Re(O)(=CH-CH=CPh2)(OtBuF6)3(THF), the corresponding well-defined Re oxo alkylidene surface species can be generated on both silica and silica-alumina supports. While inactive on the silica support, it displays very good activity, even for functionalized olefins, on the silica-alumina support. PMID:26756446

  18. Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

    NASA Astrophysics Data System (ADS)

    Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

    2015-01-01

    A successive anchoring of Ti(NMe2)4, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1‧-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, 13C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands.

  19. Magnetic silica supported palladium catalyst: synthesis of allyl aryl ethers in water

    EPA Science Inventory

    A simple and benign procedure for the synthesis of aryl allyl ethers has been developed using phenols, allyl acetates and magnetically recyclable silica supported palladium catalyst in water; performance of reaction in air and easy separation of the catalyst using an external mag...

  20. Polymer- and silica-supported iron BPMEN-inspired catalysts for C-H bond functionalization reactions.

    PubMed

    Feng, Yan; Moschetta, Eric G; Jones, Christopher W

    2014-11-01

    Direct catalytic C-H bond functionalization is a key challenge in synthetic chemistry, with many popular C-H activation methodologies involving precious-metal catalysts. In recent years, iron catalysts have emerged as a possible alternative to the more common precious-metal catalysts, owing to its high abundance, low cost, and low toxicity. However, iron catalysts are plagued by two key factors: the ligand cost and the low turnover numbers (TONs) typically achieved. In this work, two approaches are presented to functionalize the popular N(1),N(2)-dimethyl-N(1),N(2)-bis(pyridin-2-ylmethyl)ethane-1,2-diamine (BPMEN) ligand, so that it can be supported on porous silica or polymer resin supports. Four new catalysts are prepared and evaluated in an array of catalytic C-H functionalization reactions by using cyclohexane, cyclohexene, cyclooctane, adamantane, benzyl alcohol, and cumene with aqueous hydrogen peroxide. Catalyst recovery and recycling is demonstrated by using supported catalysts, which allows for a modest increase in the TON achieved with these catalysts.

  1. Supported porous carbon and carbon-CNT nanocomposites for supercapacitor applications

    NASA Astrophysics Data System (ADS)

    Schopf, Dimitri; Es-Souni, Mohammed

    2016-03-01

    Supported porous carbon and porous carbon-MWCNT-nanocomposite films are produced by pyrolysis of porous polyvinylidene fluoride (PVDF) or porous PVDF-MWCNT-nanocomposite films on thermally resistant substrates. All films are characterized by SEM, RAMAN and XRD. The application of these films as supercapacitors is explored with outstanding supercapacitance values ranging from 80 to 120 F g-1 (up to 70 mF cm-2) in a three-electrode set-up in 1 M KOH, depending on microstructure. Additionally, the implementation of porous nanocarbon-MWCNT-nanocomposite films as electrodes in a symmetrical supercapacitor device is investigated. In all cases, long-term charge-discharge stability is demonstrated.

  2. Decolorization of two synthetic dyes using the purified laccase of Paraconiothyrium variabile immobilized on porous silica beads

    PubMed Central

    2014-01-01

    Background Decolorization of hazardous synthetic dyes using laccases in both free and immobilized form has gained attention during the last decades. The present study was designed to prepare immobilized laccase (purified from Paraconiothyrium variabile) on porous silica beads followed by evaluation of both free and immobilized laccases for decolorization of two synthetic dyes of Acid Blue 25 and Acid Orange 7. Effects of laccase concentration, pH and temperature alteration, and presence of 1-hydroxybenzotriazole (HBT) as laccase mediator on decolorization pattern were also studied. In addition, the kinetic parameters (K m and V max ) of the free and immobilized laccases for each synthetic dye were calculated. Results Immobilized laccase represented higher temperature and pH stability compare to free one. 39% and 35% of Acid Blue 25 and Acid Orange 7 was decolorized, respectively after 65 min incubation in presence of the free laccase. In the case of immobilized laccase decolorization percent was found to be 76% and 64% for Acid Blue 25 and Acid Orange 7, respectively at the same time. Increasing of laccase activity enhanced decolorization percent using free and immobilized laccases. Relative decolorization of both applied dyes was increased after treatment by laccase-HBT system. After nine cycles of decolorization by immobilized laccase, 26% and 31% of relative activity were lost in the case of Acid Blue 25 and Acid Orange 7, respectively. Conclusions To sum up, the present investigation introduced the immobilized laccase of P. variabile on porous beads as an efficient biocatalyst for decolorization of synthetic dyes. PMID:24393474

  3. Adsorption dynamics of CO on copper and gold clusters supported on silica - How special is nanogold?

    NASA Astrophysics Data System (ADS)

    Shan, J.; Komarneni, M.; Burghaus, U.

    2011-11-01

    A twist about an atomistic explanation for the unusual particle size-dependent reactivity enhancement of supported gold clusters still exists in the surface science and catalysis communities. A molecular beam scattering technique allowed the active sites of a catalyst to be mapped. In doing so, copper and gold clusters, both supported on silica, were studied. Indeed, Au clusters showed quite unusual behavior, however, that would be consistent with the influence of defects rather than quantum size effects.

  4. Monodisperse metal nanoparticle catalysts on silica mesoporous supports: synthesis, characterizations, and catalytic reactions

    SciTech Connect

    Somorjai, G.A.

    2009-09-14

    The design of high performance catalyst achieving near 100% product selectivity at maximum activity is one of the most important goals in the modern catalytic science research. To this end, the preparation of model catalysts whose catalytic performances can be predicted in a systematic and rational manner is of significant importance, which thereby allows understanding of the molecular ingredients affecting the catalytic performances. We have designed novel 3-dimensional (3D) high surface area model catalysts by the integration of colloidal metal nanoparticles and mesoporous silica supports. Monodisperse colloidal metal NPs with controllable size and shape were synthesized using dendrimers, polymers, or surfactants as the surface stabilizers. The size of Pt, and Rh nanoparticles can be varied from sub 1 nm to 15 nm, while the shape of Pt can be controlled to cube, cuboctahedron, and octahedron. The 3D model catalysts were generated by the incorporation of metal nanoparticles into the pores of mesoporous silica supports via two methods: capillary inclusion (CI) and nanoparticle encapsulation (NE). The former method relies on the sonication-induced inclusion of metal nanoparticles into the pores of mesoporous silica, whereas the latter is performed by the encapsulation of metal nanoparticles during the hydrothermal synthesis of mesoporous silica. The 3D model catalysts were comprehensively characterized by a variety of physical and chemical methods. These catalysts were found to show structure sensitivity in hydrocarbon conversion reactions. The Pt NPs supported on mesoporous SBA-15 silica (Pt/SBA-15) displayed significant particle size sensitivity in ethane hydrogenolysis over the size range of 1-7 nm. The Pt/SBA-15 catalysts also exhibited particle size dependent product selectivity in cyclohexene hydrogenation, crotonaldehyde hydrogenation, and pyrrole hydrogenation. The Rh loaded SBA-15 silica catalyst showed structure sensitivity in CO oxidation reaction. In

  5. Acid strength of silica-supported oxide catalysts studied by microcalorimetric measurements of pyridine adsorption

    SciTech Connect

    Cardona-Martinez, N.; Dumesic, J.A. )

    1991-02-01

    Microcalorimetric measurements of the differential heat of pyridine adsorption were used to probe the distribution of acid strength on a series of silica-supported oxide catalysts. Depositing oxides of the following cations onto silica increased the acid strength of the catalyst: Ga{sup 3{plus}}, Zn{sup 2{plus}}, Al{sup 3{plus}}, Fe{sup 3{plus}}, Fe{sup 2{plus}}, Mg{sup 2{plus}}, and Sc{sup 3{plus}}. The acid strength distribution curves for the supported oxide samples showed either two or three regions of constant heat of adsorption while silica had an energetically homogeneous surface. The Ga, Al, and Sc samples were found to have both Bronsted and Lewis acidity while the remaining samples showed only Lewis acidity. Incremental adsorption of pyridine indicated that the initial region of highest heat corresponds to strong Lewis acidity while intermediate heats seemed to be due to weaker Lewis acid sites or a combination of Lewis and Bronsted acid sites. The final region of lowest heat was due to H-bonded pyridine on silica. Estimates of the entropies of adsorption were determined, providing information about the mobility of the adsorbed pyridine molecules. The initial differential heat of adsorption increases proportionally to the Sanderson electronegativity of the added oxide.

  6. A fiber-optic sensor to detect volatile organic compounds based on a porous silica xerogel film.

    PubMed

    Echeverría, Jesús C; de Vicente, Pablo; Estella, Juncal; Garrido, Julián J

    2012-09-15

    Fiber-optic sensors are increasingly used for the determination of volatile organic compounds (VOCs) in air matrices. This paper provides experimental results on the sensitivity of a fiber-optic sensor that uses a film of a porous silica xerogel as the sensing element. This film was synthesized by the sol-gel process and affixed to the end of the optical fiber by the dip-coating technique. This intrinsic sensor works in reflection mode, and the transduction takes place in the light that travels through the core of the fiber. The VOCs included in this research cover a wide range of compounds with different functional groups and polarities. The highest sensitivity was for 2-propanol (13.1±1.4 M(-1) nm(-1)), followed by toluene (11.4±1.4 M(-1) nm(-1)), and 1-butylamine (9.5±0.4 M(-1) nm(-1)). Acetone and cyclohexane had the lowest sensitivity of all studied VOCs. Limits of detection varied between 9.1×10(-5) M for 1-butylamine and 1.6×10(-3) M for ethanol. Silanol groups on the xerogel surface act as weak acids and interact strongly with molecules that contain OH groups like alcohols, π-electrons like toluene, or a lone pair of electrons like toluene. Stronger interaction of methanol and ethanol with the silanol groups on the film led to some irreversible adsorption of these analytes at room temperature.

  7. Microstructure-stability relations studies of porous chitosan microspheres supported palladium catalysts.

    PubMed

    Zeng, Minfeng; Zhang, Xin; Qi, Chenze; Zhang, Xian-Man

    2012-12-01

    In this study, polyethylene glycol (PEG) with different molecular weight, polyvinyl pyrrolidone (PVP), and polyvinyl alcohol (PVA), are chosen as porogens for preparing chitosan base porous microsphere supported palladium catalyst for coupling reactions. The pore structure of the microspheres was controlled by the compatibility of chitosan and counterpart polymers. The prepared porous chitosan microspheres supported palladium heterogeneous catalysts have been evaluated using the well-established Ullmann reductive homocoupling and the Heck cross-coupling reactions. The activities, stabilities and recyclability of the porous chitosan microspheres supported palladium catalysts are not only highly dependent upon the surface areas of the solid supports, but also upon the chemical properties of the water-soluble polymers. The degradation of the prepared heterogeneous palladium catalysts is mainly caused by a combination of the palladium leaching and the morphological transformation of the palladium species from the amorphous into the crystals.

  8. Vertically porous nickel thin film supported Mn3O4 for enhanced energy storage performance.

    PubMed

    Li, Xiao-Jun; Song, Zhi-Wei; Zhao, Yong; Wang, Yue; Zhao, Xiu-Chen; Liang, Minghui; Chu, Wei-Guo; Jiang, Peng; Liu, Ying

    2016-12-01

    Three-dimensionally porous metal materials are often used as the current collectors and support for the active materials of supercapacitors. However, the applications of vertically porous metal materials in supercapacitors are rarely reported, and the effect of vertically porous metal materials on the energy storage performance of supported metal oxides is not explored. To this end, the Mn3O4-vertically porous nickel (VPN) electrodes are fabricated via a template-free method. The Mn3O4-VPN electrode shows much higher volumetric specific capacitances than that of flat nickel film supported Mn3O4 with the same loading under the same measurement conditions. The volumetric specific capacitance of the vertically porous nickel supported Mn3O4 electrode can reach 533Fcm(-3) at the scan rate of 2mVs(-1). The fabricated flexible all-solid microsupercapacitor based on the interdigital Mn3O4-VPN electrode has a volumetric specific capacitance of 110Fcm(-3) at the current density of 20μAcm(-2). The capacitance retention rate of this microsupercapacitor reaches 95% after 5000 cycles under the current density of 20μAcm(-2). The vertical pores in the nickel electrode not only fit the micro/nanofabrication process of the Mn3O4-VPN electrode, but also play an important role in enhancing the capacitive performances of supported Mn3O4 particles.

  9. Crosslinking Amine-Modified Silica Aerogels with Epoxies: Mechanically Strong Lightweight Porous Materials

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Fabrizio, Eve F.; Ilhan, Faysal; Dass, Amala; Zhang, Guo-Hui; Vassilaras, Plousia; Johnston, J. Chris; Leventis, Nicholas

    2005-01-01

    The mesoporous surfaces of TMOS-derived silica aerogels have been modified with amines by co-polymerization of TMOS with APTES. The amine sites have become anchors for crosslinking the nanoparticles of the skeletal backbone of the aerogel by attachment of di-, tri and tetra-functional epoxies. The resulting conformal coatings increase the density of the native aerogels by a factor of 2-3 but the strength of the resulting materials may increase by more than two orders of magnitude. Processing variables such as amount of APTES used to make the gels, the epoxy type and concentration used for crosslinking, as well as the crosslinking temperature and time were varied according to a multivariable design-of-experiments (DOE) model. It was found that while elastic modulus follows a similar trend with density, maximum strength is attained neither at the maximum density nor at the highest concentration of -NH2 groups, suggesting surface saturation effects. Aerogels crosslinked with the tri-functional epoxide always show improved strength compared with aerogels crosslinked with the other two epoxides under identical conditions. Solid C-13 NMR studies show residual unreacted epoxides, which condense with ne another by heating crosslinked aerogels at 150 C.

  10. Sintering of highly porous silica-particle samples: analogues of early Solar-System aggregates

    NASA Astrophysics Data System (ADS)

    Poppe, T.

    2003-07-01

    I describe a new method to make particle layers which consist of SiO 2 spheres with 0.78 μm radius. The layers were produced by sedimentation of aggregates which had grown in ballistic particle collisions, and the layers had a porosity of 0.95. They were used for experiments on sintering, i.e., the samples were heated in an oven at varying temperatures and heating durations, and the samples were analyzed by scanning electron microscopy. Based on the change of particle diameter, surface diffusion sintering and viscous flow are identified as important transformation mechanisms. The first effect dominated at the start of restructuring and the latter at higher temperatures. The neck growth of adjacent particles was fitted to a surface diffusion sintering model and predicts neck radii as a heating temperature and duration function. Between the temperature range of neck formation and of melting, further restructuring occurred which lead to dissolution of particulate structure and to densification and which resulted in a porous object consisting of straight elongated substructures which connected kinks of higher material density. The thermal transformation is important for the change of strength, collisional behavior, light-scattering properties, and thermal conductivity with relevance to dust aggregates, planetesimals, comets, interplanetary dust particles, and regolith-covered celestial bodies.

  11. Particle size effect of redox reactions for Co species supported on silica

    NASA Astrophysics Data System (ADS)

    Chotiwan, Siwaruk; Tomiga, Hiroki; Katagiri, Masaki; Yamamoto, Yusaku; Yamashita, Shohei; Katayama, Misaki; Inada, Yasuhiro

    2016-09-01

    Conversions of chemical states during redox reactions of two silica-supported Co catalysts, which were prepared by the impregnation method, were evaluated by using an in situ XAFS technique. The addition of citric acid into the precursor solution led to the formation on silica of more homogeneous and smaller Co particles, with an average diameter of 4 nm. The supported Co3O4 species were reduced to metallic Co via the divalent CoO species during a temperature-programmed reduction process. The reduced Co species were quantitatively oxidized with a temperature-programmed oxidation process. The higher observed reduction temperature of the smaller CoO particles and the lower observed oxidation temperature of the smaller metallic Co particles were induced by the higher dispersion of the Co oxide species, which apparently led to a stronger interaction with supporting silica. The redox temperature between CoO and Co3O4 was found to be independent of the particle size.

  12. Protocells: Modular Mesoporous Silica Nanoparticle-Supported Lipid Bilayers for Drug Delivery.

    PubMed

    Butler, Kimberly S; Durfee, Paul N; Theron, Christophe; Ashley, Carlee E; Carnes, Eric C; Brinker, C Jeffrey

    2016-04-27

    Mesoporous silica nanoparticle-supported lipid bilayers, termed 'protocells,' represent a potentially transformative class of therapeutic and theranostic delivery vehicle. The field of targeted drug delivery poses considerable challenges that cannot be addressed with a single 'magic bullet'. Consequently, the protocell has been designed as a modular platform composed of interchangeable biocompatible components. The mesoporous silica core has variable size and shape to direct biodistribution and a controlled pore size and surface chemistry to accommodate diverse cargo. The encapsulating supported lipid bilayer can be modified with targeting and trafficking ligands as well as polyethylene glycol (PEG) to effect selective binding, endosomal escape of cargo, drug efflux prevention, and potent therapeutic delivery, while maintaining in vivo colloidal stability. This review describes the individual components of the platform, including the mesoporous silica nanoparticle core and supported lipid bilayer, their assembly (by multiple techniques) into a protocell, and the combined, often synergistic, performance of the protocell based on in vitro and in vivo studies, including the assessment of biocompatibility and toxicity. In closing, the many emerging variations of the protocell theme and the future directions for protocell research are commented on. PMID:26780591

  13. Protocells: Modular Mesoporous Silica Nanoparticle-Supported Lipid Bilayers for Drug Delivery.

    PubMed

    Butler, Kimberly S; Durfee, Paul N; Theron, Christophe; Ashley, Carlee E; Carnes, Eric C; Brinker, C Jeffrey

    2016-04-27

    Mesoporous silica nanoparticle-supported lipid bilayers, termed 'protocells,' represent a potentially transformative class of therapeutic and theranostic delivery vehicle. The field of targeted drug delivery poses considerable challenges that cannot be addressed with a single 'magic bullet'. Consequently, the protocell has been designed as a modular platform composed of interchangeable biocompatible components. The mesoporous silica core has variable size and shape to direct biodistribution and a controlled pore size and surface chemistry to accommodate diverse cargo. The encapsulating supported lipid bilayer can be modified with targeting and trafficking ligands as well as polyethylene glycol (PEG) to effect selective binding, endosomal escape of cargo, drug efflux prevention, and potent therapeutic delivery, while maintaining in vivo colloidal stability. This review describes the individual components of the platform, including the mesoporous silica nanoparticle core and supported lipid bilayer, their assembly (by multiple techniques) into a protocell, and the combined, often synergistic, performance of the protocell based on in vitro and in vivo studies, including the assessment of biocompatibility and toxicity. In closing, the many emerging variations of the protocell theme and the future directions for protocell research are commented on.

  14. The AMWCNTs supported porous nanocarbon composites for high-performance supercapacitor

    SciTech Connect

    Fu, Yu; Sun, Li; Tian, Chungui; Lin, Haibo

    2013-11-15

    Graphical abstract: The AMWCNTs supported porous nanocarbon composites were prepared by a easy method. The composites had shown good performances for electrochemical energy storage with high specific capacitance and good stability. - Highlights: • The AMWCNTs supported porous nanocarbon composites were prepared. • The composites have good conductivity and large BET specific surface areas. • The composites had shown high specific capacitance, and good stability. - Abstract: The porous nanocarbons supported by acid-treated multiwall carbon nanotubes (PC@ACNTs) were prepared by the combination of the hydrothermal polymerization of glucose on ACNTs, carbonization under N{sub 2} protection and final activation with ZnCl{sub 2}. The materials were characterized by transmission electron microscopy, X-ray powder diffraction and Raman spectra. The results indicated that the ACNTs distributed uniformly into the framework of the porous carbon. The composites showed the high BET specific surface area up to 1712 m{sup 2} g{sup −1} and good conductivity. The electrochemical measurements indicated that the composites processed good performances for electrochemical energy storage (210 F g{sup −1} at 0.5 A g{sup −1}), and high stability (>99.9%), much higher than the corresponding ACNTs, porous carbons and the samples prepared by using raw MWCNTs as source. The good performance of PC@ACNTs composites was relative with the synergy of good conductivity of ACNTs and large specific surface areas of PC.

  15. Local coordination and dynamics of a protic ammonium based ionic liquid immobilized in nano-porous silica micro-particles probed by Raman and NMR spectroscopy.

    PubMed

    Garaga, Mounesha N; Persson, Michael; Yaghini, Negin; Martinelli, Anna

    2016-03-01

    Room temperature ionic liquids confined in a solid material, for example, nano-porous silica, are particularly propitious for energy related applications. The aim of this study is to probe the molecular interactions established between the protic ionic liquid diethylmethylammonium methanesulfonate (DEMA-OMs) and silica, where the latter consists of nano-porous micro-particles with pores in the size range of 10 nm. The changes in the local coordination and transport properties induced by the nano-confinement of the ionic liquid are investigated by a combination of Raman and solid-state NMR spectroscopy. In particular, one-dimensional (1D) (1)H and (29)Si and two-dimensional (2D) (29)Si{(1)H} HETOCR solid-state NMR are combined to identify the sites of interaction at the silica-ionic liquid interface. Pulsed field gradient (PFG) NMR experiments are performed to estimate the self-diffusion of both bulk and nano-confined DEMA-OMs. Complementary information on the overall coordination and interaction scheme is achieved by Raman spectroscopy. All these advanced experimental techniques are revealed to be crucial to differentiate between ionic liquid molecules residing in the inter- or intra-particle domains.

  16. Preparation and evaluation of monodispersed, submicron, non-porous silica particles functionalized with β-CD derivatives for chiral-pressurized capillary electrochromatography.

    PubMed

    Yangfang, Lu; Hui, Wang; Yun, Xue; Xue, Gu; Yan, Wang; Chao, Yan

    2015-09-01

    Submicron, non-porous, chiral silica stationary phase has been prepared by the immobilization of functionalized β-CD derivatives to isocyanate-modified silica via chemical reaction and applied to the pressurized capillary electrochromatography (pCEC) enantio-separation of various chiral compounds. The submicron, non-porous, cyclodextrin-based chiral stationary phases (sub_μm-CSP2) exhibited excellent chiral recognition of a wide range of analytes including clenbuterol hydrochloride, mexiletine hydrochloride, chlorpheniramine maleate, esmolol hydrochloride, and metoprolol tartrate. The synthesized submicron particles were regularly spherical and uniformly non-porous with an average diameter of around 800 nm and a mean pore size of less than 2 nm. The synthesized chiral stationary phase was packed into 10 cm × 100 μm id capillary columns. The sub_μm-CSP2 column used in the pCEC system showed better separation of the racemates and at a higher rate compared to those used in the capillary liquid chromatography mode (cLC) system. The sub_μm-CSP2 possessed high mechanical strength, high stereoselectivity, and long lifespan, demonstrating rapid enantio-separation and good resolution of samples. The column provided an efficiency of up to 170,000 plates/m for n-propylbenzene. PMID:25990895

  17. Synthesis and Nanofiltration Membrane Performance of Oriented Mesoporous Silica Thin Films on Macroporous Supports.

    PubMed

    Clark Wooten, M Kaitlyn; Koganti, Venkat R; Zhou, Shanshan; Rankin, Stephen E; Knutson, Barbara L

    2016-08-24

    Silica thin films with accessible hexagonal close-packed (HCP) pores have been deposited on macroporous supports to achieve composite nanofiltration membranes. The properties of these pore channels have been characterized through solvent flux and solute diffusion experiments. A chemically neutral surface (provided by a cross-linked layer of P123 copolymer) for silica thin film synthesis on the alumina macroporous support promotes the alignment of HCP channels vertical to the substrate, where the mesopore templating agent is block copolymer P123 (poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol)). Vertical pore alignment is achieved for thin films (less than ∼100 nm) on a neutral surface and by sandwiching thicker films (∼240 nm) between two chemically neutral surfaces. Solvent flux through the composite membranes is consistent with accessible 10 nm diameter pores. Size selectivity of the membranes is characterized from the permeability of fluorescently tagged solutes (ranging from 4000 to 70 000 Da), where a size cut off occurs at 69 000 Da for the model protein bovine serum albumin. These permeability studies of the nanofiltration membranes serve to demonstrate solute transport in oriented silica thin film membranes and also highlight their versatility for membrane-based separations. PMID:27479791

  18. Thermal Stability and Catalytic Activity of Gold Nanoparticles Supported on Silica

    SciTech Connect

    Veith, G.; Lupini, A; Rashkeev, S; Pennycook, S; Mullins, D; Schwartz, V; Bridges, C; Dudney, N

    2009-01-01

    2.5 nm gold nanoparticles were grown on a fumed silica support, using the physical vapor deposition technique of magnetron sputtering, that are thermally stable when annealed in an oxygen containing environment up to at least 500 C. Traditional Au/TiO{sub 2} catalysts rapidly sinter to form large 13.9 nm gold clusters under these annealing conditions. This surprising stability of Au/SiO{sub 2} is attributed to the absence of residual impurities (ensured by the halide-free production method) and a strong bond between gold and defects at the silica surface (about 3 eV per bond) estimated from density functional theory (DFT) calculations. The Au/SiO{sub 2} catalysts are less active for CO oxidation than the prototypical Au/TiO2 catalysts, however they can be regenerated far more easily, allowing the activity of a catalyst to be fully recovered after deactivation.

  19. Colored porous silicon as support for plasmonic nanoparticles

    NASA Astrophysics Data System (ADS)

    Lublow, M.; Kubala, S.; Veyan, J.-F.; Chabal, Y. J.

    2012-04-01

    Colored nanoporous silicon thin films were employed as dielectric spacing layers for the enhancement of localized surface plasmon (LSP) polaritons. Upon formation of Au nanoparticles (Au-NPs) on these layers, a visible color change is observed due to multiple LSP resonance excitations. Far-field effects were assessed by angle-resolved reflectometry. Resonance enhancements, particularly for s-polarized light, account for the observed color change and are discussed in terms of effective medium and Mie scattering theory. Enhancements of the electric field strengths in the near-field and of the absorption in the substrate were deduced from finite difference time domain calculations and exceed considerably those of the non-porous Au-NP/Si interface. First results of improved photoelectrocatalytic hydrogen evolution at these interfaces are discussed. Samples were prepared by varied procedures of metal assisted etching and dry etching with XeF2. Structural and chemical properties were investigated by scanning electron and atomic force microscopy as well as energy dispersive x-ray analysis.

  20. Resolving Interparticle Heterogeneities in Composition and Hydrogenation Performance between Individual Supported Silver on Silica Catalysts

    PubMed Central

    2015-01-01

    Supported metal nanoparticle catalysts are commonly obtained through deposition of metal precursors onto the support using incipient wetness impregnation. Typically, empirical relations between metal nanoparticle structure and catalytic performance are inferred from ensemble averaged data in combination with high-resolution electron microscopy. This approach clearly underestimates the importance of heterogeneities present in a supported metal catalyst batch. Here we show for the first time how incipient wetness impregnation leads to 10-fold variations in silver loading between individual submillimeter-sized silica support granules. This heterogeneity has a profound impact on the catalytic performance, with 100-fold variations in hydrogenation performance at the same level. In a straightforward fashion, optical microscopy interlinks single support particle level catalytic measurements to structural and compositional information. These detailed correlations reveal the optimal silver loading. A thorough consideration of catalyst heterogeneity and the impact thereof on the catalytic performance is indispensable in the development of catalysts. PMID:26618052

  1. Solid polymer electrolyte composite membrane comprising laser micromachined porous support

    DOEpatents

    Liu, Han; LaConti, Anthony B.; Mittelsteadt, Cortney K.; McCallum, Thomas J.

    2011-01-11

    A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a rigid, non-electrically-conducting support, the support preferably being a sheet of polyimide having a thickness of about 7.5 to 15 microns. The support has a plurality of cylindrical pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores, which preferably have a diameter of about 5 microns, are made by laser micromachining and preferably are arranged in a defined pattern, for example, with fewer pores located in areas of high membrane stress and more pores located in areas of low membrane stress. The pores are filled with a first solid polymer electrolyte, such as a perfluorosulfonic acid (PFSA) polymer. A second solid polymer electrolyte, which may be the same as or different than the first solid polymer electrolyte, may be deposited over the top and/or bottom of the first solid polymer electrolyte.

  2. Comparison of three labeled silica nanoparticles used as tracers in transport experiments in porous media. Part II: transport experiments and modeling.

    PubMed

    Vitorge, Elsa; Szenknect, Stéphanie; Martins, Jean M-F; Barthès, Véronique; Gaudet, Jean-Paul

    2014-01-01

    Three types of labeled silica nanoparticles were used in transport experiments in saturated sand. The goal of this study was to evaluate both the efficiency of labeling techniques (fluorescence (FITC), metal (Ag(0) core) and radioactivity ((110m)Ag(0) core)) in realistic transport conditions and the reactive transport of silica nanocolloids of variable size and concentration in porous media. Experimental results obtained under contrasted experimental conditions revealed that deposition in sand is controlled by nanoparticles size and ionic strength of the solution. A mathematical model is proposed to quantitatively describe colloid transport. Fluorescent labeling is widely used to study fate of colloids in soils but was the less sensitive one. Ag(0) labeling with ICP-MS detection was found to be very sensitive to measure deposition profiles. Radiolabeled ((110m)Ag(0)) nanoparticles permitted in situ detection. Results obtained with radiolabeled nanoparticles are wholly original and might be used for improving the modeling of deposition and release dynamics.

  3. Selective adsorption mechanisms of antilipidemic and non-steroidal anti-inflammatory drug residues on functionalized silica-based porous materials in a mixed solute.

    PubMed

    Suriyanon, Nakorn; Permrungruang, Jutima; Kaosaiphun, Jidanan; Wongrueng, Aunnop; Ngamcharussrivichai, Chawalit; Punyapalakul, Patiparn

    2015-10-01

    The selective adsorption mechanisms of naproxen (NAP), acetaminophen (ACT), and clofibric acid (CFA) on silica-based porous materials were examined by single and mixed-batch adsorption. Effects of the types and densities of surface functional groups on adsorption capacities were determined, including the role of hydrophobic and hydrophilic dissolved organic matters (DOMs). Hexagonal mesoporous silica (HMS), superparamagnetic HMS (HMS-SP) and SBA-15 were functionalized and applied as adsorbents. Compared with powdered activated carbon (PAC), amine-functionalized HMS had a better adsorption capacity for CFA, but PAC possessed a higher adsorption capacity for the other pharmaceuticals than HMS and its two derivatives. In contrast to PAC, the adsorption capacity of the mesoporous silicas varied with the solution pH, being highest at pH 5. Electrostatic interactions and hydrogen bonding were found to be the main mechanisms. Increase in grafted amine group density on silica surfaces can enhance the CFA adsorption capacity. Further, hydrophilic DOM can decrease CFA adsorption capacities on amino-grafted adsorbents by adsorption site competition, while hydrophobic DOM can interfere with CFA adsorption by the interaction between hydrophobic DOM and CFA. Finally, in a competitive adsorption study, the adsorption capacity of hydrophilic adsorbents for acidic pharmaceuticals varied with their pKa values.

  4. Selective adsorption mechanisms of antilipidemic and non-steroidal anti-inflammatory drug residues on functionalized silica-based porous materials in a mixed solute.

    PubMed

    Suriyanon, Nakorn; Permrungruang, Jutima; Kaosaiphun, Jidanan; Wongrueng, Aunnop; Ngamcharussrivichai, Chawalit; Punyapalakul, Patiparn

    2015-10-01

    The selective adsorption mechanisms of naproxen (NAP), acetaminophen (ACT), and clofibric acid (CFA) on silica-based porous materials were examined by single and mixed-batch adsorption. Effects of the types and densities of surface functional groups on adsorption capacities were determined, including the role of hydrophobic and hydrophilic dissolved organic matters (DOMs). Hexagonal mesoporous silica (HMS), superparamagnetic HMS (HMS-SP) and SBA-15 were functionalized and applied as adsorbents. Compared with powdered activated carbon (PAC), amine-functionalized HMS had a better adsorption capacity for CFA, but PAC possessed a higher adsorption capacity for the other pharmaceuticals than HMS and its two derivatives. In contrast to PAC, the adsorption capacity of the mesoporous silicas varied with the solution pH, being highest at pH 5. Electrostatic interactions and hydrogen bonding were found to be the main mechanisms. Increase in grafted amine group density on silica surfaces can enhance the CFA adsorption capacity. Further, hydrophilic DOM can decrease CFA adsorption capacities on amino-grafted adsorbents by adsorption site competition, while hydrophobic DOM can interfere with CFA adsorption by the interaction between hydrophobic DOM and CFA. Finally, in a competitive adsorption study, the adsorption capacity of hydrophilic adsorbents for acidic pharmaceuticals varied with their pKa values. PMID:26025186

  5. Method of making porous conductive supports for electrodes. [by electroforming and stacking nickel foils

    NASA Technical Reports Server (NTRS)

    Schaer, G. R. (Inventor)

    1973-01-01

    Porous conductive supports for electrochemical cell electrodes are made by electroforming thin corrugated nickel foil, and by stacking pieces of the corrugated foil alternatively with pieces of thin flat nickel foil. Corrugations in successive corrugated pieces are oriented at different angles. Adjacent pieces of foil are bonded by heating in a hydrogen atmosphere and then cutting the stack in planes perpendicular to the foils.

  6. High strength porous support tubes for high temperature solid electrolyte electrochemical cells

    DOEpatents

    Rossing, Barry R.; Zymboly, Gregory E.

    1986-01-01

    A high temperature, solid electrolyte electrochemical cell is made, having an electrode and a solid electrolyte disposed on a porous, sintered support material containing thermally stabilized zirconia powder particles and from about 3 wt. % to about 45 wt. % of thermally stable oxide fibers.

  7. Wettability of modified silica layers deposited on glass support activated by plasma

    NASA Astrophysics Data System (ADS)

    Terpiłowski, Konrad; Rymuszka, Diana; Goncharuk, Olena V.; Sulym, Iryna Ya.; Gun'ko, Vladimir M.

    2015-10-01

    Fumed silica modified by hexamethyldisilazane [HDMS] and polydimethylsiloxane [PDMS] was dispersed in a polystyrene/chloroform solution. To increase adhesion between deposited silica layers and a glass surface, the latter was pretreated with air plasma for 30 s. The silica/polystyrene dispersion was deposited on the glass support using a spin coater. After deposition, the plates were dried in a desiccator for 24 h. Water advancing and receding contact angles were measured using the tilted plate method. The apparent surface free energy (γS) was evaluated using the contact angle hysteresis approach. The surface topography was determined using the optical profilometry method. Contact angles changed from 59.7° ± 4.4 (at surface coverage with trimethylsilyl groups Θ = 0.14) to 155° ± 3.1 at Θ = 1. The value of γS decreased from 51.3 ± 2.8 mJ/m2 (for the sample at the lowest value of Θ) to 1.0 ± 0.4 mJ/m2 for the most hydrophobic sample. Thus, some systems with a high degree of modification by HDMS showed superhydrophobicity, and the sliding angle amounted to about 16° ± 2.1.

  8. Stopping the growth of particles to silica-supported mono-nuclear Ru hydride surface species by tuning silica with surface silanes

    SciTech Connect

    Berthoud, Romain; Fenet, Bernard; Lukens, Wayne; Pelzer, Katrin; Basset, Jean-Marie; Candy, Jean-Pierre; Coperet, Christophe

    2007-07-11

    Tuning silica by replacing surface silanols with silanes allows chemical grafting of Ru(COD)(COT) through a covalent Ru-Si bond, as evidenced by elemental analysis, IR spectroscopy and EXAFS. Treatment of these surface species under H2 at 300 oC yields a mononuclear Ru hydride species, without any sintering of the metal according to TEM and EXAFS analyses. This supported system displays catalytic properties different from those of supported Ru particles (2 nm), selectively hydrogenating olefins over aromatics.

  9. Cooperative Effect of Monopodal Silica-Supported Niobium Complex Pairs Enhancing Catalytic Cyclic Carbonate Production.

    PubMed

    D'Elia, Valerio; Dong, Hailin; Rossini, Aaron J; Widdifield, Cory M; Vummaleti, Sai V C; Minenkov, Yury; Poater, Albert; Abou-Hamad, Edy; Pelletier, Jérémie D A; Cavallo, Luigi; Emsley, Lyndon; Basset, Jean-Marie

    2015-06-24

    Recent discoveries highlighted the activity and the intriguing mechanistic features of NbCl5 as a molecular catalyst for the cycloaddition of CO2 and epoxides under ambient conditions. This has inspired the preparation of novel silica-supported Nb species by reacting a molecular niobium precursor, [NbCl5·OEt2], with silica dehydroxylated at 700 °C (SiO(2-700)) or at 200 °C (SiO(2-200)) to generate diverse surface complexes. The product of the reaction between SiO(2-700) and [NbCl5·OEt2] was identified as a monopodal supported surface species, [≡SiONbCl4·OEt2] (1a). The reactions of SiO(2-200) with the niobium precursor, according to two different protocols, generated surface complexes 2a and 3a, presenting significant, but different, populations of the monopodal surface complex along with bipodal [(≡SiO)2NbCl3·OEt2]. (93)Nb solid-state NMR spectra of 1a-3a and (31)P solid-state NMR on their PMe3 derivatives 1b-3b led to the unambiguous assignment of 1a as a single-site monopodal Nb species, while 2a and 3a were found to present two distinct surface-supported components, with 2a being mostly monopodal [≡SiONbCl4·OEt2] and 3a being mostly bipodal [(≡SiO)2NbCl3·OEt2]. A double-quantum/single-quantum (31)P NMR correlation experiment carried out on 2b supported the existence of vicinal Nb centers on the silica surface for this species. 1a-3a were active heterogeneous catalysts for the synthesis of propylene carbonate from CO2 and propylene oxide under mild catalytic conditions; the performance of 2a was found to significantly surpass that of 1a and 3a. With the support of a systematic DFT study carried out on model silica surfaces, the observed differences in catalytic efficiency were correlated with an unprecedented cooperative effect between two neighboring Nb centers on the surface of 2a. This is in an excellent agreement with our previous discoveries regarding the mechanism of NbCl5-catalyzed cycloaddition in the homogeneous phase. PMID:25950495

  10. Iniferter-mediated grafting of molecularly imprinted polymers on porous silica beads for the enantiomeric resolution of drugs.

    PubMed

    Gutiérrez-Climente, Raquel; Gómez-Caballero, Alberto; Halhalli, Mahadeo; Sellergren, Börje; Goicolea, M Aránzazu; Barrio, Ramón J

    2016-03-01

    A surface-imprinted chiral stationary phase for the enantiomeric resolution of the antidepressant drug, citalopram, is presented in this work. N, N'-diethylaminodithiocarbamoylpropyl(trimethoxy)silane has been used as silane iniferter for the surface functionalization of the solid silica support. A molecularly imprinted polymer thin film, in the nm scale, was then grafted on the silanized silica using itaconic acid as the functional monomer and ethylene glycol dimethacrylate as the cross-linker in the presence of the template S-citalopram. The total monomer amount was calculated to obtain the desired thickness. Non-imprinted stationary phases were prepared similarly in the absence of S-citalopram. Characterization of the materials was carried out by scanning electron microscopy, thermogravimetric analysis, elemental analysis and Fourier transform infrared spectroscopy. Stationary phases have been applied to the chromatographic separation of the target. Conditions for best chromatographic resolution of the enantiomers were optimized, and it was found that a mobile phase consisting of a mixture of formate buffer (40 mM, pH 3) and acetonitrile (30:70 v/v) at 40 °C provided best results. Binding behaviour of the developed material was finally assessed by batch rebinding experiments. The obtained binding isotherm was fitted to different binding models being the Freundlich-Langmuir model, the one that best fitted the experimental data. The developed material has shown high selectivity for the target enantiomer, and the stationary phase could be undoubtedly exploited for chiral separation of the drug. PMID:25683741

  11. Solid polymer electrolyte composite membrane comprising plasma etched porous support

    DOEpatents

    Liu, Han; LaConti, Anthony B.

    2010-10-05

    A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a rigid, non-electrically-conducting support, the support preferably being a sheet of polyimide having a thickness of about 7.5 to 15 microns. The support has a plurality of cylindrical pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores, which preferably have a diameter of about 0.1 to 5 microns, are made by plasma etching and preferably are arranged in a defined pattern, for example, with fewer pores located in areas of high membrane stress and more pores located in areas of low membrane stress. The pores are filled with a first solid polymer electrolyte, such as a perfluorosulfonic acid (PFSA) polymer. A second solid polymer electrolyte, which may be the same as or different than the first solid polymer electrolyte, may be deposited over the top and/or bottom of the first solid polymer electrolyte.

  12. Silica Supported Ceria Nanoparticles: A Hybrid Nanostructure To Increase Stability And Surface Reactivity Of Nano-crystalline Ceria

    SciTech Connect

    Munusamy, Prabhakaran; Sanghavi, Shail P.; Varga, Tamas; Thevuthasan, Suntharampillai

    2014-01-21

    The mixed oxidation state (3+/4+) of ceria nanoparticles of smaller sizes make them attractive materials for their catalytic antioxidant biological properties. However the unmodified smaller ceria nanoparticles are limited in their use due to particles agglomeration and reduced surface chemical reactivity in the solutions used to disperse the nanoparticles. This work describes an effort to stabilize small ceria nanoparticles, retaining their desired activity, on a larger stable silica support. The ceria nanoparticles attached to silica was synthesized by a solution synthesis technique in which the surface functional groups of silica nanoparticles were found to be essential for the formation of smaller ceria nanoparticles. The surface chemical and vibrational spectroscopy analysis revealed cerium–silicate (Ce-O-Si) covalent bond linkage between silica and cerium oxide nanoparticles. The colloidal properties (agglomerate particle size and suspension stability) of ceria attached to silica was significantly improved due to inherent physico-chemical characteristics of silica against random collision and gravitation settling as opposed to unmodified ceria nanoparticles in solution. The bio-catalytic activity of ceria nanoparticles in the 3+ oxidation state was not found to be limited by attachment to the silica support as measured by free radical scavenging activity in different biological media conditions.

  13. Silica-Supported Oligomeric Benzyl Phosphate (Si-OBP) and Triazole Phosphate (Si-OTP) Alkylating Reagents.

    PubMed

    Maity, Pradip K; Faisal, Saqib; Rolfe, Alan; Stoianova, Diana; Hanson, Paul R

    2015-10-16

    The syntheses of silica-supported oligomeric benzyl phosphates (Si-OBP(n)) and triazole phosphates (Si-OTP(n)) using ring-opening metathesis polymerization (ROMP) for use as efficient alkylating reagents is reported. Ease of synthesis and grafting onto the surface of norbornenyl-tagged (Nb-tagged) silica particles has been demonstrated for benzyl phosphate and triazole phosphate monomers. It is shown that these silica polymer hybrid reagents, Si-OBP(n) and Si-OTP(n), can be used to carry out alkylation reactions with an array of different nucleophiles to afford the corresponding benzylated and (triazolyl)methylated products in good yield and high purity. PMID:26430955

  14. Functionalized porous silica&maghemite core-shell nanoparticles for applications in medicine: design, synthesis, and immunotoxicity

    PubMed Central

    Zasońska, Beata A.; Líšková, Aurélia; Kuricová, Miroslava; Tulinská, Jana; Pop-Georgievski, Ognen; Čiampor, Fedor; Vávra, Ivo; Dušinská, Mária; Ilavská, Silvia; Horváthová, Mira; Horák, Daniel

    2016-01-01

    Aim To determine cytotoxicity and effect of silica-coated magnetic nanoparticles (MNPs) on immune response, in particular lymphocyte proliferative activity, phagocytic activity, and leukocyte respiratory burst and in vitro production of interleukin-6 (IL-6) and 8 (IL-8), interferon-gamma (IFN-γ), tumor necrosis factor-alpha (TNF-α), and granulocyte macrophage colony stimulating factor (GM-CSF). Methods Maghemite was prepared by coprecipitation of iron salts with ammonia, oxidation with NaOCl and modified by tetramethyl orthosilicate and aminosilanes. Particles were characterized by transmission electron microscopy (TEM), dynamic light scattering (DLS), Fourier-transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS). Cytotoxicity and lymphocyte proliferative activity were assessed using [3H]-thymidine incorporation into DNA of proliferating human peripheral blood cells. Phagocytic activity and leukocyte respiratory burst were measured by flow cytometry; cytokine levels in cell supernatants were determined by ELISA. Results γ-Fe2O3&SiO2-NH2 MNPs were 13 nm in size. According to TEM, they were localized in the cell cytoplasm and extracellular space. Neither cytotoxic effect nor significant differences in T-lymphocyte and T-dependent B-cell proliferative response were found at particle concentrations 0.12-75 μg/cm2 after 24, 48, and 72 h incubation. Significantly increased production of IL-6 and 8, and GM-CSF cytokines was observed in the cells treated with 3, 15, and 75 µg of particles/cm2 for 48 h and stimulated with pokeweed mitogen (PHA). No significant changes in TNF-α and IFN-γ production were observed. MNPs did not affect phagocytic activity of monocytes and granulocytes when added to cells for 24 and 48 h. Phagocytic respiratory burst was significantly enhanced in the cultures exposed to 75 µg MNPs/cm2 for 48 h. Conclusions The cytotoxicity and in vitro immunotoxicity were found to be minimal in the newly developed porous core-shell γ-Fe2

  15. Efficient photocatalytic hydrogen generation by silica supported and platinum promoted titanium dioxide

    SciTech Connect

    Joshi, Meenal M.; Labhsetwar, Nitin K.; Parwate, D.V.; Rayalu, Sadhana S.

    2013-09-01

    Graphical abstract: Titanium dioxide was supported on mesoporous silica and promoted with Pt and Ru. The supported photocatalysts show high surface area and better photocatalytic activity in visible light as compared to the benchmark Degussa P25. These photocatalysts were characterized using XRD, BET-SA, and UV-DRS techniques. The surface area of supported photocatalyst was 140.6 m{sup 2}/g which is higher than Degussa P-25. Supported photocatalyst was evaluated for hydrogen evolution via water splitting reaction using ethanol as a sacrificial donor. Hydrogen yield observed is 4791.43 μmol/h/g of TiO{sub 2} and that for P-25 is 161 μmol/h/g of TiO{sub 2} under visible light irradiation. The value is 30 times higher than benchmark material Degussa P-25. This photocatalyst is also found stable up to 24 h without replenishing with sacrificial donor ethanol. - Highlights: • Semiconductor titanium dioxide has been supported on silica gel and promoted with Pt by simple wet impregnation route. • This synthesized photocatalyst is showing high surface area of 140.6 m{sup 2}/g with crystallite size in the range of 15.44 Å. • This photocatalyst is showing enhanced hydrogen yield of about 4791.43 μmol/h/g of TiO{sub 2}. • This photocatalyst is also found stable up to 24 h without replenishing with sacrificial donor ethanol. • The effect of various operating parameters on supported photocatalyst also has been studied. - Abstract: Titanium dioxide was supported on mesoporous silica and promoted with Pt and Ru. The supported photocatalysts show high surface area and better photocatalytic activity in visible light as compared to the benchmark Degussa P25. These photocatalysts were characterized using XRD, BET-SA, and UV-DRS techniques. The surface area of supported photocatalyst was 140.6 m{sup 2}/g which is higher than Degussa P-25. Supported photocatalyst was evaluated for hydrogen evolution via water splitting reaction using ethanol as a sacrificial donor

  16. Tunable thick porous silica coating fabricated by multilayer-by-multilayer bonding of silica nanoparticles for open-tubular capillary chromatographic separation.

    PubMed

    Qu, Qishu; Liu, Yuanyuan; Shi, Wenjun; Yan, Chao; Tang, Xiaoqing

    2015-06-19

    A simple coating procedure employing a multilayer-by-multilayer process to modify the inner surface of bare fused-silica capillaries with silica nanoparticles was established. The silica nanoparticles were adsorbed onto the capillary wall via a strong electrostatic interaction between amino functional groups and silica particles. The thickness of the coating could be tuned from 130 to 600 nm by increasing the coating cycles from one to three. Both the retention factor and the resolution were greatly increased with increasing coating cycles. The loading capacity determined by naphthalene in the column with three coating cycles is 152.1 pmol. The effects of buffer concentration and pH value on the stability of the coating were evaluated. The retention reproducibility of the separation of toluene was 0.8, 1.2, 2.3, and 4.5%, respectively, for run-to-run, day-to-day, column-to-column, and batch-to-batch, respectively. The chromatographic performance of these columns was evaluated by both capillary liquid chromatography and open-tubular capillary electrochromatography (OT-CEC). Separation of aromatic hydrocarbons in the column with three coating cycles provided high theoretical plate numbers (up to 269,280 plates m(-1) for toluene) and short separation time (<15 min) by using OT-CEC mode. The method was also used to separate egg white proteins. Both acidic and basic proteins as well as four glycoisoforms were separated in a single run.

  17. Tunable thick porous silica coating fabricated by multilayer-by-multilayer bonding of silica nanoparticles for open-tubular capillary chromatographic separation.

    PubMed

    Qu, Qishu; Liu, Yuanyuan; Shi, Wenjun; Yan, Chao; Tang, Xiaoqing

    2015-06-19

    A simple coating procedure employing a multilayer-by-multilayer process to modify the inner surface of bare fused-silica capillaries with silica nanoparticles was established. The silica nanoparticles were adsorbed onto the capillary wall via a strong electrostatic interaction between amino functional groups and silica particles. The thickness of the coating could be tuned from 130 to 600 nm by increasing the coating cycles from one to three. Both the retention factor and the resolution were greatly increased with increasing coating cycles. The loading capacity determined by naphthalene in the column with three coating cycles is 152.1 pmol. The effects of buffer concentration and pH value on the stability of the coating were evaluated. The retention reproducibility of the separation of toluene was 0.8, 1.2, 2.3, and 4.5%, respectively, for run-to-run, day-to-day, column-to-column, and batch-to-batch, respectively. The chromatographic performance of these columns was evaluated by both capillary liquid chromatography and open-tubular capillary electrochromatography (OT-CEC). Separation of aromatic hydrocarbons in the column with three coating cycles provided high theoretical plate numbers (up to 269,280 plates m(-1) for toluene) and short separation time (<15 min) by using OT-CEC mode. The method was also used to separate egg white proteins. Both acidic and basic proteins as well as four glycoisoforms were separated in a single run. PMID:25952665

  18. Investigation of Hexagonal Mesoporous Silica-Supported Composites for Trace Moisture Adsorption

    NASA Astrophysics Data System (ADS)

    Li, Li; Tang, Nian; Wang, Yaxue; Cen, Wanglai; Liu, Jie; Zhou, Yongyan

    2015-11-01

    Moisture control is an important part of effective maintenance program for gas-insulated switchgear (GIS). Herein, hexagonal mesoporous silica (HMS) materials were synthesized by adopting dodecylamine as a structure directing agent, which was then employed as a host for supporting polyethylenimine (PEI) without further calcinations or extraction treatment. The physicochemical properties of the silica support and composites were characterized, and the moisture adsorption capacity of these composites was determined. The reserved template agents resulted in a dramatic improvement in moisture adsorption amount. Among them, 50PEI/DHMS showed the highest adsorption value. The enhanced adsorption could be attributed to the generated hydrogen bonding between amino groups and H2O molecules and the improved diffusion of moisture into the bulk networks of PEI polymers due to its better spatial dispersion imposed by the long alkyl chains of template agents, which was confirmed by thermogravimetry results and hydrogen efficiency analysis. Moreover, the maintained terminal amino groups of templates could also function as active sites for moisture adsorption. The results herein imply that the PEI/DHMS composites could be appealing materials for capturing moisture in GIS.

  19. C₁₈-bound porous silica monolith particles as a low-cost high-performance liquid chromatography stationary phase with an excellent chromatographic performance.

    PubMed

    Ali, Faiz; Cheong, Won Jo

    2014-12-01

    Ground porous silica monolith particles with an average particle size of 2.34 μm and large pores (363 Å) exhibiting excellent chromatographic performance have been synthesized on a relatively large scale by a sophisticated sol-gel procedure. The particle size distribution was rather broad, and the d(0.1)/d(0.9) ratio was 0.14. The resultant silica monolith particles were chemically modified with chlorodimethyloctadecylsilane and end-capped with a mixture of hexamethyldisilazane and chlorotrimethylsilane. Very good separation efficiency (185,000/m) and chromatographic resolution were achieved when the C18 -bound phase was evaluated for a test mixture of five benzene derivatives after packing in a stainless-steel column (1.0 mm × 150 mm). The optimized elution conditions were found to be 70:30 v/v acetonitrile/water with 0.1% trifluoroacetic acid at a flow rate of 25 μL/min. The column was also evaluated for fast analysis at a flow rate of 100 μL/min, and all the five analytes were eluted within 3.5 min with reasonable efficiency (ca. 60,000/m) and resolution. The strategy of using particles with reduced particle size and large pores (363 Å) combined with C18 modification in addition to partial-monolithic architecture has resulted in a useful stationary phase (C18 -bound silica monolith particles) of low production cost showing excellent chromatographic performance.

  20. Porous metallic MoO2-supported MoS2 nanosheets for enhanced electrocatalytic activity in the hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Yang, Linjing; Zhou, Weijia; Hou, Dongman; Zhou, Kai; Li, Guoqiang; Tang, Zhenghua; Li, Ligui; Chen, Shaowei

    2015-03-01

    Advanced materials for electrocatalytic water splitting are central to renewable energy research. In this work, MoS2 nanosheets supported on porous metallic MoO2 (MoS2/MoO2) were produced by sulfuration treatments of porous and highly conductive MoO2 for the hydrogen evolution reaction. Porous MoO2 with one-dimensional channel-like structures was prepared by calcination at elevated temperatures using phosphomolybdic acid as the precursor and mesoporous silica (SBA-15) as the template, and the subsequent hydrothermal treatment in the presence of thioacetamide led to the transformation of the top layers to MoS2 forming MoS2/MoO2 composites. Electrochemical studies showed that the obtained composites exhibited excellent electrocatalytic activity for HER with an onset potential of -104 mV (vs. RHE), a large current density (10 mA cm-2 at -0.24 V), a small Tafel slope of 76.1 mV dec-1 and robust electrochemical durability. The performance might be ascribed to the high electrical conductivity and porous structures of MoO2 with one-dimensional channels of 3 to 4 nm in diameter that allowed for fast charge transport and collection.Advanced materials for electrocatalytic water splitting are central to renewable energy research. In this work, MoS2 nanosheets supported on porous metallic MoO2 (MoS2/MoO2) were produced by sulfuration treatments of porous and highly conductive MoO2 for the hydrogen evolution reaction. Porous MoO2 with one-dimensional channel-like structures was prepared by calcination at elevated temperatures using phosphomolybdic acid as the precursor and mesoporous silica (SBA-15) as the template, and the subsequent hydrothermal treatment in the presence of thioacetamide led to the transformation of the top layers to MoS2 forming MoS2/MoO2 composites. Electrochemical studies showed that the obtained composites exhibited excellent electrocatalytic activity for HER with an onset potential of -104 mV (vs. RHE), a large current density (10 mA cm-2 at -0.24 V), a

  1. High-performance PdRu bimetallic catalyst supported on mesoporous silica nanoparticles for phenol hydrogenation

    NASA Astrophysics Data System (ADS)

    Huang, Chao; Yang, Xu; Yang, Hui; Huang, Peiyan; Song, Huiyu; Liao, Shijun

    2014-10-01

    A high-performance PdRu bimetallic catalyst supported on mesoporous silica nanoparticles (MSN), PdRu/MSN, was prepared by a facile impregnation-hydrogen reduction method. It was found that PdRu/MSN showed 5 times higher activity than that of Pd/MSN towards the liquid-phase hydrogenation of phenol. The catalysts were characterized comprehensively by multiple techniques, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature program reduction (TPR). It was revealed that adding Ru could effectively improve the Pd dispersion and promote the electronic interaction between the Pd and Ru, both of which contribute to enhancing the catalytic activity.

  2. Size control of rhodium particles of silica-supported catalysts using water-in-oil microemulsion

    NASA Astrophysics Data System (ADS)

    Kishida, Masahiro; Hanaoka, Toshiaki; Kim, Won Young; Nagata, Hideo; Wakabayashi, Katsuhiko

    1997-11-01

    Effects of components of water-in-oil microemulsions on rhodium particle sizes of silica-supported rhodium catalysts were investigated in the catalyst preparation method using microemulsion. In the case of the microemulsion of polyoxyethylene(23)dodecyl ether/ n-alcohols/RhCl 3 aq., the rhodium particle size increased from 3.4 to 5.0 nm as the specific permittivity of the organic solvent increased. The chain length of hydrophilic group of polyoxyethylene- p-nonylphenyl ether ( n = 5 to 15) employed as surfactants had an effect on the rhodium particle size where the rhodium size ranged between 2.0 and 3.6 nm. The rhodium particle size was 1.5 nm in the case of sodium bis(2-ethylhexyl) sulfocuccinate and this value was found to be the smallest. These results could be interpreted in terms of the adsorption of the surfactant on rhodium-hydrazine particle surface.

  3. Effect of particle size on CO hydrogenation activity of silica supported cobalt catalysts

    SciTech Connect

    Ho, Suiwen; Houalla, M.; Hercules, D.M. )

    1990-08-09

    Two series of silica supported cobalt catalysts were prepared by incipient wetness impregnation, one by varying the calcination temperature (200-400{degree}C, 3 wt % Co) and the other by changing the cobalt loading (1-10 wt % Co). Examination by ESCA, XRD, and H{sub 2} chemisorption showed that Co{sub 3}O{sub 4} is the dominant phase. The cobalt phase is reduced to cobalt metal at 400{degree}C. The cobalt particle sizes obtained from ESCA correlated well with those derived from H{sub 2} chemisorption and XRD line broadening. The turnover frequency of Co/SiO{sub 2} for CO hydrogenation was invariant with cobalt dispersion in the range of 6-20% dispersion.

  4. Recycling of fly ash for preparing porous mullite membrane supports with titania addition.

    PubMed

    Dong, Yingchao; Hampshire, Stuart; Zhou, Jian-er; Lin, Bin; Ji, Zhanlin; Zhang, Xiaozhen; Meng, Guangyao

    2010-08-15

    In order to effectively utilize industrial waste fly ash, porous mullite ceramic membrane supports were prepared from fly ash and calcined bauxite with chemically pure titania as sintering additive. The effects of TiO(2) on the sintering behaviors and main properties of porous mullite were studied in detail. Due to the addition of titania, the sintering of the flyash-based mullite was inhibited at low temperatures, but effectively improved at high temperatures, the latter is suitable for preparing porous mullite membrane supports by incomplete sintering. Titania entered into liquid glassy phase with low high-temperature viscosity during sintering, resulting in the improvement of sintering activity, as well as the lowering of secondary mullitization temperature (where 2.0% titania). Between 1300 and 1500 degrees C, with increasing titania content, the samples exhibit increased trends in both linear shrinkage percent and bulk density, but a slightly decreased trend in open porosity, at all sintering temperatures. At 1300-1500 degrees C, the samples sintered at 1450 degrees C for 2h exhibit the lowest shrinkage and bulk density, as well as the highest open porosities in the investigated titania content range of 0-6.0 wt.%. Also, with increasing titania content, the pore size decreases slightly but the three-point flexural strength increases gradually at 1450 degrees C.

  5. Organically functionalized mesoporous silica as a support for synthesis and catalysis

    NASA Astrophysics Data System (ADS)

    McEleney, Kevin Andrew

    Mesoporous silicates are excellent materials for supported catalysis due to their ease of functionalization, tunable pore size and high surface areas. Mesoporous silicates have been utilized in a variety of applications such as drug delivery scaffolds and catalyst supports. Functionalization of the surface can be achieved by either grafting of alkoxy silanes or co-condensation of the organosilane with the inorganic silica source. My research in this area can be divided into two components. In the first, we address the significant issue of metal contamination after reactions that are catalyzed by transition metals. In the second, we examine the design of new catalysts based on organic/inorganic composites. Ruthenium catalyzed processes such as olefin metathesis or asymmetric hydrogenation, are often underutilized due to the difficulty of removing the ruthenium by-products. Attempts to remove ruthenium involve treating the solution with a scavenging reagent followed by silica chromatography. Often these scavenging agents are expensive phosphines or toxic agents like lead tetra-acetate. SBA-15 functionalized with aminopropyl triethoxysilane displays a high affinity for ruthenium. Furthermore, it can be utilized to remove ruthenium by-products from olefin metathesis or hydrogenation reactions without the need for silica chromatography. We have also prepared sulfur-functionalized mesoporous silicates that have a high affinity for palladium. The materials after loading prove to be active catalysts for a variety of palladium catalyzed processes such as Suzuki-Miyaura and Sonogashira couplings. The catalysts are recyclable with moderate loss of activity and structure, depending on the method of incorporation of the thiol. We have characterized the as-synthesized and used catalysts by nitrogen sorption, TEM, X-ray photoelectron spectroscopy (XPS) and a variety of homogeneity tests were performed on the catalysts. Periodic mesoporous organosilicates (PMOs) are a well known

  6. Formation of supported lipid bilayers on silica: relation to lipid phase transition temperature and liposome size.

    PubMed

    Jing, Yujia; Trefna, Hana; Persson, Mikael; Kasemo, Bengt; Svedhem, Sofia

    2014-01-01

    DPPC liposomes ranging from 90 nm to 160 nm in diameter were prepared and used for studies of the formation of supported lipid membranes on silica (SiO2) at temperatures below and above the gel to liquid-crystalline phase transition temperature (Tm = 41 °C), and by applying temperature gradients through Tm. The main method was the quartz crystal microbalance with dissipation (QCM-D) technique. It was found that liposomes smaller than 100 nm spontaneously rupture on the silica surface when deposited at a temperature above Tm and at a critical surface coverage, following a well-established pathway. In contrast, DPPC liposomes larger than 160 nm do not rupture on the surface when adsorbed at 22 °C or at 50 °C. However, when liposomes of this size are first adsorbed at 22 °C and at a high enough surface coverage, after which they are subject to a constant temperature gradient up to 50 °C, they rupture and fuse to a bilayer, a process that is initiated around Tm. The results are discussed and interpreted considering a combination of effects derived from liposome-surface and liposome-liposome interactions, different softness/stiffness and shape of liposomes below and above Tm, the dynamics and thermal activation of the bilayers occurring around Tm and (for liposomes containing 33% of NaCl) osmotic pressure. These findings are valuable both for preparation of supported lipid bilayer cell membrane mimics and for designing temperature-responsive material coatings. PMID:24651504

  7. Formation of supported lipid bilayers on silica: relation to lipid phase transition temperature and liposome size.

    PubMed

    Jing, Yujia; Trefna, Hana; Persson, Mikael; Kasemo, Bengt; Svedhem, Sofia

    2014-01-01

    DPPC liposomes ranging from 90 nm to 160 nm in diameter were prepared and used for studies of the formation of supported lipid membranes on silica (SiO2) at temperatures below and above the gel to liquid-crystalline phase transition temperature (Tm = 41 °C), and by applying temperature gradients through Tm. The main method was the quartz crystal microbalance with dissipation (QCM-D) technique. It was found that liposomes smaller than 100 nm spontaneously rupture on the silica surface when deposited at a temperature above Tm and at a critical surface coverage, following a well-established pathway. In contrast, DPPC liposomes larger than 160 nm do not rupture on the surface when adsorbed at 22 °C or at 50 °C. However, when liposomes of this size are first adsorbed at 22 °C and at a high enough surface coverage, after which they are subject to a constant temperature gradient up to 50 °C, they rupture and fuse to a bilayer, a process that is initiated around Tm. The results are discussed and interpreted considering a combination of effects derived from liposome-surface and liposome-liposome interactions, different softness/stiffness and shape of liposomes below and above Tm, the dynamics and thermal activation of the bilayers occurring around Tm and (for liposomes containing 33% of NaCl) osmotic pressure. These findings are valuable both for preparation of supported lipid bilayer cell membrane mimics and for designing temperature-responsive material coatings.

  8. Comparison of three labeled silica nanoparticles used as tracers in transport experiments in porous media. Part I: syntheses and characterizations.

    PubMed

    Vitorge, Elsa; Szenknect, Stéphanie; Martins, Jean M F; Barthès, Véronique; Auger, Aurélien; Renard, Oliver; Gaudet, Jean-Paul

    2014-01-01

    The synthesis and the characterization of three kinds of labeled silica nanoparticles were performed. Three different labeling strategies were investigated: fluorescent organic molecule (FITC) embedded in silica matrix, heavy metal core (Ag(0)) and radioactive core ((110m)Ag) surrounded by a silica shell. The main properties and the suitability of each kind of labeled nanoparticle in terms of size, surface properties, stability, detection limits, and cost were determined and compared regarding its use for transport studies. Fluorescent labeling was found the most convenient and the cheapest, but the best detection limits were reached with chemical (Ag(0)) and radio-labeled ((110m)Ag) nanoparticles, which also allowed nondestructive quantifications. This work showed that the choice of labeled nanoparticles as surrogates of natural colloids or manufactured nanoparticles strongly depends on the experimental conditions, especially the concentration and amount required, the composition of the effluent, and the timescale of the experiment.

  9. Corrugation of Phase-Separated Lipid Bilayers Supported by Nanoporous Silica Xerogel Surfaces

    SciTech Connect

    Goksu, E I; Nellis, B A; Lin, W; Satcher Jr., J H; Groves, J T; Risbud, S H; Longo, M L

    2008-10-30

    Lipid bilayers supported by substrates with nanometer-scale surface corrugations holds interest in understanding both nanoparticle-membrane interactions and the challenges of constructing models of cell membranes on surfaces with desirable properties, e.g. porosity. Here, we successfully form a two-phase (gel-fluid) lipid bilayer supported by nanoporous silica xerogel. Surface topology, diffusion, and lipid density in comparison to mica-supported lipid bilayers were characterized by AFM, FRAP, FCS, and quantitative fluorescence microscopy, respectively. We found that the two-phase lipid bilayer follows the xerogel surface contours. The corrugation imparted on the lipid bilayer results in a lipid density that is twice that on a flat mica surface. In direct agreement with the doubling of actual bilayer area in a projected area, we find that the lateral diffusion coefficient (D) of lipids on xerogel ({approx}1.7 {micro}m{sup 2}/s) is predictably lower than on mica ({approx}4.1 {micro}m{sup 2}/s) by both FRAP and FCS techniques. Furthermore, the gel-phase domains on xerogel compared to mica were larger and less numerous. Overall, our results suggest the presence of a relatively defect-free continuous two-phase bilayer that penetrates approximately midway into the first layer of {approx}50 nm xerogel beads.

  10. Transport of oxidized multi-walled carbon nanotubes through silica based porous media: influences of aquatic chemistry, surface chemistry, and natural organic matter.

    PubMed

    Yang, Jin; Bitter, Julie L; Smith, Billy A; Fairbrother, D Howard; Ball, William P

    2013-12-17

    This paper provides results from studies of the transport of oxidized multi-walled carbon nanotubes (O-MWCNTs) of varying surface oxygen concentrations under a range of aquatic conditions and through uniform silica glass bead media. In the presence of Na(+), the required ionic strength (IS) for maximum particle attachment efficiency (i.e., the critical deposition concentration, or CDC) increased as the surface oxygen concentration of the O-MWCNTs or pH increased, following qualitative tenets of theories based on electrostatic interactions. In the presence of Ca(2+), CDC values were lower than those with Na(+) present, but were no longer sensitive to surface oxygen content, suggesting that Ca(2+) impacts the interactions between O-MWCNTs and glass beads by mechanisms other than electrostatic alone. The presence of Suwannee River natural organic matter (SRNOM) decreased the attachment efficiency of O-MWCNTs in the presence of either Na(+) or Ca(2+), but with more pronounced effects when Na(+) was present. Nevertheless, low concentrations of SRNOM (<4 mg/L of dissolved organic carbon) were sufficient to mobilize all O-MWCNTs studied at CaCl2 concentrations as high as 10 mM. Overall, this study reveals that NOM content, pH, and cation type show more importance than surface chemistry in affecting O-MWCNTs deposition during transport through silica-based porous media.

  11. Modification of the sensitivity and selectivity of thin porous layers coated by the sol-gel method on silica optical fibers to gases

    NASA Astrophysics Data System (ADS)

    Matejec, Vlastimil; Berkova, Daniela; Chomat, Miroslav; Kuncova, Gabriela

    1999-12-01

    It has been found that thin layers of aerogels applied by the sol-gel method on silica optical fibers change their optical properties due to the interaction with gases such as hydrocarbons. This paper deals with modification of the sensitivity and selectivity to vapors of hydrocarbons and chlorinated hydrocarbons of siloxane aerogel layers based on their doping with TiOTi chains and/or immobilizing in them Cu-ephedrine and Cu-phthalocyanine. The sensing fibers were prepared by the sol-gel application of porous siloxane and doped-siloxane layers on bare cores of PCS fibers. By using the excitation of the fiber with inclined laser beams it is experimentally shown that there are positive or negative changes of the output optical power from the fibers due to bringing the prepared layers into contact with vapors of aliphatic, aromatic and chlorinated hydrocarbons in nitrogen. These effects may be related to a difference between the refractive index of the layer and refractive index of liquid hydrocarbon or hydrocarbon its derivative. It is shown experimentally that doping porous siloxane layers with copper complexes changes their refractive index and optical losses changing thus their sensitivity and selectivity to hydrocarbons and hydrocarbon derivatives.

  12. Electron beam-induced immobilization of laccase on porous supports for waste water treatment applications.

    PubMed

    Jahangiri, Elham; Reichelt, Senta; Thomas, Isabell; Hausmann, Kristin; Schlosser, Dietmar; Schulze, Agnes

    2014-08-08

    The versatile oxidase enzyme laccase was immobilized on porous supports such as polymer membranes and cryogels with a view of using such biocatalysts in bioreactors aiming at the degradation of environmental pollutants in wastewater. Besides a large surface area for supporting the biocatalyst, the aforementioned porous systems also offer the possibility for simultaneous filtration applications in wastewater treatment. Herein a "green" water-based, initiator-free, and straightforward route to highly reactive membrane and cryogel-based bioreactors is presented, where laccase was immobilized onto the porous polymer supports using a water-based electron beam-initiated grafting reaction. In a second approach, the laccase redox mediators 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) and syringaldehyde were cross-linked instead of the enzyme via electron irradiation in a frozen aqueous poly(acrylate) mixture in a one pot set-up, yielding a mechanical stable macroporous cryogel with interconnected pores ranging from 10 to 50 µm in size. The membranes as well as the cryogels were characterized regarding their morphology, chemical composition, and catalytic activity. The reactivity towards waste- water pollutants was demonstrated by the degradation of the model compound bisphenol A (BPA). Both membrane- and cryogel-immobilized laccase remained highly active after electron beam irradiation. Apparent specific BPA removal rates were higher for cryogel- than for membrane-immobilized and free laccase, whereas membrane-immobilized laccase was more stable with respect to maintenance of enzymatic activity and prevention of enzyme leakage from the carrier than cryogel-immobilized laccase. Cryogel-immobilized redox mediators remained functional in accelerating the laccase-catalyzed BPA degradation, and especially ABTS was found to act more efficiently in immobilized than in freely dissolved state.

  13. Mesoporous silica-supported lipid bilayers (protocells) for DNA cargo delivery to the spinal cord.

    PubMed

    Dengler, Ellen C; Liu, Juewen; Kerwin, Audra; Torres, Sergio; Olcott, Clara M; Bowman, Brandi N; Armijo, Leisha; Gentry, Katherine; Wilkerson, Jenny; Wallace, James; Jiang, Xingmao; Carnes, Eric C; Brinker, C Jeffrey; Milligan, Erin D

    2013-06-10

    Amorphous mesoporous silica nanoparticles ('protocells') that support surface lipid bilayers recently characterized in vitro as carrier constructs for small drug and DNA delivery are reported here as highly biocompatible both in vitro and in vivo, involving the brain and spinal cord following spinal delivery into the lumbosacral subarachnoid space (intrathecal; i.t.). Specifically, positively charged, 1, 2-Dioleoyl-3-Trimethylammonium-Propane (DOTAP)-cholesterol (DOTAP:Chol) liposome-formulated protocells revealed stable in vitro cargo release kinetics and cellular interleukin-10 (IL-10) transgene transfection. Recent approaches using synthetic non-viral vector platforms to deliver the pain-suppressive therapeutic transgene, IL-10, to the spinal subarachnoid space have yielded promising results in animal models of peripheral neuropathy, a condition involving aberrant neuronal communication within sensory pathways in the nervous system. Non-viral drug and gene delivery protocell platforms offer potential flexibility because cargo release-rates can be pH-dependent. We report here that i.t. delivery of protocells, with modified chemistry supporting a surface coating of DOTAP:Chol liposomes and containing the IL-10 transgene, results in functional suppression of pain-related behavior in rats for extended periods. This study is the first demonstration that protocell vectors offer amenable and enduring in vivo biological characteristics that can be applied to spinal gene delivery. PMID:23517784

  14. Anchoring and promotion effects of metal oxides on silica supported catalytic gold nanoparticles.

    PubMed

    Luo, Jingjie; Ersen, Ovidiu; Chu, Wei; Dintzer, Thierry; Petit, Pierre; Petit, Corinne

    2016-11-15

    The understanding of the interactions between the different components of supported metal doped gold catalysts is of crucial importance for selecting and designing efficient gold catalysts for reactions such as CO oxidation. To progress in this direction, a unique supported nano gold catalyst Au/SS was prepared, and three doped samples (Au/SS@M) were elaborated. The samples before and after test were characterized by Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). It is found that the doping metal species prefer to be located on the surface of gold nanoparticles and that a small amount of additional reductive metal leads to more efficient reaction. During the catalytic test, the nano-structure of the metal species transforms depending on its chemical nature. This study allows one to identify and address the contribution of each metal on the CO reaction in regard to oxidative species of gold, silica and dopants. Metal doping leads to different exposure of interface sites between Au and metal oxide, which is one of the key factors for the change of the catalytic activity. The metal oxides help the activation of oxygen by two actions: mobility inside the metal bulk and transfer of water species onto of gold nanoparticles.

  15. Mesoporous silica-supported lipid bilayers (protocells) for DNA cargo delivery to the spinal cord

    PubMed Central

    Dengler, Ellen C.; Liu, Juewen; Kerwin, Audra; Torres, Sergio; Olcott, Clara M.; Bowman, Brandi N.; Armijo, Leisha; Gentry, Katherine; Wilkerson, Jenny; Wallace, James; Jiang, Xingmao; Carnes, Eric C.; Brinker, C. Jeffrey; Milligan, Erin D.

    2013-01-01

    Amorphous mesoporous silica nanoparticles (‘protocells’) that support surface lipid bilayers recently characterized in vitro as carrier constructs for small drug and DNA delivery are reported here as highly biocompatible both in vitro and in vivo, involving the brain and spinal cord following spinal delivery into the lumbosacral subarachnoid space (intrathecal; i.t.). Specifically, positively charged, 1, 2-Dioleoyl-3-Trimethylammonium-Propane (DOTAP) -cholesterol (DOTAP:Chol) liposome-formulated protocells revealed stable in vitro cargo release kinetics and cellular interleukin-10 (IL-10) transgene transfection. Recent approaches using synthetic non-viral vector platforms to deliver the pain-suppressive therapeutic transgene, IL-10, to the spinal subarachnoid space has yielded promising results in animal models of peripheral neuropathy, a condition involving aberrant neuronal communication within sensory pathways in the nervous system. Non-viral drug and gene delivery protocell platforms offer potential flexibility because cargo release-rates can be pH-dependent. We report here that i.t. delivery of protocells, with modified chemistry supporting a surface coating of DOTAP:Chol liposomes and containing the IL-10 transgene, results in functional suppression of pain-related behavior in rats for extended periods. This study is the first demonstration that protocell vectors offer amenable and enduring in vivo biological characteristics that can be applied to spinal gene delivery. PMID:23517784

  16. Anchoring and promotion effects of metal oxides on silica supported catalytic gold nanoparticles.

    PubMed

    Luo, Jingjie; Ersen, Ovidiu; Chu, Wei; Dintzer, Thierry; Petit, Pierre; Petit, Corinne

    2016-11-15

    The understanding of the interactions between the different components of supported metal doped gold catalysts is of crucial importance for selecting and designing efficient gold catalysts for reactions such as CO oxidation. To progress in this direction, a unique supported nano gold catalyst Au/SS was prepared, and three doped samples (Au/SS@M) were elaborated. The samples before and after test were characterized by Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). It is found that the doping metal species prefer to be located on the surface of gold nanoparticles and that a small amount of additional reductive metal leads to more efficient reaction. During the catalytic test, the nano-structure of the metal species transforms depending on its chemical nature. This study allows one to identify and address the contribution of each metal on the CO reaction in regard to oxidative species of gold, silica and dopants. Metal doping leads to different exposure of interface sites between Au and metal oxide, which is one of the key factors for the change of the catalytic activity. The metal oxides help the activation of oxygen by two actions: mobility inside the metal bulk and transfer of water species onto of gold nanoparticles. PMID:27501036

  17. Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds

    EPA Science Inventory

    One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...

  18. Comparison of stress, strain, and elastic properties for porous silicon layers supported by substrate and corresponding membranes

    NASA Astrophysics Data System (ADS)

    Dariani, R. S.; Nazari, M.

    2016-09-01

    This paper describes characterization of mechanical properties of porous silicon (PS) layers with different porosities using high resolution XRD. The XRD measurement determined various mechanical properties of PS such as; Young modulus, Poisson's ratio, and lattice parameter expansion. Our results indicated that mechanical properties reduce with increasing porosity. Also, the mechanical properties of two different porous layers, either supported by or detached from the substrate were examined. Comparison of the two porous layers showed that the constraint in the interatomic spacing is the origin of the lattice constant expansion in the planes perpendicular to the surface. This phenomenon can be useful for gas sensor applications.

  19. Mesoporous Silica Supported Pd-MnOx Catalysts with Excellent Catalytic Activity in Room-Temperature Formic Acid Decomposition

    NASA Astrophysics Data System (ADS)

    Jin, Min-Ho; Oh, Duckkyu; Park, Ju-Hyoung; Lee, Chun-Boo; Lee, Sung-Wook; Park, Jong-Soo; Lee, Kwan-Young; Lee, Dong-Wook

    2016-09-01

    For the application of formic acid as a liquid organic hydrogen carrier, development of efficient catalysts for dehydrogenation of formic acid is a challenging topic, and most studies have so far focused on the composition of metals and supports, the size effect of metal nanoparticles, and surface chemistry of supports. Another influential factor is highly desired to overcome the current limitation of heterogeneous catalysis for formic acid decomposition. Here, we first investigated the effect of support pore structure on formic acid decomposition performance at room temperature by using mesoporous silica materials with different pore structures such as KIE-6, MCM-41, and SBA-15, and achieved the excellent catalytic activity (TOF: 593 h‑1) by only controlling the pore structure of mesoporous silica supports. In addition, we demonstrated that 3D interconnected pore structure of mesoporous silica supports is more favorable to the mass transfer than 2D cylindrical mesopore structure, and the better mass transfer provides higher catalytic activity in formic acid decomposition. If the pore morphology of catalytic supports such as 3D wormhole or 2D cylinder is identical, large pore size combined with high pore volume is a crucial factor to achieve high catalytic performance.

  20. Mesoporous Silica Supported Pd-MnOx Catalysts with Excellent Catalytic Activity in Room-Temperature Formic Acid Decomposition

    PubMed Central

    Jin, Min-Ho; Oh, Duckkyu; Park, Ju-Hyoung; Lee, Chun-Boo; Lee, Sung-Wook; Park, Jong-Soo; Lee, Kwan-Young; Lee, Dong-Wook

    2016-01-01

    For the application of formic acid as a liquid organic hydrogen carrier, development of efficient catalysts for dehydrogenation of formic acid is a challenging topic, and most studies have so far focused on the composition of metals and supports, the size effect of metal nanoparticles, and surface chemistry of supports. Another influential factor is highly desired to overcome the current limitation of heterogeneous catalysis for formic acid decomposition. Here, we first investigated the effect of support pore structure on formic acid decomposition performance at room temperature by using mesoporous silica materials with different pore structures such as KIE-6, MCM-41, and SBA-15, and achieved the excellent catalytic activity (TOF: 593 h−1) by only controlling the pore structure of mesoporous silica supports. In addition, we demonstrated that 3D interconnected pore structure of mesoporous silica supports is more favorable to the mass transfer than 2D cylindrical mesopore structure, and the better mass transfer provides higher catalytic activity in formic acid decomposition. If the pore morphology of catalytic supports such as 3D wormhole or 2D cylinder is identical, large pore size combined with high pore volume is a crucial factor to achieve high catalytic performance. PMID:27666280

  1. Thin Porous Metal Sheet-Supported NaA Zeolite Membrane for Water/Ethanol Separation

    SciTech Connect

    Zhang, Jian; Liu, Wei

    2011-04-01

    This paper reports preparation and separation testing results of water-selective zeolite membrane, such as NaA (or 4A-type), supported on a robust, porous metal sheet of 50um thickness. The thin sheet support is of large potential for development of a low-cost, inorganic membrane module of high surface area packing density. The porous Ni alloy sheet of micrometer or sub-micrometer mean pore size, which was prepared by a proprietary process, is used to evaluate different zeolite membrane deposition methods and conditions. The membranes are characterized by SEM, XRD and water/ethanol separation tests. Quality NaA zeolite membrane at thickness <2um is obtained with the secondary hydrothermal growth method. This membrane shows water/ethanol separation factor of >10,000 and water permeation flux of about 4 kg/(m2•h) at 75ºC with a feed of 10wt% water in ethanol. The membrane is also demonstrated with good stability in 66-hour continuous testing at 75ºC and 90ºC.

  2. Carbon molecular sieve membranes on porous composite tubular supports for high performance gas separations

    DOE PAGES

    Lee, Pyung -Soo; Bhave, Ramesh R.; Nam, Seung -Eun; Kim, Daejin

    2016-01-11

    Thin carbon molecular sieve membranes (<500 nm) were fabricated inside of long geometry (9 inch) of stainless steel tubes with all welded construction. Alumina intermediate layer on porous stainless steel tube support was used to reduce effective support pore size and to provide a more uniform surface roughness. Novolac phenolic resin solution was then coated on the inside of porous stainless steel tube by slip casting while their viscosities were controlled from 5 centipoises to 30 centipoises. Carbonization was carried out at 700 °C in which thermal stress was minimized and high quality carbon films were prepared. The highest separationmore » performance characteristics were obtained using 20 cP phenolic resin solutions. The fabricated CMSM showed good separation factor for He/N2 462, CO2/N2 97, and O2/N2 15.4. As the viscosity of polymer precursor solution was reduced from 20 cP to 15 cP, gas permeance values almost doubled with somewhat lower separation factor He/N2 156, CO2/N2 88, and O2/N2 7.7.« less

  3. Removal of hexavalent chromium in soil and groundwater by supported nano zero-valent iron on silica fume.

    PubMed

    Li, Yongchao; Jin, Zhaohui; Li, Tielong; Li, Shujing

    2011-01-01

    Silica fume supported-Fe(0) nanoparticles (SF-Fe(0)) were prepared using commercial silica fume as a support. The feasibility of using this SF-Fe(0) for reductive immobilization of Cr(VI) was investigated through batch tests. Compared with unsupported Fe(0), SF-Fe(0) was significantly more active in Cr(VI) removal especially in 84 wt% silica fume loading. Silica fume had also been found to inhibit the formation of Fe(III)/Cr(III) precipitation on Fe nanoparticles' surface, which was increasing the deactivation resistance of iron. Cr(VI) was removed through physical adsorption of Cr(VI) onto the SF-Fe(0) surface and subsequent reduction of Cr(VI) to Cr(III). The rate of reduction of Cr(VI) could be expressed by pseudo first-order reaction kinetics. The rate constant increased with the increase in iron loading but decreased with the increase in initial Cr(VI) concentration. Furthermore, column tests showed that the SF-Fe(0) could be readily transported in model soil.

  4. Dehydration of Glycerin to Acrolein Over Heteropolyacid Nano-Catalysts Supported on Silica-Alumina.

    PubMed

    Kang, Tae Hun; Choi, Jung Ho; Choi, Jun Seon; Song, In Kyu

    2015-10-01

    A series of H3PW12O40 nano-catalysts supported on silica-alumina (XH3PW12O40/SA (X = 10, 15, 20, 25, and 30)) with different H3PW12O40 content (X, wt%) were prepared, and they were applied to the dehydration of glycerin to acrolein. The effect of H3PW12O40 content on the physicochemical properties and catalytic activities of XH3PW12O40/SA nano-catalysts was investigated. Surface area and pore volume of XH3PW12O40/SA catalysts decreased with increasing H3PW12O40 content. Formation of H3PW12O40 aggregates was observed in the catalysts with high H3PW12O40 loading. Brønsted acidity of the catalysts showed a volcano-shaped trend with respect to H3PW12O40 content. It was revealed that yield for acrolein increased with increasing Brønsted acidity of XH3PW12O40/SA catalysts. Brønsted acidity of XH3PW12O40/SA catalysts served as a crucial factor determining the catalytic performance in the dehydration of glycerin. Among the catalysts tested, 25H3PW12O40/SA catalyst with the largest Brønsted acidity showed the best catalytic performance. PMID:26726511

  5. Promotion by tetrachloromethane of the oxidative coupling of methane on silica-supported alkaline earth oxides

    SciTech Connect

    Ahmed, S.; Moffat, J.B. )

    1990-02-01

    The introduction of a small quantity of tetrachloromethane (TEM) into the feed stream has been shown to remarkably enhance the oxidative coupling of methane over alkaline earth oxides supported on silica. That this enhancement, in terms of both selectivity and yield to C{sub 2} hydrocarbons, occurs over a wide range of catalyst loading, feed composition, reaction temperature, and contact time has been illustrated using BaO/SiO{sub 2} as the catalyst. It has been demonstrated that over this catalyst, the coupling and nonselective oxidation processes occur predominantly independently of each other. The high ratio of C{sub 2}H{sub 4}/C{sub 2}H{sub 6} observed in the products is accounted for by the rapid homogeneous oxidative dehydrogenation of C{sub 2}H{sub 6}, a process which is evidently further enhanced by the presence of TCM. It is suggested that TCM promotes the coupling reaction by facilitating the hydrogen abstraction step from methane. Continuous cofeeding of the additive is required to maintain high selectivity and yield of C{sub 2} hydrocarbons in the products.

  6. Delivery of Small Interfering RNA by Peptide-Targeted Mesoporous Silica Nanoparticle-Supported Lipid Bilayers

    PubMed Central

    Ashley, Carlee E.; Carnes, Eric C.; Epler, Katharine E.; Padilla, David P.; Phillips, Genevieve K.; Castillo, Robert E.; Wilkinson, Dan C.; Wilkinson, Brian S.; Burgard, Cameron A.; Sewell, Robin M.; Townson, Jason L.; Chackerian, Bryce; Willman, Cheryl L.; Peabody, David S.; Wharton, Walker; Brinker, C. Jeffrey

    2012-01-01

    The therapeutic potential of small interfering RNAs (siRNAs) is severely limited by the availability of delivery platforms that protect siRNA from degradation, deliver it to the target cell with high specificity and efficiency, and promote its endosomal escape and cytosolic dispersion. Here we report that mesoporous silica nanoparticle-supported lipid bilayers (or ‘protocells’), exhibit multiple properties that overcome many of the limitations of existing delivery platforms. Protocells have a 10- to 100-fold greater capacity for siRNA than corresponding lipid nanoparticles and are markedly more stable when incubated under physiological conditions. Protocells loaded with a cocktail of siRNAs bind to cells in a manner dependent on the presence of an appropriate targeting peptide and, through an endocytic pathway followed by endosomal disruption, promote delivery of the silencing nucleotides to the cytoplasm. The expression of each of the genes targeted by the siRNAs was shown to be repressed at the protein level, resulting in a potent induction of growth arrest and apoptosis. Incubation of control cells that lack expression of the antigen recognized by the targeting peptide with siRNA-loaded protocells induced neither repression of protein expression nor apoptosis, indicating the precise specificity of cytotoxic activity. In terms of loading capacity, targeting capabilities, and potency of action, protocells provide unique attributes as a delivery platform for therapeutic oligonucleotides. PMID:22309035

  7. Selective catalytic reduction of nitric oxide with ammonia over silica-supported vanadium oxide catalyst

    SciTech Connect

    Qajar, J.; Mowla, D.

    2009-07-01

    The selective catalytic reduction (SCR) of nitric oxide with excess ammonia in the presence of oxygen on silica-supported vanadium oxide catalyst was studied in a packed-bed reactor, and a mathematical model was proposed for the processes occurring in the reactor. Experimental data were presented for evaluation of the accuracy of the proposed model. Good agreement was observed between the measured and calculated values of the conversion in the outlet of the reactor. Once the validity of the proposed model was verified, it was used to examine the effects of different parameters such as feed temperature, inlet feed composition, and gas hourly space velocity (GHSV) on the conversion of NO over V{sub 2}O{sub 5}/SiO{sub 2} catalyst for practical application. The results for the employed catalyst showed that high NO conversion occurred at temperatures of 280-300C, GHSV less than 2000h{sup -1} (STP), and O{sub 2} concentration greater than 10% v/v. These results clearly demonstrate the high potential for this catalyst to be applied commercially for the control of NOx emissions from flue gases of different sources.

  8. Dehydration of Glycerin to Acrolein Over Heteropolyacid Nano-Catalysts Supported on Silica-Alumina.

    PubMed

    Kang, Tae Hun; Choi, Jung Ho; Choi, Jun Seon; Song, In Kyu

    2015-10-01

    A series of H3PW12O40 nano-catalysts supported on silica-alumina (XH3PW12O40/SA (X = 10, 15, 20, 25, and 30)) with different H3PW12O40 content (X, wt%) were prepared, and they were applied to the dehydration of glycerin to acrolein. The effect of H3PW12O40 content on the physicochemical properties and catalytic activities of XH3PW12O40/SA nano-catalysts was investigated. Surface area and pore volume of XH3PW12O40/SA catalysts decreased with increasing H3PW12O40 content. Formation of H3PW12O40 aggregates was observed in the catalysts with high H3PW12O40 loading. Brønsted acidity of the catalysts showed a volcano-shaped trend with respect to H3PW12O40 content. It was revealed that yield for acrolein increased with increasing Brønsted acidity of XH3PW12O40/SA catalysts. Brønsted acidity of XH3PW12O40/SA catalysts served as a crucial factor determining the catalytic performance in the dehydration of glycerin. Among the catalysts tested, 25H3PW12O40/SA catalyst with the largest Brønsted acidity showed the best catalytic performance.

  9. Tubular solid oxide fuel cells with porous metal supports and ceramic interconnections

    SciTech Connect

    Huang, Kevin; Ruka, Roswell J.

    2012-05-08

    An intermediate temperature solid oxide fuel cell structure capable of operating at from 600.degree. C. to 800.degree. C. having a very thin porous hollow elongated metallic support tube having a thickness from 0.10 mm to 1.0 mm, preferably 0.10 mm to 0.35 mm, a porosity of from 25 vol. % to 50 vol. % and a tensile strength from 700 GPa to 900 GPa, which metallic tube supports a reduced thickness air electrode having a thickness from 0.010 mm to 0.2 mm, a solid oxide electrolyte, a cermet fuel electrode, a ceramic interconnection and an electrically conductive cell to cell contact layer.

  10. Porous hollow carbon spheres for electrode material of supercapacitors and support material of dendritic Pt electrocatalyst

    NASA Astrophysics Data System (ADS)

    Fan, Yang; Liu, Pei-Fang; Huang, Zhong-Yuan; Jiang, Tong-Wu; Yao, Kai-Li; Han, Ran

    2015-04-01

    Porous hollow carbon spheres (PHCSs) are prepared through hydrothermal carbonization of alginic acid and subsequent chemical activation by KOH. The porosity of the alginic acid derived PHCSs can be finely modulated by varying activation temperature in the range of 600-900 °C. The PHCSs activated at 900 °C possess the largest specific surface area (2421 m2 g-1), well-balanced micro- and mesoporosity, as well as high content of oxygen-containing functional groups. As the electrode material for supercapacitors, the PHCSs exhibit superior capacitive performance with specific capacitance of 314 F g-1 at current density of 1 A g-1. Pt nanodendrites supported on the PHCSs are synthesized by polyol reduction method which exhibit high electrocatalytic activity towards methanol oxidation reaction (MOR). Moreover, CO-poisoning tolerance of the Pt nanodendrites is greatly enhanced owing to the surface chemical property of the PHCSs support.

  11. A study on the preparation and gas permeation of porous alumina supports

    SciTech Connect

    Ting-Chia Huang; Huey-Ing Chen

    1995-06-01

    The preparation and gas permeation of porous alumina supports were studied. The influence of the amount of PVA on the properties of the alumina slips, microstructure of the supports, and gas permeation were investigated. The experimental results show that the addition of PVA in the preparation process is useful for controlling the porosity of the supports without significantly changing other microstructural properties. Permeation measurements of H{sub 2}, He, Ch{sub 4}, N{sub 2}, O{sub 2}, and CO{sub 2} showed that gas transport through various supports under low transmembrane pressures (100-220 kPa) at room temperature (26.5{degrees}C) was in the transition region, which combined the Knudsen diffusion and Poiseuille flow. The average radii of active pores for the supports, calculated from the gas permeability method, were compared with those measured by mercury porosimetry. The porosity-tortuosity factors and the tortuosity factors of the supports were also estimated and are discussed.

  12. Synthesis of small-sized, porous, and low-toxic magnetite nanoparticles by thin POSS silica coating.

    PubMed

    Yen, Swee Kuan; Varma, D Prathyusha; Guo, Wei Mei; Ho, Vincent H B; Vijayaragavan, Vimalan; Padmanabhan, Parasuraman; Bhakoo, Kishore; Selvan, Subramanian Tamil

    2015-03-01

    In this communication, we report the synthesis of small-sized (<10 nm), water-soluble, magnetic nanoparticles (MNPs) coated with polyhedral oligomeric silsesquioxanes (POSS), which contain either polyethylene glycol (PEG) or octa(tetramethylammonium) (OctaTMA) as functional groups. The POSS-coated MNPs exhibit superparamagnetic behavior with saturation magnetic moments (51-53 emu g(-1)) comparable to silica-coated MNPs. They also provide good colloidal stability at different pH and salt concentrations, and low cytotoxicity to MCF-7 human breast epithelial cells. The relaxivity data and magnetic resonance (MR) phantom images demonstrate the potential application of these MNPs in bioimaging.

  13. Silica Embedded Metal Hydrides

    SciTech Connect

    Heung, L.K.; Wicks, G.G.

    1998-08-01

    A method to produce silica embedded metal hydride was developed. The product is a composite in which metal hydride particles are embedded in a matrix of silica. The silica matrix is highly porous. Hydrogen gas can easily reach the embedded metal hydride particles. The pores are small so that the metal hydride particles cannot leave the matrix. The porous matrix also protects the metal hydride particles from larger and reactive molecules such as oxygen, since the larger gas molecules cannot pass through the small pores easily. Tests show that granules of this composite can absorb hydrogen readily and withstand many cycles without making fines.

  14. Ultrathin silica films immobilized on gold supports: fabrication, characterization, and modification.

    PubMed

    Macech, Piotr; Pemberton, Jeanne E

    2007-09-11

    A novel method for covalent attachment of ultrathin silica films (thickness <10 nm) to gold substrates is reported. Silica layers were prepared using spin-coating of sol-gel precursor solutions onto gold substrates that were cleaned and oxidized using UV photo-oxidation in an ozone atmosphere. The gold oxide layer resulting from this process acts as a wetting control and adhesive agent for the ultrathin silica layer. Control of silica layer thickness between approximately 6 and 60 nm through modification of precursor solution composition or by repetitive deposition is demonstrated. Films were characterized using infrared spectroscopy, ellipsometry, atomic force microscopy, and cyclic voltammetry. For the standard deposition parameters developed here, films were determined to be 5.5 +/- 0.75 nm thick, and were stable in aqueous solutions ranging in pH from 2 to 10 for at least 30 min. Films contained nanoscopic defects with radii of silica films were also modified with self-assembled monolayers of octadecylsilane, demonstrating the surface chemistry of bulk silica.

  15. Cation effects in the oxidative coupling of methane on silica-supported binary alkali and alkaline earths

    SciTech Connect

    Voyatzis, R.; Moffat, J.B. )

    1993-07-01

    The oxidative coupling of methane has been investigated with a series of silica-supported binary oxide catalysts containing alkali or alkaline earths or combinations of the former and latter. The conversion of methane and the stability of the silica-supported binary alkali metal oxides were found to increase with decreasing cation mobility, while the selectivities and conversions observed with the binary alkaline earths increase with cation size. The selectivities and conversions of binary alkali/alkaline earths appear to depend upon the size of the alkali and alkaline earth cations, respectively. With small quantities of TCM (CCl[sub 4]) added continuously to the feedstream, catalysts containing small alkali and large alkaline earth cations produced the largest selectivities and conversions. 23 refs., 14 figs., 2 tabs.

  16. Osseointegration properties of titanium dental implants modified with a nanostructured coating based on ordered porous silica and bioactive glass nanoparticles

    NASA Astrophysics Data System (ADS)

    Covarrubias, Cristian; Mattmann, Matías; Von Marttens, Alfredo; Caviedes, Pablo; Arriagada, Cristián; Valenzuela, Francisco; Rodríguez, Juan Pablo; Corral, Camila

    2016-02-01

    The fabrication of a nanoporous silica coating loaded with bioactive glass nanoparticles (nBG/NSC) on titanium dental implant surface and its in vitro and in vivo evaluation is presented. The coating was produced by a combined sol-gel and evaporation induced self-assembly process. In vitro bioactivity was assessed in simulated body fluid (SBF) and investigating the osteogenic differentiation of human bone marrow mesenchymal stem cells (hBMSCs). A rat tibial model was employed to analyze the bone response to nBG/NSC-modified titanium implant surface in vivo. The nBG/NSC coating was confirmed at nano level to be constituted by a highly ordered nanoporous silica structure. The coating nanotopography in conjunction with the bioactivity of the BG particles accelerate the in vitro apatite formation and promote the osteogenic differentiation of hBMSCs in absence of osteogenic supplements. These properties accelerate the formation of bone tissue in the periphery of the implant after 3 weeks of implantation. Backscattered scanning electron microscopy images revealed the presence of gaps and soft tissue in the unmodified implant after 6 weeks, whereas the nBG/NSC-modified implant showed mature bone in intimate contact with the implant surface. The nBG/NSC coating appears promising for accelerating the osseointegration of dental implants.

  17. In situ assembly of porous Au-paper electrode and functionalization of magnetic silica nanoparticles with HRP via click chemistry for Microcystin-LR immunoassay.

    PubMed

    Ge, Shenguang; Liu, Weiyan; Ge, Lei; Yan, Mei; Yan, Jixian; Huang, Jiadong; Yu, Jinghua

    2013-11-15

    A simple, low-cost and sensitive origami electrochemical immunoassay-device was developed based on a novel gold nanoparticle modified porous paper working electrode (Au-PWE) for point-of-care testing. Azide-functionalized Au-PWE was prepared by the functionalization of Au-PWE with 1-azidoundecan-11-thiol. Alkyne end-terminated antibody was prepared with 4-pentynoic acid and antibody by the 1-ethyl-3-(3-(dimethylamino) propyl) carbodiimide hydrochloride and N-hydroxysuccinimide activation reaction. Alkyne-antibody was coupled to azido-Au-PWE by click reaction as a recognition element. Nearly monodispersed sphere-like silica-coated ferroferric oxide (Fe3O4@SiO2) nanoparticles were prepared via the reverse microemulsion method. Azide-functionalized Fe3O4@SiO2 was prepared by the functionalization of silica shell with 3-bromopropyltrichlorosilane followed by substitution with sodium azide. Alkyne-functionalized antibody and horse radish peroxidase were coupled to azide-functionalized Fe3O4@SiO2 by click reaction as signal label. Horse radish peroxidase and ferroferric oxide could catalyze the oxidation of thionine in the presence of hydrogen peroxide. After the sandwich immunoreaction, the current was proportional to the logarithm of the Microcystin-LR. The linear regression equation was i(μA)=119.89+46.27 log cMC-LR (μg/mL) in the range from 0.01 to 200 μg/mL. The limit of detection was 0.004 μg/mL. This immunoassay would provide a universal immunoassay method in environmental monitoring and public health. PMID:23728196

  18. An Efficient, Versatile, and Safe Access to Supported Metallic Nanoparticles on Porous Silicon with Ionic Liquids.

    PubMed

    Darwich, Walid; Haumesser, Paul-Henri; Santini, Catherine C; Gaillard, Frédéric

    2016-06-03

    The metallization of porous silicon (PSi) is generally realized through physical vapor deposition (PVD) or electrochemical processes using aqueous solutions. The former uses a strong vacuum and does not allow for a conformal deposition into the pores. In the latter, the water used as solvent causes oxidation of the silicon during the reduction of the salt precursors. Moreover, as PSi is hydrophobic, the metal penetration into the pores is restricted to the near-surface region. Using a solution of organometallic (OM) precursors in ionic liquid (IL), we have developed an easy and efficient way to fully metallize the pores throughout the several-µm-thick porous Si. This process affords supported metallic nanoparticles characterized by a narrow size distribution. This process is demonstrated for different metals (Pt, Pd, Cu, and Ru) and can probably be extended to other metals. Moreover, as no reducing agent is necessary (the decomposition in an argon atmosphere at 50 °C is fostered by surface silicon hydride groups borne by PSi), the safety and the cost of the process are improved.

  19. An Efficient, Versatile, and Safe Access to Supported Metallic Nanoparticles on Porous Silicon with Ionic Liquids

    PubMed Central

    Darwich, Walid; Haumesser, Paul-Henri; Santini, Catherine C.; Gaillard, Frédéric

    2016-01-01

    The metallization of porous silicon (PSi) is generally realized through physical vapor deposition (PVD) or electrochemical processes using aqueous solutions. The former uses a strong vacuum and does not allow for a conformal deposition into the pores. In the latter, the water used as solvent causes oxidation of the silicon during the reduction of the salt precursors. Moreover, as PSi is hydrophobic, the metal penetration into the pores is restricted to the near-surface region. Using a solution of organometallic (OM) precursors in ionic liquid (IL), we have developed an easy and efficient way to fully metallize the pores throughout the several-µm-thick porous Si. This process affords supported metallic nanoparticles characterized by a narrow size distribution. This process is demonstrated for different metals (Pt, Pd, Cu, and Ru) and can probably be extended to other metals. Moreover, as no reducing agent is necessary (the decomposition in an argon atmosphere at 50 °C is fostered by surface silicon hydride groups borne by PSi), the safety and the cost of the process are improved. PMID:27271608

  20. Strong, Lightweight, Porous Materials

    NASA Technical Reports Server (NTRS)

    Leventis, Nicholas; Meador, Mary Ann B.; Johnston, James C.; Fabrizio, Eve F.; Ilhan, Ulvi

    2007-01-01

    A new class of strong, lightweight, porous materials has been invented as an outgrowth of an effort to develop reinforced silica aerogels. The new material, called X-Aerogel is less hygroscopic, but no less porous and of similar density to the corresponding unmodified aerogels. However, the property that sets X-Aerogels apart is their mechanical strength, which can be as much as two and a half orders of magnitude stronger that the unmodified aerogels. X-Aerogels are envisioned to be useful for making extremely lightweight, thermally insulating, structural components, but they may also have applications as electrical insulators, components of laminates, catalyst supports, templates for electrode materials, fuel-cell components, and filter membranes.

  1. A Simple, Efficient Synthesis of 2-Aryl Benzimidazoles Using Silica Supported Periodic Acid Catalyst and Evaluation of Anticancer Activity

    PubMed Central

    Sontakke, Vyankat A.; Ghosh, Sougata; Lawande, Pravin P.; Chopade, Balu A.; Shinde, Vaishali S.

    2013-01-01

    A new, efficient method for the synthesis of 2-aryl substituted benzimidazole by using silica supported periodic acid (H5IO6-SiO2) as a catalyst has been developed. The salient feature of the present method includes mild reaction condition, short reaction time, high yield and easy workup procedure. The synthesized benzimidazoles exhibited potent anticancer activity against MCF7 and HL60 cell lines. PMID:24052861

  2. Silica gel as a support for inorganic ion- exchangers for the determination of caesium-137 in natural waters.

    PubMed

    Terada, K; Hayakawa, H; Sawada, K; Kiba, T

    1970-10-01

    The preparation and characteristics of ammonium molybdophosphate and potassium or ammonium hexacyanocobalt ferrate supported in silica gel, and their application to the determination of (137)Cs in natural waters are described. Use of columns of these materials gives better recovery of (137)Cs from natural waters (in comparison with co-precipitation with ammonium molybdophosphate), requires less exchanger, so raising the gamma-counting efficiency of (137)Cs, and permits elimination of other radionuclides by washing with hydrofluoric acid.

  3. Tailoring Silica-alumina Supported Pt-Pd As Poison Tolerant Catalyst For Aromatics Hydrogenation

    SciTech Connect

    Yu, Yanzhe; Gutierrez, Oliver Y.; Haller, Gary L.; Colby, Robert J.; Kabius, Bernd C.; Rob van Veen, J. A.; Jentys, Andreas; Lercher, Johannes A.

    2013-08-01

    The tailoring of the physicochemical and catalytic properties of mono- and bimetallic Pt-Pd catalysts supported on amorphous silica-alumina is studied. Electron energy loss spectroscopy and extended X-ray absorption fine structure analyses indicated that bimetallic Pt-Pd and relatively large monometallic Pd particles were formed, whereas the X-ray absorption near edge structure provided direct evidence for the electronic deficiency of the Pt atoms. The heterogeneous distribution of metal particles was also shown by high resolution transmission electron microscopy. The average structure of the bimetallic particles (Pt-rich core and Pd-rich shell) and the presence of Pd particles led to surface Pd enrichment, which was independently shown by IR spectra of adsorbed CO. The specific metal distribution, average size, and surface composition of the Pt-Pd particles depend to a large extent on the metal precursors. In the presence of NH3 ligands, Pt-Pd particles with a fairly homogeneous bulk and surface metal distribution were formed. Also high Lewis acid site concentration of the carrier leads to more homogeneous bimetallic particles. All catalysts were active for the hydrogenation of tetralin in the absence and presence of quinoline and dibenzothiophene (DBT). Monometallic Pt catalysts had the highest hydrogenation activity in poison-free and quinoline-containing feed. When DBT was present, bimetallic Pt-Pd catalysts with the most homogenous metal distribution showed the highest activity. The higher resistance of bimetallic catalysts towards sulfur poisoning compared to their monometallic Pt counterparts results from the weakened metal-sulfur bond on the electron deficient Pt atoms. Thus, increasing the fraction of electron deficient Pt on the surface of the bimetallic particles increases the efficiency of the catalyst in the presence of sulfur.

  4. Impact of pore characteristics of silica materials on loading capacity and release behavior of ibuprofen.

    PubMed

    Numpilai, Thanapha; Muenmee, Suthaporn; Witoon, Thongthai

    2016-02-01

    Impact of pore characteristics of porous silica supports on loading capacity and release behavior of ibuprofen was investigated. The porous silica materials and ibuprofen-loaded porous silica materials were thoroughly characterized by N2-sorption, thermal gravimetric and derivative weight analyses (TG-DTW), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), transmission electron microscope (TEM) to determine the physical properties of materials, amount of ibuprofen adsorbed and position of ibuprofen. The detailed characterization reveals that the ibuprofen molecules adsorbed inside the mesopores. Increasing the mesopore size from 5nm to 10nm increased the ibuprofen loading from 0.74 to 0.85mmol/g, respectively. Incorporation of macropore into the structure of porous silica materials enhanced the ibuprofen loading capacity of 11.8-20.3%. The ibuprofen-loaded bimodal meso-macroporous silica materials exhibited the highest dissolution of 92wt.% within an hour. The ibuprofen particles deposited on the external surface of the porous silica materials showed a lower dissolution rate than the ibuprofen adsorbed inside the mesopores due to the formation of ibuprofen crystalline.

  5. Impact of pore characteristics of silica materials on loading capacity and release behavior of ibuprofen.

    PubMed

    Numpilai, Thanapha; Muenmee, Suthaporn; Witoon, Thongthai

    2016-02-01

    Impact of pore characteristics of porous silica supports on loading capacity and release behavior of ibuprofen was investigated. The porous silica materials and ibuprofen-loaded porous silica materials were thoroughly characterized by N2-sorption, thermal gravimetric and derivative weight analyses (TG-DTW), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), transmission electron microscope (TEM) to determine the physical properties of materials, amount of ibuprofen adsorbed and position of ibuprofen. The detailed characterization reveals that the ibuprofen molecules adsorbed inside the mesopores. Increasing the mesopore size from 5nm to 10nm increased the ibuprofen loading from 0.74 to 0.85mmol/g, respectively. Incorporation of macropore into the structure of porous silica materials enhanced the ibuprofen loading capacity of 11.8-20.3%. The ibuprofen-loaded bimodal meso-macroporous silica materials exhibited the highest dissolution of 92wt.% within an hour. The ibuprofen particles deposited on the external surface of the porous silica materials showed a lower dissolution rate than the ibuprofen adsorbed inside the mesopores due to the formation of ibuprofen crystalline. PMID:26652347

  6. Confinement-induced infrared absorption by H2 and N2 gases in a porous silica aerogel

    NASA Astrophysics Data System (ADS)

    Vander Auwera, J.; Boulet, C.; Carré, Y.; Kocon, L.; Hartmann, J.-M.

    2016-10-01

    Transmission spectra in the fundamental bands of H2 and N2 gas inside the pores of a silica aerogel sample were recorded at room temperature and for several pressures using a Fourier transform spectrometer. They first show that, as the absorption is proportional to the pressure, it is due to the interactions of the molecules with the inner surfaces of the pores and not to the dipole induced during gas-phase molecule-molecule collisions. Furthermore, the analysis of the widths and areas of the observed absorption structures indicate that, for the considered aerogel sample, most of the absorption is likely due to "free" molecules moving within the pores with a weak contribution of adsorbed molecules.

  7. Chromatographic retention behaviour of monosubstituted benzene derivatives on porous graphitic carbon and octadecyl-bonded silica studied using molecular modelling and quantitative structure-retention relationships.

    PubMed

    De Matteis, Cristina I; Simpson, David A; Euerby, Melvin R; Shaw, P Nicholas; Barrett, David A

    2012-03-16

    The retention behaviour of a series of 28 monosubstituted benzenes, representing a diverse range of functional groups and substituent shape, were investigated using porous graphitic carbon (PGC) and octadecyl-bonded silica (ODS) stationary phases. For the majority of analytes retention on PGC was greater than on ODS, and in most cases this effect occurred at both pH 2.5 and 7.0. The main trends observed on PGC (in comparison with ODS) were: (i) similar or reduced retention of low polarity molecules such as the hydrocarbon and halogenated analytes; (ii) increased retention of conjugated analytes with extended planarity; (iii) increased retention of polar and charged species; and (iv) substantial increases in retention for selected polar and negatively charged analytes, including some ionised and unionised acid analytes. Poor retention of positively charged analytes was observed on both stationary phases. Molecular modelling studies have explored the geometry of π-π stacking interactions in retention on PGC and have highlighted the strong retention of large conjugated analytes, with extended planar conformations, which can interact with the graphite surface with cofacial geometry. Quantitative structure-retention relationships showed the importance of hydrophobic (π) and electronic factors (e.g. mean polarisability and LUMO energy) in retention on PGC, whilst retention on ODS was correlated to hydrophobicity (logP and π). PMID:22305358

  8. Bimodal porous silica microspheres decorated with polydopamine nano-particles for the adsorption of methylene blue in fixed-bed columns.

    PubMed

    Ataei-Germi, Taher; Nematollahzadeh, Ali

    2016-05-15

    Bimodal meso/macro-porous silica microspheres (MSM) were synthesized by a modified sol-emulsion-gel method and then the surface was coated with polydopamine (PDA) nano-particles of 39nm in size. Focusing on the encouraging properties of the synthesized adsorbent, such as high specific surface area (612.3m(2)g(-1), because of mesopores), fast mass transfer (0.9-2.67×10(-3)mLmin(-1)mg, because of macropores), and abundant "adhesive" functional groups of PDA, it was used for the removal of methylene blue (MB) from aqueous solution in a fixed-bed column. The effect of different parameters such as pH, initial concentration, and flow rate was studied. The results revealed that an appropriate sorption condition is an alkaline solution of MB (e.g., pH 10) at low flow rate (less than 5mLmin(-1)). Furthermore, the compatibility of the experimental data with mathematical models such as Thomas and Adams-Bohart was investigated. Both of the models showed a good agreement with the experimental data (R(2)=0.9954-0.9994), and could be applied for the prediction of the column properties and breakthrough curves. Regeneration of the column was performed by using HCl solution with a concentration of 0.1M as an eluent. PMID:26943002

  9. Development and characterization of ultra-porous silica films made by the sol-gel method. Application to biosensing

    NASA Astrophysics Data System (ADS)

    Desfours, Caroline; Calas-Etienne, Sylvie; Horvath, Robert; Martin, Marta; Gergely, Csilla; Cuisinier, Frédéric; Etienne, Pascal

    2014-02-01

    The aim of this work is to demonstrate the sensing ability of reverse-symmetry waveguides to investigate adsorption of casein and build-up of poly-L-lysine mediated casein multilayers. A first part of this study is dedicated to the elaboration and characterization of ultra-porous thin films with very low refractive indices by an appropriate sol-gel method. This will form the basis of our planar optical sensors. Optical waveguide light mode spectroscopy is a real-time and sensitive method to study protein adsorption kinetics and lipid bilayers. We used it to test the obtained waveguides for in-situ monitoring of biomolecule adsorption. As a result, significant changes in the incoupling peak position were observed during the layer-by-layer adsorption. Finally, refractive index and thickness of the adsorbed layers were established.

  10. Micro-tubular solid oxide fuel cell based on a porous yttria-stabilized zirconia support

    PubMed Central

    Panthi, Dhruba; Tsutsumi, Atsushi

    2014-01-01

    Solid oxide fuel cells (SOFCs) are promising electrochemical energy conversion devices owing to their high power generation efficiency and environmentally benign operation. Micro-tubular SOFCs, which have diameters ranging from a few millimeters to the sub-millimeter scale, offer several advantages over competing SOFCs such as high volumetric power density, good endurance against thermal cycling, and flexible sealing between fuel and oxidant streams. Herein, we successfully realized a novel micro-tubular SOFC design based on a porous yttria-stabilized zirconia (YSZ) support using multi-step dip coating and co-sintering methods. The micro-tubular SOFC consisted of Ni-YSZ, YSZ, and strontium-doped lanthanum manganite (LSM)–YSZ as the anode, electrolyte, and cathode, respectively. In addition, to facilitate current collection from the anode and cathode, Ni and LSM were applied as an anode current collector and cathode current collector, respectively. Micro-crystalline cellulose was selected as a pore former to achieve better shrinkage behavior of the YSZ support so that the electrolyte layer could be densified at a co-sintering temperature of 1300°C. The developed micro-tubular design showed a promising electrochemical performance with maximum power densities of 525, 442, and 354 mW cm−2 at 850, 800, and 750°C, respectively. PMID:25169166

  11. Temperature-programmed desorption study of the selective oxidation of alcohols on silica-supported vanadium oxide.

    PubMed

    Feng, T; Vohs, J M

    2005-02-17

    The partial oxidation of methanol and ethanol on silica-supported vanadium oxide catalysts was studied using temperature-programmed desorption (TPD), Raman spectroscopy, and diffuse reflectance infrared spectroscopy (DRIFTS). Methanol TPD results for V2O5/SiO2 samples as a function of vanadia loading in conjunction with X-ray diffraction data and Raman spectra indicated that dispersed vanadia on silica agglomerates into vanadia crystallites during a CH3OH TPD experiment. For ethanol-dosed samples, agglomeration of the dispersed vanadia was less severe, and it was possible to measure the activation energy for the dehydrogenation of adsorbed ethoxides to produce CH3CHO. Assuming a preexponential factor of 10(13) s(-1), the activation energy for this reaction was estimated to be 132 kJ/mol. The results of this study further demonstrate that there is a relatively weak interaction between vanadia and silica and suggest that adsorbed methoxide species help facilitate agglomeration of dispersed vanadia. PMID:16851203

  12. Tubular ceramic-supported sol-gel silica-based membranes for flue gas carbon dioxide capture and sequestration.

    SciTech Connect

    Tsai, C. Y.; Xomeritakis, George K.; Brinker, C. Jeffrey; Jiang, Ying-Bing

    2009-03-01

    Pure, amine-derivatized and nickel-doped sol-gel silica membranes have been developed on tubular Membralox-type commercial ceramic supports for the purpose of carbon dioxide separation from nitrogen under coal-fired power plant flue gas conditions. An extensive synthetic and permeation test study was carried out in order to optimize membrane CO{sub 2} permeance, CO{sub 2}:N{sub 2} separation factor and resistance against densification. Pure silica membranes prepared under optimized conditions exhibited an attractive combination of CO{sub 2} permeance of 2.0 MPU (1 MPU = 1 cm{sup 3}(STP) {center_dot} cm{sup -2} min{sup -1} atm{sup -1}) and CO{sub 2}:N{sub 2} separation factor of 80 with a dry 10:90 (v/v) CO{sub 2}:N{sub 2} feed at 25 C. However, these membranes exhibited flux decline phenomena under prolonged exposure to humidified feeds, especially in the presence of trace SO{sub 2} gas in the feed. Doping the membranes with nickel (II) nitrate salt was effective in retarding densification, as manifested by combined higher permeance and higher separation factor of the doped membrane compared to the pure (undoped) silica membrane after 168 hours exposure to simulated flue gas conditions.

  13. Self-Immolative Linkers as Caps for the Design of Gated Silica Mesoporous Supports.

    PubMed

    Juárez, L Alberto; Añón, Elena; Giménez, Cristina; Sancenón, Félix; Martínez-Máñez, Ramón; Costero, Ana M; Gaviña, Pablo; Parra, Margarita; Bernardos, Andrea

    2016-09-26

    A new hybrid material based on sulforhodamine B dye-loaded silica mesoporous nanoparticles capped with a self-immolative gate has been synthesized and characterized. The gated material's controlled release behavior is monitored under different pH conditions. Under acidic and neutral conditions, a low level of dye release is detected. However, at slightly basic pH, significant dye release occurs owing to deprotonation of the phenol moiety in the capping molecule, which results in its disassembly. PMID:27304830

  14. Self-Immolative Linkers as Caps for the Design of Gated Silica Mesoporous Supports.

    PubMed

    Juárez, L Alberto; Añón, Elena; Giménez, Cristina; Sancenón, Félix; Martínez-Máñez, Ramón; Costero, Ana M; Gaviña, Pablo; Parra, Margarita; Bernardos, Andrea

    2016-09-26

    A new hybrid material based on sulforhodamine B dye-loaded silica mesoporous nanoparticles capped with a self-immolative gate has been synthesized and characterized. The gated material's controlled release behavior is monitored under different pH conditions. Under acidic and neutral conditions, a low level of dye release is detected. However, at slightly basic pH, significant dye release occurs owing to deprotonation of the phenol moiety in the capping molecule, which results in its disassembly.

  15. Role of Surface Cobalt Silicate in Single-Walled Carbon Nanotube Synthesis from Silica-Supported Cobalt Catalysts

    SciTech Connect

    Li, N.; Wang, X; Derrouiche, S; Haller, G; Pfefferle, L

    2010-01-01

    A silica-supported cobalt catalyst has been developed via incipient wetness impregnation for high-yield synthesis of single-walled carbon nanotubes (SWNTs). Co/SiO{sub 2}-impregnated catalysts have not been observed to be efficient for SWNT synthesis. Using an appropriately chosen precursor, we show that effective catalysts can be obtained for SWNT synthesis with yields up to 75 wt %. Detailed characterization indicates that the active sites for SWNT synthesis are small cobalt particles resulting from the reduction of a highly dispersed surface cobalt silicate species. The SWNTs produced by this catalyst are of high quality and easy to purify, and the process is simple and scalable.

  16. Role of surface cobalt silicate in single-walled carbon nanotube synthesis from silica-supported cobalt catalysts.

    PubMed

    Li, Nan; Wang, Xiaoming; Derrouiche, Salim; Haller, Gary L; Pfefferle, Lisa D

    2010-03-23

    A silica-supported cobalt catalyst has been developed via incipient wetness impregnation for high-yield synthesis of single-walled carbon nanotubes (SWNTs). Co/SiO2-impregnated catalysts have not been observed to be efficient for SWNT synthesis. Using an appropriately chosen precursor, we show that effective catalysts can be obtained for SWNT synthesis with yields up to 75 wt %. Detailed characterization indicates that the active sites for SWNT synthesis are small cobalt particles resulting from the reduction of a highly dispersed surface cobalt silicate species. The SWNTs produced by this catalyst are of high quality and easy to purify, and the process is simple and scalable. PMID:20201563

  17. Structure and Oxidation State of Silica-Supported Manganese Oxide Catalysts and Reactivity for Acetone Oxidation with Ozone

    SciTech Connect

    Reed,C.; Lee, Y.; Oyama, S.

    2006-01-01

    Silica-supported manganese oxide catalysts with loadings of 3, 10, 15, and 20 wt % (as MnO{sub 2}) were characterized with use of X-ray absorption spectroscopy and X-ray diffraction (XRD). The edge positions in the X-ray absorption spectra indicated that the oxidation state for the manganese decreased with increasing metal oxide loading from a value close to that of Mn{sub 2}O{sub 3} (+3) to a value close to that of Mn{sub 3}O{sub 4} (+2 2/3). The XRD was consistent with these results as the diffractograms for the supported catalysts of higher manganese oxide loading matched those of a Mn{sub 3}O{sub 4} reference. The reactivity of the silica-supported manganese oxide catalysts in acetone oxidation with ozone as an oxidant was studied over the temperature range of 300 to 600 K. Both oxygen and ozone produced mainly CO{sub 2} as the product of oxidation, but in the case of ozone the reaction temperature and activation energy were significantly reduced. The effect of metal oxide loading was investigated, and the activity for acetone oxidation was greater for a 10 wt % MnO{sub x}/SiO{sub 2} catalyst sample compared to a 3 wt % MnO{sub x}/SiO{sub 2} sample.

  18. Behaviour of Silica and Florisil as Solid Supports in the Removal Process of As(V) from Aqueous Solutions

    PubMed Central

    Gabor, Andreea; Davidescu, Corneliu Mircea; Negrea, Adina; Ciopec, Mihaela; Lupa, Lavinia

    2015-01-01

    In this study two solid supports, silica and florisil, were impregnated with crown ether (dibenzo-18-crown-6) and Fe(III) ions and their efficiency was compared in the adsorption process of As(V) from aqueous solutions. The solid supports were impregnated with crown ether due to their ability to build complexes with positives ions. Fe(III) was used because of As(V) affinity for it. The impregnated solid supports were characterized by energy dispersive X-ray analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, and the specific surface area. The influence of the solid : liquid ratio on the adsorption process, kinetic studies for the pseudo-first-order and pseudo-second-order, and activation energy were studied. Thermodynamic studies as well as equilibrium studies were carried out. The obtained results showed that, from the two considered materials, impregnated silica presents a higher efficiency with a good selectivity, able to remove As(V) from aqueous solutions containing trace concentrations. PMID:25821633

  19. Construction of a multi-functional cryogenic propellant tank with cross-linked silica aerogel

    NASA Astrophysics Data System (ADS)

    Reinheimer, Preston Glenn

    Aerogels are low-density nanostructured porous materials, whose practical applications have been limited by their poor mechanical properties. Crosslinking the nanoparticle building blocks of silica aerogels with polymeric tethers increases both the modulus and the strength significantly. The polymer coating preserves the mesoporous structure of the silica framework while retaining its low thermal conductivity. The uniqueness of crosslinked silica aerogel has load carrying capabilities in which are determined in tensile, compression and flexural bending tests. Crosslinked silica aerogel testing displays specific compressive strength of 389000 Nm/Kg. Ballistic testing of crosslinked silica aerogel also corroborates its mechanical properties displaying a ballistic limit up to 80 m/s. Its thermal conductivity at 0.041 W/mK supports the use of crosslinked silica aerogel in cryogenic fuel cell applications. Manufacturing practices have been evaluated to obtain an optimal process which reduces time, money and difficulty.

  20. A density functional theory study of the oxidation of methanol to formaldehyde over vanadia supported on silica, titania, and zirconia

    SciTech Connect

    Khaliullin, Rustam Z.; Bell, Alexis T.

    2002-09-05

    Density functional theory was used to investigate the mechanism and kinetics of methanol oxidation to formaldehyde over vanadia supported on silica, titania, and zirconia. The catalytically active site was modeled as an isolated VO{sub 4} unit attached to the support. The calculated geometry and vibrational frequencies of the active site are in good agreement with experimental measurements both for model compounds and oxide-supported vanadia. Methanol adsorption is found to occur preferentially with the rupture of a V-O-M bond (M = Si, Ti, Zr) and with preferential attachment of a methoxy group to V. The vibrational frequencies of the methoxy group are in good agreement with those observed experimentally as are the calculated isobars. The formation of formaldehyde is assumed to occur via the transfer of an H atom of a methoxy group to the O atom of the V=O group. The activation energy for this process is found to be in the range of 199-214 kJ/mol and apparent activation energies for the overall oxidation of methanol to formaldehyde are predicted to lie in the range of 112-123 kJ/mol, which is significantly higher than that found experimentally. Moreover, the predicted turnover frequency (TOF) for methanol oxidation is found to be essentially independent of support composition, whereas experiments show that the TOF is 10{sup 3} greater for titania- and zirconia-supported vanadia than for silica-supported vanadia. Based on these findings, it is proposed that the formation of formaldehyde from methoxy groups may require pairs of adjacent VO{sub 4} groups or V{sub 2}O{sub 7} dimer structures.

  1. Application of Silica-Supported Alkylating Reagents in a One-Pot, Sequential Protocol to Diverse Benzoxathiazepine 1,1-Dioxides.

    PubMed

    Faisal, Saqib; Maity, Pradip K; Zang, Qin; Samarakoon, Thiwanka B; Sourk, Robert L; Hanson, Paul R

    2016-07-11

    Applications of silica-ROMP reagents in a one-pot, sequential protocol have been developed for the synthesis of a variety of diverse benzoxathiazepine 1,1-dioxides. This protocol includes sulfonylation, intramolecular SNAr, alkylation with silica-supported oligomeric benzyl (Si-OBPn) and triazole (Si-OTPn) phosphates, and intermolecular SNAr addition with a number of secondary amines in one-pot to afford a variety of unique benzoxathiazepine 1,1-dioxides sultams in good to excellent yields.

  2. Transport of carbon colloid supported nanoscale zero-valent iron in saturated porous media.

    PubMed

    Busch, Jan; Meißner, Tobias; Potthoff, Annegret; Oswald, Sascha E

    2014-08-01

    Injection of nanoscale zero-valent iron (nZVI) has recently gained great interest as emerging technology for in-situ remediation of chlorinated organic compounds from groundwater systems. Zero-valent iron (ZVI) is able to reduce organic compounds and to render it to less harmful substances. The use of nanoscale particles instead of granular or microscale particles can increase dechlorination rates by orders of magnitude due to its high surface area. However, classical nZVI appears to be hampered in its environmental application by its limited mobility. One approach is colloid supported transport of nZVI, where the nZVI gets transported by a mobile colloid. In this study transport properties of activated carbon colloid supported nZVI (c-nZVI; d50=2.4μm) are investigated in column tests using columns of 40cm length, which were filled with porous media. A suspension was pumped through the column under different physicochemical conditions (addition of a polyanionic stabilizer and changes in pH and ionic strength). Highest observed breakthrough was 62% of the injected concentration in glass beads with addition of stabilizer. Addition of mono- and bivalent salt, e.g. more than 0.5mM/L CaCl2, can decrease mobility and changes in pH to values below six can inhibit mobility at all. Measurements of colloid sizes and zeta potentials show changes in the mean particle size by a factor of ten and an increase of zeta potential from -62mV to -80mV during the transport experiment. However, results suggest potential applicability of c-nZVI under field conditions.

  3. Characterization of 430L porous supports obtained by powder extrusion moulding for their application in solid oxide fuel cells

    SciTech Connect

    Sotomayor, María Eugenia Ospina, Liliana María Levenfeld, Belén Várez, Alejandro

    2013-12-15

    The characterization of 430L stainless steel planar porous supports obtained by powder extrusion moulding was performed in this work. A thermoplastic multicomponent binder based on high density polyethylene and paraffin wax was selected for the process. Green supports were shaped by extrusion moulding, and subsequently the binder was removed by a thermal cycle previously optimized. Sintering was carried out at different temperatures in low vacuum. Density of sintered parts was measured by Archimedes' method and porosity was also evaluated through a microstructural analysis by optical microscopy. The porosity degree of samples sintered at low temperature was close to 35% which is a very suitable value for their application in SOFCs. Tensile tests were carried out in order to determine mechanical strength as a function of porosity degree. Based on these results, the best feedstock composition and processing parameters were selected. The oxidation behaviour in static air at high temperature was studied, and formed oxides were characterized in a scanning electron microscope equipped with energy dispersive analysis of X-rays. X-ray diffraction experiments were performed in order to identify the formed oxides based on formula Fe{sub 2−x}Cr{sub x}O{sub 3}. The results of these studies showed that this kind of ferritic stainless steel would be more suitable to be used as anodic supports where a rich hydrogen atmosphere is employed. Preliminary deposition tests allowed obtaining a homogeneous Ni–YSZ anode layer with a thickness of 10 μm on the porous metallic substrates. - Highlights: • 430L stainless steel porous supports were obtained by powder extrusion moulding. • Porosity degree was controlled sintering at different temperatures in low vacuum. • Tensile tests allowed determining mechanical strength of porous supports. • A study about its oxidation behaviour in static air at high temperature was realized. • After oxidation, formed oxides were

  4. Evaluation of the capacity of mosaic-like porous ceramics with designed pores to support osteoconduction.

    PubMed

    Teraoka, Kay; Kato, Tomotaka; Hattori, Koji; Ohgushi, Hajime

    2013-12-01

    Under osteoconductive conditions, porous calcium phosphate ceramics are known to induce new bone formation within their pores. A critical aspect of the design of porous ceramics is the geometrical features of their pores, with regard to promoting bone formation and mass transfer management in pore networks. However, the pore geometries of common porous ceramics lack clear details. Further, the connections between pores are hard to characterize and thus have not been thoroughly researched. To address these issues, we have developed an original method for fabricating porous ceramics, which we have termed "mosaic-like ceramics fabrication (MLCF)." Using MLCF, pore geometries can be designed and fabricated by each unit, and a network covering all the pores can be fabricated. Furthermore, MLCF can be used to build porous ceramics with custom-made shapes. In this study, we assessed the osteogenic influences of MLCF products (MLPC) composed of hydroxyapatite units on the differentiation of rat bone-marrow-derived mesenchymal stem cells (MSCs) in vitro and in vivo. Two types of commercial porous artificial bone were used as positive controls. MLPC was superior in osteogenic potential, and proved to be a reliable scaffold for bone tissue engineering. Furthermore, this study succeeded in defining the important geometries for osteoconduction.

  5. Fabrication of SrCo{sub 0.5}FeO{sub x} oxygen separation membranes on porous supports

    SciTech Connect

    Man Fai Ng; Riechert, T.L.; Schwartz, R.W.; Collins, J.P.

    1996-09-01

    SrCo{sub 0.5}FeO{sub x} (SCF) is an attractive material for oxygen separation membranes and for use in catalytic membrane reactors. While tubes of this material have been prepared by extrusion, further improvements in oxygen transport performance may be gained by preparing thinner membranes on porous supports. In this paper, we will discuss the deposition of thick films by spray deposition and centrifugal casting, and thin films by pyrolysis of chemical precursors. For the chemically derived thin films, porous MgO supports were used as membrane supports. Three types of precursor solutions were employed for dipcoating: a Pechini type solution, a nitrate-based solution, and a citrate-based solution. To prevent the infiltration of the precursor into the support, the support was backfilled with a material that decomposed at higher temperatures than the precursors. Cracking due to the volume changes during drying and pyrolysis of the precursors is discussed. Thick films were prepared by spray coating and centrifugal casting. Spray deposition of thick film membranes was accomplished by air brushing SCF from a water-based suspension onto the surface of a porous MgO support. Films on the interior surface of the supports were prepared by centrifugal casting using a xylene/butanol-based SCF suspension. Unlike extruded tubes, thick films undergo constrained sintering due to the presence of the support, which greatly reduces the densification rate. For membranes prepared by both approaches, we will discuss the effects of heating schedules on membrane microstructure, densification behavior, and cracking.

  6. Autocatalytic-Assisted Photorelease of a Sensitizer Drug Bound to a Silica Support

    PubMed Central

    Bartusik, Dorota; Minnis, Mihaela; Ghosh, Goutam; Greer, Alexander

    2013-01-01

    The photorelease of a sensitizer from a fluorinated silica surface occurs by a reaction of singlet oxygen with the vinyl ether bond linking with scission of a dioxetane intermediate. Irradiation of the released sensitizer generates singlet oxygen, which accelerates the release of more sensitizer via an autocatalytic reaction. Sigmoidal behavior of sensitizer release in n-butanol and n-octanol occurs at the optimal temperature of 20 °C. The photorelease efficiency was reduced at low temperatures, where the sensitizer was retained on the surface due to a long-lived dioxetane with inefficient scission; and also reduced at high temperatures, due to a slower reaction of 1O2 with the vinyl ether bond. Immediate acceleration is a result of released sensitizer being used as a dopant to eliminate the induction step further implicating an autocatalytic mechanism. However, the sigmoidal sensitizer release was not correlated to solvent viscosity, heat or light from the dioxetane decomposition, or to minor O2 solubility enhancements caused by the fluorinated silica. The mechanistic information collected here can be used to help control the pace of drug release; however, it remains to be seen whether an autocatalytic-based drug delivery system has an advantage to those with non-sigmoidal kinetics. PMID:23899089

  7. Enhanced CO2 adsorption over polymeric amines supported on heteroatom-incorporated SBA-15 silica: impact of heteroatom type and loading on sorbent structure and adsorption performance.

    PubMed

    Kuwahara, Yasutaka; Kang, Dun-Yen; Copeland, John R; Bollini, Praveen; Sievers, Carsten; Kamegawa, Takashi; Yamashita, Hiromi; Jones, Christopher W

    2012-12-21

    Silica supported amine materials are promising compositions that can be used to effectively remove CO(2) from large stationary sources, such as flue gas generated from coal-fired power plants (ca. 10 % CO(2)) and potentially from ambient air (ca. 400 ppm CO(2)). The CO(2) adsorption characteristics of prototypical poly(ethyleneimine)-silica composite adsorbents can be significantly enhanced by altering the acid/base properties of the silica support by heteroatom incorporation into the silica matrix. In this study, an array of poly(ethyleneimine)-impregnated mesoporous silica SBA-15 materials containing heteroatoms (Al, Ti, Zr, and Ce) in their silica matrices are prepared and examined in adsorption experiments under conditions simulating flue gas (10 % CO(2) in Ar) and ambient air (400 ppm CO(2) in Ar) to assess the effects of heteroatom incorporation on the CO(2) adsorption properties. The structure of the composite adsorbents, including local information concerning the state of the incorporated heteroatoms and the overall surface properties of the silicate supports, are investigated in detail to draw a relationship between the adsorbent structure and CO(2) adsorption/desorption performance. The CO(2) adsorption/desorption kinetics are assessed by thermogravimetric analysis and in situ FT-IR measurements. These combined results, coupled with data on adsorbent regenerability, demonstrate a stabilizing effect of the heteroatoms on the poly(ethyleneimine), enhancing adsorbent capacity, adsorption kinetics, regenerability, and stability of the supported aminopolymers over continued cycling. It is suggested that the CO(2) adsorption performance of silica-aminopolymer composites may be further enhanced in the future by more precisely tuning the acid/base properties of the support. PMID:23165918

  8. Cationic Silica-Supported N-Heterocyclic Carbene Tungsten Oxo Alkylidene Sites: Highly Active and Stable Catalysts for Olefin Metathesis.

    PubMed

    Pucino, Margherita; Mougel, Victor; Schowner, Roman; Fedorov, Alexey; Buchmeiser, Michael R; Copéret, Christophe

    2016-03-18

    Designing supported alkene metathesis catalysts with high activity and stability is still a challenge, despite significant advances in the last years. Described herein is the combination of strong σ-donating N-heterocyclic carbene ligands with weak σ-donating surface silanolates and cationic tungsten sites leading to highly active and stable alkene metathesis catalysts. These well-defined silica-supported catalysts, [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(OTf)] and [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(+) ][B(Ar(F) )4 (-) ] [IMes=1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene, B(Ar(F) )4 =B(3,5-(CF3 )2 C6 H3 )4 ] catalyze alkene metathesis, and the cationic species display unprecedented activity for a broad range of substrates, especially for terminal olefins with turnover numbers above 1.2 million for propene.

  9. Cationic Silica-Supported N-Heterocyclic Carbene Tungsten Oxo Alkylidene Sites: Highly Active and Stable Catalysts for Olefin Metathesis.

    PubMed

    Pucino, Margherita; Mougel, Victor; Schowner, Roman; Fedorov, Alexey; Buchmeiser, Michael R; Copéret, Christophe

    2016-03-18

    Designing supported alkene metathesis catalysts with high activity and stability is still a challenge, despite significant advances in the last years. Described herein is the combination of strong σ-donating N-heterocyclic carbene ligands with weak σ-donating surface silanolates and cationic tungsten sites leading to highly active and stable alkene metathesis catalysts. These well-defined silica-supported catalysts, [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(OTf)] and [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(+) ][B(Ar(F) )4 (-) ] [IMes=1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene, B(Ar(F) )4 =B(3,5-(CF3 )2 C6 H3 )4 ] catalyze alkene metathesis, and the cationic species display unprecedented activity for a broad range of substrates, especially for terminal olefins with turnover numbers above 1.2 million for propene. PMID:26928967

  10. Effects of surface activation on the structural and catalytic properties of ruthenium nanoparticles supported on mesoporous silica

    NASA Astrophysics Data System (ADS)

    Ma, Xianfeng; Lin, Rui; Beuerle, Christopher; Jackson, James E.; Obare, Sherine O.; Ofoli, Robert Y.

    2014-01-01

    Using colloid-based methods to prepare supported catalytic metallic nanoparticles (NPs) often faces the challenge of removing the stabilizer used during synthesis and activating the catalyst without modifying the particles or the support. We explored three surface activation protocols (thermal oxidation at 150 ° C, thermal reduction at 350 ° C, and argon-protected calcination at 650 ° C) to activate ruthenium NPs supported on mesoporous silica (MSU-F), and assessed their effects on the structural and catalytic properties of the catalysts, and their activity by the aqueous phase hydrogenation of pyruvic acid. The NPs were synthesized by polyol reduction using poly-N-vinyl-2-pyrrolidone (PVP) as a stabilizer, and supported on MSU-F by sonication-assisted deposition. The NPs maintained their original morphology on the support during activation. Ar-protected calcination was the most efficient of the three for completely removing PVP from particle surfaces, and provided the highest degree of particle crystallinity and a metal dispersion comparable to commercial Ru/SiO2. Its catalytic performance was significantly higher than the other two protocols, although all three thermally activated catalysts achieved higher activity than the commercial catalyst at the same Ru loading. Post-reaction analysis also showed that the supported catalyst activated at 650 ° C retained its morphology during the reaction, which is an important requirement for recyclability.

  11. Preconcentration and purification of rare earth elements in natural waters using silica-immobilized 8-hydroxyquinoline and a supported organophosphorus extractant

    SciTech Connect

    Esser, B.K.; Volpe, A.; Kenneally, J.M.; Smith, D.K. )

    1994-05-15

    8-Hydroxyquinoline immobilized on silica gel (silica-8HQ) and RE-Spec, a supported organophosphorus extractant, were used to preconcentrate and purify rare earth elements (REEs) from natural waters prior to their determination by isotope-dilution inductivity coupled plasma mass spectrometry (ID-ICPMS). Preconcentration onto silica-8HQ is applicable to a wide range of trace metals, making it suitable for multielement ID-ICPMS studies. The silica-8HQ, RE-Spec technique concentrates REEs from 1 L or less of water into 1 mL of salt-free 0.1% nitric acid. The technique is rapid and has high REE yields (>80%) and low REE blanks (<2[minus]6 pg). In addition, Ba separation is high, allowing determination of La and Eu by ID-<300 pg of Ba is present in the final concentrates of sample solutions initially containing > 4 [mu]g of Ba. 24 refs., 2 figs., 4 tabs.

  12. Design and characterization of Ni2+ and Co2+ decorated Porous Magnetic Silica spheres synthesized by hydrothermal-assisted modified-Stöber method for His-tagged proteins separation.

    PubMed

    Benelmekki, M; Xuriguera, E; Caparros, C; Rodríguez-Carmona, E; Mendoza, R; Corchero, J L; Lanceros-Mendez, S; Martinez, Ll M

    2012-01-01

    The complete elimination of enzymes from the reaction mixture and the possibility of its recycling for several rounds result in great benefits, allowing the reduction of the enzyme consumption and their usability in continuous processes. In this work, it is evaluated the capture of a H6-tagged green fluorescence protein (GFP-H6) on porous magnetic spheres using the Co(2+) and Ni(2+) affinity adsorption as a possible cost-effective and up-scaled alternative way for the immobilization of His-tagged proteins. For this purpose, Porous Magnetic Silica (PMS) spheres were synthesized by one-step hydrothermal-assisted modified-Stöber method. The obtained spheres have a homogenous size distribution of 400 nm diameter. The γ-Fe(2)O(3) nanoparticles are homogenously distributed in the silica matrix. The obtained PMS spheres have a saturation magnetization of about 10 emu/g. Magnetophoresis measurements show a total separation time of 16 min at 60 T/m. The obtained PMS spheres were successfully and homogenously decorated with Co(2+) and Ni(2+) and then evaluated for the capture of a GFP-H6 protein. The results were compared with the performance of the commercial beads Dynabeads® His-Tag Isolation & Pulldown. PMID:21996010

  13. Gold nanoparticles supported on mesoporous silica: origin of high activity and role of Au NPs in selective oxidation of cyclohexane

    PubMed Central

    Wu, Pingping; Bai, Peng; Yan, Zifeng; Zhao, George X. S.

    2016-01-01

    Homogeneous immobilization of gold nanoparticles (Au NPs) on mesoporous silica has been achieved by using a one-pot synthesis method in the presence of organosilane mercapto-propyl-trimethoxysilane (MPTMS). The resultant Au NPs exhibited an excellent catalytic activity in the solvent-free selective oxidation of cyclohexane using molecular oxygen. By establishing the structure-performance relationship, the origin of the high activity of mesoporous supported Au catalyst was identified to be due to the presence of low-coordinated Au (0) sites with high dispersion. Au NPs were confirmed to play a critical role in the catalytic oxidation of cyclohexane by promoting the activation of O2 molecules and accelerating the formation of surface-active oxygen species. PMID:26729288

  14. Mesoporous silica nanoparticle supported PdIr bimetal catalyst for selective hydrogenation, and the significant promotional effect of Ir

    NASA Astrophysics Data System (ADS)

    Yang, Hui; Huang, Chao; Yang, Fan; Yang, Xu; Du, Li; Liao, Shijun

    2015-12-01

    A mesoporous silica nanoparticle (MSN) supported bimetal catalyst, PdIr/MSN, was prepared by a facile impregnation and hydrogen reduction method. The strong promotional effect of Ir was observed and thoroughly investigated. At the optimal molar ratio of Ir to Pd (NIr/NPd = 0.1), the activity of PdIr0.1/MSN was up to eight times and 28 times higher than that of monometallic Pd/MSN and Ir/MSN, respectively. The catalysts were characterized comprehensively by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and hydrogen temperature programmed reduction, which revealed that the promotional effect of Ir may be due to the enhanced dispersion of active components on the MSN, and to the intensified Pd-Ir electronic interaction caused by the addition of Ir.

  15. Effects of Silica Nanoparticle Supported Ionic Liquid as Additive on Thermal Reversibility of Human Carbonic Anhydrase II

    PubMed Central

    Fallahbagheri, Azadeh; Saboury, Ali Akbar; Ma'mani, Leila; Taghizadeh, Mohammad; Khodarahmi, Reza; Ranjbar, Samira; Bohlooli, Mousa; Shafiee, Abbas; Foroumadi, Alireza; Sheibani, Nader; Moosavi-Movahedi, Ali Akbar

    2013-01-01

    Silica nanoparticle supported imidazolium ionic liquid [SNImIL] was synthesized and utilized as a biocompatible additive for studying the thermal reversibility of human carbonic anhydrase II (HCA II). For this purpose, we prepared additive by modification of nanoparticles through the grafting of ionic liquids on the surface of nanoparticles (SNImIL). The SNImIL were fully characterized by Fourier Transform Infrared spectroscopy, scanning electron microscopy and thermo gravimetric analysis. The characterization of HCA II was investigated by various techniques including UV–Vis and ANS fluorescence spectrophotometry, differential scanning calorimetry, and docking study. SNImIL induced disaggregation, enhanced protein stability and increased thermal reversibility of HCA II by up to 42% at pH 7.75. PMID:22829053

  16. Ruthenium carbenes supported on mesoporous silicas as highly active and selective hybrid catalysts for olefin metathesis reactions under continuous flow.

    PubMed

    Bru, Miriam; Dehn, Richard; Teles, J Henrique; Deuerlein, Stephan; Danz, Manuel; Müller, Imke B; Limbach, Michael

    2013-08-26

    In the search for a highly active and selective heterogenized metathesis catalyst, we systematically varied the pore geometry and size of various silica-based mesoporous (i.e., MCM-41, MCM-48, and SBA-15) and microporous (ZSM-5 and MWW) versus macroporous materials (D11-10 and Aerosil 200), besides other process parameters (temperature, dilution, and mean residence time). The activity and, especially, selectivity of such "linker-free" supports for ruthenium metathesis catalysts were evaluated in the cyclodimerization of cis-cyclooctene to form 1,9-cyclohexadecadiene, a valuable intermediate in the flavor and fragrance industry. The optimized material showed not only exceptionally high selectivity to the valuable product, but also turned out to be a truly heterogeneous catalyst with superior activity relative to the unsupported homogeneous complex. PMID:23852995

  17. Ruthenium carbenes supported on mesoporous silicas as highly active and selective hybrid catalysts for olefin metathesis reactions under continuous flow.

    PubMed

    Bru, Miriam; Dehn, Richard; Teles, J Henrique; Deuerlein, Stephan; Danz, Manuel; Müller, Imke B; Limbach, Michael

    2013-08-26

    In the search for a highly active and selective heterogenized metathesis catalyst, we systematically varied the pore geometry and size of various silica-based mesoporous (i.e., MCM-41, MCM-48, and SBA-15) and microporous (ZSM-5 and MWW) versus macroporous materials (D11-10 and Aerosil 200), besides other process parameters (temperature, dilution, and mean residence time). The activity and, especially, selectivity of such "linker-free" supports for ruthenium metathesis catalysts were evaluated in the cyclodimerization of cis-cyclooctene to form 1,9-cyclohexadecadiene, a valuable intermediate in the flavor and fragrance industry. The optimized material showed not only exceptionally high selectivity to the valuable product, but also turned out to be a truly heterogeneous catalyst with superior activity relative to the unsupported homogeneous complex.

  18. Gold nanoparticles supported on mesoporous silica: origin of high activity and role of Au NPs in selective oxidation of cyclohexane

    NASA Astrophysics Data System (ADS)

    Wu, Pingping; Bai, Peng; Yan, Zifeng; Zhao, George X. S.

    2016-01-01

    Homogeneous immobilization of gold nanoparticles (Au NPs) on mesoporous silica has been achieved by using a one-pot synthesis method in the presence of organosilane mercapto-propyl-trimethoxysilane (MPTMS). The resultant Au NPs exhibited an excellent catalytic activity in the solvent-free selective oxidation of cyclohexane using molecular oxygen. By establishing the structure-performance relationship, the origin of the high activity of mesoporous supported Au catalyst was identified to be due to the presence of low-coordinated Au (0) sites with high dispersion. Au NPs were confirmed to play a critical role in the catalytic oxidation of cyclohexane by promoting the activation of O2 molecules and accelerating the formation of surface-active oxygen species.

  19. Silica-Supported Titania-Zirconia Nanocomposites: Structural and Morphological Characteristics in Different Media.

    PubMed

    Sulym, Iryna; Goncharuk, Olena; Sternik, Dariusz; Skwarek, Ewa; Derylo-Marczewska, Anna; Janusz, Wladyslaw; Gun'ko, Vladimir M

    2016-12-01

    A series of TiO2-ZrO2/SiO2 nanocomposites were synthesized using a liquid-phase method and characterized by various techniques, namely, nitrogen adsorption-desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, high-resolution transmission electron microscopy, and photon correlation spectroscopy (PCS). It was revealed that the component ratio and calcination temperature affect the phase composition of nanocomposites. Composites TiZrSi1 (TiO2:ZrO2:SiO2 = 3:10:87) and TiZrSi2 (10:10:80) calcined at 1100 °С demonstrate the presence of t-ZrO2 crystallites in TiZrSi1 and ZrTiO4 phase in TiZrSi2. The samples calcined at 550 °С were amorphous as it was found from XRD data. According to the Raman spectra, the bands specific for anatase are observed in TiZrSi2. According to XPS data, Zr and Ti are in the highest oxidation state (+4). Textural analysis shows that initial silica is mainly meso/macroporous, but composites are mainly macroporous. The particle size distributions in aqueous media showed a tendency of increasing particle size with increasing TiO2 content in the composites.

  20. Silica-Supported Titania-Zirconia Nanocomposites: Structural and Morphological Characteristics in Different Media

    NASA Astrophysics Data System (ADS)

    Sulym, Iryna; Goncharuk, Olena; Sternik, Dariusz; Skwarek, Ewa; Derylo-Marczewska, Anna; Janusz, Wladyslaw; Gun'ko, Vladimir M.

    2016-02-01

    A series of TiO2-ZrO2/SiO2 nanocomposites were synthesized using a liquid-phase method and characterized by various techniques, namely, nitrogen adsorption-desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, high-resolution transmission electron microscopy, and photon correlation spectroscopy (PCS). It was revealed that the component ratio and calcination temperature affect the phase composition of nanocomposites. Composites TiZrSi1 (TiO2:ZrO2:SiO2 = 3:10:87) and TiZrSi2 (10:10:80) calcined at 1100 °C demonstrate the presence of t-ZrO2 crystallites in TiZrSi1 and ZrTiO4 phase in TiZrSi2. The samples calcined at 550 °C were amorphous as it was found from XRD data. According to the Raman spectra, the bands specific for anatase are observed in TiZrSi2. According to XPS data, Zr and Ti are in the highest oxidation state (+4). Textural analysis shows that initial silica is mainly meso/macroporous, but composites are mainly macroporous. The particle size distributions in aqueous media showed a tendency of increasing particle size with increasing TiO2 content in the composites.

  1. Development of a simple method for the preparation of novel egg-shell type Pt catalysts using hollow silica nanostructures as supporting precursors

    SciTech Connect

    Wang Jiexin; Chen Jianfeng

    2008-04-01

    A simple method for the preparation of novel egg-shell type platinum catalysts was developed and achieved by utilizing unique hollow silica nanostructures, i.e., hollow silica nanospheres and nanotubes, as supports. The observation by transmission electron microscopy indicated that the well-dispersed hollow silica supported Pt catalysts with a Pt particle diameter of 8-14 nm can be successfully prepared by wet impregnation process and heat treatment. The Pt-loaded hollow silica nanostructures were also characterized by inductively coupled plasma, X-ray diffraction, specific surface area, Fourier transformation infrared spectroscopy, X-ray photoelectron spectroscopy and energy dispersive spectroscopy. It was thus demonstrated that a higher Pt loading amount (0.392%) could be obtained under the same conditions except the addition of ammonia, which was found to be more effective than that (0.061%) with the addition of HCl in the immobilization of Pt. In addition, the effect of soaking time, Pt precursor concentration and calcination temperature on the loading of Pt in hollow silica nanostructures were investigated as well.

  2. Ni Nanoparticles Supported on Cage-Type Mesoporous Silica for CO2 Hydrogenation with High CH4 Selectivity.

    PubMed

    Budi, Canggih Setya; Wu, Hung-Chi; Chen, Ching-Shiun; Saikia, Diganta; Kao, Hsien-Ming

    2016-09-01

    Ni nanoparticles (around 4 nm diameter) were successfully supported on cage-type mesoporous silica SBA-16 (denoted as Ni@SBA-16) via wet impregnation at pH 9, followed by the calcination-reduction process. The Ni@SBA-16 catalyst with a very high Ni loading amount (22.9 wt %) exhibited exceptionally high CH4 selectivity for CO2 hydrogenation. At a nearly identical loading amount, the Ni@SBA-16 catalysts with smaller particle size of Ni NPs surprisingly exhibited a higher catalytic activity of CO2 hydrogenation and also led to a higher selectivity on CH4 formation than the Ni@SiO2 catalysts. This enhanced activity of the Ni@SBA-16 catalyst is suggested to be an accumulative result of the advantageous structural properties of the support SBA-16 and the well confined Ni NPs within the support; both induced a favorable reaction pathway for high selectivity of CH4 in CO2 hydrogenation. PMID:27531065

  3. pH-Responsive Fe3O4 Nanopartilces-Capped Mesoporous Silica Supports for Protein Delivery.

    PubMed

    Gan, Qi; Zhu, Jiaoyang; Yuan, Yuan; Liu, Changsheng

    2016-06-01

    Delivery of proteins and peptides with excellent bioactivity and controlled release still is a great challenge nowadays. In this study, a pH-responsive delivery system obtained by anchoring 8-nm Fe3O4 nanoparticles (NPs) onto SBA-15 supports with a particle diameter in the range of 0.6-1 μm and a pore size of 6.2 nm was synthesized and investigated. The pH-stimulative response is based on the interaction between the tris(aminomethyl)ethane (TAE) groups anchored onto the pore outlet of mesoporous silica scaffolds and the carboxybenzaldehyde (CBA) groups coated on the Fe3O4 NPs, which can lead to a rapid release under the acid condition (pH = 5) and a zero release with the increase of pH value (pH = 7.4). With BMP-2 as a model protein, this Fe3O4 nanopartilces-capped mesoporous silica showed a rapid response to the change of pH for protein delivery. Furthermore, the released BMP-2 could still maintain its bioactivity and induce the osteoblast differentiation of BMSCs. Besides, the magnetic orientation mainly attributes to the Fe3O4 NPs served as the nanocaps. The excellent bio-compatibility is demonstrated by the MTT assay on BMSCs model cells. These results show that Fe3O4 NPs-capped SBA-15 materials have an effective load for large molecule size proteins, such as BMP-2, and show an excellent applied prospect in pH-responsive controlled release system. PMID:27427586

  4. Selective oxidation of ethane to acetaldehyde and acrolein over silica-supported vanadium catalysts using oxygen as oxidant

    SciTech Connect

    Zhao, Zhen; Yamada, Yusuke; Teng, Yonghong; Ueda, Atsushi; Nakagawa, Kiyoharu; Kobayashi, Tetsuhiko

    2000-03-10

    The oxidation of ethane by oxygen was studied over silica catalysts supporting different amounts of vanadium with and without cesium. Three different catalytic properties of the product selectivity were observed, aldehyde formation, oxidative dehydrogenation (ODH), and combustion, depending upon the vanadium loading amount and the presence or the absence of cesium. A very low loading of vanadium (V:Si = 0.02--0.1 at.%) and the addition of Cs (Cs:Si = 1 at.%) on silica were found to be important for the formation of aldehyde. Not only acetaldehyde but also acrolein were observed in the aldehyde formation from ethane. On the other hand, catalysts with medium and high vanadium loadings (V:Si = 0.5--20 at.%) gave a dehydrogenated product, ethene, when Cs was not added to the catalysts. The addition of cesium to the catalysts with medium and high vanadium loadings changed the catalytic property from ODH to combustion. The different types of vanadyl species were identified by UV-visible and IR measurements in samples with different vanadium loadings. It was estimated that isolated vanadyl species with tetrahedral coordination, which were found mainly on the catalysts with vanadium loading lower than 0.5 at.%, became the active site for the aldehyde formation through the interaction with Cs. As a plausible reaction path giving acrolein from ethane, cesium-catalyzed cross-condensation between acetaldehyde and formaldehyde, formed in the reaction, was proposed. Polymeric vanadyl species with octahedral coordination were detected in the samples with medium (0.5--5.0 at.%) and high (10 and 20 at.%) vanadium loadings, respectively. Both species show the ODH catalytic property without cesium, but they bring about a deep oxidation of ethane if cesium is added to the catalysts.

  5. Quantitatively analyzing metathesis catalyst activity and structural features in silica-supported tungsten imido-alkylidene complexes.

    PubMed

    Mougel, Victor; Santiago, Celine B; Zhizhko, Pavel A; Bess, Elizabeth N; Varga, Jeno; Frater, Georg; Sigman, Matthew S; Copéret, Christophe

    2015-05-27

    A broad series of fully characterized, well-defined silica-supported W metathesis catalysts with the general formula [(≡SiO)W(═NAr)(═CHCMe2R)(X)] (Ar = 2,6-iPr2C6H3 (AriPr), 2,6-Cl2C6H3 (ArCl), 2-CF3C6H4 (ArCF3), and C6F5 (ArF5); X = OC(CF3)3 (OtBuF9), OCMe(CF3)2 (OtBuF6), OtBu, OSi(OtBu)3, 2,5-dimethylpyrrolyl (Me2Pyr) and R = Me or Ph) was prepared by grafting bis-X substituted complexes [W(NAr)(═CHCMe2R)(X)2] on silica partially dehydroxylated at 700 °C (SiO2-(700)), and their activity was evaluated with the goal to obtain detailed structure-activity relationships. Quantitative influence of the ligand set on the activity (turnover frequency, TOF) in self-metathesis of cis-4-nonene was investigated using multivariate linear regression analysis tools. The TOF of these catalysts (activity) can be well predicted from simple steric and electronic parameters of the parent protonated ligands; it is described by the mutual contribution of the NBO charge of the nitrogen or the IR intensity of the symmetric N-H stretch of the ArNH2, corresponding to the imido ligand, together with the Sterimol B5 and pKa of HX, representing the X ligand. This quantitative and predictive structure-activity relationship analysis of well-defined heterogeneous catalysts shows that high activity is associated with the combination of X and NAr ligands of opposite electronic character and paves the way toward rational development of metathesis catalysts.

  6. Catalytically Active Bimetallic Nanoparticles Supported on Porous Carbon Capsules Derived From Metal-Organic Framework Composites.

    PubMed

    Yang, Hui; Bradley, Siobhan J; Chan, Andrew; Waterhouse, Geoffrey I N; Nann, Thomas; Kruger, Paul E; Telfer, Shane G

    2016-09-14

    We report a new methodology for producing monometallic or bimetallic nanoparticles confined within hollow nitrogen-doped porous carbon capsules. The capsules are derived from metal-organic framework (MOF) crystals that are coated with a shell of a secondary material comprising either a metal-tannic acid coordination polymer or a resorcinol-formaldehyde polymer. Platinum nanoparticles are optionally sandwiched between the MOF core and the shell. Pyrolysis of the MOF-shell composites produces hollow capsules of porous nitrogen-doped carbon that bear either monometallic (Pt, Co, and Ni) or alloyed (PtCo and PtNi) metal nanoparticles. The Co and Ni components of the bimetallic nanoparticles are derived from the shell surrounding the MOF crystals. The hollow capsules prevent sintering and detachment of the nanoparticles, and their porous walls allow for efficient mass transport. Alloyed PtCo nanoparticles embedded in the capsule walls are highly active, selective, and recyclable catalysts for the hydrogenation of nitroarenes to anilines. PMID:27575666

  7. Rh-catalyzed borylation of N-adjacent C(sp3)-H bonds with a silica-supported triarylphosphine ligand.

    PubMed

    Kawamorita, Soichiro; Miyazaki, Tatsuya; Iwai, Tomohiro; Ohmiya, Hirohisa; Sawamura, Masaya

    2012-08-01

    Direct C(sp(3))-H borylation of amides, ureas, and 2-aminopyridine derivatives at the position α to the N atom, which gives the corresponding α-aminoalkylboronates, has been achieved with a heterogeneous catalyst system consisting of [Rh(OMe)(cod)]2 and a silica-supported triarylphosphine ligand (Silica-TRIP) that features an immobilized triptycene-type cage structure with a bridgehead P atom. The reaction occurs not only at terminal C-H bonds but also at internal secondary C-H bonds under mild reaction conditions (25-100 °C, 0.1-0.5 mol % Rh). PMID:22816772

  8. Strong oxide-oxide interactions in silica-supported magnetite catalysts. IV. Catalytic consequences of the interaction in water-gas shift

    SciTech Connect

    Lund, C.R.F.; Dumesic, J.A.

    1982-07-01

    Water-gas shift was studied at 663 K and 0.1 MPa over a series of silica-supported magnetite (Fe/sub 3/O/sub 4/) catalysts having magnetite particles from ca. 10 to 160 nm in size. The surface sites on these catalysts were titrated using NO adsorption at 273 K and adsorption from a CO/sub 2//CO gas mixture (CO/sub 2/:CO = 85:15) at 663 K. For these silica-supported catalysts, the water-gas shift turnover frequency, based on NO adsorption for site titration, decreased with decreasing particle size. In contrast, unsupported magnetite did not show this particle size dependence. For the smallest silica-supported magnetite particles, the turnover frequency was three orders of magnitude lower than over unsupported magnetite. The extent of CO and CO/sub 2/ adsorption, per surface site as titrated by NO, was also observed to decrease with decreasing particle size; and, the water-gas shift turnover frequency, based on CO/sub 2//CO adsorption for site titration, is independent of particle size. Thus, while NO adsorption can be used to measure the magnetite surface area of silica-supported samples, the CO/sub 2//CO adsorption uptake is proportional to the number of active sites on the magnetite surface. Compared to unsupported magnetite, the origin of the low catalytic activity of silica-supported magnetite (based on NO adsorption for site titration) is interpreted as being due to the effects of Si/sup 4 +/ substitution into the surface of magnetite, which causes the iron cations at the surface to become electron deficient and coordinatively more saturated with oxygen anions. 2 figures, 1 table.

  9. Mesoporous Silica-Based Supports for the Controlled and Targeted Release of Bioactive Molecules in the Gastrointestinal Tract.

    PubMed

    Pérez-Esteve, Édgar; Ruiz-Rico, María; Martínez-Máñez, Ramón; Barat, José Manuel

    2015-11-01

    Mesoporous silica particles (MSPs) have attracted increasing interest as supports in the design of controlled delivery materials. Besides their excellent properties as loading supports (that is, large surface area and pore volume), the modification of their external surface with molecular/supramolecular ensembles allows the design of gated MSPs. Delivery systems based on gated MSPs show "zero delivery" until an adequate stimulus is present and triggers gate opening and the cargo is released. Encapsulation of bioactive molecules in gated MSPs may improve biological stability, facilitate component handling, mask unpleasant sensorial properties, and modulate the bioaccessibility of target molecules along the gastrointestinal tract. These properties make gated MSPs excellent candidates for encapsulating bioactive molecules and their subsequent utilization in the formulation of functional foods. This text highlights the most significant endogenous triggering stimuli that might be applied to design these site-specific delivery systems, as well as the strategies to develop them. Given the novelty of using MSPs in the food sector, the benefits and current potential limitations of employing MSPs in human food have been identified and discussed.

  10. Controlling Ethylene Hydrogenation Reactivity on Pt13 Clusters by Varying the Stoichiometry of the Amorphous Silica Support.

    PubMed

    Crampton, Andrew S; Rötzer, Marian D; Schweinberger, Florian F; Yoon, Bokwon; Landman, Uzi; Heiz, Ueli

    2016-07-25

    Ethylene hydrogenation was investigated on size-selected Pt13 clusters supported on three amorphous silica (a-SiO2 ) thin films with different stoichiometries. Activity measurements of the reaction at 300 K revealed that on a silicon-rich and a stoichiometric film, Pt13 exhibits a similar activity to that of Pt(111), in line with the known structure insensitivity of the reaction. On an oxygen-rich film, a threefold increased rate was measured. Pulsing ethylene at 400 K, then measuring the activity at 300 K, resulted in complete loss of activity on the silicon-rich surface compared to only marginal losses on the other surfaces. The measured reactivity trends correlate with charging characteristics of a Pt13 cluster on the SiO2 films, predicted through first-principle calculations. The results reveal that the stoichiometry-dependent charging by the support can be used to tune the selectivity of reaction pathways during a catalytic hydrogenation reaction.

  11. In-situ growth of porous alumino-silicates and fabrication of nano-porous membranes

    NASA Astrophysics Data System (ADS)

    Kodumuri, Pradeep

    2009-12-01

    Feasibility of depositing continuous films of nano-porous alumino-silicates, primarily zeolites and MCM-41, on metallic and non-metallic substrates was examined with an aim to develop membranes for separation of gaseous mixtures and also for application as hydrogen storage material. Mesoporous silica was deposited in-side the pores of these nano-porous disks with an aim to develop membranes for selective separations. Our study involves supported zeolite film growth on substrates using in-situ hydrothermal synthesis. Faujasite, Silicalite and Mesoporous silica have been grown on various metallic and non-metallic supports. Metallic substrates used for film growth included anodized titanium, sodium hydroxide treated Titanium, Anodized aluminum, and sintered copper. A non-metallic substrate used was nano-porous aluminum oxide. Zeolite film growth was characterized using Scanning Electron Microscope (AMRAY 1820) and High Resolution Transmission electron microscope. Silicalite was found to grow uniformly on all the substrates to form a uniform and closely packed film. Faujasite tends to grow in the form of individual particles which do not inter-grow like silicalite to form a continuous film. Mesoporous silica was found to grow uniformly on anodized aluminum compared to growth on sintered copper and anodized titanium. Mesoporous silica growth on AnodiscRTM was found to cover more than half the surface of the substrate. Commercially obtained AnodiscRTM was found to have cylindrical channels of the pore branching into each other and since we needed pore channels of uniform dimension for Mesoporous silica growth, we have fabricated nano-porous alumina with uniform pore channels. Nano-porous alumina membranes containing uniform distribution of through thickness cylindrical pore channels were fabricated using anodization of aluminum disks. Free-standing nano-porous alumina membranes were used as templates for electro-deposition in order to fabricate nickel and palladium nano

  12. Structure sensitive adsorption of hydrogen on ruthenium and ruthenium-silver catalysts supported on silica

    SciTech Connect

    Kumar, N.

    1999-02-12

    Supported metal catalysts typically consist of particles with sizes less than 10 nm, and because of the small crystallite size, low coordination number sites (edges and corners) represent a significant fraction of all surface sites. Furthermore, it has been demonstrated that adsorption rates can be much greater at these low coordination sites than on basal plane sites. What has not been generally appreciated, however, is that preferential adsorption at edge and corner sites may explain the mechanism by which a promoter, or the addition of a second metal to form a bimetallic, can alter the selectivity and rate of reaction. For example, the measurements of hydrogen adsorption onto supported Ru-Ag catalysts show marked decreases in the amount of hydrogen adsorbed relative to the amount adsorbed on Ru catalysts. Although it is known that Ag does not dissociatively adsorb hydrogen, this decrease cannot be explained by a simple one-to-one site blocking mechanism unless Ag preferentially populates edges and corners, thereby reducing the number of Ru edge sites. Indeed, Monte Carlo simulations of Ru-Group IB metal catalysts predict that Group IB metal atoms preferentially populate corner and edge sites of ruthenium crystals. This evidence, taken together, suggests that adsorption occurs preferentially at Ru corner and edge sites, which act as portals onto basal planes. A model based on this portal theory for hydrogen adsorption onto supported ruthenium bimetallic catalysts has been developed using a rate equation approach. Specifically, the model accounts for the following features: (1) preferential adsorption through portals, (2) basal plane site-energy multiplicity, and (3) hydrogen spillover onto the support. A comparison of model predictions with experiment is presented for different concentration of Ag in Ru-Ag catalysts. The portal model of hydrogen adsorption can explain the observed decreased in the amount of hydrogen adsorbed on Ru-Ag catalysts. The model can be

  13. A porous silica rock ("tripoli") in the footwall of the Jurassic Úrkút manganese deposit, Hungary: composition, and origin through carbonate dissolution

    USGS Publications Warehouse

    Polgari, Marta; Szabo, Zoltan; Szabo-Drubina, Magda; Hein, James R.; Yeh, Hsueh-Wen

    2005-01-01

    The mineralogical, chemical, and isotopic compositions were determined for a white tripoli from the footwall of the Jurassic Úrkút Mn-oxide ore deposit in the Bakony Mountains, Hungary. The tripoli consists of quartz and chalcedony, with SiO2 contents up to 100 wt.%; consequently, trace-element contents are very low. Oxygen isotopes and quartz crystallinity indicate a low-temperature diagenetic origin for this deposit. The tripoli was formed by dissolution of the carbonate portion of the siliceous (sponge spicules) Isztimér Limestone. Dissolution of the carbonate was promoted by inorganic and organic acids generated during diagensis and left a framework composed of diagenetic silica that preserved the original volume of the limestone layer. The relative enrichment of silica and high porosity is the result of that carbonate dissolution. The silty texture of this highly friable rock is due to the structurally weak silica framework.

  14. Solid-State NMR and DFT Studies on the Formation of Well-Defined Silica-Supported Tantallaaziridines: From Synthesis to Catalytic Application.

    PubMed

    Hamzaoui, Bilel; Pelletier, Jérémie D A; Abou-Hamad, Edy; Chen, Yin; El Eter, Mohamed; Chermak, Edrisse; Cavallo, Luigi; Basset, Jean-Marie

    2016-02-24

    Single-site, well-defined, silica-supported tantallaaziridine intermediates [≡Si-O-Ta(η(2) -NRCH2 )(NMe2 )2 ] [R=Me (2), Ph (3)] were prepared from silica-supported tetrakis(dimethylamido)tantalum [≡Si-O-Ta(NMe2 )4 ] (1) and fully characterized by FTIR spectroscopy, elemental analysis, and (1) H,(13) C HETCOR and DQ TQ solid-state (SS) NMR spectroscopy. The formation mechanism, by β-H abstraction, was investigated by SS NMR spectroscopy and supported by DFT calculations. The C-H activation of the dimethylamide ligand is favored for R=Ph. The results from catalytic testing in the hydroaminoalkylation of alkenes were consistent with the N-alkyl aryl amine substrates being more efficient than N-dialkyl amines. PMID:26875939

  15. Characterizing Surface Acidic Sites in Mesoporous-Silica-Supported Tungsten Oxide Catalysts Using Solid State NMR and Quantum Chemistry Calculations

    SciTech Connect

    Hu, Jian Z.; Kwak, Ja Hun; Wang, Yong; Hu, Mary Y.; Turcu, Romulus VF; Peden, Charles HF

    2011-10-18

    The acidic sites in dispersed tungsten oxide supported on SBA-15 mesoporous silica were investigated using a combination of pyridine titration, both fast-, and slow-MAS {sup 15}N NMR, static {sup 2}H NMR, and quantum chemistry calculations. It is found that the bridged acidic -OH groups in surface adsorbed tungsten dimers (i.e., W-OH-W) are the Broensted acid sites. The unusually strong acidity of these Broensted acid sites is confirmed by quantum chemistry calculations. In contrast, terminal W-OH sites are very stable and only weakly acidic as are terminal Si-OH sites. Furthermore, molecular interactions between pyridine molecules and the dimer Broensted and terminal W-OH sites for dispersed tungsten oxide species is strong. This results in restricted molecular motion for the interacting pyridine molecules even at room temperature, i.e., a reorientation mainly about the molecular 2-fold axis. This restricted reorientation makes it possible to estimate the relative ratio of the Broensted (tungsten dimer) to the weakly acidic terminal W-OH sites in the catalyst using the slow-MAS {sup 1}H-{sup 15}N CP PASS method.

  16. Preparation and adsorption behavior of berberine hydrochloride imprinted polymers by using silica gel as sacrificed support material

    NASA Astrophysics Data System (ADS)

    Li, Hui; Li, Yuzhuo; Li, Zhiping; Peng, Xiyang; Li, Yanan; Li, Gui; Tan, Xianzhou; Chen, Gongxi

    2012-03-01

    Preparation of berberine hydrochloride (B-Cl) imprinted polymers (MIPs) based on surface imprinting technique with silica gel as sacrificial support material was performed successfully by using B-Cl as template, methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) as functional monomer and cross-linker, respectively. The prepared polymers were characterized by Fourier transmission infrared spectrometry (FTIR) and scanning electron microscopy (SEM). Adsorption behavior of the MIPs for the template and its structural analogues was investigated. Sites distribution on the surface of MIPs was explored by using different isotherm adsorption models and thermodynamic parameters for the adsorption of B-Cl on the MIPs determined. Sample application and reusability for the MIPs was also evaluated. Results indicated the strong adsorption and high selectivity of the MIPs for B-Cl. Saturated adsorption capacity reached 27.2 μmol g-1 and the selectivity coefficient of the MIPs for B-Cl relative to jatrorrhizine hydrochloride (J-Cl) and palmatine palmatus hydrochloride (P-Cl) are 3.70 and 6.03, respectively. In addition, the MIPs were shown with good reusability and selectively retention ability in sample application.

  17. Studies of n-butane conversion over silica-supported platinum, platinum-silver and platinum-copper catalysts

    SciTech Connect

    Gu, Junhua.

    1992-06-09

    The present work was undertaken to elucidate effect of adding silver and copper to silica-supported platinum catalyst on the activity and selectivity in the n-butane reactions. At the conditions of this study n-butane underwent both hydrogenolysis and structural isomerization. The catalytic activity and selectivities between hydrogenolysis and isomerization and within hydrogenolysis were measured at temperature varying from 330 C to 370 C. For platinum-silver catalysts, at lower temperatures studied the catalytic activity per surface platinum atom (turnover frequency) remained constant at lower silver content (between 0 at. % and 30 at. %) and decreased with further increased silver loading, suggesting that low- index planes could be dominant in the hydrogenolysis of n-butane. Moreover, increasing silver content resulted in an enhancement of the selectivity of isomerization products relative to hydrogenolysis products. At the higher temperature studied, no suppression in catalytic activity was observed. It is postulated that surface structure could change due to the mobility of surface silver atoms, leading to surface silver atoms forming islands or going to the bulk, and leaving large portions of basal planes exposed with active platinum atoms. It is also suggested that the presence of inert silver atoms results in weakening of the H-surface bond. This results in increased mobility of hydrogen atoms on the surface and hence, higher reactivity with other adsorbed species. For platinum copper catalysts, the mixed ensembles could play an active role in the hydrogenolysis of n-butane.

  18. Amorphous vanadium oxide matrixes supporting hierarchical porous Fe3O4/graphene nanowires as a high-rate lithium storage anode.

    PubMed

    An, Qinyou; Lv, Fan; Liu, Qiuqi; Han, Chunhua; Zhao, Kangning; Sheng, Jinzhi; Wei, Qiulong; Yan, Mengyu; Mai, Liqiang

    2014-11-12

    Developing electrode materials with both high energy and power densities holds the key for satisfying the urgent demand of energy storage worldwide. In order to realize the fast and efficient transport of ions/electrons and the stable structure during the charge/discharge process, hierarchical porous Fe3O4/graphene nanowires supported by amorphous vanadium oxide matrixes have been rationally synthesized through a facile phase separation process. The porous structure is directly in situ constructed from the FeVO4·1.1H2O@graphene nanowires along with the crystallization of Fe3O4 and the amorphization of vanadium oxide without using any hard templates. The hierarchical porous Fe3O4/VOx/graphene nanowires exhibit a high Coulombic efficiency and outstanding reversible specific capacity (1146 mAh g(-1)). Even at the high current density of 5 A g(-1), the porous nanowires maintain a reversible capacity of ∼500 mAh g(-1). Moreover, the amorphization and conversion reactions between Fe and Fe3O4 of the hierarchical porous Fe3O4/VOx/graphene nanowires were also investigated by in situ X-ray diffraction and X-ray photoelectron spectroscopy. Our work demonstrates that the amorphous vanadium oxides matrixes supporting hierarchical porous Fe3O4/graphene nanowires are one of the most attractive anodes in energy storage applications.

  19. The structure of amorphous bulk and silica-supported copper(II) hydroxides

    SciTech Connect

    Kriventsov, V.V.; Kochubey, D.I.; Elizarova, G.L.; Matvienko, L.G.; Parmon, V.N.

    1999-07-01

    Determination of the structure of surface hydroxocompounds is one of the most delicate areas of environmental chemistry, geochemistry, and catalysis. In nature, these compounds are formed everywhere, mostly by absorption of multicharged metal cations on different soil constitutents from water solutions. The data obtained show that at pH 7 copper(II) ions are adsorbed on a SiO{sub 2} surface as polymeric species of hydroxide nature. The structure of these species is similar to that of the bulk amorphous copper hydroxide. The amorphous state of supported Cu(OH){sub 2} is caused by a small (ca. 11 {angstrom}) size of the surface particles. In contrast, the overstoichiometric water molecules seem to act as ``amorphizers`` of the bulk copper hydroxide. The structures of the bulk and dispersed amorphous copper(II) hydroxide were determined. The amorphous Cu(OH){sub 2} has a layered structure close to the structure of the crystalline hydroxide, but the layers in the amorphous hydroxide are shifted toward one another approximately for {1/4} of the c period of the lattice.

  20. Structure-Property Relationships in Porous 3-D Nanostructures as a Function of Preparation Conditions: Isocyanate Cross-Linked Silica Aerogels

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Capadona, Lynn A.; McCorkle, Linda; Padadopoulos, Demetrios S.; Leventis, Nicholas

    2007-01-01

    Sol-gel derived silica aerogels are attractive candidates for many unique thermal, optical, catalytic, and chemical applications because of their low density and high mesoporosity. However, their inherent fragility has restricted use of aerogel monoliths to applications where they are not subject to any load. We have previously reported cross-linking the mesoporous silica structure of aerogels with di-isocyanates, styrenes or epoxies reacting with amine decorated silica surfaces. These approaches have been shown to significantly increase the strength of aerogels with only a small effect on density or porosity. Though density is a prime predictor of properties such as strength and thermal conductivity for aerogels, it is becoming clear from previous studies that varying the silica backbone and size of the polymer cross-link independently can give rise to combinations of properties which cannot be predicted from density alone. Herein, we examine the effects of four processing parameters for producing this type of polymer cross-linked aerogel on properties of the resulting monoliths. We focus on the results of C-13 CP-MAS NMR which gives insight to the size and structure of polymer cross-link present in the monoliths, and relates the size of the cross-links to microstructure, mechanical properties and other characteristics of the materials obtained.

  1. Structure-Property Relationships in Porous 3-D Nanostructures as a Function of Preparation Conditions: Isocyanate Cross-Linked Silica Aerogels

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Capadona, Lynn A.; McCorkle, Linda; Papadopoulos, Demetrios S.; Leventis, Nicholas

    2007-01-01

    Sol-gel derived silica aerogels are attractive candidates for many unique thermal, optical, catalytic, and chemical applications because of their low density and high mesoporosity. However, their inherent fragility has restricted use of aerogel monoliths to applications where they are not subject to any load. We have previously reported cross-linking the mesoporous silica structure of aerogels with di-isocyanates, styrenes or epoxies reacting with amine decorated silica surfaces. These approaches have been shown to significantly increase the strength of aerogels with only a small effect on density or porosity. Though density is a prime predictor of properties such as strength and thermal conductivity for aerogels, it is becoming clear from previous studies that varying the silica backbone and size of the polymer cross-link independently can give rise to combinations of properties which cannot be predicted from density alone. Herein, we examine the effects of four processing parameters for producing this type of polymer cross-linked aerogel on properties of the resulting monoliths. We focus on the results of 13C CP-MAS NMR which gives insight to the size and structure of polymer cross-link present in the monoliths, and relates the size of the cross-links to microstructure, mechanical properties and other characteristics of the materials obtained.

  2. Investigation into the diffusion and oxidation behavior of the interface between a plasma-sprayed anode and a porous steel support for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Zhang, Shan-Lin; Li, Cheng-Xin; Li, Chang-Jiu; Liu, Meilin; Yang, Guan-Jun

    2016-08-01

    Porous metal-supported solid oxide fuel cells (SOFCs) have attracted much attention because their potential to dramatically reduce the cost while enhancing the robustness and manufacturability. In particular, 430 ferritic steel (430L) is one of the popular choice for SOFC support because of its superior performance and low cost. In this study, we investigate the oxidation and diffusion behavior of the interface between a Ni-based anode and porous 430L support exposed to a humidified (3% H2O) hydrogen atmosphere at 700 °C. The Ni-GDC (Ce0.8Gd0.2O2-δ) cermet anodes are deposited on the porous 430L support by atmospheric plasma spraying (APS). The effect of exposure time on the microstructure and phase structure of the anode and the supports is studied and the element diffusion across the support/anode interface is characterized. Results indicate that the main oxidation product of the 430L support is Cr2O3, and that Cr and Fe will diffuse to the anode and the diffusion thickness increases with the exposure time. The diffusion thickness of Cr and Fe reach about 5 and 2 μm, respectively, after 1000 h exposure. However, the element diffusion and oxidation has little influence on the area-specific resistance, indicating that the porous 430L steel and plasma sprayed Ni-GDC anode are promising for durable SOFCs.

  3. Mesoporous Silica Nanoparticle-Supported Lipid Bilayers (Protocells) for Active Targeting and Delivery to Individual Leukemia Cells.

    PubMed

    Durfee, Paul N; Lin, Yu-Shen; Dunphy, Darren R; Muñiz, Ayşe J; Butler, Kimberly S; Humphrey, Kevin R; Lokke, Amanda J; Agola, Jacob O; Chou, Stanley S; Chen, I-Ming; Wharton, Walker; Townson, Jason L; Willman, Cheryl L; Brinker, C Jeffrey

    2016-09-27

    Many nanocarrier cancer therapeutics currently under development, as well as those used in the clinical setting, rely upon the enhanced permeability and retention (EPR) effect to passively accumulate in the tumor microenvironment and kill cancer cells. In leukemia, where leukemogenic stem cells and their progeny circulate within the peripheral blood or bone marrow, the EPR effect may not be operative. Thus, for leukemia therapeutics, it is essential to target and bind individual circulating cells. Here, we investigate mesoporous silica nanoparticle (MSN)-supported lipid bilayers (protocells), an emerging class of nanocarriers, and establish the synthesis conditions and lipid bilayer composition needed to achieve highly monodisperse protocells that remain stable in complex media as assessed in vitro by dynamic light scattering and cryo-electron microscopy and ex ovo by direct imaging within a chick chorioallantoic membrane (CAM) model. We show that for vesicle fusion conditions where the lipid surface area exceeds the external surface area of the MSN and the ionic strength exceeds 20 mM, we form monosized protocells (polydispersity index <0.1) on MSN cores with varying size, shape, and pore size, whose conformal zwitterionic supported lipid bilayer confers excellent stability as judged by circulation in the CAM and minimal opsonization in vivo in a mouse model. Having established protocell formulations that are stable colloids, we further modified them with anti-EGFR antibodies as targeting agents and reverified their monodispersity and stability. Then, using intravital imaging in the CAM, we directly observed in real time the progression of selective targeting of individual leukemia cells (using the established REH leukemia cell line transduced with EGFR) and delivery of a model cargo. Overall, we have established the effectiveness of the protocell platform for individual cell targeting and delivery needed for leukemia and other disseminated disease. PMID:27419663

  4. Mesoporous Silica Nanoparticle-Supported Lipid Bilayers (Protocells) for Active Targeting and Delivery to Individual Leukemia Cells.

    PubMed

    Durfee, Paul N; Lin, Yu-Shen; Dunphy, Darren R; Muñiz, Ayşe J; Butler, Kimberly S; Humphrey, Kevin R; Lokke, Amanda J; Agola, Jacob O; Chou, Stanley S; Chen, I-Ming; Wharton, Walker; Townson, Jason L; Willman, Cheryl L; Brinker, C Jeffrey

    2016-09-27

    Many nanocarrier cancer therapeutics currently under development, as well as those used in the clinical setting, rely upon the enhanced permeability and retention (EPR) effect to passively accumulate in the tumor microenvironment and kill cancer cells. In leukemia, where leukemogenic stem cells and their progeny circulate within the peripheral blood or bone marrow, the EPR effect may not be operative. Thus, for leukemia therapeutics, it is essential to target and bind individual circulating cells. Here, we investigate mesoporous silica nanoparticle (MSN)-supported lipid bilayers (protocells), an emerging class of nanocarriers, and establish the synthesis conditions and lipid bilayer composition needed to achieve highly monodisperse protocells that remain stable in complex media as assessed in vitro by dynamic light scattering and cryo-electron microscopy and ex ovo by direct imaging within a chick chorioallantoic membrane (CAM) model. We show that for vesicle fusion conditions where the lipid surface area exceeds the external surface area of the MSN and the ionic strength exceeds 20 mM, we form monosized protocells (polydispersity index <0.1) on MSN cores with varying size, shape, and pore size, whose conformal zwitterionic supported lipid bilayer confers excellent stability as judged by circulation in the CAM and minimal opsonization in vivo in a mouse model. Having established protocell formulations that are stable colloids, we further modified them with anti-EGFR antibodies as targeting agents and reverified their monodispersity and stability. Then, using intravital imaging in the CAM, we directly observed in real time the progression of selective targeting of individual leukemia cells (using the established REH leukemia cell line transduced with EGFR) and delivery of a model cargo. Overall, we have established the effectiveness of the protocell platform for individual cell targeting and delivery needed for leukemia and other disseminated disease.

  5. Automated oligonucleotide solid-phase synthesis on nanosized silica particles using nano-on-micro assembled particle supports.

    PubMed

    Farre, Carole; Lansalot, Muriel; Bazzi, Rana; Roux, Stéphane; Marquette, Christophe A; Catanante, Gaëlle; Blum, Loïc J; Charvet, Nicolas; Louis, Cédric; Chaix, Carole

    2010-04-01

    This article describes an original strategy to enable solid-phase oligodeoxyribonucleotide (ODN) synthesis on nanosized silica particles. It consists of the reversible immobilization of silica nanoparticles (NPs) on micrometric silica beads. The resulting assemblies, called nano-on-micro (NOM) systems, are well adapted to ODN synthesis in an automated instrument. First, NPs are derivatized with OH functions. For NOM assembly preparation, these functions react with the silanols of the microbeads under specific experimental conditions. Furthermore, OH groups allow ODN synthesis on the nanoparticles via phosphoramidite chemistry. The stability of the NOM assemblies during ODN solid-phase synthesis is confirmed by scanning and transmission electron microscopy (SEM and TEM, respectively), together with dynamic light scattering analyses. Then, the release of ODN-functionalized nanoparticles is performed under mild conditions (1% NH(4)OH in water, 1 h, 60 degrees C). Our technique provides silica nanoparticles well functionalized with oligonucleotides, as demonstrated by hybridization experiments conducted with the cDNA target.

  6. A novel processing approach for free-standing porous non-oxide ceramic supports from polycarbosilane and polysilazane precursors

    PubMed Central

    Konegger, Thomas; Patidar, Rajesh; Bordia, Rajendra K.

    2015-01-01

    In this contribution, a low-pressure/low-temperature casting technique for the preparation of novel free-standing macrocellular polymer-derived ceramic support structures is presented. Preceramic polymers (polycarbosilane and poly(vinyl)silazane) are combined with sacrificial porogens (ultra-high molecular weight polyethylene microbeads) to yield porous ceramic materials in the Si—C or Si—C—N systems, exhibiting well-defined pore structures after thermal conversion. The planar-disc-type specimens were found to exhibit biaxial flexural strengths of up to 60 MPa. In combination with their observed permeability characteristics, the prepared structures were found to be suitable for potential applications in filtration, catalysis, or membrane science. PMID:26339126

  7. Silica, hybrid silica, hydride silica and non-silica stationary phases for liquid chromatography.

    PubMed

    Borges, Endler M

    2015-04-01

    Free silanols on the surface of silica are the "villains", which are responsible for detrimental interactions of those compounds and the stationary phase (i.e., bad peak shape, low efficiency) as well as low thermal and chemical stability. For these reasons, we began this review describing new silica and hybrid silica stationary phases, which have reduced and/or shielded silanols. At present, in liquid chromatography for the majority of analyses, reversed-phase liquid chromatography is the separation mode of choice. However, the needs for increased selectivity and increased retention of hydrophilic bases have substantially increased the interest in hydrophilic interaction chromatography (HILIC). Therefore, stationary phases and this mode of separation are discussed. Then, non-silica stationary phases (i.e., zirconium oxide, titanium oxide, alumina and porous graphitized carbon), which afford increased thermal and chemical stability and also selectivity different from those obtained with silica and hybrid silica, are discussed. In addition, the use of these materials in HILIC is also reviewed.

  8. Infrared study of the adsorption and reaction of methyl chloride and methyl iodide on silica-supported Pt catalysts

    SciTech Connect

    McGee, K.C.; Driessen, M.D.; Grassian, V.H.

    1996-03-01

    The low-temperature adsorption of methyl chloride and methyl iodide on silica-supported Pt catalysts has been investigated by transmission Fourier transform infrared spectroscopy. The IR data show that methyl chloride and methyl iodide dissociate at low temperatures (near 200 K) to form an adsorbed hydrocarbon fragment on the surface, identified as methyl groups. Methyl groups are characterized by a single infrared absorption band near 2965 cm{sup -1}. Methyl groups react with hydrogen to form gas-phase methane as the sample is warmed between 200 and 473 K. Reaction of approximately 10 Torr of methyl chloride at 473 K over a Pt/SiO{sub 2} catalyst shows that only 20% of the methyl chloride decomposes to form gas-phase methane and hydrogen chloride in the absence of hydrogen. However, in the presence of an equal amount of hydrogen, all of the methyl chloride is converted to methane and hydrogen chloride. In contrast to the quantitative conversion of methyl chloride, less than 10% of the initial 10 Torr of methyl iodide forms methane at 473 K and no hydrogen iodide forms in the presence or absence of hydrogen gas. Although the activation barrier for C-Cl bond dissociation in adsorbed methyl chloride is higher than the barrier for C-I bond dissociation in adsorbed methyl iodide, the lower energy barrier for removal of adsorbed chlorine compared to adsorbed iodine is the cause of the higher catalytic activity of Pt/SiO{sub 2} toward methyl chloride decomposition. In addition to the thermal decomposition of CH{sub 3}Cl, the authors have investigated the possibility of using solar radiation for the decomposition of CH{sub 3}Cl on Pt/SiO{sub 2}. The results for the photo-assisted decomposition of CH{sub 3}Cl adsorbed on Pt/SiO{sub 2} are presented and discussed. 39 refs., 12 figs., 3 tabs.

  9. TiO{sub 2} supported on rod-like mesoporous silica SBA-15: Preparation, characterization and photocatalytic behaviour

    SciTech Connect

    Li, Yanjuan; Li, Nan; Tu, Jinchun; Li, Xiaotian; Wang, Beibei; Chi, Yue; Liu, Darui; Yang, Dianfan

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer Rod-like SBA-15 and normal SBA-15 were used to prepare TiO{sub 2}/SBA-15 composites. Black-Right-Pointing-Pointer TiO{sub 2}/SBA-15 composites were studied as catalysts for methyl orange photodegradation. Black-Right-Pointing-Pointer TiO{sub 2}/Rod-SBA-15 exhibited higher photocatalytic activity than TiO{sub 2}/Nor-SBA-15. Black-Right-Pointing-Pointer The higher catalytic activity was a result of the controlled morphology of SBA-15. -- Abstract: TiO{sub 2} nanoparticles have been successfully incorporated in the pores of mesoporous silica SBA-15 with different morphologies by a wet impregnation method. The composites were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma (ICP) emission spectroscopy, transmission electron microscopy (TEM), N{sub 2}-sorption and UV-Vis diffuse reflectance spectroscopy. The photodegradation of methyl orange (MO) was used to study their photocatalytic property. It is indicated that the morphology of SBA-15 had a great influence on the photocatalytic activity of the composites. When TiO{sub 2}/SBA-15 composite was prepared by loading TiO{sub 2} nanoparticles on uniform rod-like SBA-15 of 1 {mu}m length, it showed higher photocatalytic degradation rate than that on less regular but much larger SBA-15 support. This difference was rationalized in terms of the homogeneously distributed and shorter channels of rod-like SBA-15, which favored mass transport and improved the efficient utilization of the pore surface.

  10. Fabrication of self-supporting porous silicon membranes and tuning transport properties by surface functionalization

    NASA Astrophysics Data System (ADS)

    Velleman, Leonora; Shearer, Cameron James; Ellis, Amanda Vera; Losic, Dusan; Voelcker, Nicolas Hans; Shapter, Joseph George

    2010-09-01

    This study presents a simple approach to perform selective mass transport through freestanding porous silicon (pSi) membranes. pSi membranes were fabricated by the electrochemical etching of silicon to produce membranes with controlled structure and pore sizes close to molecular dimensions (~12 nm in diameter). While these membranes are capable of size-exclusion based separations, chemically specific filtration remains a great challenge especially in the biomedical field. Herein, we investigate the transport properties of chemically functionalized pSi membranes. The membranes were functionalized using silanes (heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethylchlorosilane (PFDS) and N-(triethoxysilylpropyl)-o-polyethylene oxide urethane (PEGS) to give membranes hydrophobic (PFDS) and hydrophilic (PEGS) properties. The transport of probe dyes tris(2,2'-bipyridyl)dichlororuthenium(ii) hexahydrate (Rubpy) and Rose Bengal (RB) through these functionalized membranes was examined to determine the effect surface functionalization has on the selectivity and separation ability of pSi membranes. This study provides the basis for further investigation into more sophisticated surface functionalization and coupled with the biocompatibility of pSi will lead to new advances in membrane based bio-separations.

  11. High speed immuno-affinity chromatography on supports with gigapores and porous glass.

    PubMed

    Schuste, M; Wasserbauer, E; Neubauer, A; Jungbauer, A

    2000-01-01

    Immuno-affinity chromatography exploiting the Ca2+ dependent interaction of the anti-Flag antibody and Flag-tagged proteins has been investigated. The antibody has been immobilized on porous glass beads (Prosep) containing gigapores and on a monolith, the polymethacrylate based Convective Interactive Media (CIM) column at a ligand density of 2 mg/g and 10 mg/ml respectively. The performance of the columns was assessed by applying clarified yeast culture supernatant containing overexpressed Flag-human serum albumin. Dynamic binding capacity and purity was checked at various flow rates ranging from 100 cm/h to 800 cm/h. 95% purity could be obtained. Anti Flag-CIM columns showed a higher unspecific adsorption, requiring a longer wash cycle to obtain the same purity compared to the Prosep column. Anti Flag-CIM columns showed a flow independent performance, which is explained by its monolithic structure. A decreasing dynamic binding capacity with flow was observed with anti-Flag-Prosep columns. Both columns are suited to purify milligrams of protein out of a yeast culture supernatant within a few minutes. We considered them as promising candidates for high throughput screening, where fast purification is a necessity.

  12. New reversed-phase/anion-exchange/hydrophilic interaction mixed-mode stationary phase based on dendritic polymer-modified porous silica.

    PubMed

    Li, Yun; Yang, Jiajia; Jin, Jing; Sun, Xiaoli; Wang, Longxing; Chen, Jiping

    2014-04-11

    A novel dendritic polymer-modified silica (DPS) stationary phase was prepared by a divergent synthesis scheme starting from propylamine on silica by consecutive amine-epoxy reactions with 1,4-butanedioldiglycidyl ether and aniline. Both elemental analysis and infrared spectra data shows the successful growth of dendritic polymer on silica particles. The carbon and nitrogen contents increased with an increasing number of reaction cycles and achieved 25.2% and 2.1% (w/w) after 11 reaction cycles. The combination of a phenyl ring with a quaternary ammonium, or a tertiary amine at the branch point along with embedded polar functionalities (including ether and hydroxyl groups) in the branch, generated hydrophobic, electrostatic, as well as hydrophilic interactive domains. Depending on solute structure and mobile phase composition, the DPS stationary phase provided multiple retention mechanisms, including reversed phase (RP), anion-exchange (AEX), and hydrophilic interactions. The RP capability achieved separation of polycyclic aromatic hydrocarbons. Basic, neutral and acidic molecules were well separated under RP/AEX mixed mode. Effective separation of small polar compounds (such as nucleobases and nucleosides) was also obtained under hydrophilic interaction liquid chromatography (HILIC) mode. PMID:24630062

  13. Hydrogenated uniform Pt clusters supported on porous CaMnO(3) as a bifunctional electrocatalyst for enhanced oxygen reduction and evolution.

    PubMed

    Han, Xiaopeng; Cheng, Fangyi; Zhang, Tianran; Yang, Jingang; Hu, Yuxiang; Chen, Jun

    2014-04-01

    Hydrogenated uniform Pt clusters supported on porous CaMnO3 nanocomposites are synthesized and investigated as a new electrocatalytic material for oxygen reduction and evolution reactions. Due to the synergistic effect of Pt and CaMnO3, the nanocomposites exhibit superior activity and durability to the benchmark Pt/C catalyst.

  14. Effects of porogen and cross-linking agents on improved properties of silica-supported macroporous chitosan membranes for enzyme immobilization.

    PubMed

    Yang, Wen-Yi; Thirumavalavan, Munusamy; Lee, Jiunn-Fwu

    2015-04-01

    A series of silica-supported macroporous chitosan membranes (CM15, CM20, and CM25) was prepared by varying the ratio of 70-230-μm-sized silica particles. These synthesized membranes were further cross-linked using different cross-linking agents for covalent immobilization of biological macromolecules especially enzymes and in this study, Bovine serum albumin and laccase. Effects of silica particle and cross-linking agents on their flow rates, surface properties, and chemical and biological properties were explored. Pore size of as-synthesized membranes was 0.1192, 0.1268, and 0.1623 μm, respectively, for CM15, CM20, and CM25. The effect of various parameters such as temperature and pH on the relative activity of both free and immobilized enzymes was studied in details. The relative enzyme activity upon immobilization was greatly enhanced several folds of its original activity. The stability of enzymes over a range of temperature and pH was significantly improved by immobilization. The optimum temperature and pH were determined to be 50 °C and pH 3, respectively, for both the free and the immobilized enzymes. The immobilized enzyme possessed good operational stability and reusability properties that support its potentiality for practical applications. Among three membranes, CM25 is confirmed to be efficient candidate due to its improved characteristics. PMID:25432857

  15. Diesel spray interaction with highly porous structures for supporting of liquid distribution in space and its vaporization

    NASA Astrophysics Data System (ADS)

    Weclas, M.; Cypris, J.; Maksoud, T. M. A.

    2012-05-01

    If a free high velocity jet (Diesel spray) propagating in space outwards of the nozzle exit collides (impinges onto) with highly porous structure (PM) the results of such an interaction is characterized by significant radial spreading of the spray, reduced axial penetration length, significantly increase spray surface area, reduced propagating velocity after interaction with PM and enhanced vaporization if the porous structure is hot. Due to those effects a very quick spray distribution in space is observed. This effect can, for example, be used for mixture homogenization for a clean combustion process. The rapid radial spreading of the spray by interaction with a porous structure is a result of multi-jet splitting. To some extent, Diesel jet interaction with a three-dimensional porous structure could be simulated by jet interaction with small cylindrical obstacles simulating wall junctions of a real porous medium. Based on the principles of spray interaction with porous structure there are two different cases to be considered: 1-porous medium in the form of thin ring positioned around the fuel nozzle (called distribution nozzle); 2-porous medium in the form of three-dimensional volumetric reactor. In the case of the distribution nozzle the target is to distribute fuel in space outside the porous ring and to enhance the vaporization process. In the case of combustion reactor the spray interacts with a number of wall junctions inside the porous structure and the main target is to homogeneously distribute the spray in PM volume, to evaporate the fuel and to mix with combustion air. The jets leaving diesel nozzle very early interact with porous ring resulting in a shining-like fuel distribution in space: for a cold ring a multi-jet splitting is responsible for observed fuel distribution in space; for a hot porous ring a superposition of fuel distribution and fuel vaporization must be considered.

  16. Molecular sieving silica membrane fabrication process

    DOEpatents

    Raman, N.K.; Brinker, C.J.

    1999-08-10

    A process is described for producing a molecular sieve silica membrane comprising depositing a hybrid organic-inorganic polymer comprising at least one organic constituent and at least one inorganic constituent on a porous substrate material and removing at least a portion of the at least one organic constituent of the hybrid organic-inorganic polymer, forming a porous film. 11 figs.

  17. Molecular sieving silica membrane fabrication process

    DOEpatents

    Raman, Narayan K.; Brinker, Charles Jeffrey

    1999-01-01

    A process for producing a molecular sieve silica membrane comprising depositing a hybrid organic-inorganic polymer comprising at least one organic constituent and at least one inorganic constituent on a porous substrate material and removing at least a portion of the at least one organic constituent of the hybrid organic-inorganic polymer, forming a porous film.

  18. Molecular sieving silica membrane fabrication process

    DOEpatents

    Raman, Narayan K.; Brinker, Charles Jeffrey

    1998-01-01

    A process for producing a molecular sieve silica membrane comprising depositing a hybrid organic-inorganic polymer comprising at least one organic constituent and at least one inorganic constituent on a porous substrate material and removing at least a portion of the at least one organic constituent of the hybrid organic-inorganic polymer, forming a porous film.

  19. Endurance Evaluation of Sintered, Porous, Strut-Supported Turbine Blades made by Federal-Mogul-Bower-Bearings, Incorporated, under Bureau of Aeronautics Contract NOas 55-124-C

    NASA Technical Reports Server (NTRS)

    Hickel, Robert O.; Richards, Hadley T.

    1957-01-01

    Four strut-supported, transpiration-cooled turbine blades were investigated experimentally in a turbojet engine. The blade shells were fabricated by the mold-sintering method with spherical stainless-steel powder. Two blades were investigated in order to evolve suitable capping methods for the blade tip. Two other blades were used to evaluate the durability of the porous-shell material. The blades were investigated at a turbine-tip speed of 1305 feet per second, an average turbine-inlet temperature of about 1670 F, and at a porous-shell temperature limited to a maximum of approximately 1040 F.

  20. One-pot synthesis of magnetically recyclable mesoporous silica supported acid-base catalysts for tandem reactions.

    PubMed

    Jun, Samuel Woojoo; Shokouhimehr, Mohammadreza; Lee, Dong Jun; Jang, Youngjin; Park, Jinkyung; Hyeon, Taeghwan

    2013-09-14

    We report one-pot synthesis of magnetically recyclable mesoporous silica catalysts for tandem acid-base reactions. The catalysts could be easily recovered from the reaction mixture using a magnet, and the pore size of the catalysts could be controlled by introducing a swelling agent, resulting in the significant enhancement of the reaction rate.

  1. Effect of the porous structure of the support on hydrocarbon distribution in the Fischer-Tropsch reaction

    NASA Astrophysics Data System (ADS)

    Bartolini, Monica; Molina, Jhoanna; Alvarez, Juan; Goldwasser, Mireya; Pereira Almao, Pedro; Zurita, M. Josefina Pérez

    2015-07-01

    Emissions standards are increasingly stringent due mainly to its impact on the environment. Although the diesel engine is an attractive solution for carbon dioxide reduction, a challenge remains to simultaneously control nitrogen oxides and matter particulate emissions to accepted levels. On engine tests, it has been observed that Fischer-Tropsch diesel significantly reduces CO, HC, PAHs and particulate emissions compared to oil derived diesel. However, selectivity control in Fischer Tropsch Synthesis is still a key challenge due the Anderson-Schultz-Flory polymerization mechanism followed by hydrocarbon distribution. In this work we are presenting the first steps towards a new strategy that can tune, in one step, the selectivity to desired products by taking advantage of the shape selectivity properties of SBA-15 mesoporous silica used as support. Co-SBA-15 (30%wt) catalysts with different pore size were prepared by excess solution impregnation. Our results show that pore diameter not only affects the size and reducibility of Co particles but it also significantly influence the liquid products distribution, with the high molecular weight hydrocarbon fraction increasing on large pores, attributed to the existence of a shape selectivity effect induced by the textural properties of the catalyst namely its pore size and pore volume.

  2. Effect of the support and the reduction temperature on the formation of metallic nickel phase in Ni/silica gel precursors of vegetable oil hydrogenation catalysts

    NASA Astrophysics Data System (ADS)

    Gabrovska, M.; Krstić, J.; Tzvetkov, P.; Tenchev, K.; Shopska, M.; Vukelić, N.; Jovanović, D.

    2011-12-01

    Ni/SiO2 materials with identical composition (SiO2/Ni = 1.0) have been synthesized by precipitation of Ni(NO3)2 · 6H2O solution with Na2CO3 solution on the silica gel, obtained at three different pH values. The present investigation was undertaken in an endeavor to study the effects of the silica gel support type and the reduction temperature on the formation and dispersion of the metallic nickel phase in the reduced Ni/SiO2 precursors of the vegetable oil hydrogenation catalyst. The physicochemical characterization of the unreduced and reduced precursors has been accomplished appropriately by powder X-ray diffraction, infrared spectroscopy, temperature programmed reduction and H2-chemisorption techniques. It can be stated that the texture peculiarities of the silica gels used as supports influence on the crystalline state and distribution of the deposited Ni-containing phases during the preparation of the precursors, on the reduction temperature of the investigated solids as well as on the bulk size and surface dispersion of the arising metallic nickel particles. It was shown that two types of Ni2+-species are formed during the synthesis procedure, namely basic nickel carbonate-like and Ni-phyllosilicate with different extent of presence, location and strength of interaction. The different location of these species is supposed to result in various strength of Ni-O and Ni-O-Si interaction, thus determining the overall reducibility of the precursors. It was specified that the Ni2+-species are strongly bonded to the surface of the silica gel obtained at neutral pH value and weakly bonded to the surface of those prepared in acidic and alkaline conditions. It was established that the precursor, derivates from the silica gel obtained at alkaline conditions, demonstrates both significant reduction of the Ni2+ ions at 430°C and finely dispersed metallic nickel particles on its surface. High dispersion of the metallic nickel might be the crucial reason for achieving of

  3. Silica-Supported Cationic Gold(I) Complexes as Heterogeneous Catalysts for Regio- and Enantioselective Lactonization Reactions.

    PubMed

    Shu, Xing-Zhong; Nguyen, Son C; He, Ying; Oba, Fadekemi; Zhang, Qiao; Canlas, Christian; Somorjai, Gabor A; Alivisatos, A Paul; Toste, F Dean

    2015-06-10

    An efficient method for the synthesis of heterogeneous gold catalysts has been developed. These catalysts were easily assembled from readily available silica materials and gold complexes. The heterogeneous catalysts exhibited superior reactivity in various reactions where protodeauration is the rate-limiting step. Dramatic enhancement in regio- and enantioselectivity was observed when compared to the homogeneous unsupported gold catalyst. The catalysts are easily recovered and recycled up to 11 times without loss of enantioselectivity. PMID:26023883

  4. Laser 3D printing with sub-microscale resolution of porous elastomeric scaffolds for supporting human bone stem cells.

    PubMed

    Petrochenko, Peter E; Torgersen, Jan; Gruber, Peter; Hicks, Lucas A; Zheng, Jiwen; Kumar, Girish; Narayan, Roger J; Goering, Peter L; Liska, Robert; Stampfl, Jürgen; Ovsianikov, Aleksandr

    2015-04-01

    A reproducible method is needed to fabricate 3D scaffold constructs that results in periodic and uniform structures with precise control at sub-micrometer and micrometer length scales. In this study, fabrication of scaffolds by two-photon polymerization (2PP) of a biodegradable urethane and acrylate-based photoelastomer is demonstrated. This material supports 2PP processing with sub-micrometer spatial resolution. The high photoreactivity of the biophotoelastomer permits 2PP processing at a scanning speed of 1000 mm s(-1), facilitating rapid fabrication of relatively large structures (>5 mm(3)). These structures are custom printed for in vitro assay screening in 96-well plates and are sufficiently flexible to enable facile handling and transplantation. These results indicate that stable scaffolds with porosities of greater than 60% can be produced using 2PP. Human bone marrow stromal cells grown on 3D scaffolds exhibit increased growth and proliferation compared to smooth 2D scaffold controls. 3D scaffolds adsorb larger amounts of protein than smooth 2D scaffolds due to their larger surface area; the scaffolds also allow cells to attach in multiple planes and to completely infiltrate the porous scaffolds. The flexible photoelastomer material is biocompatible in vitro and is associated with facile handling, making it a viable candidate for further study of complex 3D-printed scaffolds.

  5. Numerical analysis of electrochemical characteristics and heat/species transport for planar porous-electrode-supported SOFC

    NASA Astrophysics Data System (ADS)

    Wang, Yuzhang; Yoshiba, Fumihiko; Watanabe, Takao; Weng, Shilie

    In this work, a fully three-dimensional mathematical model for planar porous-electrode-supported (PES) solid oxide fuel cell (SOFC) has been constructed to simulate the steady state electrochemical characteristics and multi-species/heat transport. The variation of chemical species concentrations, temperature, potential, current and current density for two types of PES-SOFC developed by central research institute of electric power industry (CRIEPI) of Japan are studied in the co-flow pattern. In the numerical computation, the governing equations for continuity, momentum, mass, energy and electrical charge conservation are solved simultaneously using the finite volume method. Activation, ohmic, and concentration polarizations are considered as the main sources of irreversibility. The Butler-Volmer equation, Ohm's law, and Darcy's gas model with constant porosity and permeability are used to determine the polarization over-potential, respectively. The output voltages measured in experiments and calculated using the above models agree well. For the cell using the same material and manufacturing process, the results show the type-II PES-SOFC is with better performance. However, the electrolyte of type-II PES-SOFC should be with higher maximum ionic conductivity. Furthermore, these results will be used to evaluate the overall performance of a PES-SOFC stack, and to significantly help optimize their design and operation in practical applications.

  6. A Silica-Supported Iron Oxide Catalyst Capable of Activating Hydrogen Peroxide at Neutral pH Values

    PubMed Central

    Pham, Anh Le-Tuan; Lee, Changha; Doyle, Fiona M.; Sedlak, David L.

    2009-01-01

    Iron oxides catalyze the conversion of hydrogen peroxide (H2O2) into oxidants capable of transforming recalcitrant contaminants. Unfortunately, the process is relatively inefficient at circumneutral pH values due to competing reactions that decompose H2O2 without producing oxidants. Silica- and alumina-containing iron oxides prepared by sol-gel processing of aqueous solutions containing Fe(ClO4)3, AlCl3 and tetraethyl orthosilicate efficiently catalyzed the decomposition of H2O2 into oxidants capable of transforming phenol at circumneutral pH values. Relative to hematite, goethite and amorphous FeOOH, the silica-iron oxide catalyst exhibited a stoichiometric efficiency, defined as the number of moles of phenol transformed per mole of H2O2 consumed, that was 10 to 40 times higher than that of the iron oxides. The silica-alumina-iron oxide catalyst had a stoichiometric efficiency that was 50 to 80 times higher than that of the iron oxides. The significant enhancement in oxidant production is attributable to the interaction of Fe with Al and Si in the mixed oxides, which alters the surface redox processes, favoring the production of strong oxidants during H2O2 decomposition. PMID:19943668

  7. Synthesis of sulfated titania supported on mesoporous silica using direct impregnation and its application in esterification of acetic acid and n-butanol

    NASA Astrophysics Data System (ADS)

    Wang, Yuhong; Gan, Yunting; Whiting, Roger; Lu, Guanzhong

    2009-09-01

    A new method has been developed for the preparation of sulfated titania (S-TiO 2) supported on mesoporous silica. The use of direct exchange of metal containing precursors for the surfactants in the as-synthesized MCM-41 substrate produced a product with high sulfur content without serious blockage of the pore structure of MCM-41. The pore sizes and volumes of the resultant S-TiO 2/MCM-41 composites were found to vary markedly with the loading of TiO 2. The strong acidic character of the composites obtained was examined by using them as catalysts for the esterification of acetic acid and n-butanol.

  8. Transport of carbon colloid supported nanoscale zero-valent iron in porous media

    NASA Astrophysics Data System (ADS)

    Busch, Jan; Oswald, Sascha

    2013-04-01

    carbon supported nZVI under environmental relevant conditions. Carbo-Iron might be helpful to deliver nZVI into contaminated aquifers. There 1D and 2D results support the design of a field test and application of Carbo-Iron for nZVI delivery.

  9. Tungsten carbide/porous carbon composite as superior support for platinum catalyst toward methanol electro-oxidation

    SciTech Connect

    Jiang, Liming; Fu, Honggang; Wang, Lei; Mu, Guang; Jiang, Baojiang; Zhou, Wei; Wang, Ruihong

    2014-01-01

    Graphical abstract: The WC nanoparticles are well dispersed in the carbon matrix. The size of WC nanoparticles is about 30 nm. It can be concluded that tungsten carbide and carbon composite was successfully prepared by the present synthesis conditions. - Highlights: • The WC/PC composite with high specific surface area was prepared by a simple way. • The Pt/WC/PC catalyst has superior performance toward methanol electro-oxidation. • The current density for methanol electro-oxidation is as high as 595.93 A g{sup −1} Pt. • The Pt/WC/PC catalyst shows better durability and stronger CO electro-oxidation. • The performance of Pt/WC/PC is superior to the commercial Pt/C (JM) catalyst. - Abstract: Tungsten carbide/porous carbon (WC/PC) composites have been successfully synthesized through a surfactant assisted evaporation-induced-assembly method, followed by a thermal treatment process. In particular, WC/PC-35-1000 composite with tungsten content of 35% synthesized at the carbonized temperature of 1000 °C, exhibited a specific surface area (S{sub BET}) of 457.92 m{sup 2} g{sup −1}. After loading Pt nanoparticles (NPs), the obtained Pt/WC/PC-35-1000 catalyst exhibits the highest unit mass electroactivity (595.93 A g{sup −1} Pt) toward methanol electro-oxidation, which is about 2.6 times as that of the commercial Pt/C (JM) catalyst. Furthermore, the Pt/WC/PC-35-1000 catalyst displays much stronger resistance to CO poisoning and better durability toward methanol electrooxidation compared with the commercial Pt/C (JM) catalyst. The high electrocatalytic activity, strong poison-resistivity and good stability of Pt/WC/PC-35-1000 catalyst are attributed to the porous structures and high specific surface area of WC/PC support could facilitate the rapid mass transportation. Moreover, synergistic effect between WC and Pt NPs is favorable to the higher catalytic performance.

  10. Development of a bi-functional silica monolith for electro-osmotic pumping and DNA clean-up/extraction using gel-supported reagents in a microfluidic device.

    PubMed

    Oakley, Jennifer A; Shaw, Kirsty J; Docker, Peter T; Dyer, Charlotte E; Greenman, John; Greenway, Gillian M; Haswell, Stephen J

    2009-06-01

    A silica monolith used to support both electro-osmotic pumping (EOP) and the extraction/elution of DNA coupled with gel-supported reagents is described. The benefits of the combined EOP extraction/elution system were illustrated by combining DNA extraction and gene amplification using the polymerase chain reaction (PCR) process. All the reagents necessary for both processes were supported within pre-loaded gels that allow the reagents to be stored at 4 degrees C for up to four weeks in the microfluidic device. When carrying out an analysis the crude sample only needed to be hydrodynamically introduced into the device which was connected to an external computer controlled power supply via platinum wire electrodes. DNA was extracted with 65% efficiency after loading lysed cells onto a silica monolith. Ethanol contained within an agarose gel matrix was then used to wash unwanted debris away from the sample by EOP (100 V cm(-1) for 5 min). The retained DNA was subsequently eluted from the monolith by water contained in a second agarose gel, again by EOP using an electric field of 100 V cm(-1) for 5 min, and transferred into the PCR reagent containing gel. The eluted DNA in solution was successfully amplified by PCR, confirming that the concept of a complete self-contained microfluidic device could be realised for DNA sample clean up and amplification, using a simple pumping and on-chip reagent storage methodology.

  11. Microgravity effects on water supply and substrate properties in porous matrix root support systems.

    PubMed

    Bingham, G E; Jones, S B; Or, D; Podolski, I G; Levinskikh, M A; Sytchov, V N; Ivanova, T; Kostov, P; Sapunova, S; Dandolov, I; Bubenheim, D B; Jahns, G

    2000-12-01

    The control of water content and water movement in granular substrate-based plant root systems in microgravity is a complex problem. Improper water and oxygen delivery to plant roots has delayed studies of the effects of microgravity on plant development and the use of plants in physical and mental life support systems. Our international effort (USA, Russia and Bulgaria) has upgraded the plant growth facilities on the Mir Orbital Station (OS) and used them to study the full life cycle of plants. The Bulgarian-Russian-developed Svet Space Greenhouse (SG) system was upgraded on the Mir OS in 1996. The US developed Gas Exchange Measurement System (GEMS) greatly extends the range of environmental parameters monitored. The Svet-GEMS complex was used to grow a fully developed wheat crop during 1996. The growth rate and development of these plants compared well with earth grown plants indicating that the root zone water and oxygen stresses that have limited plant development in previous long-duration experiments have been overcome. However, management of the root environment during this experiment involved several significant changes in control settings as the relationship between the water delivery system, water status sensors, and the substrate changed during the growth cycles.

  12. Microgravity effects on water supply and substrate properties in porous matrix root support systems

    NASA Technical Reports Server (NTRS)

    Bingham, G. E.; Jones, S. B.; Or, D.; Podolski, I. G.; Levinskikh, M. A.; Sytchov, V. N.; Ivanova, T.; Kostov, P.; Sapunova, S.; Dandolov, I.; Bubenheim, D. B.; Jahns, G.; Campbell, W. F. (Principal Investigator)

    2000-01-01

    The control of water content and water movement in granular substrate-based plant root systems in microgravity is a complex problem. Improper water and oxygen delivery to plant roots has delayed studies of the effects of microgravity on plant development and the use of plants in physical and mental life support systems. Our international effort (USA, Russia and Bulgaria) has upgraded the plant growth facilities on the Mir Orbital Station (OS) and used them to study the full life cycle of plants. The Bulgarian-Russian-developed Svet Space Greenhouse (SG) system was upgraded on the Mir OS in 1996. The US developed Gas Exchange Measurement System (GEMS) greatly extends the range of environmental parameters monitored. The Svet-GEMS complex was used to grow a fully developed wheat crop during 1996. The growth rate and development of these plants compared well with earth grown plants indicating that the root zone water and oxygen stresses that have limited plant development in previous long-duration experiments have been overcome. However, management of the root environment during this experiment involved several significant changes in control settings as the relationship between the water delivery system, water status sensors, and the substrate changed during the growth cycles. c 2001 Published by Elsevier Science Ltd. All rights reserved.

  13. Chemically Layered Porous Solids

    NASA Technical Reports Server (NTRS)

    Koontz, Steve

    1991-01-01

    Aerogels and other porous solids in which surfaces of pores have chemical properties varying with depth below macroscopic surfaces prepared by sequences of chemical treatments. Porous glass or silica bead treated to make two depth zones having different chemical properties. Beads dropped along tube filled with flowing gas containing atomic oxygen, generated in microwave discharge. General class of materials treatable include oxides of aluminum, silicon, zirconium, tin, titanium, and nickel, and mixtures of these oxides. Potential uses of treated materials include chromatographic separations, membrane separations, controlled releases of chemicals, and catalysis.

  14. More sensitive and quantitative proteomic measurements using very low flow rate porous silica monolithic LC columns with electrospray ionization-mass spectrometry

    SciTech Connect

    Luo, Quanzhou; Tang, Keqi; Yang, Feng; Elias, Ayesha; Shen, Yufeng; Moore, Ronald J.; Zhao, Rui; Hixson, Kim K.; Rossie, Sandra S.; Smith, Richard D.

    2006-05-01

    The sensitivity of proteomics measurements using liquid chromatography (LC) separations interfaced with electrospray ionization-mass spectrometry (ESI-MS) improves approximately inversely with liquid flow rate, making attractive the use of smaller inner diameter LC columns. We report the development and initial application of 10 µm i.d. silica-based monolithic LC columns providing more sensitive proteomics measurements. The implementation provides robust performance and suitability for automated proteome analyses due to integration with a micro solid phase extraction pre-column for ease of sample injection and clean-up prior to the reversed phased LC separation. Greater than 10-fold improvement in sensitivity was obtained compared to analyses using more conventional capillary LC, enabling e.g. the identification of >5000 different peptides by MS/MS from 100-ng of a Shewanella oneidensis tryptic digest using an ion trap MS. The low nL/min LC flow rates provide more uniform signal intensities for different peptides, and provided improved quantitative measurements compared to conventional separation systems without the use of internal standards or isotopic labeling. The improved sensitivity allowed LC-MS measurements of immunopurified protein phosphatase 5 that were in good agreement with quantitative western blot analyses.

  15. Well-dispersed platinum nanoparticles supported on hierarchical nitrogen-doped porous hollow carbon spheres with enhanced activity and stability for methanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Jun; Ma, Li; Gan, Mengyu; Yang, Fangfang; Fu, Shenna; Li, Xiao

    2015-08-01

    Hierarchical nitrogen-doped porous hollow carbon spheres (HNPHCS) with porous-thin mesoporous shell and hollow macroporous core structure have been prepared via in-situ oxidation polymerization method using polyaniline as the precursor. After carbonization at 900 °C, the average diameter of HNPHCS is ca. 140 nm with shell thickness of ∼1 nm. Pt nanoparticles with high dispersion and small size have been successfully deposited on the HNPHCS by a microwave-assisted polyol process to synthesize Pt/HNPHCS catalyst. The obtained samples are characterized by physical characterization and electrochemical measurements. Electrochemical studies reveal that the prepared Pt/HNPHCS catalyst possesses notably higher catalytic activity and CO-tolerance, and better stability toward methanol electrooxidation in comparison with Pt/nitrogen-doped porous carbon and the commercial Pt/C catalysts. It is likely that enhanced catalytic properties of the Pt/HNPHCS could be due to the high dispersion of small Pt nanoparticles, the presence of nitrogen species, developed porous-thin mesoporous shell and hollow macroporous core structure of support HNPHCS. As a result, the as-developed Pt/HNPHCS present attractive advantages for the application in fuel cell electrocatalyst.

  16. Catalyst Structure-Performance Relationship Identified by High-Throughput Operando Method: New Insight for Silica-Supported Vanadium Oxide for Methanol Oxidation

    SciTech Connect

    Li, Guosheng; Hu, Dehong; Xia, Guanguang; Zhang, Z Conrad

    2010-02-01

    A prototype high throughput operando reactor, that integrates FT-IR imaging for rapid reaction product analysis and parallel Raman imaging for catalyst characterization, has been designed to accelerate catalyst discovery and, concurrently, fundamental research toward reliable correlations between catalyst active sites and catalyst performance for at-line real catalytic conditions. This reactor, consisting of six parallel reaction channels, is demonstrated for methanol oxidation using silica supported vanadium oxide catalysts at various reaction conditions. The results of semi-quantitative analysis of a large array of operando Raman scattering bands, specifically for C-H bonds in Si-OCH3 and V-OCH3 surface intermediates, obtained simultaneously on multiple catalyst surfaces with a time resolution of 60s for each set at different temperatures, reveal for the first time methanol activation at surface vanadium oxide cluster edge on silica support at lower reaction temperatures, <175°C. This activation phenomenon is not observed at a higher reaction temperature, 225°C.

  17. Synergy between Two Metal Catalysts: A Highly Active Silica-Supported Bimetallic W/Zr Catalyst for Metathesis of n-Decane.

    PubMed

    Samantaray, Manoja K; Dey, Raju; Kavitake, Santosh; Abou-Hamad, Edy; Bendjeriou-Sedjerari, Anissa; Hamieh, Ali; Basset, Jean-Marie

    2016-07-13

    A well-defined, silica-supported bimetallic precatalyst [≡Si-O-W(Me)5≡Si-O-Zr(Np)3] (4) has been synthesized for the first time by successively grafting two organometallic complexes [W(Me)6 (1) followed by ZrNp4 (2)] on a single silica support. Surprisingly, multiple-quantum NMR characterization demonstrates that W and Zr species are in close proximity to each other. Hydrogenation of this bimetallic catalyst at room temperature showed the easy formation of zirconium hydride, probably facilitated by tungsten hydride which was formed at this temperature. This bimetallic W/Zr hydride precatalyst proved to be more efficient (TON = 1436) than the monometallic W hydride (TON = 650) in the metathesis of n-decane at 150 °C. This synergy between Zr and W suggests that the slow step of alkane metathesis is the C-H bond activation that occurs on Zr. The produced olefin resulting from a β-H elimination undergoes easy metathesis on W. PMID:27248839

  18. An X-ray absorption spectroscopy study of the inversion degree in zinc ferrite nanocrystals dispersed on a highly porous silica aerogel matrix.

    PubMed

    Carta, D; Marras, C; Loche, D; Mountjoy, G; Ahmed, S I; Corrias, A

    2013-02-01

    The structural properties of zinc ferrite nanoparticles with spinel structure dispersed in a highly porous SiO(2) aerogel matrix were compared with a bulk zinc ferrite sample. In particular, the details of the cation distribution between the octahedral (B) and tetrahedral (A) sites of the spinel structure were determined using X-ray absorption spectroscopy. The analysis of both the X-ray absorption near edge structure and the extended X-ray absorption fine structure indicates that the degree of inversion of the zinc ferrite spinel structures varies with particle size. In particular, in the bulk microcrystalline sample, Zn(2+) ions are at the tetrahedral sites and trivalent Fe(3+) ions occupy octahedral sites (normal spinel). When particle size decreases, Zn(2+) ions are transferred to octahedral sites and the degree of inversion is found to increase as the nanoparticle size decreases. This is the first time that a variation of the degree of inversion with particle size is observed in ferrite nanoparticles grown within an aerogel matrix.

  19. An X-ray absorption spectroscopy study of the inversion degree in zinc ferrite nanocrystals dispersed on a highly porous silica aerogel matrix

    NASA Astrophysics Data System (ADS)

    Carta, D.; Marras, C.; Loche, D.; Mountjoy, G.; Ahmed, S. I.; Corrias, A.

    2013-02-01

    The structural properties of zinc ferrite nanoparticles with spinel structure dispersed in a highly porous SiO2 aerogel matrix were compared with a bulk zinc ferrite sample. In particular, the details of the cation distribution between the octahedral (B) and tetrahedral (A) sites of the spinel structure were determined using X-ray absorption spectroscopy. The analysis of both the X-ray absorption near edge structure and the extended X-ray absorption fine structure indicates that the degree of inversion of the zinc ferrite spinel structures varies with particle size. In particular, in the bulk microcrystalline sample, Zn2+ ions are at the tetrahedral sites and trivalent Fe3+ ions occupy octahedral sites (normal spinel). When particle size decreases, Zn2+ ions are transferred to octahedral sites and the degree of inversion is found to increase as the nanoparticle size decreases. This is the first time that a variation of the degree of inversion with particle size is observed in ferrite nanoparticles grown within an aerogel matrix.

  20. Nitrogen-doped hierarchical lamellar porous carbon synthesized from the fish scale as support material for platinum nanoparticle electrocatalyst toward the oxygen reduction reaction.

    PubMed

    Liu, Haijing; Cao, Yinliang; Wang, Feng; Huang, Yaqin

    2014-01-22

    Novel hierarchical lamellar porous carbon (HLPC) with high BET specific surface area of 2730 m(2) g(-1) and doped by nitrogen atoms has been synthesized from the fish scale without any post-synthesis treatment, and applied to support the platinum (Pt) nanoparticle (NP) catalysts (Pt/HLPC). The Pt NPs could be highly dispersed on the porous surface of HLPC with a narrow size distribution centered at ca. 2.0 nm. The results of the electrochemical analysis reveal that the electrochemical active surface area (ECSA) of Pt/HLPC is larger than the Pt NP electrocatalyst supported on the carbon black (Pt/Vulcan XC-72). Compared with the Pt/Vulcan XC-72, the Pt/HLPC exhibits larger current density, lower overpotential, and enhanced catalytic activity toward the oxygen reduction reaction (ORR) through the direct four-electron pathway. The improved catalytic activity is mainly attributed to the high BET specific surface area, hierarchical porous structures and the nitrogen-doped surface property of HLPC, indicating the superiority of HLPC as a promising support material for the ORR electrocatalysts.

  1. Combined homogeneous and heterogeneous catalysts. Rhodium and platinum isocyanide complexes tethered on silica-supported metal heterogeneous catalysts: Arene and cyclohexanone hydrogenation

    SciTech Connect

    Gao, H.; Angelici, R.J. |

    1999-03-15

    Rhodium and platinum isocyanide complexes RhCl(CO)[CN(CH{sub 2}){sub 3}Si(OC{sub 2}H{sub 5}){sub 3}]{sub 2} (Rh-CNR{sub 2}), RhCl[CN(CH{sub 2}){sub 3}Si(OC{sub 2}H{sub 5}){sub 3}]{sub 3} (Rh-CNR{sub 3}), and PtCl{sub 2}[CN(CH{sub 2}){sub 3}Si(OC{sub 2}H{sub 5}){sub 3}]{sub 2} (Pt-CNR{sub 2}) were tethered to the silica-supported metal heterogeneous catalysts M-SiO{sub 2} (M = Pd, Pt, Ru) to give the TCSM (tethered complex on supported metal) catalysts Rh-CNR{sub 2}/Pd-SiO{sub 2}, Rh-CNR{sub 3}/M-SiO{sub 2} (M = Pd, Pt, Ru), and Pt-CNR{sub 2}/Pd-SiO{sub 2}. These TCSM catalysts were used to catalyze the hydrogenation of arenes (Rh-CNR{sub 2}/Pd-SiO{sub 2} and Rh-CNR{sub 3}/M-SiO{sub 2}) and cyclohexanone (Pt-CNR{sub 2}/Pd-SiO{sub 2}) under the mild conditions of 40 C and 1 atm. They exhibit activities that are higher than those of the separate homogeneous rhodium (or platinum) isocyanide complex, the separate silica-supported metal heterogeneous catalyst, or the rhodium (or platinum) complex catalyst tethered on just SiO{sub 2}. The activities of the TCSM catalysts are strongly affected by the nature and loading of the supported metal in the catalyst. Among the three silica-supported metal M-SiO{sub 2} (M = Pd, Pt, Ru) catalysts, the rhodium complex Rh-CNR{sub 3} tethered on Pd-SiO{sub 2} exhibits the highest activity for the hydrogenation of toluene (TOF = 5.5 mol H{sub 2}/(mol Rh min) and TO = 2,420 mol H{sub 2}/mol Rh during 8.5 h). The Rh-CNR{sub 3}/Pd-SiO{sub 2} catalyst with 10 wt % Pd is more active than its counterparts with higher or lower palladium loadings. IR (DRIFT) spectral studies of the TCSM catalysts before and after being used for toluene hydrogenation show that the isocyanide ligands remain coordinated to the rhodium (or platinum) center even after extended use. Atomic emission spectroscopic analysis of hydrogenation solutions shows that there is no rhodium (or platinum) leaching into the solutions.

  2. The formation of silica, alumina and zirconia supported high surface area monometallic and bimetallic catalysts. Progress report

    SciTech Connect

    Gonzalez, R.D.

    1993-12-01

    During the current granting period, 12/01/92--11/30/93, studies have progressed along four fronts: (1) Preparation of high surface area Pt/SiO{sub 2} catalysts; (2) preparation of high surface area Pt/Al{sub 2}O{sub 3} catalysts; (3) preparation of high surface area promoted zirconia superacid catalysts and, (4) stabilization and sintering of porous Pt/SiO{sub 2} catalysts. In addition to these current studies a major review article on previously funded DOE research has been completed and will appear in Catalysis Reviews. Results of these studies are briefly described.

  3. Automation of static and dynamic non-dispersive liquid phase microextraction. Part 2: Approaches based on impregnated membranes and porous supports.

    PubMed

    Alexovič, Michal; Horstkotte, Burkhard; Solich, Petr; Sabo, Ján

    2016-02-11

    A critical overview on automation of modern liquid phase microextraction (LPME) approaches based on the liquid impregnation of porous sorbents and membranes is presented. It is the continuation of part 1, in which non-dispersive LPME techniques based on the use of the extraction phase (EP) in the form of drop, plug, film, or microflow have been surveyed. Compared to the approaches described in part 1, porous materials provide an improved support for the EP. Simultaneously they allow to enlarge its contact surface and to reduce the risk of loss by incident flow or by components of surrounding matrix. Solvent-impregnated membranes or hollow fibres are further ideally suited for analyte extraction with simultaneous or subsequent back-extraction. Their use can therefore improve the procedure robustness and reproducibility as well as it "opens the door" to the new operation modes and fields of application. However, additional work and time are required for membrane replacement and renewed impregnation. Automation of porous support-based and membrane-based approaches plays an important role in the achievement of better reliability, rapidness, and reproducibility compared to manual assays. Automated renewal of the extraction solvent and coupling of sample pretreatment with the detection instrumentation can be named as examples. The different LPME methodologies using impregnated membranes and porous supports for the extraction phase and the different strategies of their automation, and their analytical applications are comprehensively described and discussed in this part. Finally, an outlook on future demands and perspectives of LPME techniques from both parts as a promising area in the field of sample pretreatment is given.

  4. Pure Silica Zeolite Beta Membrane: A Potential Low Dielectric Constant Material For Microprocessor Application

    NASA Astrophysics Data System (ADS)

    Fong, Yeong Yin; Bhatia, Subhash

    The semiconductor industry needs low dielectric constant (low k-value) materials for more advance microprocessor and chips by reducing the size of the device features. In fabricating these contents, a new material with lower k-value than conventional silica (k = 3.9-4.2) is needed in order to improve the circuit performance. The choice of the inorganic zeolite membrane is an attractive option for low k material and suitable for microprocessor applications. A pure silica zeolite beta membrane was synthesized and coated on non-porous stainless steel support using insitu crystallization in the presence of tetraethylammonium hydroxide, TEA (OH), as structure directing agent, fumed silica, HF and deionized water at pH value of 9. The crystallization was carried out for the duration of 14 days under hydrothermal conditions at 130°C. The membrane was characterized by thermogravimetric analysis (TGA), nitrogen adsorption and Scanning Electron Microscope (SEM). SEM results show a highly crystalline; with a truncated square bipyramidal morphology of pure silica zeolite beta membrane strongly adhered on the non-porous stainless steel support. In the present work, the k-value of the membrane was measured as 2.64 which make it suitable for the microprocessor applications.

  5. Unusual reinforcement of silicone rubber compounds containing mesoporous silica particles as inorganic fillers.

    PubMed

    Suzuki, Norihiro; Kiba, Shosuke; Kamachi, Yuichiro; Miyamoto, Nobuyoshi; Yamauchi, Yusuke

    2012-03-14

    We fabricate mesoporous silica/silicone composites in a simple way and systematically examine their thermal stability, swelling characteristic, mechanical strength, and transparency. Simple calculations show that more than 90 vol% of mesopores are filled with silicone rubbers. Compared to non-porous silica/silicone composites, mesoporous silica/silicone composites showed a lower coefficient of linear thermal expansion (CTE). In addition, dramatic improvements of the tensile strength and Young's modulus are obtained with mesoporous silica/silicone composites. Furthermore, mesoporous silica/silicone composites show higher transparency than non-porous silica/silicone composites.

  6. Ultra-fast high-efficiency enantioseparations by means of a teicoplanin-based chiral stationary phase made on sub-2 μm totally porous silica particles of narrow size distribution.

    PubMed

    Ismail, Omar H; Ciogli, Alessia; Villani, Claudio; De Martino, Michela; Pierini, Marco; Cavazzini, Alberto; Bell, David S; Gasparrini, Francesco

    2016-01-01

    A new ultra-high performance teicoplanin-based stationary phase was prepared starting from sub-2 μm totally porous silica particles of narrow size distribution. Columns of different lengths were packed at high pressure and a deep and systematic evaluation of kinetic performance, in terms of van Deemter analysis, was performed under different elution conditions (HILIC, POM, RP and NP) by using both achiral and chiral probes. For the achiral probes, the efficiency of the columns at the minimum of the van Deemter curves were very high leading to some 278,000, 270,000, 262,000 and 232,000 plates/m in hydrophilic interaction liquid chromatography (HILIC), polar organic mode (POM), normal phase (NP) and reversed phase (RP) respectively. The lowest plate height, Hmin=3.59 μm (h(/)=1.89), was obtained under HILIC conditions at a flow rate of 1.4 mL/min. Efficiency as high as 200,000-250,000 plates/m (at the optimum flow rate) was obtained in the separation of the enantiomers of chiral probes under HILIC/POM conditions. N-protected amino acids, α-aryloxy acids, herbicides, anti-inflammatory agents were baseline separated on short (2-cm) and ultra-short (1-cm) columns, with analysis time in the order of 1 min. The enantiomers of N-BOC-d,l-methionine were successfully baseline separated in only 11s in HILIC mode. Several examples of fast and efficient resolutions in sub/supercritical fluid chromatography were also obtained for a range of chiral carboxylic acids.

  7. Ultra-fast high-efficiency enantioseparations by means of a teicoplanin-based chiral stationary phase made on sub-2 μm totally porous silica particles of narrow size distribution.

    PubMed

    Ismail, Omar H; Ciogli, Alessia; Villani, Claudio; De Martino, Michela; Pierini, Marco; Cavazzini, Alberto; Bell, David S; Gasparrini, Francesco

    2016-01-01

    A new ultra-high performance teicoplanin-based stationary phase was prepared starting from sub-2 μm totally porous silica particles of narrow size distribution. Columns of different lengths were packed at high pressure and a deep and systematic evaluation of kinetic performance, in terms of van Deemter analysis, was performed under different elution conditions (HILIC, POM, RP and NP) by using both achiral and chiral probes. For the achiral probes, the efficiency of the columns at the minimum of the van Deemter curves were very high leading to some 278,000, 270,000, 262,000 and 232,000 plates/m in hydrophilic interaction liquid chromatography (HILIC), polar organic mode (POM), normal phase (NP) and reversed phase (RP) respectively. The lowest plate height, Hmin=3.59 μm (h(/)=1.89), was obtained under HILIC conditions at a flow rate of 1.4 mL/min. Efficiency as high as 200,000-250,000 plates/m (at the optimum flow rate) was obtained in the separation of the enantiomers of chiral probes under HILIC/POM conditions. N-protected amino acids, α-aryloxy acids, herbicides, anti-inflammatory agents were baseline separated on short (2-cm) and ultra-short (1-cm) columns, with analysis time in the order of 1 min. The enantiomers of N-BOC-d,l-methionine were successfully baseline separated in only 11s in HILIC mode. Several examples of fast and efficient resolutions in sub/supercritical fluid chromatography were also obtained for a range of chiral carboxylic acids. PMID:26687167

  8. Silica Precursors Derived From TEOS

    NASA Technical Reports Server (NTRS)

    Philipp, Warren H.

    1993-01-01

    Two high-char-yield polysiloxane polymers developed. Designated as TEOS-A and TEOS-B with silica char yields of 55% and 22%, respectively. These free-flowing polymers are Newtonium liquids instead of thick gels. Easily synthesized by controlled hydrolysis of inexpensive tetraethoxysilane (TEOS). Adhesive properties of TEOS-A suggest its use as binder for fabrication of ceramic articles from oxide powders. Less-viscous and more-fluid lower-molecular-weight TEOS-B used to infiltrate already-formed porous ceramic compacts to increase densities without effecting shrinkage. Also used as paint to coat substrate with silica, and to make highly pure silicate powders.

  9. Synthesis, characterization and catalytic activity of carbon-silica hybrid catalyst from rice straw

    NASA Astrophysics Data System (ADS)

    Janaun, J.; Safie, N. N.; Siambun, N. J.

    2016-07-01

    The hybrid-carbon catalyst has been studied because of its promising potential to have high porosity and surface area to be used in biodiesel production. Silica has been used as the support to produce hybrid carbon catalyst due to its mesoporous structure and high surface area properties. The chemical synthesis of silica-carbon hybrid is expensive and involves more complicated preparation steps. The presence of natural silica in rice plants especially rice husk has received much attention in research because of the potential as a source for solid acid catalyst synthesis. But study on rice straw, which is available abundantly as agricultural waste is limited. In this study, rice straw undergone pyrolysis and functionalized using fuming sulphuric acid to anchor -SO3H groups. The presence of silica and the physiochemical properties of the catalyst produced were studied before and after sulphonation. The catalytic activity of hybrid carbon silica acid catalyst, (H-CSAC) in esterification of oleic acid with methanol was also studied. The results showed the presence of silica-carbon which had amorphous structure and highly porous. The carbon surface consisted of higher silica composition, had lower S element detected as compared to the surface that had high carbon content but lower silica composition. This was likely due to the fact that Si element which was bonded to oxygen was highly stable and unlikely to break the bond and react with -SO3H ions. H-CSAC conversions were 23.04 %, 35.52 % and 34.2 7% at 333.15 K, 343.15 K and 353.15 K, respectively. From this research, rice straw can be used as carbon precursor to produce hybrid carbon-silica catalyst and has shown catalytic activity in biodiesel production. Rate equation obtained is also presented.

  10. The Role of Silica in Precious Metal Supported Titania Hybrid Mesoporous Materials for Remediation and Energy Production

    NASA Astrophysics Data System (ADS)

    Kibombo, Harrison S.

    Semiconductor photocatalysis is an advanced oxidation process (AOP) that continues to show promise for the concomitant mineralization of non--biodegradable noxious and persistent organic pollutants (POPs) to environmentally benign products, and the splitting of water. This work examined the use of sol--gel chemistry as a viable approach for the incorporation of transparent silica (SiO2) matrix and/or platinum onto titania (TiO2) so as to optimize physico-chemical properties such as charge separation, crystallinity, surface area, and particle size. It was determined that crystallinity of anatase in the mixed oxide photocatalyst can be improved by the addition of simple non-polar aromatic co-solvents in the sol-gel route, and subsequently enhance the photocatalytic degradation of phenol under UV--light irradiation. The Pt of smaller particle sizes in Pt--TiO2--SiO 2 resulted in higher phenol degradation efficiencies under solar simulated conditions, irrespective of the synthesis method employed. The presence of Pt in the lowest oxidation state, Pt0, is crucial for enhanced phenol degradation whereas PtO2 (Pt4+) serves as a mild recombination center for photogenerated charge carriers rather than demonstrating total inactivity. The production of ·OH radicals was shown to be imperative for sustaining the degradation process. In the water splitting reaction for hydrogen production, the role of the crystallinity of anatase is reaffirmed when TiO2--SiO2 is used, as the surface defects present in the silica phase seem to serve as recombination centers. However, in Pt--TiO2 photocatalysts, the presence of Pt 0 or PtO2 in close contact with TiO2 (heterojunction) allows for more efficient electron propagation and facilitates minimization of electron--hole recombination, hence improved solar simulated photocatalytic hydrogen evolution. Extensive characterization of the photocatalysts were carried out by powder X--ray Diffraction (XRD), Nitrogen Physisorption Studies, Diffuse

  11. Lactic acid conversion to 2,3-pentanedione and acrylic acid over silica-supported sodium nitrate: Reaction optimization and identification of sodium lactate as the active catalyst

    SciTech Connect

    Wadley, D.C.; Tam, M.S.; Miller, D.J.

    1997-01-15

    Lactic acid is converted to 2,3-pentanedione, acrylic acid, and other products in vapor-phase reactions over silica-supported sodium lactate formed from sodium nitrate. Multiparameter optimization of reaction conditions using a Box-Benkhen experimental design shows that the highest yield and selectivity to 2,3-pentanedione are achieved at low temperature, elevated pressure, and long contact time, while yield and selectivity to acrylic acid are most favorable at high temperature, low pressure, and short contact time. Post-reaction Fourier transform infrared spectroscopic analyses of the catalyst indicate that sodium nitrate as the initial catalyst material is transformed to sodium lactate at the onset of reaction via proton transfer from lactic acid to nitrate. The resultant nitric acid vaporizes as it is formed, leaving sodium lactate as the sole sodium-bearing species on the catalyst during reaction. 19 refs., 8 figs., 5 tabs.

  12. Vinyl sulfone silica: application of an open preactivated support to the study of transnitrosylation of plant proteins by S-nitrosoglutathione

    PubMed Central

    2013-01-01

    Background S-nitrosylaton is implicated in the regulation of numerous signaling pathways with a diversity of regulatory roles. The high lability of the S-NO bond makes the study of proteins regulated by S-nitrosylation/denitrosylation a challenging task and most studies have focused on already S-nitrosylated proteins. We hypothesize that: i) S-nitrosoglutathione (GSNO) transnitrosylation is a feasible mechanism to account for the physiological S-nitrosylation of rather electropositive sulfur atoms from proteins, ii) affinity chromatography is a suitable approach to isolate proteins that are prone to undergo S-transnitrosylation and iii) vinyl sulfone silica is a suitable chromatographic bead. Results The combination of vinyl sulfone silica with GSNO yielded an affinity resin that withstood high ionic strength without shrinking or deforming and that it was suitable to isolate potential GSNO transnitrosylation target candidates. Fractions eluted at 1500 mM NaCl resulted in a symmetrical peak for both, protein and S-nitrosothiols, supporting the idea of transnitrosylation by GSNO as a selective process that involves strong and specific interactions with the target protein. Proteomic analysis led to the identification of 22 physiological significant enzymes that differ with the tissue analyzed, being regulatory proteins the most abundant group in hypocotyls. The identification of chloroplastidic FBPase, proteasome, GTP-binding protein, heat shock Hsp70, syntaxin, catalase I, thioredoxin peroxidase and cytochrome P450 that have already been reported as S-nitrosylated by other techniques can be considered as internal positive controls that validate our experimental approach. An additional validation was provided by the prediction of the S-nitrosylation sites in 19 of the GSNO transnitrosylation target candidates. Conclusions Vinyl sulfone silica is an open immobilization support that can be turned ad hoc and in a straightforward manner into an affinity resin. Its

  13. Preparation of silica or alumina pillared crystalline titanates

    SciTech Connect

    Udomsak, S.; Nge, R.; Dufner, D.C.; Anthony, R.G.; Lott, S.E.

    1994-05-01

    Layered crystalline titanates (CT) [Anthony and Dosch, US Patent 5 177 045 (1993)] are pillared with tetraethyl orthosilicate, 3-aminopropyltrimethoxysilane, and aluminum acetylacetonate to prepare porous and high surface area supports for sulfided NiMo catalyst. Tetra-ethyl orthosilicate or aluminum acetylacetonate intercalated CT are prepared by stepwise intercalation. First, the basal distance is increased by n-alkylammonium ions prior to intercalation with inorganic compounds. However, an aqueous solution of 3-aminopropyltrimethoxysilane could directly pillar CT without first swelling the titanate with n-alkylamine. The catalytic activities for hydrogenation of pyrene of sulfided NiMo supported silica or alumina pillared CT were higher than those of commercial catalysts (Shell324 and Amocat1C). The silicon and aluminum contents of the pillared CT, used as supports, have a considerable effect on the catalytic activities and physical properties of the supports.

  14. In-situ aging microwave heating synthesis of LTA zeolite layer on mesoporous TiO2 coated porous alumina support

    NASA Astrophysics Data System (ADS)

    Baig, Mirza A.; Patel, Faheemuddin; Alhooshani, Khalid; Muraza, Oki; Wang, Evelyn N.; Laoui, Tahar

    2015-12-01

    LTA zeolite layer was successfully grown on a superhydrophilic mesoporous titania layer coated onto porous α-alumina substrate. Mesoporous titania layer was formed as an intermediate bridge in the pore size variation between the macroporous α-alumina support and micro-porous LTA zeolite layer. In-situ aging microwave heating synthesis method was utilized to deposit the LTA zeolite layer. Mesoporous titania layer was pre-treated with UV photons and this was observed to have played a major role in improving the surface hydrophilicity of the substrate leading to formation of increased number of Ti-OH groups on the surface. This increase in Ti-OH groups enhanced the interaction between the synthesis gel and the substrate leading to strong attachment of the amorphous gel on the substrate, thus enhancing coverage of the LTA zeolite layer to almost the entire surface of the 1-inch (25.4 mm) diameter membrane. LTA zeolite layer was developed via in-situ aged under microwave irradiation to study the effect of synthesis parameters such as in-situ aging time and synthesis time on the formation of the LTA zeolite layer. Optimized process parameters resulted in the formation of crack-free porous zeolite layer yielding a zeolite-titania-alumina multi-layer membrane with a gradient in porosity.

  15. Porous and single-skinned polyethersulfone membranes support the growth of HepG2 cells: a potential biomaterial for bioartificial liver systems.

    PubMed

    Zhang, Shi-Chang; Liu, Tao; Wang, Ying-Jie

    2012-09-01

    In this study, we evaluated a porous and single-layer skin polyethersulfone (PES) membrane as a material for use in hybrid bioartificial liver support systems. The PES membrane has been characterized as a single-layer skin structure, with a rough porous surface. Specifically, we studied the ability of the human hepatoblastoma cell lines (HepG2) to adhere, grow, and spread on the PES membrane. Furthermore, we examined albumin secretion, low-density lipoprotein uptake, and CYP450 activity of HepG2 cells that grew on the membrane. HepG2 cells readily adhered onto the outer surfaces of PES membranes. Over time, HepG2 cells proliferated actively, and confluent monolayer of cells covered the available surface area of the membrane, eventually forming cell clusters and three-dimensional aggregates. Furthermore, HepG2 cells grown on PES membranes maintained highly specific functions, including uptake capability, biosynthesis and biotransformation. These results indicate that PES membranes are potential substrates for the growth of human liver cells and may be useful in the construction of hollow fiber bioreactors. Porous and single-layer skin PES membranes and HepG2 cells may be potential biomaterials for the development of biohybrid liver devices.

  16. Nanoscale control of silica particle formation via silk-silica fusion proteins for bone regeneration.

    PubMed

    Mieszawska, Aneta J; Nadkarni, Lauren D; Perry, Carole C; Kaplan, David L

    2010-10-26

    The biomimetic design of silk/silica fusion proteins was carried out, combining the self assembling domains of spider dragline silk (Nephila clavipes) and silaffin derived R5 peptide of Cylindrotheca fusiformis that is responsible for silica mineralization. Genetic engineering was used to generate the protein-based biomaterials incorporating the physical properties of both components. With genetic control over the nanodomain sizes and chemistry, as well as modification of synthetic conditions for silica formation, controlled mineralized silk films with different silica morphologies and distributions were successfully generated; generating 3D porous networks, clustered silica nanoparticles (SNPs), or single SNPs. Silk serves as the organic scaffolding to control the material stability and multiprocessing makes silk/silica biomaterials suitable for different tissue regenerative applications. The influence of these new silk-silica composite systems on osteogenesis was evaluated with human mesenchymal stem cells (hMSCs) subjected to osteogenic differentiation. hMSCs adhered, proliferated, and differentiated towards osteogenic lineages on the silk/silica films. The presence of the silica in the silk films influenced osteogenic gene expression, with the upregulation of alkaline phosphatase (ALP), bone sialoprotein (BSP), and collagen type 1 (Col 1) markers. Evidence for early bone formation as calcium deposits was observed on silk films with silica. These results indicate the potential utility of these new silk/silica systems towards bone regeneration. PMID:20976116

  17. Highly porous PEM fuel cell cathodes based on low density carbon aerogels as Pt-support: Experimental study of the mass-transport losses

    NASA Astrophysics Data System (ADS)

    Marie, Julien; Chenitz, Regis; Chatenet, Marian; Berthon-Fabry, Sandrine; Cornet, Nathalie; Achard, Patrick

    Carbon aerogels exhibiting high porous volumes and high surface areas, differentiated by their pore-size distributions were used as Pt-supports in the cathode catalytic layer of H 2/air-fed PEM fuel cell. The cathodes were tested as 50 cm 2 membrane electrode assemblies (MEAs). The porous structure of the synthesized catalytic layers was impacted by the nanostructure of the Pt-doped carbon aerogels (Pt/CAs). In this paper thus we present an experimental study aiming at establishing links between the porous structure of the cathode catalytic layers and the MEAs performances. For that purpose, the polarization curves of the MEAs were decomposed in 3 contributions: the kinetic loss, the ohmic loss and the mass-transport loss. We showed that the MEAs made with the different carbon aerogels had similar kinetic activities (low current density performance) but very different mass-transport voltage losses. It was found that the higher the pore-size of the initial carbon aerogel, the higher the mass-transport voltage losses. Supported by our porosimetry (N 2-adsorption and Hg-porosimetry) measurement, we interpret this apparent contradiction as the consequence of the more important Nafion penetration into the carbon aeorogel with larger pore-size. Indeed, the catalytic layers made from the larger pore-size carbon aerogel had lower porosities. We thus show in this work that carbon aerogels are materials with tailored nanostructured structure which can be used as model materials for experimentally testing the optimization of the PEM fuel cell catalytic layers.

  18. Silica in alkaline brines

    USGS Publications Warehouse

    Jones, B.F.; Rettig, S.L.; Eugster, H.P.

    1967-01-01

    Analysis of sodium carbonate-bicarbonate brines from closed basins in volcanic terranes of Oregon and Kenya reveals silica contents of up to 2700 parts per million at pH's higher than 10. These high concentrations of SiO 2 can be attributed to reaction of waters with silicates, and subsequent evaporative concentration accompanied by a rise in pH. Supersaturation with respect to amorphous silica may occur and persist for brines that are out of contact with silicate muds and undersaturated with respect to trona; correlation of SiO2 with concentration of Na and total CO2 support this interpretation. Addition of moredilute waters to alkaline brines may lower the pH and cause inorganic precipitation of substantial amounts of silica.

  19. Influence of surface composition on hydrogen peroxide decomposition catalyzed by Co(II) aminopyridine-supported compounds on amorphous silica gel.

    PubMed

    de Farias, Robson F; Gonçalves, Afonso S; Airoldi, Claudio

    2002-03-01

    Cobalt compounds supported on 2-, 3-, and 4-aminopyridine-modified silica surfaces, named Sil2Co, Sil3Co, and Sil4Co, respectively, were used to catalyze the decomposition of hydrogen peroxide on ethanolic solutions at 293, 298, and 303 K. The calculated k values (x10(-4) s(-1)) for Sil2Co, Sil3Co, and Sil4Co are 0.65, 1.24, and 4.78 (293 K); 1.23, 1.87, and 6.33 (298 K); and 1.80, 2.80, and 10.30 (303 K), respectively. All obtained results evidence that such decomposition is a first-order reaction. Zinc-, nickel-, and copper-supported compounds were also tested, but exhibited a very low catalytic activity. By using the k values at 298 and 303 K, and employing the equation ln (k1/k2) = E(a)/R(1/T2-1/T1), the activation energy values for the considered reaction were Sil2Co = 57.20, Sil3Co = 60.60, and Sil4Co = 73.10 kJ mol(-1), respectively. The low values calculated for E(a) are in agreement with a free-radical mechanism.

  20. LPS inmobilization on porous and non-porous supports as an approach for the isolation of anti-LPS host-defense peptides

    PubMed Central

    López-Abarrategui, Carlos; del Monte-Martínez, Alberto; Reyes-Acosta, Osvaldo; Franco, Octavio L.; Otero-González, Anselmo J.

    2013-01-01

    Lipopolysaccharides (LPSs) are the major molecular component of the outer membrane of Gram-negative bacteria. This molecule is recognized as a sign of bacterial infection, responsible for the development of local inflammatory response and, in extreme cases, septic shock. Unfortunately, despite substantial advances in the pathophysiology of sepsis, there is no efficacious therapy against this syndrome yet. As a consequence, septic shock syndrome continues to increase, reaching mortality rates over 50% in some cases. Even though many preclinical studies and clinical trials have been conducted, there is no Food and Drug Administration-approved drug yet that interacts directly against LPS. Cationic host-defense peptides (HDPs) could be an alternative solution since they possess both antimicrobial and antiseptic properties. HDPs are small, positively charged peptides which are evolutionarily conserved components of the innate immune response. In fact, binding to diverse chemotypes of LPS and inhibition of LPS-induced pro-inflammatory cytokines from macrophages have been demonstrated for different HDPs. Curiously, none of them have been isolated by their affinity to LPS. A diversity of supports could be useful for such biological interaction and suitable for isolating HDPs that recognize LPS. This approach could expand the rational search for anti-LPS HDPs. PMID:24409171

  1. LPS inmobilization on porous and non-porous supports as an approach for the isolation of anti-LPS host-defense peptides.

    PubMed

    López-Abarrategui, Carlos; Del Monte-Martínez, Alberto; Reyes-Acosta, Osvaldo; Franco, Octavio L; Otero-González, Anselmo J

    2013-01-01

    Lipopolysaccharides (LPSs) are the major molecular component of the outer membrane of Gram-negative bacteria. This molecule is recognized as a sign of bacterial infection, responsible for the development of local inflammatory response and, in extreme cases, septic shock. Unfortunately, despite substantial advances in the pathophysiology of sepsis, there is no efficacious therapy against this syndrome yet. As a consequence, septic shock syndrome continues to increase, reaching mortality rates over 50% in some cases. Even though many preclinical studies and clinical trials have been conducted, there is no Food and Drug Administration-approved drug yet that interacts directly against LPS. Cationic host-defense peptides (HDPs) could be an alternative solution since they possess both antimicrobial and antiseptic properties. HDPs are small, positively charged peptides which are evolutionarily conserved components of the innate immune response. In fact, binding to diverse chemotypes of LPS and inhibition of LPS-induced pro-inflammatory cytokines from macrophages have been demonstrated for different HDPs. Curiously, none of them have been isolated by their affinity to LPS. A diversity of supports could be useful for such biological interaction and suitable for isolating HDPs that recognize LPS. This approach could expand the rational search for anti-LPS HDPs. PMID:24409171

  2. Iridium nanoparticles supported on hierarchical porous N-doped carbon: an efficient water-tolerant catalyst for bio-alcohol condensation in water

    NASA Astrophysics Data System (ADS)

    Liu, Di; Chen, Xiufang; Xu, Guoqiang; Guan, Jing; Cao, Quan; Dong, Bo; Qi, Yunfei; Li, Chunhu; Mu, Xindong

    2016-02-01

    Nitrogen-doped hierarchical porous carbons were synthesized successfully by a controllable one-pot method using glucose and dicyandiamide as carbon source and nitrogen source via hydrothermal carbonization process. The nitrogen-doped materials, possessing high nitrogen content (up to 7 wt%), large surface area (>320 m2 g-1) and excellent hierarchical nanostructure, were employed as catalyst supports for immobilization of iridium nanoparticles for bio-alcohol condensation in water. The introduction of nitrogen atoms into the carbon framework significantly improved iridium nanoparticles dispersion and stabilization. The novel iridium catalysts exhibited superior catalytic activity in the aqueous phase condensation of butanol, offering high butanol conversion of 45% with impressive 2-ethylhexanol selectivity of 97%. The heterogeneous catalysts had great advantages of easy recovery and high catalytic stability. The outstanding catalytic performance could be attributed to excellent dispersion of iridium nanoparticles, stronger iridium-support interactions and interaction of nitrogen species with alcohol substrates.

  3. Au-NiCo2O4 supported on three-dimensional hierarchical porous graphene-like material for highly effective oxygen evolution reaction

    NASA Astrophysics Data System (ADS)

    Xia, Wei-Yan; Li, Nan; Li, Qing-Yu; Ye, Kai-Hang; Xu, Chang-Wei

    2016-03-01

    A three-dimensional hierarchical porous graphene-like (3D HPG) material was synthesized by a one-step ion-exchange/activation combination method using a cheap metal ion exchanged resin as carbon precursor. The 3D HPG material as support for Au-NiCo2O4 gives good activity and stability for oxygen evolution reaction (OER). The 3D HPG material is induced into NiCo2O4 as conductive support to increase the specific area and improve the poor conductivity of NiCo2O4. The activity of and stability of NiCo2O4 significantly are enhanced by a small amount of Au for OER. Au is a highly electronegative metal and acts as an electron adsorbate, which is believed to facilitate to generate and stabilize Co4+ and Ni3+ cations as the active centres for the OER.

  4. Au-NiCo2O4 supported on three-dimensional hierarchical porous graphene-like material for highly effective oxygen evolution reaction.

    PubMed

    Xia, Wei-Yan; Li, Nan; Li, Qing-Yu; Ye, Kai-Hang; Xu, Chang-Wei

    2016-03-21

    A three-dimensional hierarchical porous graphene-like (3D HPG) material was synthesized by a one-step ion-exchange/activation combination method using a cheap metal ion exchanged resin as carbon precursor. The 3D HPG material as support for Au-NiCo2O4 gives good activity and stability for oxygen evolution reaction (OER). The 3D HPG material is induced into NiCo2O4 as conductive support to increase the specific area and improve the poor conductivity of NiCo2O4. The activity of and stability of NiCo2O4 significantly are enhanced by a small amount of Au for OER. Au is a highly electronegative metal and acts as an electron adsorbate, which is believed to facilitate to generate and stabilize Co(4+) and Ni(3+) cations as the active centres for the OER.

  5. Iridium nanoparticles supported on hierarchical porous N-doped carbon: an efficient water-tolerant catalyst for bio-alcohol condensation in water

    PubMed Central

    Liu, Di; Chen, Xiufang; Xu, Guoqiang; Guan, Jing; Cao, Quan; Dong, Bo; Qi, Yunfei; Li, Chunhu; Mu, Xindong

    2016-01-01

    Nitrogen-doped hierarchical porous carbons were synthesized successfully by a controllable one-pot method using glucose and dicyandiamide as carbon source and nitrogen source via hydrothermal carbonization process. The nitrogen-doped materials, possessing high nitrogen content (up to 7 wt%), large surface area (>320 m2 g−1) and excellent hierarchical nanostructure, were employed as catalyst supports for immobilization of iridium nanoparticles for bio-alcohol condensation in water. The introduction of nitrogen atoms into the carbon framework significantly improved iridium nanoparticles dispersion and stabilization. The novel iridium catalysts exhibited superior catalytic activity in the aqueous phase condensation of butanol, offering high butanol conversion of 45% with impressive 2-ethylhexanol selectivity of 97%. The heterogeneous catalysts had great advantages of easy recovery and high catalytic stability. The outstanding catalytic performance could be attributed to excellent dispersion of iridium nanoparticles, stronger iridium-support interactions and interaction of nitrogen species with alcohol substrates. PMID:26912370

  6. Au-NiCo2O4 supported on three-dimensional hierarchical porous graphene-like material for highly effective oxygen evolution reaction

    PubMed Central

    Xia, Wei-Yan; Li, Nan; Li, Qing-Yu; Ye, Kai-Hang; Xu, Chang-Wei

    2016-01-01

    A three-dimensional hierarchical porous graphene-like (3D HPG) material was synthesized by a one-step ion-exchange/activation combination method using a cheap metal ion exchanged resin as carbon precursor. The 3D HPG material as support for Au-NiCo2O4 gives good activity and stability for oxygen evolution reaction (OER). The 3D HPG material is induced into NiCo2O4 as conductive support to increase the specific area and improve the poor conductivity of NiCo2O4. The activity of and stability of NiCo2O4 significantly are enhanced by a small amount of Au for OER. Au is a highly electronegative metal and acts as an electron adsorbate, which is believed to facilitate to generate and stabilize Co4+ and Ni3+ cations as the active centres for the OER. PMID:26996816

  7. Nanoporous Silica Templated HeteroEpitaxy: Final LDRD Report.

    SciTech Connect

    Burckel, David Bruce; Koleske, Daniel; Rowen, Adam M.; Williams, John Dalton; Fan, Hongyou; Arrington, Christian Lew

    2006-11-01

    This one-year out-of-the-box LDRD was focused on exploring the use of porous growth masks as a method for defect reduction during heteroepitaxial crystal growth. Initially our goal was to investigate porous silica as a growth mask, however, we expanded the scope of the research to include several other porous growth masks on various size scales, including mesoporous carbon, and the UV curable epoxy, SU-8. Use of SU-8 as a growth mask represents a new direction, unique in the extensive literature of patterned epitaxial growth, and presents the possibility of providing a single step growth mask. Additional research included investigation of pore viability via electrochemical deposition into high aspect ratio photoresist patterns and pilot work on using SU-8 as a DUV negative resist, another significant potential result. While the late start nature of this project pushed some of the initial research goals out of the time table, significant progress was made. 3 Acknowledgements This work was performed in part at the Nanoscience @ UNM facility, a member of the National Nanotechnology Infrastructure Network, which is supported by the National Science Foundation (Grant ECS 03-35765). Sandia is multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United Stated Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000. This work was supported under the Sandia LDRD program (Project 99405). 4

  8. Prefunctionalized Porous Organic Polymers: Effective Supports of Surface Palladium Nanoparticles for the Enhancement of Catalytic Performances in Dehalogenation.

    PubMed

    Zhong, Hong; Liu, Caiping; Zhou, Hanghui; Wang, Yangxin; Wang, Ruihu

    2016-08-22

    Three porous organic polymers (POPs) containing H, COOMe, and COO(-) groups at 2,6-bis(1,2,3-triazol-4-yl)pyridyl (BTP) units (i.e., POP-1, POP-2, and POP-3, respectively) were prepared for the immobilization of metal nanoparticles (NPs). The ultrafine palladium NPs are uniformly encapsulated in the interior pores of POP-1, whereas uniform- and dual-distributed palladium NPs are located on the external surface of POP-2 and POP-3, respectively. The presence of carboxylate groups not only endows POP-3 an outstanding dispersibility in H2 O/EtOH, but also enables the palladium NPs at the surface to show the highest catalytic activity, stability, and recyclability in dehalogenation reactions of chlorobenzene at 25 °C. The palladium NPs on the external surface are effectively stabilized by the functionalized POPs containing BTP units and carboxylate groups, which provides a new insight for highly efficient catalytic systems based on surface metal NPs of porous materials. PMID:27465930

  9. Optical ammonia gas sensor based on a porous silicon rugate filter coated with polymer-supported dye.

    PubMed

    Shang, Yunling; Wang, Xiaobo; Xu, Erchao; Tong, Changlun; Wu, Jianmin

    2011-01-24

    An ammonia gas sensor chip was prepared by coating an electrochemically-etched porous Si rugate filter with a chitosan film that is crosslinked by glycidoxypropyltrimethoxysilane (GPTMS). The bromothylmol blue (BTB), a pH indicator, was loaded in the film as ammonia-sensing molecules. White light reflected from the porous Si has a narrow bandwidth spectrum with a peak at 610 nm. Monitoring reflective optical intensity at the peak position allows for direct, real-time observation of changes in the concentration of ammonia gas in air samples. The reflective optical intensity decreased linearly with increasing concentrations of ammonia gas over the range of 0-100 ppm. The lowest detection limit was 0.5 ppm for ammonia gas. At optimum conditions, the full response time of the ammonia gas sensor was less than 15s. The sensor chip also exhibited a good long-term stability over 1 year. Therefore, the simple sensor design has potential application in miniaturized optical measurement for online ammonia gas detection.

  10. Graphene-supported ultrafine metal nanoparticles encapsulated by mesoporous silica: robust catalysts for oxidation and reduction reactions.

    PubMed

    Shang, Lu; Bian, Tong; Zhang, Baihui; Zhang, Donghui; Wu, Li-Zhu; Tung, Chen-Ho; Yin, Yadong; Zhang, Tierui

    2014-01-01

    Graphene nanosheet-supported ultrafine metal nanoparticles encapsulated by thin mesoporous SiO2 layers were prepared and used as robust catalysts with high catalytic activity and excellent high-temperature stability. The catalysts can be recycled and reused in many gas- and solution-phase reactions, and their high catalytic activity can be fully recovered by high-temperature regeneration, should they be deactivated by feedstock poisoning. In addition to the large surface area provided by the graphene support, the enhanced catalytic performance is also attributed to the mesoporous SiO2 layers, which not only stabilize the ultrafine metal nanoparticles, but also prevent the aggregation of the graphene nanosheets. The synthetic strategy can be extended to other metals, such as Pd and Ru, for preparing robust catalysts for various reactions.

  11. Copper(0) nanoparticles supported on silica-coated cobalt ferrite magnetic particles: cost effective catalyst in the hydrolysis of ammonia-borane with an exceptional reusability performance.

    PubMed

    Kaya, Murat; Zahmakiran, Mehmet; Ozkar, Saim; Volkan, Mürvet

    2012-08-01

    Herein we report the development of a new and cost-effective nanocomposite catalyst for the hydrolysis of ammonia-borane (NH(3)BH(3)), which is considered to be one of the most promising solid hydrogen carriers because of its high gravimetric hydrogen storage capacity (19.6% wt) and low molecular weight. The new catalyst system consisting of copper nanoparticles supported on magnetic SiO(2)/CoFe(2)O(4) particles was reproducibly prepared by wet-impregnation of Cu(II) ions on SiO(2)/CoFe(2)O(4) followed by in situ reduction of the Cu(II) ions on the surface of magnetic support during the hydrolysis of NH(3)BH(3) and characterized by ICP-MS, XRD, XPS, TEM, HR-TEM and N(2) adsorption-desorption technique. Copper nanoparticles supported on silica coated cobalt(II) ferrite SiO(2)/CoFe(2)O(4) (CuNPs@SCF) act as highly active catalyst in the hydrolysis of ammonia-borane, providing an initial turnover frequency of TOF = 2400 h(-1) at room temperature, which is not only higher than all the non-noble metal catalysts but also higher than the majority of the noble metal based homogeneous and heterogeneous catalysts employed in the same reaction. More importantly, they were easily recovered by using a permanent magnet in the reactor wall and reused for up to 10 recycles without losing their inherent catalytic activity significantly, which demonstrates the exceptional reusability of the CuNPs@SCF catalyst. PMID:22856878

  12. Decisive influence of colloidal suspension conductivity during electrophoretic impregnation of porous anodic film supported on 1050 aluminium substrate.

    PubMed

    Fori, B; Taberna, P L; Arurault, L; Bonino, J P

    2014-01-01

    The present paper studies the influence of suspension conductivity on the electrophoretic deposition (EPD) of nanoparticles inside a porous anodic aluminium oxide film. It is shown that an increase in the suspension's conductivity enhances impregnation of the anodic film by the nanoparticles. Two mechanisms are seen to promote the migration of particles into the pores. Indeed an increase in the suspension conductivity leads on the one hand to a strengthening of the electric field in the anodic film and on the other hand to a thinning of the electric double layer on the pore walls. The results of our study confirm that colloidal suspension conductivity is a key parameter governing the electrophoretic impregnation depth.

  13. Investigation of oxygen reduction and methanol oxidation reaction activity of PtAu nano-alloy on surface modified porous hybrid nanocarbon supports

    NASA Astrophysics Data System (ADS)

    Parambath Vinayan, Bhaghavathi; Nagar, Rupali; Ramaprabhu, Sundara

    2016-09-01

    We investigate the electrocatalytic activity of PtAu alloy nanoparticles supported on various chemically modified carbon morphologies towards oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). The surface-modification of graphene nanosheets (f-G), multi-walled carbon nanotubes (f-MWNTs) and (graphene nanosheets-carbon nanotubes) hybrid support (f-G-MWNTs) were carried out by soft functionalization method using a cationic polyelectrolyte poly-(diallyldimethyl ammonium chloride). The Pt and PtAu alloy nanoparticles were dispersed over chemically modified carbon supports by sodium-borohydride assisted modified polyol reduction method. The electrochemical performance of all electrocatalysts were studied by half- and full-cell proton exchange membrane fuel cell (PEMFC) measurements and PtAu/f-G-MWNTs catalyst comparatively yielded the best catalytic performance. PEMFC full cell measurements of PtAu/f-G-MWNTs cathode electrocatalyst yield a maximum power density of 319 mW cm-2 at 60 °C without any back pressure,which is 2.1 times higher than that of cathode electrocatalyst Pt on graphene support. The high ORR and MOR activity of PtAu/f-G-MWNTs electrocatalyst is due to the alloying effect and inherent beneficial properties of porous hybrid nanocarbon support.

  14. Synthesis of sulfated titania supported on mesoporous silica using direct impregnation and its application in esterification of acetic acid and n-butanol

    SciTech Connect

    Wang Yuhong; Gan Yunting; Whiting, Roger; Lu Guanzhong

    2009-09-15

    A new method has been developed for the preparation of sulfated titania (S-TiO{sub 2}) supported on mesoporous silica. The use of direct exchange of metal containing precursors for the surfactants in the as-synthesized MCM-41 substrate produced a product with high sulfur content without serious blockage of the pore structure of MCM-41. The pore sizes and volumes of the resultant S-TiO{sub 2}/MCM-41 composites were found to vary markedly with the loading of TiO{sub 2}. The strong acidic character of the composites obtained was examined by using them as catalysts for the esterification of acetic acid and n-butanol. - Abstract: XRD profiles of the composites of S-TiO{sub 2}/MCM-41 with different TiO{sub 2} contents. The low angle peaks indicate the MCM-41-like structure retained and a TiO{sub 2} phase appeared at high angle region. Display Omitted

  15. The structure and activity of silica-supported palladium-cobalt alloys. I. Alloy homogeneity, surface composition, and activity for neopentane conversion

    SciTech Connect

    Juszczyk, W.; Karpinski, Z.; Lomot, D.; Pielaszek, J. ); Paal, Z. ); Stakheev, A.Yu. )

    1993-08-01

    Chemisorption of H[sub 2] and CO, temperature-programmed reduction (TPR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and neopentane conversion show that differences in preparation method and overall metal loading lead to the formation of different Pd-Co bimetallic materials (changes in reducibility, metal particle size, and lateral homogeneity). Well-homogenized Pd-Co particles exhibit a very pronounced minimum in the plot of catalytic activity versus Pd-Co alloy composition. At the same time, a maximum exists in the isomerization selectivity vs the alloy composition. These deviations from the catalytic behavior of physical mixtures of the monometallic (Pd and Co) catalysts provide a basis for the estimation of how two metals interact with each other in a supported catalyst. Incipient wetness impregnation of silica by considerable amounts (10 wt%) of metal salts leads to the formation of catalyst precursors which are fully reduced at 380[degrees]C yielding good dispersion and lateral homogeneity. Chemisorption and in situ XRD studies are compatible with the kinetic investigations, but information on metal interaction by these methods is less clear. For high metal-loaded Pd-Co/SiO[sub 2] catalysts, comparison of H[sub 2] chemisorption and XRD data suggests surface enrichment in palladium, which is confirmed by XPS. 26 refs., 6 figs., 4 tabs.

  16. Porous ZnS/ZnO microspheres prepared through the spontaneous organization of nanoparticles and their application as supports of holding CdTe quantum dots

    SciTech Connect

    Cao Xuebo Lan Xianmei; Zhao Cui; Shen Wenjun; Yao Dan

    2008-05-06

    This manuscript describes a self-organization method for the large-scale production of porous ZnS/ZnO composite microspheres and their application as supports of CdTe quantum dots. Through the reaction of Zn{sup 2+} and urea and thioacetamide at 85 deg. C for 10 min, nanoparticles of cubic ZnS and amorphous ZnO were formed and they present a strong tendency to organize into regular microspheres. The formation of nanopores within the microspheres is related to Ostwald ripening: some small nanoparticles within the microspheres were merged by the larger ones, and as a result, numerous nanopores were generated. Furthermore, when a solvothermal ripening is applied for the porous microspheres, the components within them can be transformed into hexagonal ZnS and ZnO. CdTe quantum dots were introduced into the nanopores to achieve luminescent microspheres through in situ nucleation and growth. And it is expected that, besides semiconducting quantum dots, other functional units, such as magnetic and catalytically activated nanoparticles, can also be introduced into them.

  17. A new electrochemical sensor of nitro aromatic compound based on three-dimensional porous Pt-Pd nanoparticles supported by graphene-multiwalled carbon nanotube composite.

    PubMed

    Yuan, Cai-Xia; Fan, Yan-Ru; Tao-Zhang; Guo, Hui-Xia; Zhang, Jing-Xuan; Wang, Yong-Lan; Shan, Duo-Liang; Lu, Xiao-Quan

    2014-08-15

    In this study, an electrochemical sensor of nitro aromatic compound based on three-dimensional porous Pt-Pd nanoparticles (Pt-Pd NPs) supported by reduced graphene oxide (rGO) nanosheets-multiwalled carbon nanotube (CNTs) nanocomposite (marked as Pt-Pd NPs/CNTs-rGO) was investigated for the first time. This hybrid nanocomposite has been prepared via a facile and versatile hydrothermal synthetic strategy while its structure and property are evaluated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and electrochemical impedance spectroscopy (EIS). The result shows that 3D porous Pt-Pd NPs/CNTs-rGO nanocomposite has a large specific surface area of 326.6m(2)g(-1) and exhibited ultrahigh rate capability and good cycling properties at high rates. Electrochemical studies have been performed for the nitro aromatic compounds detection by using different pulse voltammetry (DPV) techniques. The proposed nanocomposite exhibited much enhanced elctrocatalytic activity and high sensitivity toward the detection of nitro aromatic compounds which compared with Pt-Pd NPs dispersed on functionalized rGO, Pt-Pd NPs dispersed on functionalized CNTs, rGO-CNTs and bare glass carbon electrode (GCE). On the basis of the above synergetic electrochemical sensing and synthesis procedure, the hybrid material can be recommended as a robust material for sensor-related applications. Moreover, the proposed sensor exhibits high reproducibility, long-time storage stability and satisfactory anti-interference ability.

  18. Enhanced visible-light photocatalytic activities of porous olive-shaped sulfur-doped BiVO4-supported cobalt oxides

    NASA Astrophysics Data System (ADS)

    Zhao, Zhenxuan; Dai, Hongxing; Deng, Jiguang; Liu, Yuxi; Au, Chak Tong

    2013-04-01

    Porous S-doped bismuth vanadate with an olive-like morphology and its supported cobalt oxide (y wt% CoOx/BiVO4-δS0.08, y = 0.1, 0.8, and 1.6) photocatalysts were fabricated using the dodecylamine-assisted alcohol-hydrothermal and incipient wetness impregnation methods, respectively. It is shown that the y wt% CoOx/BiVO4-δS0.08 photocatalysts were single-phase with a monoclinic scheetlite structure, a porous olive-like morphology, a surface area of 8.8-9.2 m2/g, and a bandgap energy of 2.38-2.41 eV. There was the co-presence of surface Bi5+, Bi3+, V5+, V3+, Co3+, and Co2+ species in y wt% CoOx/BiVO4-δS0.08. The 0.8 wt% CoOx/BiVO4-δS0.08 sample performed the best for methylene blue degradation under visible-light illumination. The photocatalytic mechanism was also discussed. We believe that the sulfur and CoOx co-doping, higher oxygen adspecies concentration, and lower bandgap energy were responsible for the excellent visible-light-driven catalytic activity of 0.8 wt% CoOx/BiVO4-δS0.08.

  19. Silylation of low-density silica and bridged polysilsesquioxane aerogels

    SciTech Connect

    DeFriend, K. A.; Loy, D. A.; Salazar, K. V.; Wilson, K. V.

    2004-01-01

    Silica and bridged polysilsesquioxane aerogels are low-density materials that are attractive for applications such as thermal insulation, porous separation media or catalyst supports, adsorbents, and cometary dust capture agents. However, aerogels are notoriously weak and brittle making it difficult to handle and machine monoliths into desired forms. This complication prevents the development of many applications that would otherwise benefit from the use of the low-density materials. Here, we will describe our efforts to chemically modify and mechanically enhance silica-based aerogels using chemical vapor techniques without sacrificing their characteristic low densities. Monolithic silica and organic-bridged polysilsesquioxane aerogels were prepared by sol-gel polymerization of the respective methoxysilane monomers followed by supercritical carbon dioxide drying of the gels. Then the gels were reactively modified with silylating agents to demonstrate the viability of CVD modification of aerogels, and to determine the effects of silylation of surface silanols on the morphology, surface area, and mechanical properties of the resulting aerogels.

  20. Structural characterization of vanadium oxide catalysts supported on nanostructured silica SBA-15 using X-ray absorption spectroscopy

    PubMed Central

    2010-01-01

    The local structure of vanadium oxide supported on nanostructured SiO2 (VxOy/SBA-15) was investigated by in situ X-ray absorption spectroscopy (XAS). Because the number of potential parameters in XAS data analysis often exceeds the number of "independent" parameters, evaluating the reliability and significance of a particular fitting procedure is mandatory. The number of independent parameters (Nyquist) may not be sufficient. Hence, in addition to the number of independent parameters, a novel approach to evaluate the significance of structural fitting parameters in XAS data analysis is introduced. Three samples with different V loadings (i.e. 2.7 wt %, 5.4 wt %, and 10.8 wt %) were employed. Thermal treatment in air at 623 K resulted in characteristic structural changes of the V oxide species. Independent of the V loading, the local structure around V centers in dehydrated VxOy/SBA-15 corresponded to an ordered arrangement of adjacent V2O7 units. Moreover, the V2O7 units were found to persist under selective oxidation reaction conditions. PMID:20181222

  1. Formation and Stabilization of Combustion-Generated, Environmentally Persistent Radicals on Ni(II)O Supported on a Silica Surface

    PubMed Central

    Vejerano, Eric; Lomnicki, Slawomir M.; Dellinger, Barry

    2013-01-01

    Previous studies have indicated Environmentally Persistent Free Radicals (EPFRs) are formed when hydroxyl- and chlorine-substituted aromatics chemisorbed on Cu(II)O and Fe(III)2O3 surfaces and were stabilized through their interactions with the surface metal cation. The current study reports our laboratory investigation on the formation and stabilization of EPFRs on an Ni(II)O surface. The EPFRs were produced by the chemisorption of adsorbates on the supported metal oxide surface and transfer of an electron from the adsorbate to the metal center, resulting in reduction of the metal cation. Depending on the temperature and the nature of the adsorbate, more than one type of organic radical was formed. A phenoxyl-type radical, with g-value between 2.0029 and 2.0044, and a semiquinone-type radical, with g-value from 2.0050 to as high as 2.0081, were observed. The half-lives on Ni(II)O were long and ranged from 1.5 to 5.2 days, which were similar to what were observed on Fe(III)2O3,. The yields of the EPFRs formed on Ni(II)O was ~ 8x higher than on Cu(II)O and ~50x higher than on Fe(III)2O3. PMID:22831558

  2. Bifunctional heterogeneous catalysis of silica-alumina-supported tertiary amines with controlled acid-base interactions for efficient 1,4-addition reactions.

    PubMed

    Motokura, Ken; Tanaka, Satoka; Tada, Mizuki; Iwasawa, Yasuhiro

    2009-10-19

    We report the first tunable bifunctional surface of silica-alumina-supported tertiary amines (SA-NEt(2)) active for catalytic 1,4-addition reactions of nitroalkanes and thiols to electron-deficient alkenes. The 1,4-addition reaction of nitroalkanes to electron-deficient alkenes is one of the most useful carbon-carbon bond-forming reactions and applicable toward a wide range of organic syntheses. The reaction between nitroethane and methyl vinyl ketone scarcely proceeded with either SA or homogeneous amines, and a mixture of SA and amines showed very low catalytic activity. In addition, undesirable side reactions occurred in the case of a strong base like sodium ethoxide employed as a catalytic reagent. Only the present SA-supported amine (SA-NEt(2)) catalyst enabled selective formation of a double-alkylated product without promotions of side reactions such as an intramolecular cyclization reaction. The heterogeneous SA-NEt(2) catalyst was easily recovered from the reaction mixture by simple filtration and reusable with retention of its catalytic activity and selectivity. Furthermore, the SA-NEt(2) catalyst system was applicable to the addition reaction of other nitroalkanes and thiols to various electron-deficient alkenes. The solid-state magic-angle spinning (MAS) NMR spectroscopic analyses, including variable-contact-time (13)C cross-polarization (CP)/MAS NMR spectroscopy, revealed that acid-base interactions between surface acid sites and immobilized amines can be controlled by pretreatment of SA at different temperatures. The catalytic activities for these addition reactions were strongly affected by the surface acid-base interactions.

  3. Cube-like α-Fe2O3 supported on ordered multimodal porous carbon as high performance electrode material for supercapacitors.

    PubMed

    Chaudhari, Nitin K; Chaudhari, Sudeshna; Yu, Jong-Sung

    2014-11-01

    Well-dispersed cube-like iron oxide (α-Fe2O3) nanoparticles (NPs) supported on ordered multimodal porous carbon (OMPC) are synthesized for the first time by a facile and efficient glycine-assisted hydrothermal route. The effect of OPMC support on growth and formation mechanism of the Fe2O3 NPs is discussed. OMPC as a supporting material plays a pivotal role of controlling the shape, size, and dispersion of the Fe2O3 NPs. As-synthesized α-Fe2O3/OMPC composites reveal significant improvement in the performance as electrode material for supercapacitors. Compared to the bare Fe2O3 and OMPC, the composite exhibits excellent cycling stability, rate capability, and enhanced specific capacitances of 294 F g(-1) at 1.5 A g(-1), which is twice that of OMPC (145 F g(-1)) and about four times higher than that of bare Fe2O3 (85 F g(-1)). The improved electrochemical performance of the composite can be attributed to the well-defined structure, high conductivity, and hierarchical porosity of OMPC as well as the unique α-Fe2O3 NPs with cube-like morphology well-anchored on the OMPC support, which makes the composite a promising candidate for supercapacitors.

  4. Beneficial role of ZnO photocatalyst supported with porous activated carbon for the mineralization of alizarin cyanin green dye in aqueous solution

    PubMed Central

    Muthirulan, P.; Meenakshisundararam, M.; Kannan, N.

    2012-01-01

    The present investigation depicts the development of a simple and low cost method for the removal of color from textile dyeing and printing wastewater using ZnO as photocatalyst supported with porous activated carbon (AC). Photocatalytic degradation studies were carried out for water soluble toxic alizarin cyanin green (ACG) dye in aqueous suspension along with activated carbon (AC) as co-adsorbent. Different parameters like concentration of ACG dye, irradiation time, catalyst concentration and pH have also been studied. The pseudo first order kinetic equation was found to be applicable in the present dye-catalyst systems. It was observed that photocatalytic degradation by ZnO along with AC was a more effective and faster mode of removing ACG from aqueous solutions than the ZnO alone. PMID:25685455

  5. Open-Pore Two-Dimensional MFI Zeolite Nanosheets for the Fabrication of Hydrocarbon-Isomer-Selective Membranes on Porous Polymer Supports.

    PubMed

    Zhang, Han; Xiao, Qiang; Guo, Xianghai; Li, Najun; Kumar, Prashant; Rangnekar, Neel; Jeon, Mi Young; Al-Thabaiti, Shaeel; Narasimharao, Katabathini; Basahel, Sulaiman Nasir; Topuz, Berna; Onorato, Frank J; Macosko, Christopher W; Mkhoyan, K Andre; Tsapatsis, Michael

    2016-06-13

    Two-dimensional zeolite nanosheets that do not contain any organic structure-directing agents were prepared from a multilamellar MFI (ML-MFI) zeolite. ML-MFI was first exfoliated by melt compounding and then detemplated by treatment with a mixture of H2 SO4 and H2 O2 (piranha solution). The obtained OSDA-free MFI nanosheets disperse well in water and can be used for coating applications. Deposits made on porous polybenzimidazole (PBI) supports by simple filtration of these suspensions exhibit an n-butane/isobutane selectivity of 5.4, with an n-butane permeance of 3.5×10(-7)  mol m(-2)  s(-1)  Pa(-1) (ca. 1000 GPU). PMID:27101318

  6. Comparative Investigation on Thermal Insulation of Polyurethane Composites Filled with Silica Aerogel and Hollow Silica Microsphere.

    PubMed

    Liu, Chunyuan; Kim, Jin Seuk; Kwon, Younghwan

    2016-02-01

    This paper presents a comparative study on thermal conductivity of PU composites containing open-cell nano-porous silica aerogel and closed-cell hollow silica microsphere, respectively. The thermal conductivity of PU composites is measured at 30 degrees C with transient hot bridge method. The insertion of polymer in pores of silica aerogel creates mixed interfaces, increasing the thermal conductivity of resulting composites. The measured thermal conductivity of PU composites filled with hollow silica microspheres is estimated using theoretical models, and is in good agreement with Felske model. It appears that the thermal conductivity of composites decreases with increasing the volume fraction (phi) when hollow silica microsphere (eta = 0.916) is used. PMID:27433652

  7. Comparative Investigation on Thermal Insulation of Polyurethane Composites Filled with Silica Aerogel and Hollow Silica Microsphere.

    PubMed

    Liu, Chunyuan; Kim, Jin Seuk; Kwon, Younghwan

    2016-02-01

    This paper presents a comparative study on thermal conductivity of PU composites containing open-cell nano-porous silica aerogel and closed-cell hollow silica microsphere, respectively. The thermal conductivity of PU composites is measured at 30 degrees C with transient hot bridge method. The insertion of polymer in pores of silica aerogel creates mixed interfaces, increasing the thermal conductivity of resulting composites. The measured thermal conductivity of PU composites filled with hollow silica microspheres is estimated using theoretical models, and is in good agreement with Felske model. It appears that the thermal conductivity of composites decreases with increasing the volume fraction (phi) when hollow silica microsphere (eta = 0.916) is used.

  8. Fungus-mediated biotransformation of amorphous silica in rice husk to nanocrystalline silica.

    PubMed

    Bansal, Vipul; Ahmad, Absar; Sastry, Murali

    2006-11-01

    Rice husk is a cheap agro-based waste material, which harbors a substantial amount of silica in the form of amorphous hydrated silica grains. However, there have been no attempts at harnessing the enormous amount of amorphous silica present in rice husk and its room-temperature biotransformation into crystalline silica nanoparticles. In this study, we address this issue and describe how naturally deposited amorphous biosilica in rice husk can be bioleached and simultaneously biotransformed into high value crystalline silica nanoparticles. We show here that the fungus Fusarium oxysporum rapidly biotransforms the naturally occurring amorphous plant biosilica into crystalline silica and leach out silica extracellularly at room temperature in the form of 2-6 nm quasi-spherical, highly crystalline silica nanoparticles capped by stabilizing proteins; that the nanoparticles are released into solution is an advantage of this process with significant application and commercial potential. Calcination of the silica nanoparticles leads to loss of occluded protein and to an apparently porous structure often of cubic morphology. The room-temperature synthesis of oxide nanomaterials using microorganisms starting from potential cheap agro-industrial waste materials is an exciting possibility and could lead to an energy-conserving and economically viable green approach toward the large-scale synthesis of oxide nanomaterials.

  9. Fungus-mediated biotransformation of amorphous silica in rice husk to nanocrystalline silica.

    PubMed

    Bansal, Vipul; Ahmad, Absar; Sastry, Murali

    2006-11-01

    Rice husk is a cheap agro-based waste material, which harbors a substantial amount of silica in the form of amorphous hydrated silica grains. However, there have been no attempts at harnessing the enormous amount of amorphous silica present in rice husk and its room-temperature biotransformation into crystalline silica nanoparticles. In this study, we address this issue and describe how naturally deposited amorphous biosilica in rice husk can be bioleached and simultaneously biotransformed into high value crystalline silica nanoparticles. We show here that the fungus Fusarium oxysporum rapidly biotransforms the naturally occurring amorphous plant biosilica into crystalline silica and leach out silica extracellularly at room temperature in the form of 2-6 nm quasi-spherical, highly crystalline silica nanoparticles capped by stabilizing proteins; that the nanoparticles are released into solution is an advantage of this process with significant application and commercial potential. Calcination of the silica nanoparticles leads to loss of occluded protein and to an apparently porous structure often of cubic morphology. The room-temperature synthesis of oxide nanomaterials using microorganisms starting from potential cheap agro-industrial waste materials is an exciting possibility and could lead to an energy-conserving and economically viable green approach toward the large-scale synthesis of oxide nanomaterials. PMID:17061888

  10. Nanoparticle-doped radioluminescent silica optical fibers

    NASA Astrophysics Data System (ADS)

    Mrazek, J.; Nikl, M.; Kasik, I.; Podrazky, O.; Aubrecht, J.; Beitlerova, A.

    2014-05-01

    This contribution deals with the preparation and characterization of the silica optical fibers doped by nanocrystalline zinc silicate. The sol-gel approach was employed to prepare colloidal solution of zinc silicate precursors. Prepared sol was thermally treated to form nanocrystalline zinc silicate disperzed inside amorphous silica matrix or soaked inside the porous silica frit deposed inside the silica substrate tube which was collapsed into preform and drawn into optical fiber. Single mode optical fiber with the core diameter 15 μm and outer diamer 125 μm was prepared. Optical and waveguiding properties of the fiber were analyzed. Concentration of the zinc silicate in the fiber was 0.93 at. %. Radioluminescence properties of nanocrystalline zinc silicate powder and of the prepared optical fiber were investigated. The nanoparticle doped samples appear a emission maximum at 390 nm.

  11. A kinetic study on the adsorption and reaction of hydrogen over silica-supported ruthenium and silver-ruthenium catalysts during the hydrogenation of carbon monoxide

    SciTech Connect

    VanderWiel, D.P.

    1999-02-12

    Although the catalytic hydrogenation of carbon monoxide has been a subject of considerable investigation for many years, its increasing economical attractiveness as an industrial source of hydrocarbons has recently led to a search for more active and selective catalysts. A fundamental problem in the development of such catalysts is an incomplete knowledge of the operative surface processes, due in large part to the inability to accurately measure surface concentrations of reactant species during reaction. Specifically, the concentration of surface hydrogen proves difficult to estimate using normally revealing techniques such as transient isotopic exchange due to kinetic isotope effects. Knowledge of such concentrations is essential to the determination of the mechanisms of adsorption and reaction, since many kinetic parameters are concentration dependent. It is the aim of this research to investigate the mechanism and kinetics of the adsorption and reaction of hydrogen on silica-supported ruthenium and silver-ruthenium catalysts during the hydrogenation of carbon monoxide. By preadsorbing carbon monoxide onto the surface of ruthenium and silver-ruthenium catalysts, the kinetics of hydrogen adsorption and reaction can be monitored upon exposure of this surface to ambient hydrogen gas. This is accomplished by conducting identical experiments on two separate systems. First, the formation of methane is monitored using mass spectroscopy, and specific reaction rates and apparent activation energies are measured. Next, in situ {sup 1}H-NMR is used to monitor the amount of hydrogen present on the catalyst surface during adsorption and reaction. The results for these two sets of experiments are then combined to show a correlation between the rate of reaction and the surface hydrogen concentration. Finally, transition state theory is applied to this system and is used to explain the observed change in the apparent activation energy. The structure sensitivity of hydrogen

  12. Silica reusable surface insulation

    NASA Technical Reports Server (NTRS)

    Goldstein, H. E.; Smith, M.; Leiser, D. B. (Inventor)

    1976-01-01

    A reusable silica surface insulation material is provided by bonding amorphous silica fibers with colloidal silica at an elevated temperature. The surface insulation is ordinarily manufactured in the form of blocks (i.e., tiles).

  13. Lipase immobilized on hydrophobic porous polymer supports prepared by concentrated emulsion polymerization and their activity in the hydrolysis of triacylglycerides.

    PubMed

    Ruckenstein, E; Wang, X

    1993-09-20

    Microporous polymer supports for the immobilization of lipase have been prepared by the polymerization of a concentrated emulsion precursor. The concentrated emulsion consists of a mixture of styrene and divinyl-benzene containing a suitable surfactant and an initiator as the continuous phase and water as the dispersed phase. The volume fraction of the latter phase was greater than 0.74, which is the volume fraction of the dispersed phase for the most compact arrangement of spheres of equal radius. The lipase from Candida rugosa has been immobilized on the internal surface of the hydrophobic microporous poly(styrene-divinyl benzene) supports and used as biocatalysts for the hydrolysis of triacylglycerides. The effects of the amount of surfactant, of the molar ratio of divinylbenzene/styrene in the continuous phase, and of the aquaphilicity of the supports on the adsorption, activity, and stability of the immobilized lipase have been investigated. The microporous poly(styrene-divinylbenzene) adsorbents constitute excellent supports for lipase because both the amount adsorbed is large and the rate of enzymatic reaction per molecule of lipase is higher for the immobilized enzyme than for the free one.

  14. Method of making porous ceramic fluoride

    DOEpatents

    Reiner, Robert H.; Holcombe, Cressie E.

    1990-01-01

    A process for making a porous ceramic composite where fumed silica particles are coated with a nitrate, preferably aluminum nitrate. Next the nitrate is converted to an oxide and formed into a desired configuration. This configuration is heated to convert the oxide to an oxide silicate which is then react with HF, resulting in the fluoride ceramic, preferably aluminum fluoride.

  15. Absorption of ozone by porous particles

    SciTech Connect

    Afanas'ev, V.P.; Dorofeev, S.B.; Sinitsyn, V.I.; Smirnov, B.M.

    1981-11-01

    The absorption of ozone by porous zeolite, silica gel, and activated carbon particles has been studied experimentally. It was shown that in addition to absorption, dissociation of ozone on the surface plays an important and sometimes decisive role. The results obtained were used to analyze the nature of ball lightning.

  16. Silica powders for powder evacuated thermal insulating panel and method

    DOEpatents

    Harris, Michael T.; Basaran, Osman A.; Kollie, Thomas G.; Weaver, Fred J.

    1996-01-01

    A powder evacuated thermal insulating panel using generally spherical and porous silica particles of a median size less than about 100 nanometers in diameter, a pour packing density of about 0.4 to 0.6 g/cm.sup.3 and an external surface area in the range of about 90 to 600 m.sup.2/ g is described. The silica powders are prepared by reacting a tetraakyl silicate with ammonia and water in an alcohol solvent, distilling the solution after the reaction to remove the ammonia and recover the alcohol. The resulting aqueous slurry was dried, ball-milled, and dried again to provide the silica particles with defined internal and external porosity. The nanometer size and the large external surface area of the silica particles along with the internal and external porosity of the silica particles provide powder evacuated thermal insulating panels with significantly higher R-values than obtainable using previously known silica powders.

  17. Silica powders for powder evacuated thermal insulating panel and method

    DOEpatents

    Harris, Michael T.; Basaran, Osman A.; Kollie, Thomas G.; Weaver, Fred J.

    1994-01-01

    A powder evacuated thermal insulating panel using generally spherical and porous silica particles of a median size less than about 100 nanometers in diameter, a pour packing density of about 0.4 to 0.6 g/cm.sup.3 and an external surface area in the range of about 90 to 600 m.sup.2 /g is described. The silica powders are prepared by reacting a tetraakyl silicate with ammonia and water in an alcohol solvent, distilling the solution after the reaction to remove the ammonia and recover the alcohol. The resulting aqueous slurry was dried, ball-milled, and dried again to provide the silica particles with defined internal and external porosity. The nanometer size and the large external surface area of the silica particles along with the internal and external porosity of the silica particles provide powder evacuated thermal insulating panels with significantly higher R-values than obtainable using previously known silica powders.

  18. Silica powders for powder evacuated thermal insulating panel and method

    DOEpatents

    Harris, M.T.; Basaran, O.A.; Kollie, T.G.; Weaver, F.J.

    1996-01-02

    A powder evacuated thermal insulating panel using generally spherical and porous silica particles of a median size less than about 100 nanometers in diameter, a pour packing density of about 0.4 to 0.6 g/cm{sup 3} and an external surface area in the range of about 90 to 600 m{sup 2}/g is described. The silica powders are prepared by reacting a tetraalkyl silicate with ammonia and water in an alcohol solvent, distilling the solution after the reaction to remove the ammonia and recover the alcohol. The resulting aqueous slurry was dried, ball-milled, and dried again to provide the silica particles with defined internal and external porosity. The nanometer size and the large external surface area of the silica particles along with the internal and external porosity of the silica particles provide powder evacuated thermal insulating panels with significantly higher R-values than obtainable using previously known silica powders. 2 figs.

  19. Silica powders for powder evacuated thermal insulating panel and method

    DOEpatents

    Harris, Michael T.; Basaran, Osman A.; Kollie, Thomas G.; Weaver, Fred J.

    1995-01-01

    A powder evacuated thermal insulating panel using generally spherical and porous silica particles of a median size less than about 100 nanometers in diameter, a pour packing density of about 0.4 to 0.6 g/cm.sup.3 and an external surface area in the range of about 90 to 600 m.sup.2/ g is described. The silica powders are prepared by reacting a tetraakyl silicate with ammonia and water in an alcohol solvent, distilling the solution after the reaction to remove the ammonia and recover the alcohol. The resulting aqueous slurry was dried, ball-milled, and dried again to provide the silica particles with defined internal and external porosity. The nanometer size and the large external surface area of the silica particles along with the internal and external porosity of the silica particles provide powder evacuated thermal insulating panels with significantly higher R-values than obtainable using previously known silica powders.

  20. Modified silica-based heterogeneous catalysts for etherification of glycerol

    SciTech Connect

    Gholami, Zahra; Abdullah, Ahmad Zuhairi Gholami, Fatemeh; Vakili, Mohammadtaghi

    2015-07-22

    The advent of mesoporous silicas such as MCM-41 has provided new opportunities for research into supported metal catalysis. The loading of metals into framework structures and particularly into the pores of porous molecular sieves, has long been of interest because of their potential catalytic activity. Stable heterogeneous mesoporous basic catalysts were synthesized by wet impregnation of MCM-41 with calcium nitrate and lanthanum nitrate. The surface and structural properties of the prepared catalysts were characterized using BET surface analysis, SEM and TEM. MCM-41 and modified MCM-41 were used in the solventless etherification of glycerol to produce diglycerol as the desired product. The reaction was performed at 250 °C for 8 h, and catalyst activity was evaluated. Catalytic etherification over the 20%Ca{sub 1.6}La{sub 0.6}/MCM-41 catalyst resulted in the highest glycerol conversion of 91% and diglycerol yield of 43%.

  1. Silver nanoparticles incorporated onto ordered mesoporous silica from Tollen's reagent

    NASA Astrophysics Data System (ADS)

    Zienkiewicz-Strzałka, M.; Pasieczna-Patkowska, S.; Kozak, M.; Pikus, S.

    2013-02-01

    Noble metal nanostructures supported on mesoporous silica are bridge between traditional silica adsorbents and modern catalysts. In this work the Ag/SBA-15 mesoporous materials were synthesized and characterized. Various forms of nanosilver supported on ordered mesoporous template have been successfully obtained via proposed procedures. In all synthesized materials, Tollen's reagent (diammine silver complex [Ag(NH3)2]+) was used as a silver source. Silver nanoparticles were prepared by reduction of ammoniacal silver complex by formaldehyde in the solution of stabilizer. After reduction, Ag nanoparticles could be deposited on SBA-15, or added during traditional synthesis of SBA-15 giving silver or silver chloride nanoparticles in the combination with porous silica. Silver nanostructures as nanoparticles or nanowires were also embedded onto the SBA-15 by incipient wetness impregnation of silver ions. Absorbed silver ions were next reduced under hydrogen at high temperature. There are many advantages of utilized ammoniacal silver complex as a silver source. Proposed method is capable to synthesis of various metal nanostructures with controlled composition and morphology. The silver ammonia complex is composed of two ions surrounding and protecting the central silver ion, so it is possible to obtain very small nanoparticles using simple approach without any functionalization of external and internal surface of SBA-15. This approach allows obtaining greatly small silver nanoparticles on SBA-15 (4 nm) or nanowires depending on the metal loading amount. Moreover, the colloidal silver solution prepared from Tollen's reagent, in the presence of triblock copolymer, remains stable for a long time. Reduction of Tollen's reagent to silver colloidal solution seems to be efficient, fast and interesting approach for the preparation of supported silver nanostructures Obtained samples were characterized by powder X-ray diffraction, small angle X-ray scattering (SAXS), UV

  2. Mesochanneled hierarchically porous aluminosiloxane aerogel microspheres as a stable support for pH-responsive controlled drug release.

    PubMed

    Vazhayal, Linsha; Talasila, Sindhoor; Abdul Azeez, Peer Mohamed; Solaiappan, Ananthakumar

    2014-09-10

    The molecular-scale self-assembly of a 3D aluminosiloxane (Al-O-Si) hybrid gel network was successfully performed via the cocondensation of hydrolyzed alumina (AlOOH) and (3-aminopropyl)trimethoxysilane (APS). It was transformed into a microspherical aerogel framework of Al-O-Si containing mesochannels with tunable hierarchically bimodal meso/macroporosities by a subcritical drying technique. Good homogeneity of AlOOH and APS brought during the synthesis guaranteed a uniform distribution of two metal oxides in a single body. A systematic characterization of the aerogel support was carried out using FTIR, SEM, TEM, nitrogen adsorption/desorption analysis, WAXS, SAXS, and ξ-potential measurement in order to explore the material for drug uptake and release. The drug loading and release capacity and chemical stability of an aluminosiloxane aerogel were studied using two nonsteroidal antiinflammatory drugs, ibuprofen and aspirin. A comprehensive evaluation of the aluminosiloxane aerogel with ordered mesoporous MCM-41 was also performed. Aerogel supports showed a high drug loading capacity and a pH-responsive controlled-release property compared to MCM-41. Meanwhile, kinetic modeling studies indicate that the drug releases with a zero-order profile following the Korsmeyer-Peppas model. The biocompatibility of aluminosiloxane aerogels was established via ex vivo and in vivo studies. We also outline the use of aluminosiloxane aerogel as a support for a possible 3D matrix for an osteoconductive structure for bone tissue engineering.

  3. Diatom-inspired microfluidic generation of tunable emulsions for macroporous silica

    NASA Astrophysics Data System (ADS)

    Zendejas, Frank Jesse

    emulsification steps, orthosilicic acid (1 M) and triethylenetetramine (6.7 mM) are both introduced into the intermediate phase separately using the two microchannels causing the intermediate phase to form a templated silica gel around the inner monodisperse oil droplets. After calcinations, the resulting porous silica particles were 150 mum in diameter with pore sizes on the order of 5 mum. The incorporation of gold nanoparticles within the intermediate phase of the double emulsion embedded them within the templated silica. During the calcination process in air, the gold nanoparticles served as catalysts as was clearly evident from the 20--40 mum diameter nanowires observed in the silica. Using diatoms as inspiration, a new technique was demonstrated to create ordered macroporous materials efficiently, by combing template-directed synthesis and biomimetic chemistry with microfluidics. This technique opens the possibility of tailoring materials specific to their intended applications such as bioseparation filters, high surface area catalytic supports, tissue engineering supports, size-exclusion chromatography, and three-dimensional metamaterials for photonics applications.

  4. Applying a tapered electrode on a porous ceramic support tube by masking a band inside the tube and drawing in electrode material from the outside of the tube by suction

    DOEpatents

    Vasilow, T.R.; Zymboly, G.E.

    1991-12-17

    An electrode is deposited on a support by providing a porous ceramic support tube having an open end and closed end; masking at least one circumferential interior band inside the tube; evacuating air from the tube by an evacuation system, to provide a permeability gradient between the masked part and unmasked part of the tube; applying a liquid dispersion of solid electrode particles to the outside surface of the support tube, where liquid flows through the wall, forming a uniform coating over the unmasked support part and a tapered coating over the masked part. 2 figures.

  5. Applying a tapered electrode on a porous ceramic support tube by masking a band inside the tube and drawing in electrode material from the outside of the tube by suction

    DOEpatents

    Vasilow, Theodore R.; Zymboly, Gregory E.

    1991-01-01

    An electrode is deposited on a support by providing a porous ceramic support tube (10) having an open end (14) and closed end (16); masking at least one circumferential interior band (18 and 18') inside the tube; evacuating air from the tube by an evacuation system (30), to provide a permeability gradient between the masked part (18 and 18') and unmasked part (20) of the tube; applying a liquid dispersion of solid electrode particles to the outside surface of the support tube, where liquid flows through the wall, forming a uniform coating (42) over the unmasked support part (20) and a tapered coating over the masked part (18 and 18').

  6. In situ synthesis of molecularly imprinted nanoparticles in porous support membranes using high-viscosity polymerization solvents.

    PubMed

    Renkecz, Tibor; László, Krisztina; Horváth, Viola

    2012-06-01

    There is a growing need in membrane separations for novel membrane materials providing selective retention. Molecularly imprinted polymers (MIPs) are promising candidates for membrane functionalization. In this work, a novel approach is described to prepare composite membrane adsorbers incorporating molecularly imprinted microparticles or nanoparticles into commercially available macroporous filtration membranes. The polymerization is carried out in highly viscous polymerization solvents, and the particles are formed in situ in the pores of the support membrane. MIP particle composite membranes selective for terbutylazine were prepared and characterized by scanning electron microscopy and N₂ porosimetry. By varying the polymerization solvent microparticles or nanoparticles with diameters ranging from several hundred nanometers to 1 µm could be embedded into the support. The permeability of the membranes was in the range of 1000 to 20,000 Lm⁻²  hr⁻¹  bar⁻¹. The imprinted composite membranes showed high MIP/NIP (nonimprinted polymer) selectivity for the template in organic media both in equilibrium-rebinding measurements and in filtration experiments. The solid phase extraction of a mixture of the template, its analogs, and a nonrelated compound demonstrated MIP/NIP selectivity and substance selectivity of the new molecularly imprinted membrane. The synthesis technique offers a potential for the cost-effective production of selective membrane adsorbers with high capacity and high throughput. PMID:22641529

  7. Free-Form-Fabricated Commercially Pure Ti and Ti6Al4V Porous Scaffolds Support the Growth of Human Embryonic Stem Cell-Derived Mesodermal Progenitors

    PubMed Central

    de Peppo, G. M.; Palmquist, A.; Borchardt, P.; Lennerås, M.; Hyllner, J.; Snis, A.; Lausmaa, J.; Thomsen, P.; Karlsson, C.

    2012-01-01

    Commercially-pure titanium (cp-Ti) and the titanium-aluminum-vanadium alloy (Ti6Al4V) are widely used as reconstructive implants for skeletal engineering applications, due to their good mechanical properties, biocompatibility and ability to integrate with the surrounding bone. Electron beam melting technology (EBM) allows the fabrication of customized implants with tailored mechanical properties and high potential in the clinical practice. In order to augment the interaction with the biological tissue, stem cells have recently been combined with metallic scaffolds for skeletal engineering applications. We previously demonstrated that human embryonic stem cell-derived mesodermal progenitors (hES-MPs) hold a great potential to provide a homogeneous and unlimited supply of cells for bone engineering applications. This study demonstrates the effect of EBM-fabricated cp-Ti and Ti6Al4V porous scaffolds on hES-MPs behavior, in terms of cell attachment, growth and osteogenic differentiation. Displaying different chemical composition but similar surface properties, EBM-fabricated cp-Ti and Ti6Al4V scaffolds supported cell attachment and growth, and did not seem to alter the expression of genes involved in osteogenic differentiation and affect the alkaline phosphatase activity. In conclusion, interfacing hES-MPs to EBM-fabricated scaffolds may represent an interesting strategy for design of third-generation biomaterials, with the potential to promote implant integration in clinical conditions characterized by poor bone quality. PMID:22262956

  8. Porous VOxNy nanoribbons supported on CNTs as efficient and stable non-noble electrocatalysts for the oxygen reduction reaction

    PubMed Central

    Huang, K.; Bi, K.; Lu, Y. K.; Zhang, R.; Liu, J.; Wang, W. J.; Tang, H. L.; Wang, Y. G.; Lei, M.

    2015-01-01

    Novel nanocomposites of carbon nanotubes supported porous VOxNy nonoribbons (VOxNy-CNTs) have been synthesized by the annealing of the sol-gel mixture of CNTs and V2O5 under NH3 atmosphere as well as the ageing process in air. Besides the morphological and structural characterizations revealed by TEM, SEAD, EDS, XRD and XPS measurements, typical electrochemical tests including cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry have been employed to determine the oxygen reduction reaction (ORR) performance of VOxNy-CNTs. Inspiringly, the results indicate that VOxNy-CNTs catalyst exhibits a 0.4 mA/cm2 larger diffusion-limited current density, a 0.10  V smaller onset potential value, a 10.73% less of ORR current decay and an excellent methanol-tolerance compared with commercial Pt/C catalyst. Therefore, we have reasonable grounds to believe that this new VOxNy-CNTs nanocomposites can be regarded as a promising non-precious methanol-tolerant ORR catalyst candidate for alkaline fuel cells. PMID:26616719

  9. Porous VO(x)N(y) nanoribbons supported on CNTs as efficient and stable non-noble electrocatalysts for the oxygen reduction reaction.

    PubMed

    Huang, K; Bi, K; Lu, Y K; Zhang, R; Liu, J; Wang, W J; Tang, H L; Wang, Y G; Lei, M

    2015-01-01

    Novel nanocomposites of carbon nanotubes supported porous VO(x)N(y) nonoribbons (VO(x)N(y)-CNTs) have been synthesized by the annealing of the sol-gel mixture of CNTs and V2O5 under NH3 atmosphere as well as the ageing process in air. Besides the morphological and structural characterizations revealed by TEM, SEAD, EDS, XRD and XPS measurements, typical electrochemical tests including cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry have been employed to determine the oxygen reduction reaction (ORR) performance of VO(x)N(y)-CNTs. Inspiringly, the results indicate that VO(x)N(y)-CNTs catalyst exhibits a 0.4 mA/cm(2) larger diffusion-limited current density, a 0.10  V smaller onset potential value, a 10.73% less of ORR current decay and an excellent methanol-tolerance compared with commercial Pt/C catalyst. Therefore, we have reasonable grounds to believe that this new VO(x)N(y)-CNTs nanocomposites can be regarded as a promising non-precious methanol-tolerant ORR catalyst candidate for alkaline fuel cells. PMID:26616719

  10. The effect of ionic species on pH dependent response of silica coated optical fibers

    NASA Astrophysics Data System (ADS)

    Elwood, Jacqueline; Ohodnicki, Paul R.

    2016-05-01

    Optical fiber pH sensors functionalized with a gold nanoparticle (AuNP)/porous silica film were developed. The transmission of light through the fiber is affected by the change in the refractive index of the porous silica-based nanocomposite coated film as ionic species are concentrated into the coating film when the silica surface becomes negatively charged with increasing pH. To investigate the dependence of the response on the ionic species in solution, we report the optical response of Au/silica film coated fibers in a variety of salt solutions. The response is indeed sensitive to different ionic species in solution. The details of the response are likely also sensitive to the microstructure of the porous silica-based sensing layer.

  11. One-pot preparation of silica-supported hybrid immobilized metal affinity adsorbent with macroporous surface based on surface imprinting coating technique combined with polysaccharide incorporated sol--gel process.

    PubMed

    Li, Feng; Li, Xue-Mei; Zhang, Shu-Sheng

    2006-10-01

    A simple and reliable one-pot approach using surface imprinting coating technique combined with polysaccharide incorporated sol-gel process was established to synthesize a new organic-inorganic hybrid matrix possessing macroporous surface and functional ligand. Using mesoporous silica gel being a support, immobilized metal affinity adsorbent with a macroporous shell/mesoporous core structure was obtained after metal ion loading. In the prepared matrix, covalently bonded coating and morphology manipulation on silica gel was achieved by using one-pot sol-gel process starting from an inorganic precursor, -glycidoxypropyltrimethoxysiloxane (GPTMS), and a functional biopolymer, chitosan (CS) at the atmosphere of imprinting polyethylene glycol (PEG). Self-hydrolysis of GPTMS, self-condensation, and co-condensation of silanol groups (Si-OH) from siloxane and silica gel surface, and in situ covalent cross-linking of CS created an orderly coating on silica gel surface. PEG extraction using hot ammonium hydroxide solution gave a chemically and mechanically stabilized pore structure and deactivated residual epoxy groups. The prepared matrix was characterized by using X-ray energy dispersion spectroscopy (EDX), scanning electron microscopy (SEM) and mercury intrusion porosimetry. The matrix possessed a high capacity for copper ion loading. Protein adsorption performance of the new immobilized metal affinity adsorbent was evaluated by batch adsorption and column chromatographic experiment using bovine serum albumin (BSA) as a simple model protein. Under the optimized coating conditions, the obtained macroporous surface resulted in a fast kinetics and high capability for protein adsorption, while the matrix non-charged with metal ions offered a low non-specific adsorption. PMID:16860332

  12. Adsorption on Highly Ordered Porous Alumina

    NASA Astrophysics Data System (ADS)

    Mistura, Giampaolo; Bruschi, Lorenzo; Lee, Woo

    2016-10-01

    Porous anodic aluminum oxide (AAO) is characterized by a regular arrangement of the pores with a narrow pore size distribution over extended areas, uniform pore depth, and solid pore walls without micropores. Thanks to significant improvements in anodization techniques, structural engineering of AAO allows to accurately tailor the pore morphology. These features make porous AAO an excellent substrate to study adsorption phenomena. In this paper, we review recent experiments involving the adsorption in porous AAO. Particular attention will be devoted to adsorption in straight and structured pores with a closed end which shed new light on fundamental issues like the origin of hysteresis in closed end pores and the nature of evaporation from ink-bottle pores. The results will be compared to those obtained in other synthetic materials like porous silicon and silica.

  13. Complete doping in solid-state by silica-supported perchloric acid as dopant solid acid: Synthesis and characterization of the novel chiral composite of poly [(±)-2-(sec-butyl) aniline

    NASA Astrophysics Data System (ADS)

    Farrokhzadeh, Abdolkarim; Modarresi-Alam, Ali Reza

    2016-05-01

    Poly [(±)-2-(sec-butyl) aniline]/silica-supported perchloric acid composites were synthesized by combination of poly[(±)-2-sec-butylaniline] base (PSBA) and the silica-supported perchloric acid (SSPA) as dopant solid acid in solid-state. The X-ray photoelectron spectroscopy (XPS) and CHNS results confirm nigraniline oxidation state and complete doping for composites (about 75%) and non-complete for the PSBA·HCl salt (about 49%). The conductivity of samples was (≈0.07 S/cm) in agreement with the percent of doping obtained of the XPS analysis. Also, contact resistance was determined by circular-TLM measurement. The morphology of samples by the scanning electron microscopy (SEM) and their coating were investigated by XPS, SEM-map and energy-dispersive X-ray spectroscopy (EDX). The key benefits of this work are the preparation of conductive chiral composite with the delocalized polaron structure under green chemistry and solid-state condition, the improvement of the processability by inclusion of the 2-sec-butyl group and the use of dopant solid acid (SSPA) as dopant.

  14. Fabrication of mesoporous silica for ultra-low-k interlayer dielectrics

    NASA Astrophysics Data System (ADS)

    Fujii, Nobutoshi; Kohmura, Kazuo; Nakayama, Takahiro; Tanaka, Hirofumi; Hata, Nobuhiro; Seino, Yutaka; Kikkawa, Takamaro

    2005-11-01

    We have developed sol-gel self-assembly techniques to control the pore structure and diameter of ultra-low-k interlayer dielectric (ILD) films. Porous silica films have been fabricated using cationic and nonionic surfactants as templates, resulting in 2D-hexagonal and disordered pore structures, respectively. The disordered mesoporous silica film has a worm-hole like network of pore channels having a uniform diameter. Precursors of the mesoporous silica films were synthesized by use of tetraethyl-orthosilicate (TEOS), inorganic acid, water, ethanol and various surfactants. The surfactants used were cationic alkyltrimethyl-ammonium (ATMA) chloride surfactants for 2D-hexagonal pores and nonionic tri-block copolymer for disordered structures. Dimethyldiethoxysilane (DMDEOS) was added for forming the disordered mesoporous silica. The disordered cylindrical pore structure with a uniform pore size was fabricated by controlling the static electrical interaction between the surfactant and the silica oligomer with methyl group of DMDEOS. Tetramethylcycrotetrasiloxane (TMCTS) vapor treatment was developed, which improved the mechanical strength of mesoporous silica films. The TMCTS polymer covered the pore wall surface and cross-linked to passivate the mechanical defects in the silica wall. Significant enhancement of mechanical strength was demonstrated by TMCTS vapor treatment. The porous silica film modified with a catalyst and a plasma treatment achieved higher mechanical strength and lower dielectric constant than conventional porous silica films because the TMCTS vapor treatment was more effective for mechanical reinforcement and hydrophobicity.

  15. Sample Desorption/Onization From Mesoporous Silica

    DOEpatents

    Iyer, Srinivas; Dattelbaum, Andrew M.

    2005-10-25

    Mesoporous silica is shown to be a sample holder for laser desorption/ionization of mass spectrometry. Supported mesoporous silica was prepared by coating an ethanolic silicate solution having a removable surfactant onto a substrate to produce a self-assembled, ordered, nanocomposite silica thin film. The surfactant was chosen to provide a desired pore size between about 1 nanometer diameter and 50 nanometers diameter. Removal of the surfactant resulted in a mesoporous silica thin film on the substrate. Samples having a molecular weight below 1000, such as C.sub.60 and tryptophan, were adsorbed onto and into the mesoporous silica thin film sample holder and analyzed using laser desorption/ionization mass spectrometry.

  16. Plasma Spray Physical Vapor Deposition of La1- x Sr x Co y Fe1- y O3-δ Thin-Film Oxygen Transport Membrane on Porous Metallic Supports

    NASA Astrophysics Data System (ADS)

    Jarligo, Maria Ophelia; Mauer, Georg; Bram, Martin; Baumann, Stefan; Vaßen, Robert

    2014-01-01

    Plasma spray physical vapor deposition (PS-PVD) is a very promising route to manufacture ceramic coatings, combining the efficiency of thermal spray processes and characteristic features of thin PVD coatings. Recently, this technique has been investigated to effectively deposit dense thin films of perovskites particularly with the composition of La0.58Sr0.4Co0.2Fe0.8O3-δ (LSCF) for application in gas separation membranes. Furthermore, asymmetric type of membranes with porous metallic supports has also attracted research attention due to the advantage of good mechanical properties suitable for use at high temperatures and high permeation rates. In this work, both approaches are combined to manufacture oxygen transport membranes made of gastight LSCF thin film by PS-PVD on porous NiCoCrAlY metallic supports. The deposition of homogenous dense thin film is challenged by the tendency of LSCF to decompose during thermal spray processes, irregular surface profile of the porous metallic substrate and crack and pore-formation in typical ceramic thermal spray coatings. Microstructure formation and coating build-up during PS-PVD as well as the annealing behavior at different temperatures of LSCF thin films were investigated. Finally, measurements of leak rates and oxygen permeation rates at elevated temperatures show promising results for the optimized membranes.

  17. Multifunctional mesoporous silica catalyst

    DOEpatents

    Lin, Victor Shang-Yi; Tsai, Chih-Hsiang; Chen, Hung-Ting; Pruski, Marek; Kobayashi, Takeshi

    2015-03-31

    The present invention provides bifunctional silica mesoporous materials, including mesoporous silica nanoparticles ("MSN"), having pores modified with diarylammonium triflate and perfluoroaryl moieties, that are useful for the acid-catalyzed esterification of organic acids with organic alcohols.

  18. What Is Crystalline Silica?

    MedlinePlus

    ... silica, and requires a repirator protection program until engineering controls are implemented. Additionally, OSHA has a National ... silica materials with safer substitutes, whenever possible. ■ Provide engineering or administrative controls, where feasible, such as local ...

  19. Polymer-silica hybrids for separation of CO2 and catalysis of organic reactions

    NASA Astrophysics Data System (ADS)

    Silva Mojica, Ernesto

    Porous materials comprising polymeric and inorganic segments have attracted interest from the scientific community due to their unique properties and functionalities. The physical and chemical characteristics of these materials can be effectively exploited for adsorption applications. This dissertation covers the experimental techniques for fabrication of poly(vinyl alcohol) (PVA) and silica (SiO2) porous supports, and their functionalization with polyamines for developing adsorbents with potential applications in separation of CO2 and catalysis of organic reactions. The supports were synthesized by processes involving (i) covalent cross-linking of PVA, (ii) hydrolysis and poly-condensation of silica precursors (i,e,. sol-gel synthesis), and formation of porous structures via (iii) direct templating and (iv) phase inversion techniques. Their physical structure was controlled by the proper combination of the preparation procedures, which resulted in micro-structured porous materials in the form of micro-particles, membranes, and pellets. Their adsorption characteristics were tailored by functionalization with polyethyleneimine (PEI), and their physicochemical properties were characterized by vibrational spectroscopy (FTIR, UV-vis), microscopy (SEM), calorimetry (TGA, DSC), and adsorption techniques (BET, step-switch adsorption). Spectroscopic investigations of the interfacial cross-linking reactions of PEI and PVA with glutaraldehyde (GA) revealed that PEI catalyzes the cross-linking reactions of PVA in absence of external acid catalysts. In-situ IR spectroscopy coupled with a focal plane array (FPA) image detector allowed the characterization of a gradient interface on a PEI/PVA composite membrane and the investigation of the cross-linking reactions as a function of time and position. The results served as a basis to postulate possible intermediates, and propose the reaction mechanisms. The formulation of amine-functionalized CO2 capture sorbents was based on the

  20. Silica extraction from geothermal water

    DOEpatents

    Bourcier, William L; Bruton, Carol J

    2014-09-23

    A method of producing silica from geothermal fluid containing low concentration of the silica of less than 275 ppm includes the steps of treating the geothermal fluid containing the silica by reverse osmosis treatment thereby producing a concentrated fluid containing the silica, seasoning the concentrated fluid thereby producing a slurry having precipitated colloids containing the silica, and separating the silica from the slurry.

  1. Bio-templated synthesis of highly ordered macro-mesoporous silica material for sustained drug delivery

    NASA Astrophysics Data System (ADS)

    Qu, Fengyu; Lin, Huiming; Wu, Xiang; Li, Xiaofeng; Qiu, Shilun; Zhu, Guangshan

    2010-05-01

    The bimodal porous structured silica materials consisting of macropores with the diameter of 5-20 μm and framework-like mesopores with the diameter of 4.7-6.0 nm were prepared using natural Manchurian ash and mango linin as macropored hard templates and P123 as mesopore soft templates, respectively. The macroporous structures of Manchurian ash and mango linin were replicated with the walls containing highly ordered mesoporous silica as well. As-synthesized dual porous silica was characterized by scanning electron microscope (SEM), powder X-ray diffraction (XRD), transmission electron microscope (TEM) and nitrogen adsorption/desorption, fourier transform IR (FTIR) spectroscopy, and thermo-gravimetric analyzer (TGA). Ibuprofen (Ibu) was employed as a model drug and the release profiles showed that the dual porous material had a sustained drug delivery capability. And such highly ordered dual pore silica materials may have potential applications for bimolecular adsorption/separation and tissue repairing.

  2. Binding behaviour of molecularly imprinted polymers prepared by a hierarchical approach in mesoporous silica beads of varying porosity.

    PubMed

    Baggiani, Claudio; Baravalle, Patrizia; Giovannoli, Cristina; Anfossi, Laura; Passini, Cinzia; Giraudi, Gianfranco

    2011-04-01

    One of the most interesting methods for preparing molecularly imprinted polymers with controlled morphology consists in filling the pores of silica beads with an imprinting mixture, polymerizing it and dissolving the support, leaving porous imprinted beads that are the "negative image" of the silica beads. The main advantage of such an approach consists in the easy preparation of spherical imprinted polymeric particles with narrow diameter and pore size distribution, particularly indicated for chromatographic applications. In this approach it has been shown that the resulting morphology of polymeric beads depends essentially on the porosity and surface properties of the silica beads that act as microreactors for the thermopolymerization process. Anyway, it is not yet clear if the porosity of the silica beads influences the binding properties of the resulting imprinted beads. In this paper, we report the effect of different porosities of the starting mesoporous silica beads on the resulting binding properties of imprinted polymers with molecular recognition properties towards the fungicide carbendazim. The morphological properties of the imprinted beads prepared through this hierarchical approach were measured by nitrogen adsorption porosimetry and compared with a reference imprinted material prepared by bulk polymerization. The chromatographic behaviour of HPLC columns packed with the imprinted materials were examined by eluting increasing amounts of carbendazim and extracting the binding parameters through a peak profiling approach. The experimental results obtained show that the resulting binding properties of the imprinted beads are strongly affected by the polymerization approach used but not by the initial porosity of the silica beads, with the sole exception of the binding site density, which appears to be inversely proportional to them. PMID:21349526

  3. Metal-oxide-doped silica nanoparticles for the catalytic glycolysis of polyethylene terephthalate.

    PubMed

    Imran, Muhammad; Lee, Kyoung G; Imtiaz, Qasim; Kim, Bo-Kyung; Han, Myungwan; Cho, Bong Gyoo; Kim, Do Hyun

    2011-01-01

    Polyethylene terephthalate (PET) was depolymerized to monomer bis(2-hydroxyethyl) terephthalate (BHET) using excess ethylene glycol (EG) in the presence of metal oxides that were impregnated on different forms of silica support [silica nanoparticles (SNPs) or silica microparticles (SMPs)] as glycolysis catalysts. The reactions were carried out at 300 degrees C and 1.1 MPa at an EG-to-PET molar ratio of 11:1 and a catalyst-to-PET-weight ratio of 1.0% for 40-80 min. Among the four prepared catalysts (Mn3O4/SNPs, ZnO/SNPs, Mn3O4/SMPs, and ZnO/SMPs), the Mn3O4/SNPs nanocomposite had the highest monomer yield (> 90%). This high yield may be explained by the high surface area, amorphous and porous structure, and existence of numerous active sites on the nanocomposite catalyst. The BHET yield increased with time and reached the highest level where equilibrium was established between BHET and its dimer. The catalysts were characterized by their SEM, TEM, and BET surface areas, and via XRD, whereas the monomer BHET was characterized by HPLC and FT-IR. The glycolysis with the Mn3O4/SNPs nanocomposite as the glycolysis catalyst produced a maximum BHET in a short reaction time.

  4. Charge transfer mechanism in titanium-doped microporous silica for photocatalytic water-splitting applications

    DOE PAGES

    Sapp, Wendi; Koodali, Ranjit; Kilin, Dmitri

    2016-02-29

    Solar energy conversion into chemical form is possible using artificial means. One example of a highly-efficient fuel is solar energy used to split water into oxygen and hydrogen. Efficient photocatalytic water-splitting remains an open challenge for researchers across the globe. Despite significant progress, several aspects of the reaction, including the charge transfer mechanism, are not fully clear. Density functional theory combined with density matrix equations of motion were used to identify and characterize the charge transfer mechanism involved in the dissociation of water. A simulated porous silica substrate, using periodic boundary conditions, with Ti4+ ions embedded on the inner poremore » wall was found to contain electron and hole trap states that could facilitate a chemical reaction. A trap state was located within the silica substrate that lengthened relaxation time, which may favor a chemical reaction. A chemical reaction would have to occur within the window of photoexcitation; therefore, the existence of a trapping state may encourage a chemical reaction. Furthermore, this provides evidence that the silica substrate plays an integral part in the electron/hole dynamics of the system, leading to the conclusion that both components (photoactive materials and support) of heterogeneous catalytic systems are important in optimization of catalytic efficiency.« less

  5. Imprinting Chirality in Silica Nanotubes by N-Stearoyl-serine Template.

    PubMed

    Levi, Gila; Scolnik, Yosef; Mastai, Yitzhak

    2016-09-01

    In this article, we describe the synthesis of imprinted chiral silica nanotubes based on the use of a chiral N-stearoyl l-serine (C18Ser) anionic surfactant as the chiral template. The resulting chiral silica nanotube structures were characterized by electronic microscopy (transmission electron microscopy (TEM) and scanning electron microscopy (SEM)) and nitrogen isotherms that proved the formation of well-ordered silica nanotubes. A C18Ser surfactant template was used for the preparation of the silica nanotubes, due to its effective molecular organization within the silica network. After chemical extraction of the chiral template, the enantioselectivity feature of the silica nanotubes was confirmed by selective adsorption of the enantiomers using circular dichroism (CD) and isothermal titration calorimetry (ITC) measurements. Although these measurements show a relatively low chiral selectivity of the silica nanotubes (ca. 6% enantiomeric excess), the system described here offers new approaches for the application of chiral porous materials in chirality. PMID:27533529

  6. Imprinting Chirality in Silica Nanotubes by N-Stearoyl-serine Template.

    PubMed

    Levi, Gila; Scolnik, Yosef; Mastai, Yitzhak

    2016-09-01

    In this article, we describe the synthesis of imprinted chiral silica nanotubes based on the use of a chiral N-stearoyl l-serine (C18Ser) anionic surfactant as the chiral template. The resulting chiral silica nanotube structures were characterized by electronic microscopy (transmission electron microscopy (TEM) and scanning electron microscopy (SEM)) and nitrogen isotherms that proved the formation of well-ordered silica nanotubes. A C18Ser surfactant template was used for the preparation of the silica nanotubes, due to its effective molecular organization within the silica network. After chemical extraction of the chiral template, the enantioselectivity feature of the silica nanotubes was confirmed by selective adsorption of the enantiomers using circular dichroism (CD) and isothermal titration calorimetry (ITC) measurements. Although these measurements show a relatively low chiral selectivity of the silica nanotubes (ca. 6% enantiomeric excess), the system described here offers new approaches for the application of chiral porous materials in chirality.

  7. Comparison of the mass transfer in totally porous and superficially porous stationary phases in liquid chromatography.

    PubMed

    Kiss, Ibolya; Bacskay, Ivett; Kilár, Ferenc; Felinger, Attila

    2010-06-01

    The characterization of mass-transfer processes in a chromatographic column during a separation process is essential, since the influence of the mass-transfer kinetics on the shape of the chromatographic band profiles and on the efficiency of the separation is crucial. Several sources of mass transfer in a chromatographic bed have been identified and studied: the axial dispersion in the stream of mobile phase, the external mass-transfer resistance, intraparticle diffusion, and the kinetics of adsorption-desorption. We measured and compared the characteristics and performance of a new brand of shell particles and those of a conventional brand of totally porous silica particles. The shell stationary phase was made of 2.7-microm superficially porous particles (a 1.7-microm solid core is covered with a 0.5-microm-thick shell of porous silica). The other material consisted of totally porous particles of conventional 3.5-microm commercial silica. We measured the first and second central moments of the peaks of human insulin over a wide range of mobile phase velocities (from 0.02 to 1.3 mL/min) at 20 degrees C. The plate height equations were constructed and the axial dispersion, external mass transfer, as well as the intraparticle diffusion coefficients were calculated for the two stationary phases.

  8. Effect of the preparation method on the thermal stability of silica-supported nickel oxide as studied by EXAFS and TPR techniques

    SciTech Connect

    Clause, O. ); Bonneviot, L.; Che, M. )

    1992-11-01

    EXAFS analysis and Temperature-Programmed Reduction experiments (TPR) have been carried out on calcined Ni/SiO[sub 2] materials prepared by incipient wetness impregnation at different pH values, ion exchange with ammonia and ethylenediamine solutions, and deposition-precipitation. The interaction of the Ni(II) ions with silica is shown to be dependent on the first steps of catalyst preparation, i.e., deposition, washing, and drying. Silicates with a layer structure are formed in samples prepared by deposition-precipitation and ion exchange from ammoniacal solutions. Silicate formation inhibits the NiO crystallization up to 500[degrees]C. The silicate decomposition is favored when the thermal treatment is performed under reduced pressure. The reducibility of the nickel oxide phase resulting from silicate decomposition is strongly hindered in comparison with that of unsupported nickel oxide. The silicate formation is avoided using a strong chelating ligand such as ethylenediamine during ion exchange. With ethylenediamine, isolated Ni(II) species stable to 500[degrees]C are obtained. 35 refs., 10 figs., 2 tabs.

  9. Methanol Decomposition over Palladium Particles Supported on Silica: Role of Particle Size and Co-Feeding Carbon Dioxide on the Catalytic Properties

    SciTech Connect

    Hokenek, Selma; Kuhn, John N.

    2012-10-23

    Monodisperse palladium particles of six distinct and controlled sizes between 4-16 nm were synthesized in a one-pot polyol process by varying the molar ratios of the two palladium precursors used, which contained palladium in different oxidation states. This difference permitted size control by regulation of the nucleation rate because low oxidation state metals ions nucleate quickly relative to high oxidation state ions. After immobilization of the Pd particles on silica by mild sonication, the catalysts were characterized by X-ray absorption spectroscopy and applied toward catalytic methanol decomposition. This reaction was determined as structure sensitive with the intrinsic activity (turnover frequency) increasing with increasing particle size. Moreover, observed catalytic deactivation was linked to product (carbon monoxide) poisoning. Co-feeding carbon dioxide caused the activity and the amount of deactivation to decrease substantially. A reaction mechanism based on the formation of the {pi}-bond between carbon and oxygen as the rate-limiting step is in agreement with antipathetic structure sensitivity and product poisoning by carbon monoxide.

  10. Variably porous structures

    SciTech Connect

    Braun, Paul V.; Yu, Xindi

    2011-01-18

    A method of making a monolithic porous structure, comprises electrodepositing a material on a template; removing the template from the material to form a monolithic porous structure comprising the material; and electropolishing the monolithic porous structure.

  11. Light emission from porous silicon

    NASA Astrophysics Data System (ADS)

    Penczek, John

    The continuous evolution of silicon microelectronics has produced significant gains in electronic information processing. However, greater improvements in performance are expected by utilizing optoelectronic techniques. But these techniques have been severely limited in silicon- based optoelectronics due to the lack of an efficient silicon light emitter. The recent observation of efficient light emission from porous silicon offer a promising opportunity to develop a suitable silicon light source that is compatible with silicon microelectronics. This dissertation examined the porous silicon emission mechanism via photoluminescence, and by a novel device structure for porous silicon emitters. The investigation first examined the correlation between porous silicon formation conditions (and subsequent morphology) with the resulting photoluminescence properties. The quantum confinement theory for porous silicon light emission contends that the morphology changes induced by the different formation conditions determine the optical properties of porous silicon. The photoluminescence spectral shifts measured in this study, in conjunction with TEM analysis and published morphological data, lend support to this theory. However, the photoluminescence spectral broadening was attributed to electronic wavefunction coupling between adjacent silicon nanocrystals. An novel device structure was also investigated in an effort to improve current injection into the porous silicon layer. The selective etching properties of porous silicon were used to create a p-i-n structure with crystalline silicon contacts to the porous silicon layer. The resulting device was found to have unique characteristics, with a negative differential resistance region and current-induced emission that spanned from 400 nm to 5500 nm. The negative differential resistance was correlated to resistive heating effects in the device. A numerical analysis of thermal emission spectra from silicon films, in addition to

  12. Fabrication of keratin-silica hydrogel for biomedical applications.

    PubMed

    Kakkar, Prachi; Madhan, Balaraman

    2016-09-01

    In the recent past, keratin has been fabricated into different forms of biomaterials like scaffold, gel, sponge, film etc. In lieu of the myriad advantages of the hydrogels for biomedical applications, a keratin-silica hydrogel was fabricated using tetraethyl orthosilicate (TEOS). Textural analysis shed light on the physical properties of the fabricated hydrogel, inturn enabling the optimization of the hydrogel. The optimized keratin-silica hydrogel was found to exhibit instant springiness, optimum hardness, with ease of spreadability. Moreover, the hydrogel showed excellent swelling with highly porous microarchitecture. MTT assay and DAPI staining revealed that keratin-silica hydrogel was biocompatible with fibroblast cells. Collectively, these properties make the fabricated keratin-silica hydrogel, a suitable dressing material for biomedical applications.

  13. Health hazards due to the inhalation of amorphous silica.

    PubMed

    Merget, R; Bauer, T; Küpper, H U; Philippou, S; Bauer, H D; Breitstadt, R; Bruening, T

    2002-01-01

    Occupational exposure to crystalline silica dust is associated with an increased risk for pulmonary diseases such as silicosis, tuberculosis, chronic bronchitis, chronic obstructive pulmonary disease (COPD) and lung cancer. This review summarizes the current knowledge about the health effects of amorphous (non-crystalline) forms of silica. The major problem in the assessment of health effects of amorphous silica is its contamination with crystalline silica. This applies particularly to well-documented pneumoconiosis among diatomaceous earth workers. Intentionally manufactured synthetic amorphous silicas are without contamination of crystalline silica. These synthetic forms may be classified as (1) wet process silica, (2) pyrogenic ("thermal" or "fumed") silica, and (3) chemically or physically modified silica. According to the different physicochemical properties, the major classes of synthetic amorphous silica are used in a variety of products, e.g. as fillers in the rubber industry, in tyre compounds, as free-flow and anti-caking agents in powder materials, and as liquid carriers, particularly in the manufacture of animal feed and agrochemicals; other uses are found in toothpaste additives, paints, silicon rubber, insulation material, liquid systems in coatings, adhesives, printing inks, plastisol car undercoats, and cosmetics. Animal inhalation studies with intentionally manufactured synthetic amorphous silica showed at least partially reversible inflammation, granuloma formation and emphysema, but no progressive fibrosis of the lungs. Epidemiological studies do not support the hypothesis that amorphous silicas have any relevant potential to induce fibrosis in workers with high occupational exposure to these substances, although one study disclosed four cases with silicosis among subjects exposed to apparently non-contaminated amorphous silica. Since the data have been limited, a risk of chronic bronchitis, COPD or emphysema cannot be excluded. There is no study

  14. Porous media heat transfer for injection molding

    DOEpatents

    Beer, Neil Reginald

    2016-05-31

    The cooling of injection molded plastic is targeted. Coolant flows into a porous medium disposed within an injection molding component via a porous medium inlet. The porous medium is thermally coupled to a mold cavity configured to receive injected liquid plastic. The porous medium beneficially allows for an increased rate of heat transfer from the injected liquid plastic to the coolant and provides additional structural support over a hollow cooling well. When the temperature of the injected liquid plastic falls below a solidifying temperature threshold, the molded component is ejected and collected.

  15. Sorption properties of porous melamine formaldehyde resins

    NASA Astrophysics Data System (ADS)

    Deryło-Marczewska, Anna; Goworek, Jacek; Kusak, Ryszard; Zgrajka, Wojciech

    2002-07-01

    Three types of melamine-formaldehyde porous sorbents were synthesized by using the fumed silica as an inorganic template. The changes in polymerization conditions lead to a differentiation of the porosity and surface area of these materials. This synthesis allowed preparing the materials of narrow pore size distributions with pore sizes over the range 2.8-6.8 nm, and specific surface areas up to 250 m 2/g. The analysis of pore structure was based on the comparison of nitrogen adsorption isotherms on a given porous sorbent and a standard nonporous polymer. Additionally the measurements of thermal stability and swelling of synthesized polymers were made. Adsorption of organic substances from aqueous solutions on porous polymers was also investigated.

  16. Silica-Ceria Hybrid Nanostructures

    SciTech Connect

    Munusamy, Prabhakaran; Sanghavi, Shail P.; Nachimuthu, Ponnusamy; Baer, Donald R.; Thevuthasan, Suntharampillai

    2012-04-25

    A new hybrid material system that consists of ceria attached silica nanoparticles has been developed. Because of the versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and antioxidant properties of ceria nanoparticles, this material system is ideally suited for biomedical applications. The silica particles of size ~50nm were synthesized by the Stöber synthesis method and ceria nanoparticles of size ~2-3nm was attached to the silica surface using a hetrocoagulation method. The presence of silanol groups on the surface of silica particles mediated homogenous nucleation of ceria which were attached to silica surface by Si-O-Ce bonding. The formations of silica-ceria hybrid nanostructures were characterized by X-photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HRTEM). The HRTEM image confirms the formation of individual crystallites of ceria nanoparticles attached to the silica surface. The XPS analysis indicates that ceria nanoparticles are chemically bonded to surface of silica and possess mixture of +3 and +4 chemical states.

  17. Solvated calcium ions in charged silica nanopores

    NASA Astrophysics Data System (ADS)

    Bonnaud, Patrick A.; Coasne, Benoît; Pellenq, Roland J.-M.

    2012-08-01

    Hydroxyl surface density in porous silica drops down to nearly zero when the pH of the confined aqueous solution is greater than 10.5. To study such extreme conditions, we developed a model of slit silica nanopores where all the hydrogen atoms of the hydroxylated surface are removed and the negative charge of the resulting oxygen dangling bonds is compensated by Ca2+ counterions. We employed grand canonical Monte Carlo and molecular dynamics simulations to address how the Ca2+ counterions affect the thermodynamics, structure, and dynamics of confined water. While most of the Ca2+ counterions arrange themselves according to the so-called "Stern layer," no diffuse layer is observed. The presence of Ca2+ counterions affects the pore filling for strong confinement where the surface effects are large. At full loading, no significant changes are observed in the layering of the first two adsorbed water layers compared to nanopores with fully hydroxylated surfaces. However, the water structure and water orientational ordering with respect to the surface is much more disturbed. Due to the super hydrophilicity of the Ca2+-silica nanopores, water dynamics is slowed down and vicinal water molecules stick to the pore surface over longer times than in the case of hydroxylated silica surfaces. These findings, which suggest the breakdown of the linear Poisson-Boltzmann theory, provide important information about the properties of nanoconfined electrolytes upon extreme conditions where the surface charge and ion concentration are large.

  18. Oxidative debromination and degradation of tetrabromo-bisphenol A by a functionalized silica-supported iron(III)-tetrakis(p-sulfonatophenyl)porphyrin catalyst.

    PubMed

    Zhu, Qianqian; Mizutani, Yusuke; Maeno, Shohei; Fukushima, Masami

    2013-01-01

    Tetrabromobisphenol A (TBBPA), a commonly used brominated flame retardant, also functions as an endocrine disruptor. Thus, the degradation of TBBPA has attracted considerable interest among the scientific community. Iron(III)-porphyrin complexes are generally regarded as "green" catalysts and have been reported to catalyze the efficient degradation and dehalogenation of halogenated phenols in environmental wastewaters. However, they are quickly deactivated due to self-degradation in the presence of an oxygen donor, such as KHSO₅. In the present study, an iron(III)-tetrakis (p-sulfonatophenyl)-porphyrin (FeTPPS) was immobilized on imidazole-modified silica (FeTPPS/IPS) via coordination of the Fe(III) with the nitrogen atom in imidazole to suppress self-degradation and thus enhance the catalyst reusability. The oxidative degradation and debromination of TBBPA and the influence of humic acid (HA), a major component in leachates, on the oxidation of TBBPA was investigated. More than 95% of the TBBPA was degraded in the pH range from 3 to 8 in the absence of HA, while the optimal pH for the reaction was at pH 8 in the presence of HA. Although the rate of degradation was decreased in the presence of HA, over 95% of the TBBPA was degraded within 12 h in the presence of 28 mg-C L⁻¹ of HA. At pH 8, the FeTPPS/IPS catalyst could be reused up to 10 times without any detectable loss of activity for TBBPA for degradation and debromination, even in the presence of HA. PMID:23666004

  19. Incorporation of anti-inflammatory agent into mesoporous silica

    NASA Astrophysics Data System (ADS)

    Rodrigues Braz, Wilson; Lamec Rocha, Natállia; de Faria, Emerson H.; Silva, Márcio L. A. e.; Ciuffi, Katia J.; Tavares, Denise C.; Furtado, Ricardo Andrade; Rocha, Lucas A.; Nassar, Eduardo J.

    2016-09-01

    The unique properties of macroporous, mesoporous, and microporous systems, including their ability to accommodate molecules of different sizes inside their pores and to act as drug delivery systems, have been the object of extensive studies. In this work, mesoporous silica with hexagonal structure was obtained by template synthesis via the sol-gel process. The resulting material was used as support to accommodate the anti-inflammatory agent indomethacin. The alkaline route was used to prepare the mesoporous silica; cetyltrimethylammonium bromide was employed as porogenic agent. The silica particles were functionalized with 3-aminopropyltriethoxysilane alkoxide (APTES) by the sol-gel post-synthesis method. Indomethacin was incorporated into the silica functionalized with APTES and into non-functionalized silica. The resulting systems were characterized by x-ray diffraction (XRD), specific area, infrared spectroscopy, and thermal analyses (TGA). XRD attested to formation of mesoporous silica with hexagonal structure. This structure remained after silica functionalization with APTES and incorporation of indomethacin. Typical infrared spectroscopy vibrations and organic material decomposition during TGA confirmed silica functionalization and drug incorporation. The specific surface area and pore volume of the functionalized material incorporated with indomethacin decreased as compared with the specific surface area and pore volume of the non-functionalized silica containing no drug, suggesting both the functionalizing agent and the drug were present in the silica. Cytotoxicity tests conducted on normal fibroblasts (GM0479A) cells attested that the silica matrix containing indomethacin was less toxic than the free drug.

  20. Incorporation of anti-inflammatory agent into mesoporous silica

    NASA Astrophysics Data System (ADS)

    Rodrigues Braz, Wilson; Lamec Rocha, Natállia; de Faria, Emerson H.; Silva, Márcio L. A. e.; Ciuffi, Katia J.; Tavares, Denise C.; Furtado, Ricardo Andrade; Rocha, Lucas A.; Nassar, Eduardo J.

    2016-09-01

    The unique properties of macroporous, mesoporous, and microporous systems, including their ability to accommodate molecules of different sizes inside their pores and to act as drug delivery systems, have been the object of extensive studies. In this work, mesoporous silica with hexagonal structure was obtained by template synthesis via the sol–gel process. The resulting material was used as support to accommodate the anti-inflammatory agent indomethacin. The alkaline route was used to prepare the mesoporous silica; cetyltrimethylammonium bromide was employed as porogenic agent. The silica particles were functionalized with 3-aminopropyltriethoxysilane alkoxide (APTES) by the sol–gel post-synthesis method. Indomethacin was incorporated into the silica functionalized with APTES and into non-functionalized silica. The resulting systems were characterized by x-ray diffraction (XRD), specific area, infrared spectroscopy, and thermal analyses (TGA). XRD attested to formation of mesoporous silica with hexagonal structure. This structure remained after silica functionalization with APTES and incorporation of indomethacin. Typical infrared spectroscopy vibrations and organic material decomposition during TGA confirmed silica functionalization and drug incorporation. The specific surface area and pore volume of the functionalized material incorporated with indomethacin decreased as compared with the specific surface area and pore volume of the non-functionalized silica containing no drug, suggesting both the functionalizing agent and the drug were present in the silica. Cytotoxicity tests conducted on normal fibroblasts (GM0479A) cells attested that the silica matrix containing indomethacin was less toxic than the free drug.

  1. Interactions of silica surfaces

    SciTech Connect

    Vigil, G.; Xu, Z.; Steinberg, S.; Israelachvili, J. . Dept. of Chemical and Nuclear Engineering and Materials Dept.)

    1994-07-01

    Adhesion, friction, and colloidal forces in air and aqueous salt solutions have been measured between various silica surfaces prepared by depositing amorphous but highly smooth silica films on mica. The results show four interesting and interrelated phenomena: (i) the adhesion of silica surfaces in air increases slowly with contact time, especially in humid air where the contacting surfaces become separated by an [approximately]20-[angstrom]-thick layer of hydrated silica or silica gel; (ii) the friction of two silica surfaces exhibits large sticking or stiction spikes, whose magnitude increases in the presence of water and when the surfaces are kept in contact longer before sliding; (iii) the non-DLVO repulsion commonly seen at short range (<40 A) between silica surfaces immersed in aqueous solutions is monotonically repulsive, with no oscillatory component, and is quite unlike theoretical expectations and previous measurements of forces due to solvent structure; (iv) dynamic contact angle measurements reveal time-dependent effects which cannot be due to a fixed surface chemical heterogeneity or roughness. The results indicate that silica surfaces undergo slow structural and chemical changes during interactions with water and with each other. More specifically, the authors propose that the unusual interfacial and colloidal properties of silica are due, not to hydration effects, but to the presence of an [approximately]10-[angstrom]-thick gel-like layer of protruding silanol and silicilic acid groups that grow on the surfaces in the presence of water. These protruding groups react chemically (sinter) with similar groups located on an opposing surface and give rise to the unusual time-dependent adhesion, friction, and non-DLVO forces observed. The proposed mechanism in terms of a surface layer of silica gel is consistent with the known surface chemistry of silica and accounts for the results reported and for other unusual surface and colloidal properties of silica.

  2. Silica, silicosis, and cancer

    SciTech Connect

    Goldsmith, D.F.; Winn, D.M.; Shy, C.M.

    1986-01-01

    These proceedings collect papers on occupational exposure. Topics include: measurement of silica dust, mortality in granite workers, effects of quartz in coal mine dust, pneumoconiosis, and lung cancer.

  3. Fluorescence properties of dye doped mesoporous silica

    SciTech Connect

    Carbonaro, Carlo M. Corpino, Riccardo Ricci, Pier Carlo Chiriu, Daniele; Cannas, Carla

    2014-10-21

    In this paper we present a review of the main results we obtained studying the emission properties of organic-inorganic hybrids obtained combining mesoporous silica and Xantene dyes, in particular the standard reference Rhodamine 6G. The purpose of the review is to show the possibility to efficiently 'dope' the transparent inorganic porous matrix to obtain promising systems for photonic and biomedical applications. The strategies to solve the concentration effect and the leaching phenomenon are discussed within the framework of the single exciton theory.

  4. Structure of chemical vapor deposition titania/silica gel

    SciTech Connect

    Leboda, R.; Gun'ko, V.M.; Marciniak, M.; Malygin, A.A.; Malkin, A.A.; Grzegorczyk, W.; Trznadel, B.J.; Pakhlov, E.M.; Voronin, E.F.

    1999-10-01

    The structure of porous silica gel/titania synthesized using chemical vapor deposition (CVD) of titania via repeated reactions of TiCl{sub 4} with the surface and subsequent hydrolysis of residual Ti-Cl bonds at different temperatures was investigated by means of low-temperature nitrogen adsorption-desorption, X-ray diffraction (XRD), IR spectroscopy, and theoretical methods. A globular model of porous solids with corpuscular structure was applied to estimate the porosity parameters of titania/silica gel adsorbents. The utilization of this model is useful, for example, to predict conditions for synthesis of titania/silica with a specified structure. Analysis of pore parameters and fractal dimension suggests that the porosity and fractality of samples decrease with increasing amount of TiO{sub 2} covering the silica gel surface in a nonuniform layer, which represents small particles embedded in pores and larger particles formed at the outer surface of silica globules. Theoretical simulation shows that the Si-O-Ti linkages between the cover and the substrate can be easily hydrolyzed, which is in agreement with the IR data corresponding to the absence of a band at 950 cm {sup {minus}1} (characteristic of Si-O-Ti bridges) independent of the concentration of CVD-titania.

  5. Reactivity characteristics of nanoscale zerovalent iron--silica composites for trichloroethylene remediation.

    PubMed

    Zheng, Tonghua; Zhan, Jingjing; He, Jibao; Day, Christopher; Lu, Yunfeng; McPherson, Gary L; Piringer, Gerhard; John, Vijay T

    2008-06-15

    Spherical silica particles containing nanoscale zerovalent iron were synthesized through an aerosol-assisted process. These particles are effective for groundwater remediation, with the environmentally benign silica particles serving as effective carriers for nanoiron transport. Incorporation of iron into porous sub-micrometer silica particles protects ferromagnetic iron nanoparticles from aggregation and may increase their subsurface mobility. Additionally, the presence of surface silanol groups on silica particles allows control of surface properties via silanol modification using organic functional groups. Aerosolized silica particles with functional alkyl moieties, such as ethyl groups on the surface, clearly adsorb solubilized trichloroethylene (TCE) in water. These materials may therefore act as adsorbents which have coupled reactivity characteristics. The nanoscale iron/silica composite particles with controlled surface properties have the potential to be efficiently applied for in situ source depletion and in the design of permeable reactive barriers.

  6. The design of a bipodal bis(pentafluorophenoxy)aluminate supported on silica as an activator for ethylene polymerization using surface organometallic chemistry.

    PubMed

    Sauter, Dominique W; Popoff, Nicolas; Bashir, Muhammad Ahsan; Szeto, Kai C; Gauvin, Régis M; Delevoye, Laurent; Taoufik, Mostafa; Boisson, Christophe

    2016-04-01

    A new class of well-defined activating supports for olefin polymerization was obtained via the surface organometallic chemistry approach. High activities in slurry polymerization of ethylene along with industrial-grade physical properties of the resulting polyethylene were obtained when these activators were combined with metallocene complexes in the presence of triisobutylaluminium.

  7. The design of a bipodal bis(pentafluorophenoxy)aluminate supported on silica as an activator for ethylene polymerization using surface organometallic chemistry.

    PubMed

    Sauter, Dominique W; Popoff, Nicolas; Bashir, Muhammad Ahsan; Szeto, Kai C; Gauvin, Régis M; Delevoye, Laurent; Taoufik, Mostafa; Boisson, Christophe

    2016-04-01

    A new class of well-defined activating supports for olefin polymerization was obtained via the surface organometallic chemistry approach. High activities in slurry polymerization of ethylene along with industrial-grade physical properties of the resulting polyethylene were obtained when these activators were combined with metallocene complexes in the presence of triisobutylaluminium. PMID:26899986

  8. Mesoporous silica nanoparticles for biomedical and catalytical applications

    SciTech Connect

    Sun, Xiaoxing

    2011-01-01

    Mesoporous silica materials, discovered in 1992 by the Mobile Oil Corporation, have received considerable attention in the chemical industry due to their superior textual properties such as high surface area, large pore volume, tunable pore diameter, and narrow pore size distribution. Among those materials, MCM-41, referred to Mobile Composition of Matter NO. 41, contains honeycomb liked porous structure that is the most common mesoporous molecular sieve studied. Applications of MCM-41 type mesoporous silica material in biomedical field as well as catalytical field have been developed and discussed in this thesis. The unique features of mesoporous silica nanoparticles were utilized for the design of delivery system for multiple biomolecules as described in chapter 2. We loaded luciferin into the hexagonal channels of MSN and capped the pore ends with gold nanoparticles to prevent premature release. Luciferase was adsorbed onto the outer surface of the MSN. Both the MSN and the gold nanoparticles were protected by poly-ethylene glycol to minimize nonspecific interaction of luciferase and keep it from denaturating. Controlled release of luciferin was triggered within the cells and the enzymatic reaction was detected by a luminometer. Further developments by varying enzyme/substrate pairs may provide opportunities to control cell behavior and manipulate intracellular reactions. MSN was also served as a noble metal catalyst support due to its large surface area and its stability with active metals. We prepared MSN with pore diameter of 10 nm (LP10-MSN) which can facilitate mass transfer. And we successfully synthesized an organo silane, 2,2'-Bipyridine-amide-triethoxylsilane (Bpy-amide-TES). Then we were able to functionalize LP10-MSN with bipyridinyl group by both post-grafting method and co-condensation method. Future research of this material would be platinum complexation. This Pt (II) complex catalyst has been reported for a C-H bond activation reaction as an

  9. Silica, Silicosis, and Autoimmunity

    PubMed Central

    Pollard, Kenneth Michael

    2016-01-01

    Inhalation of dust containing crystalline silica is associated with a number of acute and chronic diseases including systemic autoimmune diseases. Evidence for the link with autoimmune disease comes from epidemiological studies linking occupational exposure to crystalline silica dust with the systemic autoimmune diseases systemic lupus erythematosus, systemic sclerosis, and rheumatoid arthritis. Although little is known regarding the mechanism by which silica exposure leads to systemic autoimmune disease, there is a voluminous literature on silica exposure and silicosis that may help identify immune processes that precede development of autoimmunity. The pathophysiology of silicosis consists of deposition of silica particles in the alveoli of the lung. Ingestion of these particles by macrophages initiates an inflammatory response, which stimulates fibroblasts to proliferate and produce collagen. Silica particles are encased by collagen leading to fibrosis and the nodular lesions characteristic of the disease. The steps in the development of silicosis, including acute and chronic inflammation and fibrosis, have different molecular and cellular requirements, suggesting that silica-induced inflammation and fibrosis may be mechanistically separate. Significantly, it is unclear whether silica-induced inflammation and fibrosis contribute similarly to the development of autoimmunity. Nonetheless, the findings from human and animal model studies are consistent with an autoimmune pathogenesis that begins with activation of the innate immune system leading to proinflammatory cytokine production, pulmonary inflammation leading to activation of adaptive immunity, breaking of tolerance, and autoantibodies and tissue damage. The variable frequency of these immunological features following silica exposure suggests substantial genetic involvement and gene/environment interaction in silica-induced autoimmunity. However, numerous questions remain unanswered. PMID:27014276

  10. Synthesis and structural evolution of mesoporous silica silver nanocomposites

    NASA Astrophysics Data System (ADS)

    Armelao, L.; Bottaro, G.; Campostrini, R.; Gialanella, S.; Ischia, M.; Poli, F.; Tondello, E.

    2007-04-01

    Mesoporous silica materials were prepared by a sol-gel procedure using Si(OCH2CH3)4 (TEOS) as the silica source and the non-ionic alkyl-poly(ethyleneoxide) oligomer Brij76 as the structure-directing agent. Pure inorganic hexagonal-like mesostructured SiO2 powders were obtained after annealing, performed in air between 400 and 600 °C. Upon calcination, the organic template was removed and silica networks with a different amount of Si-OH groups as well as porous features were prepared. Ag-SiO2 nanocomposites were obtained by metallation of the mesoporous silica powders with aqueous solutions of silver acetate. Ag+ ions were chemically grafted on the silica pores by taking advantage of the basic character of acetate anions and the acidic properties of Si-OH groups. Different silver concentrations were achieved on the mesostructured silica powders, depending on their former annealing treatment. For all samples the formation of silver nanoclusters occurred spontaneously at room temperature. Monodispersed, spherical Ag crystallites, with an average diameter of a few nanometres, were obtained starting from the 400 °C-treated silica, whereas clusters with different sizes (3-20 nm) and irregular shapes were grown for metallation of the 600 °C-heated SiO2 matrix. The sample's chemical composition was studied by x-ray photoelectron spectroscopy (XPS) and x-ray excited Auger electron spectroscopy (XE-AES), whereas the porous features were investigated by N2 BET adsorption. Information concerning structure and microstructure was obtained by x-ray diffraction (XRD) and transmission electron microscopy (TEM).

  11. Solvent responsive silica composite nanofiltration membrane with controlled pores and improved ion selectivity for vanadium flow battery application

    NASA Astrophysics Data System (ADS)

    Xi, Xiaoli; Ding, Cong; Zhang, Hongzhang; Li, Xianfeng; Cheng, Yuanhui; Zhang, Huamin

    2015-01-01

    A solvent responsive sol-gel method is adopted to fabricate poly (ether sulfone) (PES)/silica composite porous membranes for vanadium flow battery (VFB) application. The pore size and pore size distribution of the composite membrane can be easily adjusted by controlling the quantity of silica gels inside the pores of pristine membranes. Fourier transform infrared spectroscopy (FT-IR) and energy dispersive spectrometer (EDS) are carried out to confirm the structure of resulted membranes. VFBs assembled with the silica modified membranes display much higher coulomb efficiency (97%) and energy efficiency (83%) than that of pristine porous membrane (CE 86%, EE 76%). Furthermore,the modified PES membranes demonstrate high oxidation stability through the long-term battery operation. The PES/silica composite porous membranes show great prospects in VFB applications.

  12. Dendrimer Templated Synthesis of One Nanometer Rh and Pt Particles Supported on Mesoporous Silica: Catalytic Activity for Ethylene and Pyrrole Hydrogenation.

    SciTech Connect

    Huang, Wenyu; Kuhn, John N.; Tsung, Chia-Kuang; Zhang, Yawen; Habas, Susan E.; Yang, Peidong; Somorjai, Gabor A.

    2008-05-09

    Monodisperse rhodium (Rh) and platinum (Pt) nanoparticles as small as {approx}1 nm were synthesized within a fourth generation polyaminoamide (PAMAM) dendrimer, a hyperbranched polymer, in aqueous solution and immobilized by depositing onto a high-surface-area SBA-15 mesoporous support. X-ray photoelectron spectroscopy indicated that the as-synthesized Rh and Pt nanoparticles were mostly oxidized. Catalytic activity of the SBA-15 supported Rh and Pt nanoparticles was studied with ethylene hydrogenation at 273 and 293 K in 10 torr of ethylene and 100 torr of H{sub 2} after reduction (76 torr of H{sub 2} mixed with 690 torr of He) at different temperatures. Catalysts were active without removing the dendrimer capping but reached their highest activity after hydrogen reduction at a moderate temperature (423 K). When treated at a higher temperature (473, 573, and 673 K) in hydrogen, catalytic activity decreased. By using the same treatment that led to maximum ethylene hydrogenation activity, catalytic activity was also evaluated for pyrrole hydrogenation.

  13. Surfactant removal and silica condensation during the photochemical calcination of thin film silica mesophases.

    PubMed

    Dattelbaum, Andrew M; Amweg, Meri L; Ruiz, Julia D; Ecke, Laurel E; Shreve, Andrew P; Parikh, Atul N

    2005-08-01

    The evolution of photochemical surfactant removal and silica condensation from organically templated thin film silica nanocomposites with mesoscopic ordering has been probed using a combined application of Fourier transform infrared (FT-IR) spectroscopy and single wavelength ellipsometry. Thin films of silica nanocomposites were prepared by a previously reported evaporation-induced self-assembly process. Specifically, oxidized silicon and gold substrates were withdrawn at 25 mm/min from a subcritical micelle concentration solution containing an ethylene oxide surfactant as a structure-directing agent and tetraethyl orthosilicate as a silica precursor. Real-time grazing incidence difference FT-IR spectra of the nanocomposite films on gold taken during exposure to short-wavelength ultraviolet light (184-257 nm) show that surfactant removal and silica condensation occur gradually and concomitantly. Surfactant removal and silica reconstructions were found to be nearly complete after 90 min of exposure. Further, a transient feature was observed in the FT-IR spectra around 1713 cm(-1) during the UV exposure process and was assigned to a carbonyl (C=O) stretching mode absorption, reflecting the transient formation of a partially oxidized surfactant intermediate. From these data we propose a stepwise model for surfactant removal from the nanocomposite films. Ellipsometrically determined index of refraction values collected as a function of UV exposure are also shown to support such a stepwise mechanism of surfactant removal from the ordered nanocomposite silica thin film mesophases studied here. PMID:16852834

  14. Experimental Simulation of Evaporation-Driven Silica Sinter Formation and Microbial Silicification in Hot Spring Systems

    PubMed Central

    Lalonde, Stefan V.; Konhauser, Kurt O.

    2013-01-01

    Abstract Evaporation of silica-rich geothermal waters is one of the main abiotic drivers of the formation of silica sinters around hot springs. An important role in sinter structural development is also played by the indigenous microbial communities, which are fossilized and eventually encased in the silica matrix. The combination of these two factors results in a wide variety of sinter structures and fabrics. Despite this, no previous experimental fossilization studies have focused on evaporative-driven silica precipitation. We present here the results of several experiments aimed at simulating the formation of sinters through evaporation. Silica solutions at different concentrations were repeatedly allowed to evaporate in both the presence and absence of the cyanobacterium Synechococcus elongatus. Without microorganisms, consecutive silica additions led to the formation of well-laminated deposits. By contrast, when microorganisms were present, they acted as reactive surfaces for heterogeneous silica particle nucleation; depending on the initial silica concentration, the deposits were then either porous with a mixture of silicified and unmineralized cells, or they formed a denser structure with a complete entombment of the cells by a thick silica crust. The deposits obtained experimentally showed numerous similarities in terms of their fabric to those previously reported for natural hot springs, demonstrating the complex interplay between abiotic and biotic processes during silica sinter growth. Key Words: Silica—Cyanobacteria—Fossilization—Hot springs—Stromatolites. Astrobiology 13, 163–176. PMID:23384170

  15. Experimental simulation of evaporation-driven silica sinter formation and microbial silicification in hot spring systems.

    PubMed

    Orange, François; Lalonde, Stefan V; Konhauser, Kurt O

    2013-02-01

    Evaporation of silica-rich geothermal waters is one of the main abiotic drivers of the formation of silica sinters around hot springs. An important role in sinter structural development is also played by the indigenous microbial communities, which are fossilized and eventually encased in the silica matrix. The combination of these two factors results in a wide variety of sinter structures and fabrics. Despite this, no previous experimental fossilization studies have focused on evaporative-driven silica precipitation. We present here the results of several experiments aimed at simulating the formation of sinters through evaporation. Silica solutions at different concentrations were repeatedly allowed to evaporate in both the presence and absence of the cyanobacterium Synechococcus elongatus. Without microorganisms, consecutive silica additions led to the formation of well-laminated deposits. By contrast, when microorganisms were present, they acted as reactive surfaces for heterogeneous silica particle nucleation; depending on the initial silica concentration, the deposits were then either porous with a mixture of silicified and unmineralized cells, or they formed a denser structure with a complete entombment of the cells by a thick silica crust. The deposits obtained experimentally showed numerous similarities in terms of their fabric to those previously reported for natural hot springs, demonstrating the complex interplay between abiotic and biotic processes during silica sinter growth.

  16. Fluorescent silica nanoparticles containing covalently bound dyes for reporter, marker, and sensor applications

    NASA Astrophysics Data System (ADS)

    Patonay, Gabor; Henary, Maged; Chapman, Gala; Emer, Kyle; Crow, Sidney

    2016-03-01

    Silica nanoparticles have proven to be useful in many bioanalytical and medical applications and have been used in numerous applications during the last decade. Combining the properties of silica nanoparticles and fluorescent dyes that may be used as chemical probes or labels can be relatively easy by simply soaking porous silica nanoparticles in a solution of the dye of interest. Under proper conditions the entrapped dye can stay inside the silica nanoparticle for several hours resulting in a useful probe. In spite of the relative durability of these probes, leaching can still occur. A much better approach is to synthesize silica nanoparticles that have the fluorescent dye covalently attached to the backbone structure of the silica nanoparticle. This can be achieved by using appropriately modified tetraethyl orthosilicate (TEOS) analogues during the silica nanoparticle synthesis. The molar ratio of TEOS and modified TEOS will determine the fluorescent dye load in the silica nanoparticle. Dependent on the chemical stability of the reporting dye either reverse micellar (RM) or Stöber method can be used for silica nanoparticle synthesis. If dye stability allows RM procedure is preferred as it results in a much easier control of the silica nanoparticle reaction itself. Also controlling the size and uniformity of the silica nanoparticles are much easier using RM method. Dependent on the functional groups present in the reporting dye used in preparation of the modified TEOS, the silica nanoparticles can be utilized in many applications such as pH sensor, metal ion sensors, labels, etc. In addition surface activated silica nanoparticles with reactive moieties are also excellent reporters or they can be used as bright fluorescent labels. Many different fluorescent dyes can be used to synthesize silica nanoparticles including visible and NIR dyes. Several bioanalytical applications are discussed including studying amoeba phagocytosis.

  17. Unraveling the Dynamics of Aminopolymer/Silica Composites

    DOE PAGES

    Carrillo, Jan-Michael Y.; Sakwa-Novak, Miles A.; Holewinski, Adam; Potter, Matthew E.; Rother, Gernot; Jones, Christopher W.; Sumpter, Bobby G.

    2016-02-25

    Branched poly(ethylenimine) (PEI) encapsulated within mesoporous silica (SBA-15), has proven to be an eective sorbent for developing carbon capture technologies. However, the structure-property correlations which govern their adsorptive properties is not well understood. By combining coarse-grained molecular dynamics simulations and neutron scattering experiments we are able to construct, and validate, a detailed model of the dynamics and morphology of the conned polymer within the mesoporous support. By varying the simulation properties we are able to probe, for the rst time, the direct relationship between the structure of the polymer and the non-monotonic dynamics of the polymer as a function ofmore » monomer concentration within an adsorbing cylindrical pore. Overall the simulation results are in good agreement with quasi-elastic neutron scattering (QENS) studies, suggesting an approach that can be a useful guide for understanding how to tune porous polymer composites for enhancing desired dynamical and structural behavior targeting enhanced carbon dioxide adsorption.« less

  18. Oriented and selective enzyme immobilization on functionalized silica carrier using the cationic binding module Z basic2: design of a heterogeneous D-amino acid oxidase catalyst on porous glass.

    PubMed

    Bolivar, Juan M; Nidetzky, Bernd

    2012-06-01

    D-amino acid oxidase from Trigonopsis variabilis (TvDAO) is applied in industry for the synthesis of pharmaceutical intermediates. Because free TvDAO is extremely sensitive to exposure to gas-liquid interfaces, biocatalytic processing is usually performed with enzyme immobilizates that offer enhanced stability under bubble aeration. We herein present an "Immobilization by Design" approach that exploits engineered charge complementarity between enzyme and carrier to optimize key features of the immobilization of TvDAO. A fusion protein between TvDAO and the positively charged module Z(basic2) was generated, and a corresponding oppositely charged carrier was obtained by derivatization of mesoporous glass with 3-(trihydroxysilyl)-1-propane-sulfonic acid. Using 250 mM NaCl for charge screening at pH 7.0, the Z(basic2) fusion of TvDAO was immobilized directly from E. coli cell extract with almost absolute selectivity and full retention of catalytic effectiveness of the isolated enzyme in solution. Attachment of the homodimeric enzyme to the carrier was quasi-permanent in low-salt buffer but fully reversible upon elution with 5 M NaCl. Immobilized TvDAO was not sensitive to bubble aeration and received substantial (≥ tenfold) stabilization of the activity at 45°C as compared to free enzyme, suggesting immobilization via multisubunit oriented interaction of enzyme with the insoluble carrier. The Z(basic2) enzyme immobilizate was demonstrated to serve as re-usable heterogeneous catalyst for D-amino acid oxidation. Z(basic2) -mediated binding on a sulfonic acid group-containing glass carrier constitutes a generally useful strategy of enzyme immobilization that supports transition from case-specific empirical development to rational design.

  19. Poisoning of a Silica-Supported Cobalt Catalyst due to Presence of Sulfur Impurities in Syngas during Fischer–Tropsch Synthesis: Effects of Chelating Agent

    SciTech Connect

    Bambal, Ashish S.; Guggilla, Vidya S.; Kugler, Edwin L.; Gardner, Todd H.; Dadyburjor, Dady B.

    2014-04-09

    The effects of sulfur impurities on the performance of cobalt-based Fischer–Tropsch catalysts are evaluated under industrially relevant operating conditions of temperature, pressure, and impurity levels. Chelating agents (CAs) were used to modify the SiO2 support, and the performances of the CA-modified catalysts are compared with conventional Co/SiO2 catalysts. For both the Co/SiO2 and CA-modified catalysts, the presence of sulfur in the inlet syngas results in a notable drop in the CO conversion, an undesired shift in the hydrocarbon selectivity toward short-chain hydrocarbons, more olefins in the products, and lower product yields. In the post-poisoning stage, i.e., after termination of sulfur introduction in the inlet syngas, the CA-modified catalysts recover activity and selectivity (to some extent at least), whereas such trends are not observed for the base-case, i.e., unmodified Co/SiO2 catalyst. Finally, the improved performance of the CA-modified catalysts in the presence of sulfur is attributed to higher densities of active sites.

  20. Electrochemical Sensors: Functionalized Silica

    SciTech Connect

    Fryxell, Glen E.; Lin, Yuehe; Yantasee, Wassana

    2009-03-24

    This chapter summarizes recent devellopment of electrochemical sensors based on functionlized mesoporous silica materials. The nanomatrials based sensors have been developed for sensitive and selective enrironmental detection of toxic heavy metal and uranium ions.

  1. Crystalline Silica Primer

    USGS Publications Warehouse

    ,

    1992-01-01

    substance and will present a nontechnical overview of the techniques used to measure crystalline silica. Because this primer is meant to be a starting point for anyone interested in learning more about crystalline silica, a list of selected readings and other resources is included. The detailed glossary, which defines many terms that are beyond the scope of this publication, is designed to help the reader move from this presentation to a more technical one, the inevitable next step.

  2. Gel barrier formation in unsaturated porous media

    NASA Astrophysics Data System (ADS)

    Kim, Meejeong; Corapcioglu, M. Yavuz

    2002-05-01

    The gel barrier formation by a gelling liquid (Colloidal Silica) injection in an unsaturated porous medium is investigated by developing a mathematical model and conducting numerical simulations. Gelation process is initiated by adding electrolytes such as NaCl, and the gel phase consisting of cross-linked colloidal silica particles grows as the gelation process proceeds. The mathematical model describing the transport and gelation of Colloidal Silica (CS) is based on coupled mass balance equations for the gel mixture (the sol phase plus the gel phase), gel phase (cross-linked colloidal silica particles plus water captured between cross-linked particles), and colloidal silica particles (discrete and cross-linked) and NaCl in the sol (suspension of discrete colloidal silica particles in water) and gel phases. The solutions in terms of volumetric fraction of the gel phase yield the gel mixture viscosity via the dependency on the volumetric fraction of gel phase. This dependency is determined from a kinetic gelation model with time-normalized viscosity curves. The proposed model is verified by comparing experimentally and numerically determined hydraulic conductivities of gel-treated soil columns at different CS injection volumes. The numerical experiments indicate that an impermeable gel layer is formed within the time period twice the gel-point in a one-dimensional flow system. At the same normalized time corresponding to twice the gel-point, the CS solutions with lower NaCl concentrations result in further migration and poor performance in plugging the pore space. The viscosity computation proposed in this study is compared with another method available in the literature. It is observed that the other method estimates the viscosity at the mixing zone higher than the one proposed by the authors. The proposed model can simulate realistic injection scenarios with various combinations of operating parameters such as NaCl concentration and NaCl mixing time, and thus

  3. Gel barrier formation in unsaturated porous media.

    PubMed

    Kim, Meejeong; Corapcioglu, M Yavuz

    2002-05-01

    The gel barrier formation by a gelling liquid (Colloidal Silica) injection in an unsaturated porous medium is investigated by developing a mathematical model and conducting numerical simulations. Gelation process is initiated by adding electrolytes such as NaCl, and the gel phase consisting of cross-linked colloidal silica particles grows as the gelation process proceeds. The mathematical model describing the transport and gelation of Colloidal Silica (CS) is based on coupled mass balance equations for the gel mixture (the sol phase plus the gel phase), gel phase (cross-linked colloidal silica particles plus water captured between cross-linked particles), and colloidal silica particles (discrete and cross-linked) and NaCl in the sol (suspension of discrete colloidal silica particles in water) and gel phases. The solutions in terms of volumetric fraction of the gel phase yield the gel mixture viscosity via the dependency on the volumetric fraction of gel phase. This dependency is determined from a kinetic gelation model with time-normalized viscosity curves. The proposed model is verified by comparing experimentally and numerically determined hydraulic conductivities of gel-treated soil columns at different CS injection volumes. The numerical experiments indicate that an impermeable gel layer is formed within the time period twice the gel-point in a one-dimensional flow system. At the same normalized time corresponding to twice the gel-point, the CS solutions with lower NaCl concentrations result in further migration and poor performance in plugging the pore space. The viscosity computation proposed in this study is compared with another method available in the literature. It is observed that the other method estimates the viscosity at the mixing zone higher than the one proposed by the authors. The proposed model can simulate realistic injection scenarios with various combinations of operating parameters such as NaCl concentration and NaCl mixing time, and thus

  4. A High Temperature Capacitive Humidity Sensor Based on Mesoporous Silica

    PubMed Central

    Wagner, Thorsten; Krotzky, Sören; Weiß, Alexander; Sauerwald, Tilman; Kohl, Claus-Dieter; Roggenbuck, Jan; Tiemann, Michael

    2011-01-01

    Capacitive sensors are the most commonly used devices for the detection of humidity because they are inexpensive and the detection mechanism is very specific for humidity. However, especially for industrial processes, there is a lack of dielectrics that are stable at high temperature (>200 °C) and under harsh conditions. We present a capacitive sensor based on mesoporous silica as the dielectric in a simple sensor design based on pressed silica pellets. Investigation of the structural stability of the porous silica under simulated operating conditions as well as the influence of the pellet production will be shown. Impedance measurements demonstrate the utility of the sensor at both low (90 °C) and high (up to 210 °C) operating temperatures. PMID:22163790

  5. Evaluating Dimethyldiethoxysilane for use in Polyurethane Crosslinked Silica Aerogels

    NASA Technical Reports Server (NTRS)

    Randall, Jason P.; Meador, Mary Ann B.; Jana, Sadhan C.

    2008-01-01

    Silica aerogels are highly porous materials which exhibit exceptionally low density and thermal conductivity. Their "pearl necklace" nanostructure, however, is inherently weak; most silica aerogels are brittle and fragile. The strength of aerogels can be improved by employing an additional crosslinking step using isocyanates. In this work, dimethyldiethoxysilane (DMDES) is evaluated for use in the silane backbone of polyurethane crosslinked aerogels. Approximately half of the resulting aerogels exhibited a core/shell morphology of hard crosslinked aerogel surrounding a softer, uncrosslinked center. Solid state NMR and scanning electron microscopy results indicate the DMDES incorporated itself as a conformal coating around the outside of the secondary silica particles, in much the same manner as isocyanate crosslinking. Response surface curves were generated from compression data, indicating levels of reinforcement comparable to that in previous literature, despite the core/shell morphology.

  6. Positron annihilation characteristics in mesostructural silica films with various porosities

    SciTech Connect

    Xiong, Bangyun; Mao, Wenfeng; Tang, Xiuqin; He, Chunqing

    2014-03-07

    Porous silica films with various porosities were prepared via a sol-gel method using a nonionic amphiphilic triblock copolymer F127 as the structure-directing agent. Doppler broadening of positron annihilation radiation (DBAR) spectra were collected for the prepared films using a variable energy slow positron beam. Different linear relationships between positron annihilation line shape parameters S and W are found for the as-deposited films and calcined ones, indicative of the decomposition of the copolymer porogen in the as-deposited films upon calcination. This also reveals the variation of positron annihilation sites as a function of F127 loading or porosity. Strong correlations between positronium 3γ annihilation fraction, S parameter and porosity of the mesoporous silica films with isolated pores are obtained, which may provide a complementary method to determine closed porosities of mesoporous silica films by DBAR.

  7. Poisoning of a silica supported cobalt catalyst due to the presence of sulfur impurities in syngas during Fischer-Tropsch synthesis: Effect of chelating agent

    SciTech Connect

    Bambal, A.S.; Gardner, T.H.; Kugler, E.L.; Dadyburjor, D.B.

    2012-01-01

    crystallite sizes and higher dispersions of cobalt on the support. Finally, the sulfur deactivation data is modeled by a simple kinetic expression to determine the deactivation constant, deactivation rates and half-life of the FT catalyst.

  8. Supported microporous ceramic membranes

    DOEpatents

    Webster, Elizabeth; Anderson, Marc

    1993-01-01

    A method for permformation of microporous ceramic membranes onto a porous support includes placing a colloidal suspension of metal or metal oxide particles on one side of the porous support and exposing the other side of the porous support to a drying stream of gas or a reactive gas stream so that the particles are deposited on the drying side of the support as a gel. The gel so deposited can be sintered to form a supported ceramic membrane useful for ultrafiltration, reverse osmosis, or molecular sieving having mean pore sizes less than 100 Angstroms.

  9. Supported microporous ceramic membranes

    DOEpatents

    Webster, E.; Anderson, M.

    1993-12-14

    A method for the formation of microporous ceramic membranes onto a porous support includes placing a colloidal suspension of metal or metal oxide particles on one side of the porous support and exposing the other side of the porous support to a drying stream of gas or a reactive gas stream so that the particles are deposited on the drying side of the support as a gel. The gel so deposited can be sintered to form a supported ceramic membrane useful for ultrafiltration, reverse osmosis, or molecular sieving having mean pore sizes less than 100 Angstroms. 4 figures.

  10. Accelerated colorimetric immunosensing using surface-modified porous monoliths and gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Chuag, Shao-Hsuan; Chen, Guan-Hua; Chou, Hsin-Hao; Shen, Shu-Wei; Chen, Chien-Fu

    2013-08-01

    A rapid and sensitive immunoassay platform integrating polymerized monoliths and gold nanoparticles (AuNPs) has been developed. The porous monoliths are photopolymerized in situ within a silica capillary and serve as solid support for high-mass transport and high-density capture antibody immobilization to create a shorter diffusion length for antibody-antigen interactions, resulting in a rapid assay and low reagent consumption. AuNPs are modified with detection antibodies and are utilized as signals for colorimetric immunoassays without the need for enzyme, substrate and sophisticated equipment for quantitative measurements. This platform has been verified by performing a human IgG sandwich immunoassay with a detection limit of 0.1 ng ml-1. In addition, a single assay can be completed in 1 h, which is more efficient than traditional immunoassays that require several hours to complete.

  11. Study of silica templates in the rice husk and the carbon-silica nanocomposites produced from rice husk

    NASA Astrophysics Data System (ADS)

    Larichev, Yu. V.; Yeletsky, P. M.; Yakovlev, V. A.

    2015-12-01

    Carbon-silica nanocomposites obtained by rice husk carbonization in a fluidized-bed reactor using a deep oxidation copper-chromium catalyst were studied. Dispersion characteristics of the silica phase in these systems were determined by small-angle X-ray scattering (SAXS) using the full contrast technique. SiO2 was found in the initial rice husk as compact nanoparticles having a wide size distribution. This distribution consists of a narrow fraction with particle sizes from 1 to 7 nm and a wider fraction with particle sizes from 8 to 22 nm. Oxidative heat treatment of rice husk in a fluidized bed in the presence of the catalyst decreased the fraction of small SiO2 particles and increased the fraction of large ones. It was demonstrated that the particle size of silica in the carbon matrix can be determined selectively for deliberate design of porous carbon materials with desired properties.

  12. Synthesis of highly emissive PIPES-stabilized gold nanoclusters and gold nanocluster-doped silica nanoparticles.

    PubMed

    Jang, Min Hoon; Pak, Joonsung; Yoo, Hyojong

    2013-04-01

    Stable and highly emissive gold nanoclusters were successfully synthesized by means of stabilization with PIPES (PIPES-Au NCs, where PIPES = 1,4-piperazinediethanesulfonic acid) using a thermal synthetic strategy. By varying the amount of PIPES, two Au NCs with different emission maxima were obtained. The synthesized Au NCs were successfully incorporated into a porous silica matrix to generate fluorescent PIPES-Au NC doped silica nanoparticles. Sequential doping of the PIPES-Au NCs with tetraethylorthosilicate (TEOS) and 3-(aminopropyl)triethoxysilane (APTS) furnished a silica matrix, which effectively protected the PIPES-Au NCs during repeated washing with polar solvent and the composite of which exhibited enhanced emission.

  13. Catalyst Of A Metal Heteropoly Acid Salt That Is Insoluble In A Polar Solvent On A Non-Metallic Porous Support And Method Of Making

    DOEpatents

    Wang. Yong; Peden. Charles H. F.; Choi. Saemin

    2004-11-09

    The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

  14. Catalyst of a metal heteropoly acid salt that is insoluble in a polar solvent on a non-metallic porous support and method of making

    DOEpatents

    Wang, Yong [Richland, WA; Peden, Charles H. F. [West Richland, WA; Choi, Saemin [Richland, WA

    2002-10-29

    The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

  15. Native silica nanoparticles are powerful membrane disruptors.

    PubMed

    Alkhammash, Hend I; Li, Nan; Berthier, Rémy; de Planque, Maurits R R

    2015-06-28

    Silica nanoparticles are under development for intracellular drug delivery applications but can also have cytotoxic effects including cell membrane damage. In this study, we investigated the interactions of silica nanospheres of different size, surface chemistry and biocoating with membranes of phosphatidylcholine lipids. In liposome leakage assays many, but not all, of these nanoparticles induced dose-dependent dye leakage, indicative of membrane perturbation. It was found that 200 and 500 nm native-silica, aminated and carboxylated nanospheres induce near-total dye release from zwitterionic phosphatidylcholine liposomes at a particle/liposome ratio of ∼1, regardless of their surface chemistry, which we interpret as particle-supported bilayer formation following a global rearrangement of the vesicular membrane. In contrast, 50 nm diameter native-silica nanospheres did not induce total dye leakage below a particle/liposome ratio of ∼8, whereas amination or carboxylation, respectively, strongly reduced or prevented dye release. We postulate that for the smaller nanospheres, strong silica-bilayer interactions are manifested as bilayer engulfment of membrane-adsorbed particles, with localized lipid depletion eventually leading to collapse of the vesicular membrane. Protein coating of the particles considerably reduced dye leakage and lipid bilayer coating prevented dye release all together, while the inclusion of 33% anionic lipids in the liposomes reduced dye leakage for both native-silica and aminated surfaces. These results, which are compared with the effect of polystyrene nanoparticles and other engineered nanomaterials on lipid bilayers, and which are discussed in relation to nanosilica-induced cell membrane damage and cytotoxicity, indicate that a native-silica nanoparticle surface chemistry is a particularly strong membrane interaction motif.

  16. Energy Landscape of Water and Ethanol on Silica Surfaces

    SciTech Connect

    Wu, Di; Guo, Xiaofeng; Sun, Hui; Navrotsky, Alexandra

    2015-06-26

    Fundamental understanding of small molecule–silica surface interactions at their interfaces is essential for the scientific, technological, and medical communities. We report direct enthalpy of adsorption (Δhads) measurements for ethanol and water vapor on porous silica glass (CPG-10), in both hydroxylated and dehydroxylated (hydrophobic) forms. Results suggest a spectrum of energetics as a function of coverage, stepwise for ethanol but continuous for water. The zero-coverage enthalpy of adsorption for hydroxylated silica shows the most exothermic enthalpies for both water (-72.7 ± 3.1 kJ/mol water) and ethanol (-78.0 ± 1.9 kJ/mol ethanol). The water adsorption enthalpy becomes less exothermic gradually until reaching its only plateau (-20.7 ± 2.2 kJ/mol water) reflecting water clustering on a largely hydrophobic surface, while the enthalpy of ethanol adsorption profile presents two well separated plateaus, corresponding to strong chemisorption of ethanol on adsorbate-free silica surface (-66.4 ± 4.8 kJ/mol ethanol), and weak physisorption of ethanol on ethanol covered silica (-4.0 ± 1.6 kJ/mol ethanol). On the other hand, dehydroxylation leads to missing water–silica interactions, whereas the number of ethanol binding sites is not impacted. The isotherms and partial molar properties of adsorption suggest that water may only bind strongly onto the silanols (which are a minor species on silica glass), whereas ethanol can interact strongly with both silanols and the hydrophobic areas of the silica surface.

  17. Energy Landscape of Water and Ethanol on Silica Surfaces

    DOE PAGES

    Wu, Di; Guo, Xiaofeng; Sun, Hui; Navrotsky, Alexandra

    2015-06-26

    Fundamental understanding of small molecule–silica surface interactions at their interfaces is essential for the scientific, technological, and medical communities. We report direct enthalpy of adsorption (Δhads) measurements for ethanol and water vapor on porous silica glass (CPG-10), in both hydroxylated and dehydroxylated (hydrophobic) forms. Results suggest a spectrum of energetics as a function of coverage, stepwise for ethanol but continuous for water. The zero-coverage enthalpy of adsorption for hydroxylated silica shows the most exothermic enthalpies for both water (-72.7 ± 3.1 kJ/mol water) and ethanol (-78.0 ± 1.9 kJ/mol ethanol). The water adsorption enthalpy becomes less exothermic gradually until reachingmore » its only plateau (-20.7 ± 2.2 kJ/mol water) reflecting water clustering on a largely hydrophobic surface, while the enthalpy of ethanol adsorption profile presents two well separated plateaus, corresponding to strong chemisorption of ethanol on adsorbate-free silica surface (-66.4 ± 4.8 kJ/mol ethanol), and weak physisorption of ethanol on ethanol covered silica (-4.0 ± 1.6 kJ/mol ethanol). On the other hand, dehydroxylation leads to missing water–silica interactions, whereas the number of ethanol binding sites is not impacted. The isotherms and partial molar properties of adsorption suggest that water may only bind strongly onto the silanols (which are a minor species on silica glass), whereas ethanol can interact strongly with both silanols and the hydrophobic areas of the silica surface.« less

  18. Comets as porous aggregates of interstellar dust.

    PubMed

    Greenberg, J M; Remo, J L

    1997-05-30

    A comet model is derived based on the interstellar dust chemical composition in dense molecular and diffuse clouds resulting from their subsequent chemical interactions and UV photoprocessing. The collapsing presolar nebula leads to a porous aggregate model for comet nuclei, from which is derived certain physical properties that include thermal conductivity and tensile strength. The porous morphological structure is also shown to imply anomalous (expansion rather than contraction) behavior when subjected to strong shock waves, which is supported by recent shock experiments on (porous) carbonaceous chondrite material.

  19. Solid polymer electrolyte composite membrane comprising a porous support and a solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide

    DOEpatents

    Liu, Han; Mittelsteadt, Cortney K; Norman, Timothy J; Griffith, Arthur E; LaConti, Anthony B

    2015-02-24

    A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a thin, rigid, dimensionally-stable, non-electrically-conducting support, the support having a plurality of cylindrical, straight-through pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores are unevenly distributed, with some or no pores located along the periphery and more pores located centrally. The pores are completely filled with a solid polymer electrolyte, the solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide. The solid polymer electrolyte may also be deposited over the top and/or bottom surfaces of the support.

  20. Synthesis of robust hierarchical silica monoliths by surface-mediated solution/precipitation reactions over different scales: designing capillary microreactors for environmental applications.

    PubMed

    García-Aguilar, J; Miguel-García, I; Berenguer-Murcia, Á; Cazorla-Amorós, D

    2014-12-24

    A synthetic procedure to prepare novel materials (surface-mediated fillings) based on robust hierarchical monoliths is reported. The methodology includes the deposition of a (micro- or mesoporous) silica thin film on the support followed by growth of a porous monolithic SiO2 structure. It has been demonstrated that this synthesis is viable for supports of different chemical nature with different inner diameters without shrinkage of the silica filling. The formation mechanism of the surface-mediated fillings is based on a solution/precipitation process and the anchoring of the silica filling to the deposited thin film. The interaction between the two SiO2 structures (monolith and thin film) depends on the porosity of the thin film and yields composite materials with different mechanical stability. By this procedure, capillary microreactors have been prepared and have been proved to be highly active and selective in the total and preferential oxidation of carbon monoxide (TOxCO and PrOxCO).

  1. Fused silica windows for solar receiver applications

    NASA Astrophysics Data System (ADS)

    Hertel, Johannes; Uhlig, Ralf; Söhn, Matthias; Schenk, Christian; Helsch, Gundula; Bornhöft, Hansjörg

    2016-05-01

    A comprehensive study of optical and mechanical properties of quartz glass (fused silica) with regard to application in high temperature solar receivers is presented. The dependence of rupture strength on different surface conditions as well as high temperature is analyzed, focussing particularly on damage by devitrification and sandblasting. The influence of typical types of contamination in combination with thermal cycling on the optical properties of fused silica is determined. Cleaning methods are compared regarding effectiveness on contamination-induced degradation for samples with and without antireflective coating. The FEM-aided design of different types of receiver windows and their support structure is presented. A large-scale production process has been developed for producing fused silica dome shaped windows (pressurized window) up to a diameter of 816 mm. Prototypes were successfully pressure-tested in a test bench and certified according to the European Pressure Vessel Directive.

  2. Toughening Mechanisms in Silica-Filled Epoxy Nanocomposites

    NASA Astrophysics Data System (ADS)

    Patel, Binay S.

    and modeled fracture energy results. Furthermore, the contribution of microcracking was most prevalent at lower filler contents which suggests that the presence of microcracking may account for the previously unexplained improvements in fracture behavior attained in silica-filled epoxy nanocomposites at low filler contents. Secondly, surface modification through the application of three different propriety surface treatments ("A", "B" and "C") was found to greatly influence the processibility and fracture behavior of silica-filled epoxy nanocomposites. B-treated silica nanoparticles were found to readily form micron-scale agglomerates, settled during nanocomposite curing and showed no improvement in fracture toughness with increasing filler content. In contrast, the nanocomposites consisting of A-treated and C-treated silica nanoparticles yielded morphologies primarily containing well-dispersed nanoparticles. Therefore, fracture toughness improved with increasing filler content. Finally, particle porosity was found to have no significant effect on fracture behavior for the range of silica-filled epoxy nanocomposites investigated. Lower density porous silica nanoparticles were just as effective toughening agents as higher density non-porous silica nanoparticles. Consequently, the potential exists for the use of toughened-epoxies in lightweight structural applications.

  3. Porous Shape Memory Polymers

    PubMed Central

    Hearon, Keith; Singhal, Pooja; Horn, John; Small, Ward; Olsovsky, Cory; Maitland, Kristen C.; Wilson, Thomas S.; Maitland, Duncan J.

    2013-01-01

    Porous shape memory polymers (SMPs) include foams, scaffolds, meshes, and other polymeric substrates that possess porous three-dimensional macrostructures. Porous SMPs exhibit active structural and volumetric transformations and have driven investigations in fields ranging from biomedical engineering to aerospace engineering to the clothing industry. The present review article examines recent developments in porous SMPs, with focus given to structural and chemical classification, methods of characterization, and applications. We conclude that the current body of literature presents porous SMPs as highly interesting smart materials with potential for industrial use. PMID:23646038

  4. Tailored Porous Materials

    SciTech Connect

    BARTON,THOMAS J.; BULL,LUCY M.; KLEMPERER,WALTER G.; LOY,DOUGLAS A.; MCENANEY,BRIAN; MISONO,MAKOTO; MONSON,PETER A.; PEZ,GUIDO; SCHERER,GEORGE W.; VARTULI,JAMES C.; YAGHI,OMAR M.

    1999-11-09

    Tailoring of porous materials involves not only chemical synthetic techniques for tailoring microscopic properties such as pore size, pore shape, pore connectivity, and pore surface reactivity, but also materials processing techniques for tailoring the meso- and the macroscopic properties of bulk materials in the form of fibers, thin films and monoliths. These issues are addressed in the context of five specific classes of porous materials: oxide molecular sieves, porous coordination solids, porous carbons, sol-gel derived oxides, and porous heteropolyanion salts. Reviews of these specific areas are preceded by a presentation of background material and review of current theoretical approaches to adsorption phenomena. A concluding section outlines current research needs and opportunities.

  5. Multifunctional antireflection coatings based on novel hollow silica-silica nanocomposites.

    PubMed

    Zhang, Xianpeng; Lan, Pinjun; Lu, Yuehui; Li, Jia; Xu, Hua; Zhang, Jing; Lee, YoungPak; Rhee, Joo Yull; Choy, Kwang-Leong; Song, Weijie

    2014-02-12

    Antireflection (AR) coatings that exhibit multifunctional characteristics, including high transparency, robust resistance to moisture, high hardness, and antifogging properties, were developed based on hollow silica-silica nanocomposites. These novel nanocomposite coatings with a closed-pore structure, consisting of hollow silica nanospheres (HSNs) infiltrated with an acid-catalyzed silica sol (ACSS), were fabricated using a low-cost sol-gel dip-coating method. The refractive index of the nanocomposite coatings was tailored by controlling the amount of ACSS infiltrated into the HSNs during synthesis. Photovoltaic transmittance (TPV) values of 96.86-97.34% were obtained over a broad range of wavelengths, from 300 to 1200 nm; these values were close to the theoretical limit for a lossy single-layered AR coating (97.72%). The nanocomposite coatings displayed a stable TPV, with degradation values of less than 4% and 0.1% after highly accelerated temperature and humidity stress tests, and abrasion tests, respectively. In addition, the nanocomposite coatings had a hardness of approximately 1.6 GPa, while the porous silica coatings with an open-pore structure showed more severe degradation and had a lower hardness. The void fraction and surface roughness of the nanocomposite coatings could be controlled, which gave rise to near-superhydrophilic and antifogging characteristics. The promising results obtained in this study suggest that the nanocomposite coatings have the potential to be of benefit for the design, fabrication, and development of multifunctional AR coatings with both omnidirectional broadband transmission and long-term durability that are required for demanding outdoor applications in energy harvesting and optical instrumentation in extreme climates or humid conditions.

  6. Synthesis of Silicon Nitride and Silicon Carbide Nanocomposites through High Energy Milling of Waste Silica Fume for Structural Applications

    NASA Astrophysics Data System (ADS)

    Suri, Jyothi

    Nanocomposites have been widely used in a multitude of applications in electronics and structural components because of their improved mechanical, electrical, and magnetic properties. Silicon nitride/Silicon carbide (Si 3N4/SiC) nanocomposites have been studied intensively for low and high temperature structural applications, such as turbine and automobile engine components, ball bearings, turbochargers, as well as energy applications due to their superior wear resistance, high temperature strength, high oxidation resistance and good creep resistance. Silica fume is the waste material produced during the manufacture of silicon and ferro-silicon alloys, and contains 94 to 97 wt.% SiO2. In the present dissertation, the feasibility of using waste silica fume as the raw material was investigated to synthesize (I) advanced nanocomposites of Si3N4/SiC, and (2) porous silicon carbide (SiC) for membrane applications. The processing approach used to convert the waste material to advanced ceramic materials was based on a novel process called, integrated mechanical and thermal activation process (IMTA) process. In the first part of the dissertation, the effect of parameters such as carbothermic nitridation and reduction temperature and the graphite concentration in the starting silica fume plus graphite mixture, were explored to synthesize nanocomposite powders with tailored amounts of Si3N4 and SiC phases. An effective way to synthesize carbon-free Si3N 4/SiC composite powders was studied to provide a clear pathway and fundamental understanding of the reaction mechanisms. Si3N4/SiC nanocomposite powders were then sintered using two different approaches, based on liquid phase sintering and spark plasma sintering processes, with Al 2O3 and Y2O3 as the sintering aids. The nanocomposites were investigated for their densification behavior, microstructure, and mechanical properties. Si3N4/SiC nanocomposites thus obtained were found to possess superior mechanical properties at much

  7. Kinetics of silica polymerization

    SciTech Connect

    Weres, O.; Yee, A.; Tsao, L.

    1980-05-01

    The polymerization of silicic acid in geothermal brine-like aqueous solutions to produce amorphous silica in colloidal form has been studied experimentally and theoretically. A large amount of high quality experimental data has been generated over the temperature rang 23 to 100{sup 0}C. Wide ranges of dissolved silica concentration, pH, and sodium chloride concentration were covered. The catalytic effects of fluoride and the reaction inhibiting effects of aluminum and boron were studied also. Two basic processes have been separately studied: the formation of new colloidal particles by the homogeneous nucleation process and the deposition of dissolved silica on pre-existing colloidal particles. A rigorous theory of the formation of colloidal particles of amorphous silica by homogeneous nucleation was developed. This theory employs the Lothe-Pound formalism, and is embodied in the computer code SILNUC which quantitatively models the homogeneous nucleation and growth of colloidal silica particles in more than enough detail for practical application. The theory and code were extensively used in planning the experimental work and analyzing the data produced. The code is now complete and running in its final form. It is capable of reproducing most of the experimental results to within experimental error. It is also capable of extrapolation to experimentally inaccessible conditions, i.e., high temperatures, rapidly varying temperature and pH, etc.

  8. Porous Carriers for Controlled/Modulated Drug Delivery

    PubMed Central

    Ahuja, G.; Pathak, K.

    2009-01-01

    Considerable research efforts have been directed in recent years towards the development of porous carriers as controlled drug delivery matrices because of possessing several features such as stable uniform porous structure, high surface area, tunable pore size and well-defined surface properties. Owing to wide range of useful properties porous carriers have been used in pharmaceuticals for many purposes including development of floating drug delivery systems, sustained drug delivery systems. Various types of pores like open, closed, transport and blind pores in the porous solid allow them to adsorb drugs and release them in a more reproducible and predictable manner. Pharmaceutically exploited porous adsorbents includes, silica (mesoporous), ethylene vinyl acetate (macroporous), polypropylene foam powder (microporous), titanium dioxide (nanoporous). When porous polymeric drug delivery system is placed in contact with appropriate dissolution medium, release of drug to medium must be preceded by the drug dissolution in the water filled pores or from surface and by diffusion through the water filled channels. The porous carriers are used to improve the oral bioavailability of poorly water soluble drugs, to increase the dissolution of relatively insoluble powders and conversion of crystalline state to amorphous state. PMID:20376211

  9. Porous carriers for controlled/modulated drug delivery.

    PubMed

    Ahuja, G; Pathak, K

    2009-11-01

    Considerable research efforts have been directed in recent years towards the development of porous carriers as controlled drug delivery matrices because of possessing several features such as stable uniform porous structure, high surface area, tunable pore size and well-defined surface properties. Owing to wide range of useful properties porous carriers have been used in pharmaceuticals for many purposes including development of floating drug delivery systems, sustained drug delivery systems. Various types of pores like open, closed, transport and blind pores in the porous solid allow them to adsorb drugs and release them in a more reproducible and predictable manner. Pharmaceutically exploited porous adsorbents includes, silica (mesoporous), ethylene vinyl acetate (macroporous), polypropylene foam powder (microporous), titanium dioxide (nanoporous). When porous polymeric drug delivery system is placed in contact with appropriate dissolution medium, release of drug to medium must be preceded by the drug dissolution in the water filled pores or from surface and by diffusion through the water filled channels. The porous carriers are used to improve the oral bioavailability of poorly water soluble drugs, to increase the dissolution of relatively insoluble powders and conversion of crystalline state to amorphous state.

  10. Generation of crystalline silica from sugarcane burning.

    PubMed

    Le Blond, Jennifer S; Horwell, Claire J; Williamson, Ben J; Oppenheimer, Clive

    2010-07-01

    Sugarcane leaves contain amorphous silica, which may crystallise to form crystalline silica polymorphs (cristobalite or quartz), during commercial sugarcane harvesting where sugarcane plants are burned. Respirable airborne particulate containing these phases may present an occupational health hazard. Following from an earlier pilot study (J. S. Le Blond, B. J. Williamson, C. J. Horwell, A. K. Monro, C. A. Kirk and C. Oppenheimer, Atmos. Environ., 2008, 42, 5558-5565) in which experimental burning of sugarcane leaves yielded crystalline silica, here we report on actual conditions during sugarcane burning on commercial estates, investigate the physico-chemical properties of the cultivated leaves and ash products, and quantify the presence of crystalline silica. Commercially grown raw sugarcane leaf was found to contain up to 1.8 wt% silica, mostly in the form of amorphous silica bodies (with trace impurities e.g., Al, Na, Mg), with only a small amount of quartz. Thermal images taken during several pre-harvest burns recorded temperatures up to 1056 degrees C, which is sufficient for metastable cristobalite formation. No crystalline silica was detected in airborne particulate from pre-harvest burning, collected using a cascade impactor. The sugarcane trash ash formed after pre-harvest burning contained between 10 and 25 wt% SiO(2), mostly in an amorphous form, but with up to 3.5 wt% quartz. Both quartz and cristobalite were identified in the sugarcane bagasse ash (5-15 wt% and 1-3 wt%, respectively) formed in the processing factory. Electron microprobe analysis showed trace impurities of Mg, Al and Fe in the silica particles in the ash. The absence of crystalline silica in the airborne emissions and lack of cristobalite in trash ash suggest that high temperatures during pre-harvest burning were not sustained long enough for cristobalite to form, which is supported by the presence of low temperature sylvite and calcite in the residual ash. The occurrence of quartz and

  11. Generation of crystalline silica from sugarcane burning.

    PubMed

    Le Blond, Jennifer S; Horwell, Claire J; Williamson, Ben J; Oppenheimer, Clive

    2010-07-01

    Sugarcane leaves contain amorphous silica, which may crystallise to form crystalline silica polymorphs (cristobalite or quartz), during commercial sugarcane harvesting where sugarcane plants are burned. Respirable airborne particulate containing these phases may present an occupational health hazard. Following from an earlier pilot study (J. S. Le Blond, B. J. Williamson, C. J. Horwell, A. K. Monro, C. A. Kirk and C. Oppenheimer, Atmos. Environ., 2008, 42, 5558-5565) in which experimental burning of sugarcane leaves yielded crystalline silica, here we report on actual conditions during sugarcane burning on commercial estates, investigate the physico-chemical properties of the cultivated leaves and ash products, and quantify the presence of crystalline silica. Commercially grown raw sugarcane leaf was found to contain up to 1.8 wt% silica, mostly in the form of amorphous silica bodies (with trace impurities e.g., Al, Na, Mg), with only a small amount of quartz. Thermal images taken during several pre-harvest burns recorded temperatures up to 1056 degrees C, which is sufficient for metastable cristobalite formation. No crystalline silica was detected in airborne particulate from pre-harvest burning, collected using a cascade impactor. The sugarcane trash ash formed after pre-harvest burning contained between 10 and 25 wt% SiO(2), mostly in an amorphous form, but with up to 3.5 wt% quartz. Both quartz and cristobalite were identified in the sugarcane bagasse ash (5-15 wt% and 1-3 wt%, respectively) formed in the processing factory. Electron microprobe analysis showed trace impurities of Mg, Al and Fe in the silica particles in the ash. The absence of crystalline silica in the airborne emissions and lack of cristobalite in trash ash suggest that high temperatures during pre-harvest burning were not sustained long enough for cristobalite to form, which is supported by the presence of low temperature sylvite and calcite in the residual ash. The occurrence of quartz and

  12. Mesostructured silica and aluminosilicate carriers for oxytetracycline delivery systems.

    PubMed

    Berger, D; Nastase, S; Mitran, R A; Petrescu, M; Vasile, E; Matei, C; Negreanu-Pirjol, T

    2016-08-30

    Oxytetracycline delivery systems containing various MCM-type silica and aluminosilicate with different antibiotic content were developed in order to establish the influence of the support structural and textural properties and aluminum content on the drug release profile. The antibiotic molecules were loaded into the support mesochannels by incipient wetness impregnation method using a drug concentrated aqueous solution. The carriers and drug-loaded materials were investigated by small- and wide-angle XRD, FTIR spectroscopy, TEM and N2 adsorption-desorption isotherms. Faster release kinetics of oxytetracycline from uncalcined silica and aluminosilicate supports was observed, whereas higher drug content led to lower delivery rate. The presence of aluminum into the silica network also slowed down the release rate. The antimicrobial assays performed on Staphylococcus aureus clinical isolates showed that the oxytetracycline-loaded materials containing MCM-41-type mesoporous silica or aluminosilicate carriers inhibited the bacterial development. PMID:26861688

  13. Mesostructured silica and aluminosilicate carriers for oxytetracycline delivery systems.

    PubMed

    Berger, D; Nastase, S; Mitran, R A; Petrescu, M; Vasile, E; Matei, C; Negreanu-Pirjol, T

    2016-08-30

    Oxytetracycline delivery systems containing various MCM-type silica and aluminosilicate with different antibiotic content were developed in order to establish the influence of the support structural and textural properties and aluminum content on the drug release profile. The antibiotic molecules were loaded into the support mesochannels by incipient wetness impregnation method using a drug concentrated aqueous solution. The carriers and drug-loaded materials were investigated by small- and wide-angle XRD, FTIR spectroscopy, TEM and N2 adsorption-desorption isotherms. Faster release kinetics of oxytetracycline from uncalcined silica and aluminosilicate supports was observed, whereas higher drug content led to lower delivery rate. The presence of aluminum into the silica network also slowed down the release rate. The antimicrobial assays performed on Staphylococcus aureus clinical isolates showed that the oxytetracycline-loaded materials containing MCM-41-type mesoporous silica or aluminosilicate carriers inhibited the bacterial development.

  14. Silica Precipitation and Lithium Sorption

    SciTech Connect

    Jay Renew

    2015-09-20

    This file contains silica precipitation and lithium sorption data from the project. The silica removal data is corrected from the previous submission. The previous submission did not take into account the limit of detection of the ICP-MS procedure.

  15. Kinetics of silica deposition from simulated geothermal brines

    SciTech Connect

    Bohlmann, E.G.; Mesmer, R.E.; Berlinski, P.

    1980-03-01

    Supersaturated brines were passed through columns packed with several forms of silica (crystalline ..cap alpha.. quartz, polycrystalline ..cap alpha.. quartz, and porous Vycor). Also, silica deposition on ThO/sub 2/ microspheres and titanium powder was studied under controlled conditions of supersaturation, pH, temperature, and salinity. The residence time was varied by adjustments of flow rate and column length. The silica contents of the input and effluent solutions were determined colorimetrically by a molybdate method which does not include polymers without special pretreatment. Essentially identical deposition behavior was observed once the substrate was thoroughly coated with amorphous silica and the BET surface area of the coated particles was taken into account. The reaction rate is not diffusion limited in the columns. The silica deposition is a function of the monomeric Si(OH)/sub 4/ concentration in the brine. The deposition on all surfaces examined was spontaneously nucleated. The dependence on the supersaturation concentration, hydroxide ion concentration, surface area, temperature and salinity were examined. Fluoride was shown to have no effect at pH 5.94 and low salinity. The empirical rate law which describes the data in 1 m NaCl in the pH range 5-7 and temperatures from 60 to 120/sup 0/C is given.

  16. Synthesis, characterisation and application of silica-magnetite nanocomposites

    NASA Astrophysics Data System (ADS)

    Bruce, Ian J.; Taylor, James; Todd, Michael; Davies, Martin J.; Borioni, Enrico; Sangregorio, Claudio; Sen, Tapas

    2004-12-01

    -phosphorylated analogue 2-deoxyguanosine (G) and a range of sequence defined oligonucleotides (NAs) and sheared salmon sperm DNA. It was found that magnetite readily adsorbed GMP via the GMP phosphate anion in water, whereas silica did not, due to electrostatic repulsion between the negatively charged surface of silica and the GMP. Both magnetite and silica magnetite were further tested in adsorption studies of G and GMP in different chaotropic media, 4 M sodium chloride or 4 M ammonium sulphate. The high salt conditions aided binding of GMP silica magnetite but inhibited adsorption to magnetite presumably due to competition for binding sites on the magnetite's surface by the chaotrope anions. Interestingly, the results from NAs binding studies indicated that sequence appeared to play an important role in adsorption of the different species to silica-magnetite composites. This may indicate a contribution by hydrophobic interactions to the binding mechanism. Multiple depositions of silica onto magnetite performed by deposition from silicic acid at pH 10 did not appear to greatly increase the composite percentage represented by silica whilst composite produced by the acid hydrolysis of TEOS at 90 °C did. However, it appeared that the silica deposited by the first method represented a complete coating of the magnetite core whilst the second method yielded a porous or incomplete coating. In comparison with commercially available silica-magnetite composite in DNA adsorption and elution, the material was observed to perform approximately 10% more efficiently. These findings indicate that it is possible to produce a consistent and cheap silica-magnetite nanoparticle on relatively large scale (greater than 20 g batch size) which is at least as good as, if not better than, a commercially available alternative.

  17. The investigation of the viscoelastic properties of silica/PMMA nanocomposites as a function of silica surface chemistry

    NASA Astrophysics Data System (ADS)

    Conway, Heather; Rende, Deniz; Ozisik, Rahmi

    2013-03-01

    Poly(methyl methacrylate), PMMA, has been used as an economic alternative to glass and polycarbonate in differing situations because of its lightweight, shatter resistance, and ease of processability. The uses of PMMA can be expanded if its weakness to impact force and its scratch resistance are improved. In the current study, viscoelastic properties of silica nanoparticle filled PMMA were investigated via nanoindentation experiments. Silica nanoparticles are known to increase the toughness of PMMA. In the current study, silica nanoparticles were chemically modified with fluorinated alkanes to alter nanofiller-polymer interactions. Results show that viscoelastic properties are strongly affected by silica surface chemistry and silica concentration. This work was partially supported by NSF CMMI-1200270 and DUE-1003574

  18. Epoxy Grout With Silica Thickener

    NASA Technical Reports Server (NTRS)

    Mcclung, C. E.

    1984-01-01

    Grout cures quickly, even in presence of hydraulic oil. Grout is mixture of aggregate particles, finely-divided silica, epoxy resin, and triethylenetetramine curing agent, with mixture containing about 85 percent silica and aggregate particle sand 15 percent resin and curing agent. Silica is thickening agent and keeps grout from sagging.

  19. Bases for the synthesis of nanoparticulated silicas with bimodal hierarchical porosity

    NASA Astrophysics Data System (ADS)

    Huerta, Lenin; Guillem, Carmen; Latorre, Julio; Beltrán, Aurelio; Martínez-Máñez, Ramón; Marcos, M. Dolores; Beltrán, Daniel; Amorós, Pedro

    2006-08-01

    Porous silicas with pore sizes at two length scales (meso and large meso/macroporous) have been prepared through a one-pot surfactant assisted procedure by using a simple template agent and starting from silicon atrane complexes as hydrolytic inorganic precursors. The special organization of these bimodal porous silicas can be related to the nanometric character of their constituent mesoporous particles. Whereas the small intra-particle mesopore system is generated by the templating effect of the surfactant, the large pore system is defined by inter-particle voids. We have studied the effect of different procedural parameters on the small pore system and also on the nucleation and growth of the nanoparticles. The formation of these hierarchical materials is explained on the basis of kinetic (hydrolysis and condensation reaction rates) and thermodynamic (silica solubility) concepts.

  20. Nanoporous microbead supported bilayers: stability, physical characterization, and incorporation of functional transmembrane proteins.

    SciTech Connect

    Davis, Ryan W. (University of New Mexico, Albuquerque, NM); Brozik, James A. (University of New Mexico, Albuquerque, NM); Brozik, Susan Marie; Cox, Jason M.; Lopez, Gabriel P.; Barrick, Todd A.; Flores, Adrean

    2007-03-01

    The introduction of functional transmembrane proteins into supported bilayer-based biomimetic systems presents a significant challenge for biophysics. Among the various methods for producing supported bilayers, liposomal fusion offers a versatile method for the introduction of membrane proteins into supported bilayers on a variety of substrates. In this study, the properties of protein containing unilamellar phosphocholine lipid bilayers on nanoporous silica microspheres are investigated. The effects of the silica substrate, pore structure, and the substrate curvature on the stability of the membrane and the functionality of the membrane protein are determined. Supported bilayers on porous silica microspheres show a significant increase in surface area on surfaces with structures in excess of 10 nm as well as an overall decrease in stability resulting from increasing pore size and curvature. Comparison of the liposomal and detergent-mediated introduction of purified bacteriorhodopsin (bR) and the human type 3 serotonin receptor (5HT3R) are investigated focusing on the resulting protein function, diffusion, orientation, and incorporation efficiency. In both cases, functional proteins are observed; however, the reconstitution efficiency and orientation selectivity are significantly enhanced through detergent-mediated protein reconstitution. The results of these experiments provide a basis for bulk ionic and fluorescent dye-based compartmentalization assays as well as single-molecule optical and single-channel electrochemical interrogation of transmembrane proteins in a biomimetic platform.