Sol-Gel Formation of Reticular Methyl-Silicate Materials by Hydrogen Peroxide Decomposition

A new method for the formation of reticular silicate and organically modified silicate is introduced. Monoliths were prepared by incorporating a few percent hydrogen peroxide in the sol-gel starting solution. For example, incorporation of 6–10% (v) hydrogen peroxide in base catalyzed sol-gel precursors of methyl-Ormosil yielded macroporous monoliths with a bi-modal pore size distribution. The average characteristic pore diameters were approximately 1.2 nm and 0.7 m, depending on the sol-gel precursors used and the preparation protocol. The specific surface area was approximately 160 m2/g, contributed mainly by the microporous structure. A similar preparation procedure without hydrogen peroxide yielded only fractured or powdery materials. Presumably, the decomposition of the hydrogen peroxide yielded microbubbles, which formed templates for the polycondensation reaction. SEM, nitrogen adsorption isotherms and small angle X-ray spectroscopy were used to characterize the reticular materials.     

Influence of Sol-Gel Synthesis Parameters on the Microstructure of Particulate Silica Xerogels

The influence of key sol-gel synthesis parameters on the pore structure of microporous silica xerogels was investigated. The silica xerogels were prepared using an acid-catalyzed aqueous sol-gel process, with tetraethoxysilane (TEOS) as the silicon-containing precursor. At high H2O : TEOS ratios, sols synthesized at pH 2–3 yielded minimum values of mean micropore diameter and micropore volume. Analysis of the resulting Type I nitrogen adsorption isotherms and the equilibrium adsorption of N(C4F9)3 indicated micropore diameters for these xerogels of less than approximately 10 Å.Xerogel micropore volumes corresponding to sols prepared at pH 3 and an H2O : TEOS ratio of r = 83 were consistent with nearly close packing of silica spheres in the xerogel. Xerogel microstructure was only weakly dependent upon H2O : TEOS ratio during sol synthesis for r > 10. Xerogel micropore volume increased rapidly with sol aging time during an initial induction period of particle formation. However, the xerogel microstructure changed only slowly with time after this initial period, suggesting potential processing advantages for the particulate sol-gel route to porous silica materials.Surface adsorption properties of the silica xerogels were investigated at ambient temperature using N2, SF6, and CO2. CO2 adsorbed most strongly, SF6 also showed measurable adsorption, and N2 adsorption was nearly zero. These results were consistent with the surface transport of CO2, and to a lesser extent SF6, observed in gas permeation studies performed through thin membrane films cast from similarly prepared silica sols.     

Membrane Emulsification Using Sol-Gel Derived Macroporous Silica Glass

A macroporous silica glass membrane with continuous cylindrical pores was prepared by a sol-gel process using phase separation. The applicability of the sol-gel derived macroporous silica to the membrane emulsification process was evaluated in comparison with a conventional SPG (Silasu Porous Glass) membrane.Aqueous colloidal silica in one side of the membrane was emulsified through the pores under an applied pressure to a toluene bath containing surfactant. With the sol-gel and SPG membranes with respective median pore diameters of 0.6 and 1.0 m, emulsions with almost the same droplet size centered around 3 m were obtained. The permeation rate of the sol-gel derived membrane was about 1.6 times faster than SPG, which reflected higher pore volume of the former one.     

Encapsulation of Water-Soluble Dye in Spherical Sol-Gel Silica Matrices

The water-soluble, Lithol rubine B, dye was encapsulated into silica microspheres matrices. Encapsulation has been carried out by sol-gel process of W/O microemulsions formed from sodium silicate and dye aqueous solution in cyclohexane medium. The average particle size could be tailored from 1–10 m, depending on the processing parameter such as homogenizing speed in the formation of W/O emulsion, the weight ratio of water to oil, and concentration of sodium silicate solution, etc. The pore size of dye-doped silica microspheres was measured by nitrogen adsorption-desorption isotherms. The leaching behavior of dye entrapped in silica matrices was investigated by UV/VIS and UV diffuse reflectance spectroscopy for the extract and solid powders after immersion for 24 h in water. The doping of GPTS (3-glycidoxypropyltrimethoxysilane) in sodium silicate and dye mixture solution greatly enhanced the stability against leaching of the dye. It was ascribed that GPTS serves simultaneously as an intermediate for the chemical bonding between the dye and silica, and as an agent for the formation of hybrid sol responsible for the shrinkage of pore size.     

Hydrogen adsorption in transition metal carbon nano-structures

Templated microporous carbons were synthesized from metal impregnated zeolite Y templates. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to characterize morphology and structure of the generated carbon materials. The surface area, micro- and meso-pore volumes, as well as the pore size distribution of all the carbon materials were determined by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. All the hydrogen adsorption isotherms were Type 1 and reversible, indicating physisorption at 77 K. Most templated carbons show good hydrogen storage with the best sample Rh-C having surface area 1817 m²/g and micropore volume 1.04 cm³/g, achieving the highest as 8.8 mmol/g hydrogen storage capacity at 77 K, 1 bar. Comparison between activated carbons and synthesized templated carbons revealed that the hydrogen adsorption in the latter carbon samples occurs mainly by pore filling and smaller pores of sizes around 6 Å to 8 Å are filled initially, followed by larger micropores. Overall, hydrogen adsorption was found to be dependent on the micropore volume as well as the pore-size, larger micropore volumes showing higher hydrogen adsorption capacity.     

Characterisation of Xerogels Derived from Sucrose Templated Sol-Gel Synthesis

This work presents the results of the nanostructural characterisation of the effect of sucrose as a template added to a sol derived from a tetraethoxysilane acid catalysed process. By increasing the sucrose template ratio, N₂ adsorption isotherms showed that the xerogel samples changed from a micropore to a mesopore nanostructure as evidenced by the formation of hysteresis at 0.5 partial pressure. In turn, this led to a direct increase in surface areas, pore volumes and average pore sizes. Sucrose has two molecular components of the same molecular weight: D-fructose and D-glucose. D-fructose resulted in the formation of higher pore volumes and pore sizes, while D-glucose formed higher surface area xerogels. Depending of the template ratio employed in the xerogel synthesis, average pore radius ranged from 8.8 to 26 Å, while surface areas increased by over two fold up to 750 m²·g^?1. However, pore volumes increased by as much as six fold, from 0.15 to almost 1 cm³·g^?1.     

Dynamic Adsorption of Vapours by Activated Carbons and by Polymer-Derived Adsorbents: 1. Adsorption at 0% R.H.

The uptakes of volatile organic compounds from a nitrogen carrier gas at 0% R.H. onto packed beds of adsorbents have been measured by monitoring the effluent vapour concentration profile as a function of time. The profiles have been quantitatively fitted by a modified Bohart-Adams equation which was then integrated to yield the adsorbent capacities. Traditional activated carbons, carbonised macroreticular resins and a macroreticular polymer were used in the study. Performance in the dynamic tests has been related to the pore volume characteristics and surface areas determined from nitrogen adsorption isotherms. Whilst the extent of micropore filling basically increased as the sorbate boiling point increased and increased capacities reflected increased micropore volumes, these trends were interrupted by size exclusion and specific polar interaction effects.     

Synthesis of ordered and disordered silicas with uniform pores on the border between micropore and mesopore regions using short double-chain surfactants.

Silica molecular sieves with uniform pores on the borderline between micropore (diameter <2 nm) and mesopore (from 2 to 50 nm) ranges were synthesized by a novel method using judiciously chosen mixtures of short double-chain alkylammonium surfactants. These silicas were characterized using X-ray diffraction (XRD), thermogravimetry, and nitrogen and argon adsorption. The calcined materials exhibited either 2-dimensional (2-D) hexagonal or disordered structures with XRD interplanar spacing from 2.51 to 2.93 nm, including the value of as small as 2.69 nm for highly ordered 2-D hexagonal silica. The dependence of the pore size and surfactant content on the surfactant chain length provided strong evidence for supramolecular templating being operative in the formation of small-pore silicas, even for the surfactant chain length of six carbon atoms. Both hexagonally ordered and disordered calcined samples were shown to exhibit narrow pore size distributions with maxima in the range from 1.96 to 2.61 nm (reliably evaluated on the basis of the unit-cell dimension and pore volume for 2-D hexagonal materials, and calculated using a properly calibrated procedure), tailored by the surfactant chain length. The samples exhibited primary pore volumes from 0.28 to 0.54 cm(3) g(-1) and specific surface areas from 730 to 930 m(2) g(-1). Because of their small yet uniform pore size and large specific surface area, the silicas reported herein promise to be useful in applications in adsorption and catalysis. Adsorption studies of these materials provided a unique new insight into the pore-filling mechanism for small-pore materials. Moreover, the approach proposed herein is expected to facilitate the synthesis of not only small-pore silicas but also materials with other framework compositions, thus largely contributing to bridging the gap in attainable pore sizes between micropore and mesopore ranges.     

Pore Modification in Porous Ceramic Membranes With Sol-Gel Process and Determination of Gas Permeability and Selectivity

Summary: The aim of the study was to investigate the variation in total surface area, porosity, pore size, Knudsen and surface diffusion coefficients, gas permeability and selectivity before and after the application of sol-gel process to porous ceramic membrane in order to determine the effect of pore modification. In this study, three different sol-gel process were applied to the ceramic support separately; one was the silica sol-gel process which was applied to increase porosity, others were silica-sol dip coating and silica-sol processing methods which were applied to decrease pore size. As a result of this, total surface area, pore size and porosity of ceramic support and membranes were determined by using BET instrument. In addition to this, Knudsen and surface diffusion coefficients were also calculated. After then, ceramic support and membranes were exposed to gas permeation experiments by using the CO₂ gas with different flow rates. Gas permeability and selectivity of those membranes were measured according to the data obtained. Thus, pore surface area, porosity, pore size and Knudsen diffusion coefficient of membrane treated with silica sol-gel process increased while total surface area was decreasing. Therefore, permeability of ceramic support and membrane treated with silica sol-gel process increased, and selectivity decreased with increasing the gas flow rate. Also, surface area, porosity, pore size, permeability, selectivity, Knudsen and surface diffusion coefficients of membranes treated with silica-sol dip coating and silica-sol processing methods were determined. As a result of this, porosity, pore size, Knudsen and surface diffusion coefficients decreased, total surface area increased in both methods. However, viscous flow and Knudsen flow permeability were detected as a consequence of gas permeability test and Knudsen flow was found to be a dominant transport mechanism in addition to surface diffusive flow owing to the small pore diameter in both methods. It was observed that silica-sol processing method had lower pore diameter and higher surface diffusion coefficient than silica-sol dip coating method.     

Synthesis of mesoporous silica materials with ascorbic acid as template via sol-gel process

Mesoporous silica materials with pore diameters of 2-5 nm have been prepared using ascorbic acid as a nonsurfactant template or pore-forming agent in HCl-catalyzed sol-gel reactions of tetraethylorthosilicate,followed by removing the ascorbic acid compound by extraction with ethanol.Characterization results from nitrogen sorption isotherm,powder X-ray diffraction and transmission electron microscopy indicate that the materials have large specific surface areas (e.g.1000 m2/g) and pore volumes (e.g.0.8 cm3/g).The rnesoporosity is arisen from interconnecting disordered wormlike channels and pores with relatively broad size distributions.As the ascorbic acid concentration is increased,the pore diameters and pore volumes of the materials increase.     

Rapid preparation of molecularly imprinted polymer by frontal polymerization

Frontal polymerization was successfully applied, for the first time, to obtain molecularly imprinted polymers (MIPs). The method provides a solvent-free polymerization mode, and the reaction can be completed in 30 min. By this approach, MIPs were synthesized using a mixture of levofloxacin (template), methacrylic acid, and divinylbenzene. The effect of template concentration and the amount of comonomer on the imprinting effect of the resulting MIPs was investigated. The textural and morphological parameters of the MIP particles were also characterized by mercury intrusion porosimetry, nitrogen adsorption isotherms, and scanning electron microscopy, providing evidence concerning median pore diameter, pore volumes, and pore size distributions. The levofloxacin-imprinted polymer formed in frontal polymerization mode showed high selectivity, with an imprinting factor of 5.78. The results suggest that frontal polymerization provides an alternative means to prepare MIPs that are difficult to synthesize and may open up new perspectives in the field of MIPs.

Thermal analysis and microstructure of solids and solid state reactions

Thermoanalytical and microstructural measurement techniques allow the characterization of solids, their transformation, decomposition, specific surface and pore structure. These techniques are of importance for solids with high specific surface and/or porosity. Thermoanalytical techniques are applied to detect solid state reactions, to determine reaction temperatures and to monitor the progress of the reaction. They are useful to simulate thermal processes in the industry and to receive meaningful results with small samples in a short time. Specific surface, cumulative pore volume and pore volume distribution are obtained by intrusion and absorption techniques. Here selected applications of thermoanalytical and microstructure investigations in modern fields of materials research will be presented, as:

-pore analysis of sintering steps of ceramics,

-secondary structure of catalyst granules,

-template decomposition in zeolites,

-firing process in a composide ceramic tape,

-ignition of coke.

     

Some Recent Developments in Aqueous Sol-Gel Processing

In this overview we describe the recent use of aqueous sol-gel processing for the preparation of ceramics that have very different end-uses. Zirconia nanofiltration membranes with 50% rejection of solutes at a molecular weight of about 1000 have been produced using zirconia sols containing inorganic polymeric particles and evaluated on the pilot-plant scale. Microporous alumina- and zirconia-pillared clays having a large and hydrothermally stable interlayer spacing (2 nm) and specific surface area (approximately 400 m2 g–1) have been prepared using similar polymeric sols. These have been produced on the 20 kg scale and evaluated for catalytic applications. Cathodoluminescent phosphor powders, based on the doped-yttrium aluminium gallium oxide system, have been synthesized for high resolution displays using a combination of aqueous sol-gel precursors and aerosol techniques to produce particles of controlled size and shape. Finally, ceramic stains for decorating ceramic bodies have been synthesized using this method, not only in powder form but also for direct application to ceramic ware by ink-jet printing. These examples illustrate the versatility of aqueous sol-gel processing for the preparation of a wide range of ceramic compositions and forms.     

SYNTHESIS OF MESOPOROUS POLY(STYRENE-co-MALEIC ANHYDRIDE)/SILICA HYBRID MATERIALS VIA A NONSURFACTANT-TEMPLATED SOL-GEL PROCESS*

Mesoporous poly (styrene-co-maleic anhydride)/silica hybrid materials have been prepared. The synthesis wasachieved by the HCl-catalyzed sol-gel reactions of tetraethyl orthosilicate (TEOS) and styrene-maleic anhydride copolymerin the presence of 3-aminopropyl triethoxysilane (APTES) as a coupling agent and citric acid as a nonsurfactant template orpore-forming agent, followed by ethanol extraction. Characterization results from nitrogen sorption isotherms and powder X-ray diffraction indicate that polymer-modified mesoporous materials with large specific surface areas (e.g. 900 m~2/g) andpore volumes (e.g. 0.6 cm~3/g) could be prepared. As the citric acid concentration is increased, the specific surface areas, porevolumes and pore diameters of the hybrid materials increase.     

INORGANIC POROUS MEMBRANES FOR LIQUID PHASE SEPARATION

Porous ceramic membranes are reviewed with reference to liquid phase separation. Methods for preparing porous ceramic membranes are summarized after a brief introduction to membranes and membrane processes. In the section on liquid phase separation, membrane materials are summarized from the viewpoint of pore size limits, since the pore sizes of porous membranes play an important role in determining separation performance. Various types of metal oxides and composite oxides have been developed by the sol-gel process; typical materials are Al₂O₃, TiO₂, SiO₂, ZrO₂, and composite oxides. The sol-gel process has a great advantage in terms of pore-size controllability over a wide range, from 0.5 ～ several ten nm, and therefore, is suitable for preparing membranes for use in liquid phase separation. Applications of inorganic membranes are reviewed in terms of water treatment, separation of nonaqueous systems, and photocatalysis.     

Preparation and Formation Mechanism of Porous TiO2 Films Using PEG and Alcohol Solvent as Double-Templates

Porous nanocrystalline TiO₂ anatase thin films have been synthesized on glass substrates via a sol-gel dip-coating method. The coating sol was obtained by suppressed hydrolysis of Ti(OC₄H₉)₄ through the addition of complexing molecules as stabilizers in an alcohol solution containing polyethylene glycol (PEG). Chemical changes taking place during the sol-gel process were discussed based on IR spectra analysis. A model concerning the pore formation was established to explain the role of PEG and solvent with core-shell configuration as double-templates. The structural characteristics of porous TiO₂ films were found to greatly depend on the concentration and molecular weight of PEG, the types of stabilizing agents and solvents. The pore size of the films was tunable in the range of 10–500 nm and their surface area varied from 51 to 72 m²·g^–1.     

Methane adsorption on microporous carbon adsorbent with wide pore size distribution

Methane adsorption on a microporous carbon adsorbent with a bimodal pore size distribution is studied at temperatures of 303–333 K at pressures up to 30 MPa. The total micropore volume of the adsorbent, as determined by the Dubinin method, is as large as 1.02 cm³/g. Maximum values of methane adsorption of ≈18 mmol/g are attained at a temperature of 303 K and a pressure of 30 MPa. Methane adsorption isosteres are plotted based on experimental data, and adsorption equilibria at low temperatures are calculated using the linearity of the plots. Experimental isotherms of methane adsorption are compared with the isotherms calculated by the Dubinin–Nikolaev equation with variations in parameters E and n. Temperature dependences of these parameters are determined. Specific characteristics of methane adsorption accumulation are calculated.     

Steam-carbon gasification catalyzed by calcium: Assessment of the porous structure of active carbons from plum stones and synthetic active carbons

A need for an elaboration of the methods for synthesis and characterization of activated carbons with a requisite porous structure has existed for a long time. One of the methods giving possibility for creating controlled mesopore and micropore structures deals with the steam gasification of various carbon materials. In this work the effects of calcium catalyst on the catalytic steam gasification of active carbons from plum stones and porous polymers are presented. Determination of micropores capacity and specific adsorption in mesopores have been performed by means of the _s method, but adsorption on the heterogeneous solids was described by the integral equation with various local isotherms. This equation has been solved by the regularization method. Based on this method the changes in structural parameters of active carbons depending on the amount of calcium catalyst were estimated.Nomenclature d width of slit-like micropore - F(x) distribution function of the half-width - p vapor pressure of sorbate - p/p _N relative pressure - PSAC Plum Stone Active Carbon - average pore radius, nm - S ₁ relative limit of the validity of experimental point on the adsorption isotherm in the computations by means of regularization method - SAC Synthetic Active Carbon - S _BET specific surface area calculated by means of BET method, m²/g - S _mes mesopore surface area, m²/g - S _mic micropore surface area, m²/g - T absolute temperature, K - V _mes sorption capacity of mesopores, cm³/g - V _mic sorption capacity of micropores, cm³/g - V _p sorption capacity of pores, cm³/g - w/w weight in weight concentration - x half-width of slit-like micropore, nm - x ₁ maximum of half-width of micropore slit, nm - average half-width of slit-like micropore, nm - X _min-X _max integration limits of thex Greek Letters Greek Letters variance of average half-width of slit-like micropore, nm² - local relative filling of micropores - total relative filling of micropores     

Poly-L-lysine templated silicas: using polypeptide secondary structure to control oxide pore architectures

Utilizing polypeptide secondary structure as a means for controlling oxide pore architectures is explored. Poly-L-lysine is used as a model polypeptide as its folding behavior is well understood and compatible with the sol-gel chemistry of silica. Here, we show that silicas synthesized with poly-L-lysine in a alpha-helix conformation possess cylindrical pores that are approximately 1.5 nm in size, whereas silicas synthesized with poly-L-lysine in a beta-sheet conformation possess larger pores, the size of which are a function of the poly-L-lysine concentration, or in other words the size of the aggregate. In both cases, highly porous materials are obtained. In-situ circular dichroism measurements of the synthesis mixtures show that the poly-L-lysine secondary structure is not perturbed during synthesis. Infrared spectroscopy of the as-synthesized materials is consistent with the poly-L-lysine retaining its secondary structure. Grand canonical Monte Carlo simulations were also performed to validate the interpretation of the experimental adsorption results. The experimental isotherms are consistent with simulated isotherms of cylindrical pores 1.3-1.7 nm in size, in good agreement with expected values. Our results suggest a new avenue for synthesizing porous oxides with highly tuneable pore sizes and shapes under mild conditions.