Pore size distribution of unsupported SnO2 membranes prepared by sol-gel process - Code: EP21

Unsupported SnO2 membranes were prepared by sol-gel process and characterized by N2 adsorption-desorption isotherms and X-ray diffraction. Results show that the texture of dried samples does not change appreciably with the concentration of electrolyte. All of the pore size range used in ultrafiltration process was screened using sintering temperature between 300 and 700°C. © 1994 Kluwer Academic Publishers.

Anisotropy of crystallite growth during sintering of SnO2 xerogels

The crytallite and pore-size evolution during isothermal sintering (400 ≤ T ≤ 700°C) of SnO2 xerogels was studied by X-ray line broadening and nitrogen adsorption-desorption isotherms. The experimental results show a strong anisotropy of crystallite growth between [110] and [101] directions. The preferential growth at [101] is followed by an increase in the mean pore size, reduction of the specific surface area and invariance of total pore volume. This behaviour is typical of grain coalescence sintering. The kinetic analysis of experimental results suggests that the crystallite coalescence at [101] is governed by lattice diffusion. The strong anisotropy of the growth causes pore-size distribution broadening, hindering the macroscopic shrinkage of the compact during sintering. © 1996 Chapman & Hall.

Determination of metal ions in fuel ethanol after preconcentration on 5-amino-1,3,4-thiadiazole-2-thiol modified silica gel

This work describes the synthesis and characterization of 5-amino-1,3,4-thiadiazole-2-thiol modified silica gel (SiATT), and the results of a study of the adsorption and preconcentration (in batch, and in flow using a column technique) of Cd(II), Co(II), Cu(II), Fe(III), Ni(II), Pb(II) and Zn(II) in ethanol medium. The adsorption capacities for each metal ion were (in mmol g -1): Cd(II) = 0.11, Co(II) = 0.10, Cu(II) = 0.20, Fe(III) = 0.20, Ni(II) = 0.16, Pb(II) = 0.08 and Zn(II) = 0.12. The results obtained in the flow experiments, showed a recovery of ca. 100% of the metal ions adsorbed in a column packed with 2 g of SiATT, using 5 mL of 2.0 mol L -1 HCl solution as eluent. The sorption-desorption of the metal ions made possible the development of a preconcentration method and quantification by Flame AAS of metal ions at trace level in fuel ethanol.

Adsorption and structure of copper(II) complexes on a silica gel surface chemically modified with 2-aminothiazole

The isotherms of adsorption of CuX2 (X=Cl-, Br-, ClO- 4) by silica gel chemically modified with 2-aminothiazole were studied in acetone and EtOH solutions, at 25°C. The 2-aminothiazole molecule, covalently bond to the silica gel surface, adsorbs CuX2 from solvent by forming a surface complex. At low loading, the electronic and E.S.R. spectral parameters indicate that the Cu2+ complexes have a distorted tetragonal symmetry. The d-d eletronic transition spectra show that for ClO- 4 complex, the peak of absorption do not change for any degree of metal loading whilst for Cl- and Br- complexes, the peak maxima shift to higher energy with lower metal loading. © Elsevier Science Ltd.

Effect of atmosphere on the sintering and grain growth of tin oxide

High purity SnO 2 powder (>99.9%) was compacted in cylindrical pellets and sintered in atmospheres of dry argon, argon with water vapor, oxygen and CO 2 using 10 °C/min up to 1200 °C or isotherms in the range of 1000 to 1200 °C. Time, temperature and sintering atmosphere have large influence on grain growth and low influence on densification of this oxide. Surface diffusion is the dominant mechanism up to 1200 °C and evaporation-condensation is dominant above 1200 °C. The maximum linear shrinkage observed was about 2.0% and attributed to structural rearrangement of particles due to high capillary stresses developed with neighboring particles. © 1999 Trans Tech Publications.

Comparative study using small-angle x-ray scattering and nitrogen adsorption in the characterization of silica xerogels and aerogels

A comparative study using small-angle x-ray scattering (SAXS) and nitrogen adsorption has been carried out in the structural characterization of silica xerogels and aerogels, obtained from tetraethoxysilane sonohydrolysis. The specific surface and the mean pore size as measured by both the techniques were found to be in notable agreement in all cases for aerogels and xerogels. According to the SAXS data, aerogels at 500 °C exhibit a mass fractal structure with fractal dimension D∼2.4 in the range between the correlation length ξ∼5.3 nm and a∼0.75 nm. An experimental method to probe the mass fractal structure of aerogels from exclusively nitrogen adsorption isotherms has been presented. For aerogels at 500 °C, we have found D∼2.4 in the range between the pore width 2rξ∼33 nm and 2ra∼4.5 nm, which is in notable agreement with the SAXS results (D ∼2.4, ξ∼5.3 nm, a∼0.75 nm) if we assign the pore width 2r probed by the Kelvin equation in the adsorption method to the Bragg distance 2π/q associated to the correlation length 1/q probed by SAXS.

Nanostructured films of perylene derivatives: High performance materials for taste sensor applications

Four perylene derivatives (PTCD) have been used as transducing materials in taste sensors fabricated with nanostructured Langmuir-Blodgett (LB) films deposited onto interdigitated gold electrodes. The Langmuir monolayers of PTCDs display considerable collapse pressures, with areas per molecule indicative of an edge-on or head-on arrangement for the molecules at the air/water interface. The sensing units for the electronic tongue were produced from 5-layer LB films of the four PTCDs, whose electrical response was characterized with impedance spectroscopy. The distinct responses of the PTCDs, attributed to differences in their molecular structures, allowed one to obtain a finger printing system that was able to distinguish tastes (salty, sweet, bitter and sour) at 1 μM concentrations, which, in some cases, are three orders of magnitude below the human threshold. Using Principal Component Analysis (PCA) data analysis, the electronic tongue also detected trace amounts of a pesticide and could distinguish among samples of ultrapure, distilled and tap water, and two brands of mineral water. © 2004 by American Scientific Publishers. All rights reserved.

Determination of Cu, Ni and Pb in Aqueous Medium by FAAS after Pre-Concentration on 2-Aminothiazole Modified Silica Gel

This work describes the synthesis and characterization of 2-aminothiazole modified silica gel (SiAT), and the results of a study of the adsorption and pre-concentration (in batch and using a flow-injection system coupled to an absorption atomic spectrometer) of Cu(II), Ni(II) and Pb(II) in aqueous medium. The adsorption capacities for each metal ions in mmol g -1 were: Cu(II)= 1.18, Ni(II)= 1.15 and Pb(II)= 1.10. The results obtained in the flow experiments showed a recovery of practically 100% of the metal ions adsorbed in a mini-column packed with 100 mg of SiAT, using 100 μL of 2.0 mol L -1 HCl solution as eluent. The sorption-desorption of the metal ions made possible the application of a flow-injection system for the pre-concentration and quantification by FAAS of metal ions at trace level in natural water samples digested and not digest by an oxidizing UV photolysis.

Corrosion behavior in graphite refractories impregnated with ZrO 2 and CeO 2 carrying solutions

This paper investigates corrosion behavior in graphite refractory hot metal impregnated with ZrO 2 and CeO 2 carrying solutions used in Blast Furnace hearth, consisting of 50% graphite and 50% anthracite. Corrosions tests were carried out by means of finger test method in an induction furnace, using bar-shaped 30×30×280 mm test specimens and hot metal from CSN#2 Blast Furnace runner. The temperature chosen for this test was 1520°C and sixty-minute isotherm. Upon test completion, test specimens were characterized by their dimensional variation, X-ray diffractometry and Scanning Electronic Microscopy (SEM).

Enhanced photocatalytic reduction of Hg(II) in aqueous medium by 2-aminothiazole-modified TiO2 particles

This work describes the synthesis and characterization of 2-aminothiazole-modified titania and its application on Hg (II) photoreduction in aqueous medium. Infrared spectroscopy confirmed the chemical modification of the titania matrix. The number of 2-aminothiazole groups attached to the titania was determined by Kjeldahl's method. The photocatalytic experiments were carried out in a cylindrical photoreactor thermostatted at 298 K. The resulting modified photocatalyst 2-aminothiazole titania (TiAT) revealed an enhance in the Hg (II) photoreduction capacity at studied pH values (3, 7 and 9). In addition, sorption studies showed that the photocatalyst TiAT presented a lower equilibrium time and a higher sorption capacity of Hg(II) ion, demonstrating that sorption plays a fundamental role in the photoreduction mechanism. ©2006 Sociedade Brasileira de Química.

Preparação e caracterização inicial de complexo de inclusão entre nitrofurazona e 2-hidroxipropil-β-ciclodextrina

Nitrofurazone (NF), 5-nitro-2-furaldehyde semicarbazone, a broad-spectrum antibiotic, has reported toxic effects and low solubility in water. It would be of great interest to form inclusion complexes between NF and a cyclodextrin, to develop more effective and safer antibiotic formulations. This paper focuses on the preparation of inclusion complexes of NF with 2-hydroxypropyl-β- cyclodextrin (HP-β-CD) and their initial characterization by evaluating rates of complex formation, photostability, solubility isotherms, release rate profiles, stoichiometry of the complexes and their morphology, as revealed by scanning electron microscopy. The kinetic tests of complex formation revealed that 17,3 h is enough for stabilization of the NF-cyclodextrin complex. The solubility isotherm studies showed that the isotherm changes from type A to type B, as a function of temperature. The photostability experiments showed that the insertion of the NF in the HP-β-CD cavity protects the drug from photodecomposition. The release kinetic tests showed that the profile of NF release from the complex is altered by the presence of HP-β-CD in the medium. A Job's plot indicated that the stoichiometry of the complex was 1:1 NF:HP-β-CD. The scanning electron micrographs showed changes in the crystal structure of NF in the complex. This study focused on the physicochemical properties of drug-delivery formulations that could potentially be developed into a novel type of therapy with NF.

Functional nanostructured catalysts based on the niobates to the dry methane reforming and ethylene homologation reactions

Catalytic activity and selectivity of niobate-based nanostructured materials were investigated. Dry methane reforming (DMR) and ethylene homologation reaction (EHR) were selected as test reactions. KSr 2Nb5O15, Sr2NaNb5O 15 and NaSr2(NiNb4)O15 δ niobate powders were prepared by the high energy ball milling method and calcined in a reductor atmosphere. N2 adsorption isotherms, X-ray diffraction and infrared spectroscopy characterization was performed. Hydrogen pretreated niobates showed from low to moderate catalytic initial activity in DMR's test, nevertheless the materials were deactivated rapidly and the kinetic parameters associated to deactivation were estimated. Otherwise, non-treated catalysts showed a high initial activity in EHR's test and KSr2Nb 5O15 catalyst requires 24 h to the total deactivation with a high selectivity to form propylene. A reaction mechanism to the propylene formation is discussed. © 2012 Elsevier Ltd. All rights reserved.

Adsorption of heavy metal ions and epoxidation catalysis using a new polyhedral oligomeric silsesquioxane

The objective of this research was the preparation of a silsesquioxane functionalized with eight chloropropyl chains (T8-PrCl) and of a new derivative functionalized with a pendant linear chain (2-amino-1,3,4-thiadiazole - ATD; T8-Pr-ATD). The two nanostructured materials were characterized by 13C and 29Si NMR, FTIR and elemental analysis. The new nanostructured material, octakis[3-(2-amino-1,3,4-thiadiazole)propyl] octasilsesquioxane (T8-Pr-ATD), was tested as a ligand for transition-metal ions with a special attention to adsorption isotherms. The adsorption was performed using a batchwise process and the organofunctionalized surface showed the ability to adsorb the metal ions Cu (II), Co (II), and Ni (II) from water and ethanol. The adsorption isotherms were fitted by Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) model. The kinetics of adsorption of metals were performed using three models such as pseudo-first order, pseudo-second order and Elovich. The Langmuir and Elovich models were the most appropriate to describe the adsorption and kinetic data, respectively. Furthermore, the T8-Pr-ATD was successfully applied to the analysis of environmental samples (river and sea water). Subsequently, a new nanomaterial was prepared by functionalization of the T8-Pr-ATD with a Mo (II) organometallic complex (T8-Pr-ATD-Mo). Only a few works in the literature have reported this type of substitution, and none dealt with ATD and Mo (II) complexes. The new Mo-silsesquioxane organometallic nanomaterial was tested as precursor in the epoxidation of cyclooctene and styrene. © 2012 Elsevier B.V.

A comparative study of glycerol dehydration catalyzed by micro/mesoporous MFI zeolites

The catalytic properties of monomodal microporous and bimodal micro-mesoporous zeolites were investigated in the gas-phase dehydration of glycerol. The desilication methodology used to produce the mesoporous zeolites minimized diffusion limitations and increased glycerol conversion in the catalytic reaction due to the hierarchical system of secondary pores created in the zeolite crystals. The chemical and structural properties of the catalyst were studied by X-ray diffraction, nitrogen adsorption-desorption isotherms, NH3-TPD and pyridine chemisorption followed by IR-spectroscopy. Although the aim was to desilicate to create mesoporosity in the zeolite crystals, the desilication promoted the formation of extra-framework aluminum species that affected the conversion of glycerol and the products distribution. The results clearly show that the mesoporous zeolites with designed mesopore structure allowed a rapid diffusion and consequently improved the reaction kinetics. However, especial attention must be given to the desilication procedure because the severity of the treatment negatively interfered on the Brønsted and Lewis acid sites relative concentration and, consequently, in the efficiency of the catalysis performed by these materials. On the other hand, during the catalytic reaction, the intracrystalline mesopores allowed carbonaceous compounds to be deposited herein, resulting in less blocked micropores and catalysts with higher long-term stability.

The role of hierarchical morphologies in the superior gas sensing performance of CuO-based chemiresistors

The development of gas sensors with innovative designs and advanced functional materials has attracted considerable scientific interest given their potential for addressing important technological challenges. This work presents new insight towards the development of high-performance p-type semiconductor gas sensors. Gas sensor test devices, based on copper (II) oxide (CuO) with innovative and unique designs (urchin-like, fiber-like, and nanorods), are prepared by a microwave-assisted synthesis method. The crystalline composition, surface area, porosity, and morphological characteristics are studied by X-ray powder diffraction, nitrogen adsorption isotherms, field-emission scanning electron microscopy and high-resolution transmission electron microscopy. Gas sensor measurements, performed simultaneously on multiple samples, show that morphology can have a substantial influence on gas sensor performance. An assembly of urchin-like structures is found to be most effective for hydrogen detection in the range of parts-per-million at 200 °C with 300-fold larger response than the previously best reported values for semiconducting CuO hydrogen gas sensors. These results show that morphology plays an important role in the gas sensing performance of CuO and can be effectively applied in the further development of gas sensors based on p-type semiconductors. High-performance gas sensors based on CuO hierarchical morphologies with in situ gas sensor comparison are reported. Urchin-like morphologies with high hydrogen sensitivity and selectivity that show chemical and thermal stability and low temperature operation are analyzed. The role of morphological influences in p-type gas sensor materials is discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.