Study of synthesis variables in the nanocrystal growth behavior of tin oxide processed by controlled hydrolysis

Tin dioxide nanoparticle suspensions were synthesized at room temperature by the hydrolysis reaction of tin chloride (II) dissolved in ethanol. The effect of the initial tin (II) ion concentration, in the ethanolic solution, on the mean particle size of the nanoparticles was studied. The Sn2+ concentration was varied from 0.0025 to 0.1 M, and all other synthesis parameters were kept fixed. Moreover, an investigation of the effect of agglomeration on the nanoparticle characteristics (i.e., size and morphology) was also done by modifying the pH of the SnO2 suspensions. The different samples were characterized by transmission electron microscopy, optical absorption spectroscopy in the ultraviolet range, and photoluminescence measurements. The results show that higher initial ion concentrations and agglomeration lead to larger nanoparticles. The concentration effect is explained by enhanced growth due to a higher supersaturation of the liquid medium. However, it was observed that the agglomeration of the nanoparticles in suspension induce coarsening by the oriented-attachment mechanism.

Sintering and crystallite growth of nanocrystalline copper doped tin oxide

The effect of Cu2+ contents and of firing temperature on sintering and crystallite growth of nanocrystalline SnO2 xerogels was analyzed by thermoanalysis (mass loss (TG), linear shrinkage, and differential thermal analysis (DTA)), X-ray powder diffraction (XRPD), and EXAFS (extended X-ray absorption fine structures) measurements. Samples were prepared by two methods: (a) coprecipitation of a colloidal suspension from aqueous solution containing both Sn(IV) and Cu(II) ions and (b) grafting copper(II) species on the surface of tin pride gel. The thermoanalysis has shown that the shrinkage associated with the mass loss decreases by increasing the amount of copper. The EXAFS measurements carried out at the Cu K edge have evidenced the presence of copper in substitutional solid solution for the dried xerogel prepared with 0.7 mol % of copper, while for higher concentration of doping, copper has been observed also at the external surface of crystallites. The solid solution is metastable and copper migrates toward the surface during firing. The XRPD and DTA results have shown a recrystallization process near 320 degrees C, which leads to crystallite growth. The presence of copper segregated near the crystallite surface controls its growth.

SAXS study of formation and growth of tin oxide nanoparticles in the presence of complexing ligands

The effect of acetylacetone (acac) complexing ligand on the formation and growth of tin oxide-based nanoparticles during thermohydrolysis at 70 degreesC of a tin precursor SnCl4-n(acac)(n) (0 less than or equal to n less than or equal to 2) solution was analyzed by in situ small-angle X-ray scattering. A. transparent and stable sol was obtained after 2 h of thermohydrolysis at 70 degreesC, allowing the quantitative determination of the particle volume distribution function and its variation with the reaction time. The number of colloidal particles for equivalent thermohydrolysis temperature and time decreases as the [acac]/[Sn] ratio in initial solution increases from 0.5 to 6. Instead, the amount of soluble species remaining in solution increases for increasing [acac]/[Sn] ratio within the same range. This indicates that increasing amounts of Sn-acetylacetone complexes partially prevent the hydrolysis and consequent formation of colloidal particles. The N-2 adsorption isotherm characterization of freeze-dried powders demonstrates that the average pore size is approximately equal to the average size (approximate to9 Angstrom) of the colloidal primary particles in the sol, and that the porosity and surface area (approximate to200 m(2) g(-1)) are independent of the acac content in the initial solution.

Electrochemical study of perchlorate reduction at tin electrodes

The electrochemical behaviour of tin in de-aerated sodium perchlorate was studied using potentiodynamic and potentiostatic techniques. Tin behaviour in sodium perchlorate has been complicated unexpectedly by the reduction of the perchlorate anion. It is shown that the reduction process takes place within a potential region comprising the negative side of the double layer region and the positive side of the hydrogen region (-0.7 less than or equal to E less than or equal to -1.3 V). The presence of oxide on the electrode surface favours the reduction reaction, which may occur in two steps: the formation of basic tin(II) chloride followed by its reduction, producing chloride.

Solid-state and solution structural study of acetylacetone-modified tin(IV) chloride used as a precursor of SnO2 nanoparticles prepared by a sol-gel route

The effect of addition of different amounts of acetylacetone (acacH) on the species formed at room temperature and after thermohydrolysis at 70 degreesC for 30 and 120 min of ethanolic SnCl4.5H(2)O solutions is followed by EXAFS spectroscopy at the Sn K-edge. We show that thermohydrolyzed solutions are a mixture of SnO2 nanoparticles and soluble tin polynuclear species. The complexation of the tin molecular precursors by acetylacetonate ligands is evidenced by H-1, C-13, and Sn-119 NMR spectroscopy and EXAFS for a acacH/Sn ratio higher than 2. Single crystals are isolated from solution and the structure, determined by X-ray diffraction, is built up from monomeric Cl-3(H2O)Sn(acac)-H2O units bridged together by hydrogen bonding. The acacH/Sn ratio in solution controls the polycondensation of the hydrolyzed species but not the crystallite size of the SnO2 nanoparticles (similar to2 nm). Because of the major presence of chelated tin mono- and dimeric complexes in solution for acacH/Sn > 2, the condensation is almost inhibited, meanwhile the decrease of amount of chelated complexes for the acacH/Sn < 2 gives rise to an increase of the number of nanoparticles.

Preparation of ceramic membranes from surface modified tin oxide nanoparticles

The preparation of crack-free SnO2 supported membranes requires the development of new strategies of synthesis capable to allow controlled changes of surface chemistry and to improve the processability of supported layers. In this way, the controlled modification of the SnO2 nanoparticle surface by adding capping molecules like Tiron(R) ((OH)(2)C6H2(SO3Na)(2)) during the sol-gel process was studied, aiming to obtain high performance membranes. Colloidal suspensions were prepared by hydrolyzing SnCl4.5H(2)O aqueous solution with NH4OH in presence of Tiron(R). The effect of the amount of Tiro(R) (from I to 20 wt.%) on the structural features of nanoparticles, powder redispersability and particle-solution interface properties was investigated by X-ray powder diffraction (XRPD), extended X-ray absorption fine structure (EXAFS), quasi-elastic light scattering and electrophoretic mobility measurements. XRPD and EXAFS results showed that the addition of Tiron(R) up to 20 wt.% to colloidal suspensions does not affect the crystallite size of SnO2 primary particles, determined around 2-3 nm. This value is comparable to the hydrodynamic size measured after redispersion of powder prepared with amount of Tiro(R) higher than 7.5 wt.%, indicating the absence of condensation reactions between primary particles after the initial precipitation step. As a consequence the powder with amount of Tiron(R) > 7.5 wt.%, can be fully redispersed in aqueous solution at pH greater than or equal to I I until a nanoparticle concentration of 6 vol.%. The electrophoresis measurements showed a decrease of the isoelectric point by increasing the amount of grafted Tiron(R) at the SnO2 nanoparticle surface, resulting in negatively charged particle-solution interface in all the studied pH range (2-11). These features govern the gelation process favoring the preparation of crack-free SnO2 supported membranes. The control exercised by Tiron(R) modifying agent in the aggregation process allows the fine-tuning of the porosity, from 0.124 to 0.065 cm(3) g(-1), and mean pore size, from 6.4 to 1.9 nm, as the amount of grafted molecules increases from 0 to 10 wt.%. In consequence, the membrane cut-off determined by filtration of polyethylene glycol standard solutions can be screened from 1500 to 3500 g mol(-1). (C) 2002 Elsevier B.V. B.V. All rights reserved.

Electrochemical decomposition of cyanides on tin dioxide electrodes in alkaline media

The electrochemical oxidation of cyanide in alkaline media was studied at different pH levels on SnO2 doped with Sb supported on titanium, at 25 degrees C, the electrooxidation of CN- at constant current follows a first-order rate law with a half life of t(1/2) = 35 min on SnO2-SbOx electrodes and t(1/2) = 69 min on SnO2-SbOx-RuO2 electrodes, in K2SO4(aq), pH 12, the reaction rate increases with the applied current and tends to reach a plateau when j > 20 mA cm(-2), In the pH range 10-13.5 the reaction rate diminishes as pH is increased owing to an increasing competition between CN- and OH- ions for the electrode surface. Addition of chloride to the solution does not alter the rate law but increases the reaction rate, A mechanism is proposed to explain the observed behaviour.

Hexagonal-shaped tin glycolate particles: A preliminary study of their suitability as li-ion insertion electrodes

Tin glycolate particles were prepared by a simple, one-step, polyol-mediated synthesis in air in which tin oxalate precursor was added to ethylene glycol and heated at reflux. Hexagonal-shaped, micron-sized tin glycolate particles were formed when the solution had cooled. A series of tin oxides was produced by calcination of the synthesized tin glycolate at 600-800 degrees C. It was revealed that the micron-sized, hexagonal-shaped tin glycolate now consisted of nanosized tin-based particles (80-120 nm), encapsulated within a tin glycolate shell. XRD, TGA, and FT-IR measurements were conducted to account for the three-dimensional growth of the tin glycolate particles. When applied as an anode material for Li-ion batteries, the synthesized tin glycolate particles showed good electro-chemical reactivity in Li-ion insertion/ deinsertion, retaining a specific capacity of 416mAhg(-1) beyond 50cycles. Ibis performance was significantly better than those of all the other tin oxides nanoparticles (< 160mAhg(-1)) obtained after heat treatment in air. We strongly believe that the buffering of the volume expansion by the glycolate upon Li-Sn alloying is the main factor for the improved cycling of the electrode.

Protective film growth on tin in perchlorate and citric acid electrolytes

Voltammetry has been employed to study the influence of systematic additions of citric acid on the E-I curves of Tin in 0.5 M NaClO4, in order to verify the film growth in the presence of the organic acid and the inhibition of the pitting corrosion of the metal. The minimum concentration of the organic acid needed to change the GI curves is 10(-2) M, in the pH range 1.0-4.0. At pH 3.0 and 4.0, the scan rate dependence on current density, in the potential region of formation and reduction of the film, showed that in a first stage adsorption occurs. In a second stage, the v(1/2) dependence found can he explained by ohmic resistance control. The formation of tin/citric acid complexes, 10(-2) M, is suggested. The pitting inhibition may be due to the formation of a mixed layer of tin in citric acid concentrations higher than 10(-2) oxide and tin citrate complexes on the electrode surface. (C) 2001 Elsevier Science B.V. All rights reserved.

Recent Insights on the Medicinal Chemistry of Sickle Cell Disease

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of pH of colloidal suspension on crystallization and activation energy of deep levels in SnO2 thin films obtained via sol-gel

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Structural Characterization of Nanocrystalline Sb-Doped SnO2 Xerogels by Multiedge X-ray Absorption Spectroscopy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Improvement of electrical properties of Sr-modified (Pb,Ca)TiO3 thin films grown by soft chemistry route

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Cellulose pyrolysis and quantum chemistry

Cellulose is the major constituent of most plants of interest as renewable sources of energy and is the most extensively studied form of biomass or biomass constituent. Predicting the mass loss and product yields when cellulose is subjected to increased temperature represents a fundamental problem in the thermal release of biomass energy. Unfortunately, at this time, there is no internally consistent model of cellulose pyrolysis that can organize the varied experimental data now available or provide a guide for additional experiments. Here, we present a model of direct cellulose pyrolysis using a multistage decay scheme that we first presented in the IJQC in 1984. This decay scheme can, with the help of an inverse method of assigning reaction rates, provide a reasonable account of the direct fast pyrolysis yield measurements. The model is suggestive of dissociation states of d-glucose (C6H10O5,), the fundamental cellulose monomer. The model raises the question as to whether quantum chemistry could now provide the dissociation energies for the principal breakup modes of glucose into C-1, C-2, C-3, C-4, and C-5 compounds. These calculations would help in achieving a more fundamental description of volatile generation from cellulose pyrolysis and could serve as a guide for treating hemicellulose and lignin, the other major biomass constituents. Such advances could lead to the development of a predictive science of biomass pyrolysis that would facilitate the design of liquifiers and gasifiers based upon renewable feedstocks. (C) 1998 John Wiley & Sons, Inc.