Degradation of dipyrone via advanced oxidation processes using a cerium nanostructured electrocatalyst material

This work studied the degradation of dipyrone, via electrochemical processes and via electro-Fenton reaction using a 4% CeO2/C gas diffusion electrode (GDE) prepared via modified polymeric precursor method. This material was used to electrochemically generate H2O2 through oxygen reduction. The mean crystallite sizes estimated by the Scherrer equation for 4% CeO2/C were 4 nm for CeO2-x (0 4 4) and 5 nm for CeO2 (1 1 1) while using transmission electron microscopy (TEM) the mean nanoparticle size was 5.4 nm. X-ray photoelectron spectroscopy (XPS) measurements revealed nearly equal concentrations of Ce(III) and Ce(IV) species on carbon, which contained high oxygenated acid species like CO and OCO. Electrochemical degradation using Vulcan XC 72R carbon showed that the dipyrone was not removed during the two hour electrolysis in all applied potentials by electro-degradation. Besides, when the Fenton process was employed the degradation was much similar when using cerium catalysts but the mineralization reaches just to 50% at -1.1 V. However, using the CeO2/C GDE, in 20 min all of the dipyrone was degraded with 26% mineralization at -1.3 V and when the Fenton process was employed, all of the dipyrone was removed after 5 min with 57% mineralization at -1.1 V. Relative to Vulcan XC72R, ceria acts as an oxygen buffer leading to an increase in the local oxygen concentration, facilitating H2O2 formation and consequently improving the dipyrone degradation © 2013 Elsevier B.V. All rights reserved.

Tuning the nanostructure of DODAB/nickel tetrasulfonated phthalocyanine bilayers in LbL films

Nanostructured films of dioctadecyldimethylammonium bromide (DODAB) and nickel tetrasulfonated phthalocyanine (NiTsPc) were layer-by-layer (LbL) assembled to achieve a synergistic effect considering the distinct properties of both materials. Prior to LbL growth, the effect of NiTsPc on the structure of DODAB vesicles in aqueous medium was investigated by differential scanning calorimetry (DSC). Therefore, DODAB/NiTsPc LbL films were prepared using NiTsPc at concentrations below and above the limit concentration of vesicle formation according to our DSC experiments. As a result, LbL films with distinct nanostructures were obtained, which were studied at micro and nanoscales by micro-Raman and atomic force microscopy, respectively. A linear growth of the LbL films was observed by ultraviolet-visible absorption spectroscopy. However, the bilayer thickness and the surface morphology of the LbL films were radically affected depending on NiTsPc concentration. The electrostatic interaction between DODAB and NiTsPc was identified via Fourier transform infrared (FTIR) absorption spectroscopy as the main driving force responsible for LbL growth. Because LbL films have been widely applied as transducers in sensing devices, DODAB/NiTsPc LbL films having distinct nanostructures were tested as proof-of-principle in preliminary sensing experiments toward dopamine detection using impedance spectroscopy (e-tongue system). The real capacitance vs. dopamine concentration curves were treated using Principal Component Analysis (PCA) and an equivalent electric circuit, revealing the role played by the LbL film nanostructure and the possibility of building calibration curves. © 2013 Elsevier B.V.

Tribocorrosion behavior of Ti-C-O-N nanostructured thin films (black) for decorative applications

Abstract: In the past few years, tribocorrosion has become a focus of research because of its relevance in terms of the future in-service degradation mechanisms of materials. In the particular case of decorative coatings, tribocorrosion is certainly one of the most important issues, and sweat corrosion and human contact wear are two other factors that may act as material selection tools. Thus, the current study aimed to investigate the tribocorrosion behavior of a new class of thin films, the Ti-C-O-N system, which is being developed to be used as a surface decorative material due to its relatively dark appearance. The films were prepared by reactive magnetron sputtering. The influence of the structural features on the tribocorrosion behavior is discussed. Crown Copyright © 2013.

Determination of copper in different ethanolic matrices using a chloropropyl silica gel modified with a nanostructured cubic octa(3-aminopropyl)octasilsesquioxane

The chloropropyl silica gel was modified with octa(3-aminopropyl) octasilsesquioxane and characterized by Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), spectroscopies, and surface and area porosity. The specific sorption capacity of metallic ions (Cu2+ and Ni2+) increases in the following solvent order: water < ethanol 42% < ethanol < ketone. The high values of the constant (K) in the order of 103 L mol-1 suggested the high adsorbent capacity of the modified silica (SGAPC) for Cu2+ and Ni2+. SGAPC was applied to a separation column and shows recoveries of around 100% of copper in samples of sugar cane spirit, vodka, ginger brandy, and ethanol fuel. © 2013 Devaney Ribeiro Do Carmo et al.

Carbon nanotubes/polyamide 6.6 nanostructured composites crystallization kinetic study

Compared with the traditional composites, the incorporation of carbon nanotubes into polymeric matrices can generate materials with superior properties, especially thermal, electrical and tribological properties. The aim of this study was to study the polyamide 6.6/carbon nanotubes (PA 6.6/CNT) nanostructured composites crystallization kinetics. The solution mixing technique was used to obtain the nanostructured composites studied in this work. PA 6.6 films were produced with amounts of 0.1, 0.5, and 1.0 wt% (weight/weight) CNT. X-ray diffraction analyses were performed in order to determine the crystallographic properties of nanostructured composite. The nanostructured composites crystallization kinetic study was performed using the differential scanning calorimetry under isothermal and nonisothermal (dynamic) conditions. The results have shown addition of CNTs in the PA 6.6 reduces the Avrami exponent, affecting the crystallization process of the composite. © The Author(s) 2012.

Solid-phase extraction of metal ions from fuel ethanol with a nanostructured adsorbent

This work describes the synthesis and characterization of a new octakis[3-(2,2'-dipyridylamine)propyl]octasilsesquioxane (T8-Pr-DPA), and a study of the metal ion preconcentration in fuel ethanol. Batch and column experiments were conducted to investigate for the removal of heavy metal ions from fuel ethanol. The results showed that the Langmuir allowed to describe the sorption equilibrium data of the metal ions on T8-Pr-DPA in a satisfactory way. The following maximum adsorption capacities (in mmolg-1) were determined: 3.62 for Fe (III), 3.32 for Cr (III), 2.15 for Cu (II), 1.80 for Co (II), 1.62 for Pb (II), 1.32 for Ni (II) and 0.88 for Zn (II). The thermodynamic parameters for the adsorption process such as free energy of adsorption (δG), enthalpy of adsorption (δH) and entropy of adsorption (δS) were calculated. Thermodynamic parameters showed that the system has favorable enthalpic, Gibbs free energy, and entropic values. The sorption-desorption of the metal ions has made possible the development of a preconcentration and determination method of metal ions at trace level in fuel ethanol. The method of quantitative analysis for Fe, Cu, Ni and Zn in fuel ethanol by Flame AAS was validated. Several parameters have been taken into account and evaluated for the validation of method, namely: linearity, limit of detection, limit of quantification, and the relative standard deviation and accuracy. The accuracy of the method was assessed by testing analyte recovery in the fuel ethanol samples. © 2013 Elsevier B.V.

Low tungsten content of nanostructured material supported on carbon for the degradation of phenol

A comparative study using different mass proportions of WO3/C (1%, 5%, 10% and 15%) for H2O2 electrogeneration and subsequent phenol degradation was performed. To include the influence of the carbon substrate and the preparation methods, all synthesis parameters were evaluated. The WO3/C materials were prepared by a modified polymeric precursor method (PPM) and the sol-gel method (SGM) on Vulcan XC 72R and Printex L6 carbon supports, verifying the most efficient metal/carbon proportion. The materials were physically characterized by X-ray diffraction (XRD) and by X-ray photoelectron spectroscopy (XPS) techniques. The XRD and the XPS techniques identified just one phase containing WO3 and elevated oxygen concentration on carbon with the presence of WO3. The oxygen reduction reaction (ORR), studied by the rotating ring-disk electrode technique, showed that WO3/C material with the lowest tungsten content (1% WO3/C), supported on Vulcan XC 72R and prepared by SGM, was the most promising electrocatalyst for H2O2 electrogeneration. This material was then analyzed using a gas diffusion electrode (GDE) and 585mgL-1 of H2O2 was produced in acid media. This GDE was employed as a working electrode in an electrochemical cell to promote phenol degradation by an advanced oxidative process. The most efficient method applied was the photo-electro-Fenton; this method allowed for 65% degradation and 11% mineralization of phenol during a 2-h period. Following 12h of exhaustive electrolysis using the photo-electro-Fenton method, the total degradation of phenol was observed after 4h and the mineralization of phenol approached 75% after 12h. © 2013 Elsevier B.V.

Nanostructured materials based on mesoporous silica and mesoporous silica/apatite as osteogenic growth peptide carriers

The aim of this work was the preparation of inorganic mesoporous materials from silica, calcium phosphate and a nonionic surfactant and to evaluate the incorporation and release of different concentrations of osteogenic growth peptide (OGP) for application in bone regeneration. The adsorption and release of the labeled peptide with 5,6-carboxyfluorescein (OGP-CF) from the mesoporous matrix was monitored by fluorescence spectroscopy. The specific surface area was 880 and 484 m2 g- 1 for pure silica (SiO) and silica/apatite (SiCaP), respectively; the area influenced the percentage of incorporation of the peptide. The release of OGP-CF from the materials in simulated body fluid (SBF) was dependent on the composition of the particles, the amount of incorporated peptide and the degradation of the material. The release of 50% of the peptide content occurred at around 4 and 30 h for SiCaP and SiO, respectively. In conclusion, the materials based on SiO and SiCaP showed in vitro bioactivity and degradation; thus, these materials should be considered as alternative biomaterials for bone regeneration. © 2013 Elsevier B.V.

Soft-chemical synthesis, characterization and humidity sensing behavior of WO3/TiO2 nanopowders

Tungsten oxide/titania (WO3/TiO2) nanopowders were synthesized by the polymeric precursor method which varied the WO3 content between 0 and 10 mol%. The powders were thermally treated in a conventional furnace and their structural, microstructural and electric properties were evaluated by X-ray diffraction (XRD), Raman spectrometry, N 2 physisorption, NH3 chemisorption, temperature-programmed reduction (TPR), X-ray absorption near-edge spectroscopy (XANES) in situ XANES and extended X-ray absorption fine structure spectroscopy (EXAFS) and transmission electron microscopy (TEM). XRD and Raman spectrometry confirmed the homogeneous distribution of an amorphous WO3 phase in the TiO 2 matrix which stabilized the anatase phase through the generation of [TiO5·V0] or [TiO5·V 0] complex sites. Conventional TPR-H2 (temperature programmed reduction) along with XANES TPR-H2 and XANES TPR-EtOH showed that WO3/TiO2 sample reduction occurs through the formation of these complex clusters. Moreover, the addition of WO3 promoted an increase in the surface acidity of doped samples as revealed by NH3 chemisorption. The WO3/TiO2 bulk-ceramic samples were further used to estimate their potential application in a humidity sensor in the range of 15-85% relative humidity. Probable reasons that lead to the different humidity sensor responses of samples were given based on the structural and surface characterizations. Correlation between the sensing performance of the sensor and its structural features are also discussed. Although all samples responded as a humidity sensor, the W2T sample (2 mol% added WO3) excelled for sensitivity due to the increase in acid sites, optimum mean pore size and pore size distribution. © 2013 Elsevier B.V.

Fabricação e caracterização morfológica de filmes layer-by-layer de DODAB/FTALOCIANINA de níquel

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Caracterização de nanoestruturas de óxido de estanho como sensores de gás

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Síntese de nanofios de óxidos semicondutores para aplicações em dispositivos ópticos e eletrônicos

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

Sensores para sistemas líquidos diluídos combinando Raman amplificado em superfície (SERS) e língua eletrônica

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Rapid preparation of alpha-FeOOH and alpha-Fe2O3 nanostructures by microwave heating and their application in electrochemical sensors

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Phase transitions and interface phenomena in the cryogenic temperature domain of a niobate nanostructured ceramic

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