38 resultados para electronic effect
em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"
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This study investigates the promoting effect of PtSnIr/C (1:1:1) electrocatalyst anode, prepared by polymeric precursor method, on the ethanol oxidation reaction in a direct ethanol fuel cell (DEFC). All of the materials used were 20% metal m/m on carbon. X-ray photoelectron spectroscopy (XPS) analysis showed the presence of Pt, PtOH 2, PtO 2, SnO 2 and IrO 2 at the electrocatalyst surface, indicating a possible decorated particle structure. X-ray diffractometry (XRD) analysis indicated metallic Pt and Ir as well as the formation of an alloy with Sn. Using the PtSnIr/C electrocatalyst prepared here with two times lower loading of Pt than PtSn/C E-tek electrocatalyst, it was possible to obtain the same maximum power density found for the commercial material. The main reaction product was acetic acid probably due to the presence of oxides, in this point the bifunctional mechanism is predominant, but an electronic effect should not be discarded. © 2012 Sociedade Brasileira de Química.
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An experimentally based kinetic and mechanistic study of the hydrogen oxidation reaction (HOR) on platinum and platinum ordered intermetallic materials in acid medium is presented. RDE kinetic data were re-evaluated and complemented by Tafel plots obtained from chronoamperometric measurements. Among the materials evaluated, PtSb and PtSn exhibited markedly improved kinetic current densities and exchange current densities, compared to Pt in the same experimental conditions. It is proposed that the intermetallic phase enhanced the adsorptive characteristic of the surface sites and, as a consequence, improved the kinetics of the adsorption steps (Tafel or Heyrovsky) of the mechanism involved. (c) 2006 Published by Elsevier B.V.
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Aiming to reduce the cost of electrocatalysts and a greater resistance to CO poisoning this work was to study the adsorption and oxidation of carbon monoxide on ordered intermetallic phases AuIn, AuSb2, AuSn, PdSb and PdSn using voltammetric techniques in alkaline electrolyte solution. The results suggest that the AuSn and PdSn intermetallics has some form of resistance to CO poisoning. It is assumed that this behavior is a result of electronic effect and the effect of the third body has been achieved by adding a second metal to Au and Pd. However, further studies should be conducted to confirm this hypothesis as to test these materials as electrocatalysts in the reaction of oxidation of fuels
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The development of electrocatalysts for the oxidation of methanol and ethanol is very important, because these alcohols may be used in the anode fuel cells which convert chemical energy directly into electrical energy with high efficiency, cleanly and with low noise. Thus, this study reports to the synthesis of nanocatalysts of PtAu supported on carbon by microemulsion method. The physical characterization of these catalysts is performed through the techniques of X-ray diffraction and transmission electron microscopy. The catalytic activity of the prepared materials was studied using conventional electrochemical techniques and also the technique of spectro-electrochemical in situ FTIR, which allows identification of intermediates and products of the reactions. From the x-ray diffraction, it was observed that the thermal treatment applied to catalysts favored incorporation of Au into the crystal lattice of Pt,that is, increased the formation of PtAu alloy. Micrographs indicated particle size about 3 nm to materials not heat treated and 9 nm to materials subjected to thermal treatment (heating at 150 ° C for 1h and 30 min in argon atmosphere). Current density oxidation of methanol on PtAu / C were superior to pure platinum. Spectroscopic results indicated the presence of formate in solution in 50:50 and the composition showed bands for CO2, indicating complete oxidation, in lower potential. During ethanol oxidation on the catalyst PtAu, the main product formed was acetate, product of incomplete oxidation. The good performance for methanol oxidation can be attributed to large amounts of oxygen species adsorbed on the catalyst surface, or an electronic effect.
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Pós-graduação em Ciência e Tecnologia de Materiais - FC
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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The widespread use of poly(3-hexylthiophene) (P3HT) in the active layers of organic solar cells indicates that it possesses chemical stability and solubility suitable for such an application. However, it would be desirable to have a material that can maintain these properties but with a smaller bandgap, which would lead to more efficient energy harvesting of the solar spectrum. Fifteen P3HT derivatives were studied using the Density Functional Theory. The conclusion is that it is possible to obtain compounds with significantly smaller bandgaps and with solubility and stability similar to that of P3HT, mostly through the binding of oxygen atoms or conjugated organic groups to the thiophenic ring. © 2013 Wiley Periodicals, Inc.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Background: Ultrasonic excitation (US) was applied to glass ionomer cement (GIC) during early set time to increase the advantageous properties of this material. Purpose: The aim of this in vitro study was to assess the inner porosity of GIC after US. Study design: A total of 16 specimens, for each material, were prepared from high-viscosity GIC Fuji IX GP, Ketac Molar, and Ketac Molar Easymix. Half of these specimens (n = 8) received 30 s of US during the initial cement setting. After completion of the material setting, specimens were fractured and observed by scanning electronic microscopy to quantitatively assay porosity inside the material using Image J software. Results: Statistical data analysis revealed that US reduced the porosity for all tested materials (P <= 0.05). The following reductions (expressed in percentages) were achieved: Fuji IX-from 3.9% to 2.8%; Ketac Molar Easy Mix-from 4.4% to 2.6%, and Ketac Molar-from 2.4% to 1.6%. Conclusion: Under the tested conditions, US was an effective method for porosity reduction inside the material. Microsc. Res. Tech. 74:54-57, 2011. (C) 2010 Wiley-Liss, Inc.
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Background: the aim of the present study was to compare the effects of Er:YAG and diode laser treatments of the root surface on intrapulpal temperature after scaling and root planing with hand instruments.Methods: Fifteen extracted single-rooted teeth were scaled and root planed with hand instruments. The teeth were divided into 3 groups of 5 each and irradiated on their buccal and lingual surfaces: group A: Er:YAG laser, 2.94 mum/100 mJ/10 Hz/ 30 seconds; group B: diode laser, 810 nm/1.0 W/0.05 ms/30 seconds; group C: diode laser, 810 nm/1.4 W/0.05 ms/30 seconds. The temperature was monitored by means of a type T thermocouple (copper-constantan) positioned in the pulp chamber to assess pulpal temperature during and before irradiation. Afterwards, the specimens were longitudinally sectioned, and the buccal and lingual surfaces of each root were analyzed by scanning electron microscopy.Results: In the Er:YAG laser group, the thermal analysis revealed an average temperature of -2.2 +/- 1.5degreesC, while in the diode laser groups, temperatures were 1.6 +/- 0.8degreesC at 1.0 W and 3.3 +/- 1.0degreesC at 1.4 W. Electronic micrographs revealed that there were no significant morphological changes, such as charring, melting, or fusion, in any group, although the specimens were found to be more irregular in the Er:YAG laser group.Conclusions: the application of Er:YAG and diode lasers at the utilized parameters did not induce high pulpal temperatures. Root surface irregularities were more pronounced after irradiation with an Er:YAG laser than with a diode laser.
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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A three-parameter correlated wave function for the helium ground state is used to study the scattering reaction e(+) + He --> He+ + Ps, where Ps stands for positronium atom. An exact analytical expression is constructed for the first Born scattering amplitude for Ps formation from helium. Based on this numerical results are presented for both differential and total cross-sections. It is demonstrated that the inner electronic correlation of the target atom plays a crucial role in explaining the discrepency between theory and experiment.