Role of Platinum Deposited on TiO2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions

Titania modified nanoparticles have been prepared by the photodeposition method employing platinum particles on the commercially available titanium dioxide (Hombikat UV 100). The properties of the prepared photocatalysts were investigated by means of the Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), atomic force microscopy (AFM), and UV-visible diffuse spectrophotometry (UV-Vis). XRD was employed to determine the crystallographic phase and particle size of both bare and platinised titanium dioxide. The results indicated that the particle size was decreased with the increasing of platinum loading. AFM analysis showed that one particle consists of about 9 to 11 crystals. UV-vis absorbance analysis showed that the absorption edge shifted to longer wavelength for 0.5% Pt loading compared with bare titanium dioxide. The photocatalytic activity of pure and Pt-loaded TiO2 was investigated employing the photocatalytic oxidation and dehydrogenation of methanol. The results of the photocatalytic activity indicate that the platinized titanium dioxide samples are always more active than the corresponding bare TiO2 for both methanol oxidation and dehydrogenation processes. The loading with various platinum amounts resulted in a significant improvement of the photocatalytic activity of TiO2. This beneficial effect was attributed to an increased separation of the photogenerated electron-hole charge carriers.

Scanning electron microscopic study of the in situ effect of salivary stimulation on erosion and abrasion in human and bovine enamel

This in situ study investigated, using scanning electron microscopy, the effect of stimulated saliva on the enamel surface of bovine and human substrates submitted to erosion followed by brushing abrasion immediately or after one hour. During 2 experimental 7-day crossover phases, 9 previously selected volunteers wore intraoral palatal devices, with 12 enamel specimens (6 human and 6 bovine). In the first phase, the volunteers immersed the device for 5 minutes in 150 ml of a cola drink, 4 times a day (8h00, 12h00, 16h00 and 20h00). Immediately after the immersions, no treatment was performed in 4 specimens (ERO), 4 other specimens were immediately brushed (0 min) using a fluoride dentifrice and the device was replaced into the mouth. After 60 min, the other 4 specimens were brushed. In the second phase, the procedures were repeated but, after the immersions, the volunteers stimulated the salivary flow rate by chewing a sugar-free gum for 30 min. Enamel superficial alterations of all specimens were then evaluated using a scanning electron microscope. Enamel prism core dissolution was seen on the surfaces submitted to erosion, while on those submitted to erosion and to abrasion (both at 0 and 60 min) a more homogeneous enamel surface was observed, probably due to the removal of the altered superficial prism layer. For all the other variables - enamel substrate and salivary stimulation -, the microscopic pattern of the enamel specimens was similar.

Comparison among four commonly used demineralizing agents for root conditioning: a scanning electron microscopy

Dental roots that have been exposed to the oral cavity and periodontal pocket environment present superficial changes, which can prevent connective tissue reattachment. Demineralizing agents have been used as an adjunct to the periodontal treatment aiming at restoring the biocompatibility of roots. OBJECTIVE: This study compared four commonly used demineralizing agents for their capacity of removing smear layer and opening dentin tubules. METHODS: Fifty fragments of human dental roots previously exposed to periodontal disease were scaled and randomly divided into the following groups of treatment: 1) CA: demineralization with citric acid for 3 min; 2) TC-HCl: demineralization with tetracycline-HCl for 3 min; 3) EDTA: demineralization with EDTA for 3 min; 4) PA: demineralization with 37% phosphoric acid for 3 min; 5) Control: rubbing of saline solution for 3 min. Scanning electron microscopy was used to check for the presence of residual smear layer and for measuring the number and area of exposed dentin tubules. RESULTS: Smear layer was present in 100% of the specimens from the groups PA and control; in 80% from EDTA group; in 33.3% from TC-HCl group and 0% from CA group. The mean numbers of exposed dentin tubules in a standardized area were: TC-HCl=43.8±25.2; CA=39.3±37; PA=12.1±16.3; EDTA=4.4±7.5 and Control=2.3±5.7. The comparison showed significant differences between the following pairs of groups: TC-HCl and Control; TC-HCl and EDTA; CA and Control; and CA and EDTA. The mean percentages of area occupied by exposed dentin tubules were: CA=0.12±0.17%; TC-HCl=0.08±0.06%; PA=0.03±0.05%; EDTA=0.01±0.01% and Control=0±0%. The CA group differed significantly from the others except for the TC-HCl group. CONCLUSION: There was a decreasing ability for smear layer removal and dentin tubule widening as follows: AC>TC-HCl>PA>EDTA. This information can be of value as an extra parameter for choosing one of them for root conditioning.

Comparative electron temperature measurements of Thomson scattering and electron cyclotron emission diagnostics in TCABR plasmas

We present the first simultaneous measurements of the Thomson scattering and electron cyclotron emission radiometer diagnostics performed at TCABR tokamak with Alfven wave heating. The Thomson scattering diagnostic is an upgraded version of the one previously installed at the ISTTOK tokamak, while the electron cyclotron emission radiometer employs a heterodyne sweeping radiometer. For purely Ohmic discharges, the electron temperature measurements from both diagnostics are in good agreement. Additional Alfven wave heating does not affect the capability of the Thomson scattering diagnostic to measure the instantaneous electron temperature, whereas measurements from the electron cyclotron emission radiometer become underestimates of the actual temperature values. (C) 2010 American Institute of Physics. [doi:10.1063/1.3494379]

Clean preparation of methyl esters in one-step oxidative esterification of primary alcohols catalyzed by supported gold nanoparticles

Methyl esters were prepared by the clean, one-step catalytic esterification of primary alcohols using molecular oxygen as a green oxidant and a newly developed SiO(2)-supported gold nanoparticle catalyst. The catalyst was highly active and selective in a broad range of pressure and temperature. At 3 atm O(2) and 130 degrees C benzyl alcohol was converted to methyl benzoate with 100% conversion and 100% selectivity in 4 h of reaction. This catalytic process is much ""greener"" than the conventional reaction routes because it avoids the use of stoichiometric environmentally unfriendly oxidants, usually required for alcohol oxidation, and the use of strong acids or excess of reactants or constant removal of products required to shift the equilibrium to the desired esterification product.

Entanglement and classical instabilities: Fingerprints of electron-hole-to-exciton phase transition in a simple model

We propose a schematic model to study the formation of excitons in bilayer electron systems. The phase transition is signalized both in the quantum and classical versions of the model. In the present contribution we show that not only the quantum ground state but also higher energy states, up to the energy of the corresponding classical separatrix orbit, ""sense"" the transition. We also show two types of one-to-one correspondences in this system: On the one hand, between the changes in the degree of entanglement for these low-lying quantum states and the changes in the density of energy levels; on the other hand, between the variation in the expected number of excitons for a given quantum state and the behavior of the corresponding classical orbit.

Defect-induced effects on carrier migration through one-dimensional poly(para-phenylenevinylene) chains

Defects in one-dimensional (1D) systems can be intrinsically distinct from its three-dimensional counterparts, and polymer films are good candidates for showing both extremes that are difficult to individuate in the experimental data. We study theoretically the impact of simple hydrogen and oxygen defects on the electron transport properties of one-dimensional poly(para-phenylenevinylene) chains through a multiscale technique, starting from classical structural simulations for crystalline films to extensive ab initio calculations within density functional theory for the defects in single crystalline-constrained chains. The most disruptive effect on carrier transport comes from conjugation breaking imposed by the overcoordination of a carbon atom in the vinyl group independently from the chemical nature of the defect. The particular case of the [C=O] (keto-defect) shows in addition unexpected electron-hole separation, suggesting that the experimentally detected photoluminescence bleaching and photoconductivity enhancement could be due to exciton dissociation caused by the 1D characteristics of the defect.

Low-energy electron scattering from methanol and ethanol

Measured and calculated differential cross sections for elastic (rotationally unresolved) electron scattering from two primary alcohols, methanol (CH(3)OH) and ethanol (C(2)H(5)OH), are reported. The measurements are obtained using the relative flow method with helium as the standard gas and a thin aperture as the collimating target gas source. The relative flow method is applied without the restriction imposed by the relative flow pressure conditions on helium and the unknown gas. The experimental data were taken at incident electron energies of 1, 2, 5, 10, 15, 20, 30, 50, and 100 eV and for scattering angles of 5 degrees-130 degrees. There are no previous reports of experimental electron scattering differential cross sections for CH(3)OH and C(2)H(5)OH in the literature. The calculated differential cross sections are obtained using two different implementations of the Schwinger multichannel method, one that takes all electrons into account and is adapted for parallel computers, and another that uses pseudopotentials and considers only the valence electrons. Comparison between theory and experiment shows that theory is able to describe low-energy electron scattering from these polyatomic targets quite well.

Strong reduction of V(4+) amount in vanadium oxide/hexadecylamine nanotubes by doping with Co(2+) and Ni(2+) ions: Electron paramagnetic resonance and magnetic studies

In this work we present a complete characterization and magnetic study of vanadium oxide/hexadecylamine nanotubes (VO(x)/Hexa NT's) doped with Co(2)+ and Ni(2+) ions. The morphology of the NT's has been characterized by transmission electron microscopy, while the metallic elements have been quantified by the instrumental neutron activation analysis technique. The static and dynamic magnetic properties were studied by collecting data of magnetization as a function of magnetic field and temperature and by electron paramagnetic resonance. At difference of the majority reports in the literature, we do not observe magnetic dimers in vanadium oxide nanotubes. Also, we observed that the incorporation of metallic ions (Co(2+), S = 3/2 and Ni(2+), S = 1) decreases notably the amount of V(4+) ions in the system, from 14-16% (nondoped case) to 2%-4%, with respect to the total vanadium atoms (fact corroborated by XPS experiments) anyway preserving the tubular nanostructure. The method to decrease the amount of V(4+) in the nanotubes improves considerably their potential technological applications as Li-ion batteries cathodes. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3580252]

In situ infrared (FTIR) study of the mechanism of the borohydride oxidation reaction

Early reports stated that Au was a catalyst of choice for the BOR because it would yield a near complete faradaic efficiency. However, it has recently been suggested that gold could yield to some extent the heterogeneous hydrolysis of BH(4)(-),therefore lowering the electron count per BH(4)(-), especially at low potential. Actually, the blur will exist regarding the BOR mechanism on Au as long as no physical proof regarding the reaction intermediates is not put forward. In that frame, in situ physical techniques like FTIR exhibit some interest to study the BOR. Consequently, in situ infrared reflectance spectroscopy measurements (SPAIRS technique) have been performed in 1 M NaOH/1 M NaBH(4) on a gold electrode with the aim to detect the intermediate species. We monitored several bands in B-H ((nu) over bar similar to 1180,1080 and 972 cm(-1)) and B-O bond regions ((nu) over bar =1325 and similar to 1425cm(-1)), which appear sequentially as a function of the electrode polarization. These absorption bands are assigned to BH(3), BH(2) and BO(2)(-) species. At the light of the experimental results, possible initial elementary steps of the BOR on gold electrode have been proposed and discussed according to the relevant literature data.

The role of the steps in the cleavage of the C-C bond during ethanol oxidation on platinum electrodes

Ethanol oxidation has been studied on stepped platinum single crystal electrodes in acid media using electrochemical and Fourier transform infrared (FTIR) techniques. The electrodes used belong to two different series of stepped surfaces: those having (111) terraces with (100) monoatomic steps and those with (111) terraces with (110) monoatomic steps. The behaviors of the two series of stepped surfaces for the oxidation of ethanol are very different. On the one hand, the presence of (100) steps on the (111) terraces provides no significant enhancement of the activity of the surfaces. On the other hand, (110) steps have a double effect on the ethanol oxidation reaction. At potentials below 0.7 V, the step catalyzes the C-C bond cleavage and also the oxidation of the adsorbed CO species formed. At higher potentials, the step is not only able to break the C-C bond, but also to catalyze the oxidation of ethanol to acetic acid and acetaldehyde. The highest catalytic activity from voltammetry for ethanol oxidation was obtained with the Pt(554) electrode.

Strength improvement of LPS-SiC ceramics by oxidation treatment

In this work, SiC ceramics were liquid phase sintered (LPS), using AIN-Y(2)O(3) as additives, and oxidized at 1400 degrees C in air for up to 120 h. Oxidation was monitored by the weight gain of the samples as function of exposition time and temperature. A parabolic growth of the oxidation layer has been observed and the coefficient of the growth rate has been determined by relating the weight gain and the surface area. The effect of oxidation on strength has been determined by 4-point bending tests. Phase analysis by Xray diffraction and microstructural observation by scanning electron microscopy indicated the formation of a uniform and dense oxidation layer. The elimination of surface flaws and pores and the generation of compressive stresses in the surface resulted in a strength increase of the oxidized samples. (C) 2009 Published by Elsevier Ltd.

Influence of hardness of the harder body on wear regime transition in a sliding pair of steels

In the unlubricated sliding wear of steels the mild-severe and severe-mild wear transitions have long been investigated. The effect of system inputs such as normal load, sliding speed, environment humidity and temperature, material properties, among others, on those transitions have also been studied. Although transitions seem to be caused by microstructural changes, surfaces oxidation and work-hardening, some questions remain regarding the way each aspect is involved. Since the early studies in sliding wear, it has usually been assumed that only the material properties of the softer body influence the wear behavior of contacting surfaces. For example, the Archard equation involves only the hardness of the softer body, without considering the hardness of the harder body. This work aims to discuss the importance of the harder body hardness in determining the wear regime operation. For this, pin-on-disk wear tests were carried out, in which the disk material was always harder than the pin material. Variations of the friction force and vertical displacement of the pin were registered during the tests. A material characterization before and after tests was conducted using stereoscopy and scanning electron microscopy (SEM) methods, in addition to mass loss, surface roughness and microhardness measurements. The wear results confirmed the occurrence of a mild-severe wear transition when the disk hardness was decreased. The disk hardness to pin hardness ratio (H(d)/H(p)) was used as a criterion to establish the nature of surface contact deformation and to determine the wear regime transition. A predominantly elastic or plastic contact, characterized by H(d)/H(p) values higher or lower than one, results in a mild or severe wear regime operation, respectively. (c) 2009 Elsevier B.V. All rights reserved.

Regeneration of Activated Carbon by (Photo)-Fenton Oxidation

This work aims to study the adsorption of phenol on activated carbons (ACs) and the consecutive in situ regeneration of carbon by Fenton oxidation. Two different operations have been carried Out: (1) a batch procedure in order to investigate the influence of Fe(2+) and H(2)O(2) concentrations; (2) continuous fixed bed adsorption, followed by a batch circulation of the Fenton`s reagent through the saturated AC bed. to examine the efficiency of the real process. Two different activated carbons have been also studied: a both micro- and mesoporous AC (L27) and an only microporous One (S23). In the batch reactor the best conditions found for pollutant mineralization in the homogeneous Fenton system are not the best For AC regeneration: a continuous reduction of adsorption capacity of L27 is observed after 3 oxidations, due to the decrease of both AC weight and surface area. Higher concentration of Fe(2+) and lower concentration of H(2)O(2) (2 times the stoichiometry) lead to a 50% recovery of the initial adsorption capacity during at least four consecutive cycles for L27, while about 20% or less for S23. In the consecutive continuous adsorption/batch Fenton oxidation process, the regeneration efficiency reaches 30-40% for L27 after two cycles whatever the feed concentration and less than 10% for S23. A photo-Fenton test performed on L27 shows almost complete mineralization (contrary to ""dark"" Fenton) and further improves recovery of AC adsorption capacity although not complete (56% after two cycles).

Effects of natural antioxidants on the lipid profile of electron beam-irradiated beef burgers

The purpose of this study was to assess the efficacy of rosemary and oregano extracts in avoiding oxidative changes in beef burgers, and to evaluate the fatty acid profile of these products after electron beam exposition. Extracts, individually or in combination, were added to beef burgers and compared to synthetic antioxidants commonly used in food (butylated hydroxytoluene, butylated hydroxyanisole). The ground beef were submitted to electron beam irradiation at doses of 0, 3.5 and 7 kGy, and stored for 90 days. At regular time intervals, lipid oxidation and fatty acid composition were evaluated through measurement of thiobarbituric acid-reactive substances (TBARS) and gas chromatography, respectively. The results indicate that, although the irradiation process triggers an increase in the lipid oxidation ratio expressed by TBARS values, great changes in the fatty acid profiles were not observed; instead, they continued to present characteristics very similar to that of non-irradiated beef. Thus, as irradiation doses of up to 7 kGy for frozen meat can make foods safe from foodborne pathogens, natural antioxidants derived from spices are able to reduce and avoid lipid changes that may cause a deterioration of the sensory quality of these foods, and these natural extracts offer a good choice for replacing synthetic additives.