912 resultados para in situ XANES hydrogen permeation


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Numerous methods are available to measure the permeation properties of concrete, which can be classified in terms of the diffusion, absorption and permeability properties. The results from these tests are generally used to infer 'quality' or relative durability. Some of these tests involve the laboratory assessment of a sample of concrete extracted from the structure. However, this Technical Note concentrates on the alternative methods appropriate for use on site. Guidance is given on the choice of an appropriate test method, which in most practical situations depends on the predominant mechanism acting on the concrete under consideration.

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This paper descirbes a simple test measuring the sorptivity (a measure of the absorption property if concrete) and the air and water permeability of concrete on site. Using this test, the decay of pressure is monitired for the air permeability test.whereas water penetrating into the concrete at a constant pressure of 0.01 bar and 1.5 bar are recorded for the sorptivity and the water permeability tests respectively. These tests are essentially non-destructive in nature and a skilled operator is not needed. It is possible to carry out a number of tests quickly and efficiently on site without prior planning. It has been found that statistically satisfactory results can be obtained from a mean of three tests. As the flow lines are largely concentrated within 40 mm from the surface, reasonably reliable results can be obtained by drying the surface even if the surface under test is initially wet.

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The change in the Pt electronic structure following the adsorption of an a,ß-unsaturated aldehyde and ketone was followed by in situ HERFD-XANES in the liquid phase. The resulting shift in the Pt Fermi energy is in good agreement with the molecule adsorption energy trends calculated by DFT and provides insight into the reaction selectivity.

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

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Hydrogen peroxide is a powerful oxidant that finds application in several areas, but most particularly in the treatment of industrial wastewaters. The aim of the present study was to investigate the effects of applied potential and electrolyte flow conditions on the in situ generation of hydrogen peroxide in an electrochemical flow-by reactor with a gas diffusion electrode (GDE). The electrolyses were performed in an aqueous acidic medium using a GDE constructed with conductive black graphite and polytetrafluoroethylene (80:20 w/w). Under laminar flow conditions (flow rate = 50 L/h), hydrogen peroxide was formed in a maximum yield of 414 mg/L after 2 h at -2.25 V vs Pt //Ag/AgCl (global rate constant = 3.1 mg/(L min); energy consumption = 22.1 kWh/kg). Under turbulent flow (300 L/h), the maximum yield obtained was 294 mg/L after 2 h at -1.75 V vs Pt//Ag/AgCl (global rate constant = 2.5 mg/ (L min); energy consumption = 30.1 kWh/kg).

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The redox property of ceria is a key factor in the catalytic activity of ceria-based catalysts. The oxidation state of well-defined ceria nanocubes in gas environments was analysed in situ by a novel combination of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) and high-energy XPS at a synchrotron X-ray source. In situ high-energy XPS is a promising new tool to determine the electronic structure of matter under defined conditions. The aim was to quantitatively determine the degree of cerium reduction in a nano-structured ceria-supported platinum catalyst as a function of the gas environment. To obtain a non-destructive depth profile at near-ambient pressure, in situ high-energy XPS analysis was performed by varying the kinetic energy of photoelectrons from 1 to 5 keV, and, thus, the probing depth. In ceria nanocubes doped with platinum, oxygen vacancies formed only in the uppermost layers of ceria in an atmosphere of 1 mbar hydrogen and 403 K. For pristine ceria nanocubes, no change in the cerium oxidation state in various hydrogen or oxygen atmospheres was observed as a function of probing depth. In the absence of platinum, hydrogen does not dissociate and, thus, does not lead to reduction of ceria.

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We used electrochemical scanning tunneling microscopy to study the intercalation of hydrogen into a Cu(111) model electrode under reactive (in operando) conditions. Hydrogen evolution causes hydrogen intermediates to migrate into the copper lattice as function of the applied potential and the resulting current density. This H-inclusion is demonstrated to be reversible. The presence of subsurface hydrogen leads to a significant surface relaxation/reconstruction affecting both the geometric and electronic structure of the electrode surface.

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Molecular hydrogen strongly interacts with vicinal Ge(100) surfaces during preparation in a metal organic vapor phase epitaxy reactor. According to X-ray photoemission spectroscopy and Fourier-transform infrared spectroscopy results, we identify two characteristic reflection anisotropy (RA) spectra for H-free and monohydride-terminated vicinal Ge(100) surfaces. RAS allows in situ monitoring of the surface termination and enables spectroscopic hydrogen kinetic desorption studies on the Ge(100) surface. Comparison of evaluated values for the activation energy and the pre-exponential factor of H desorption evaluated at different photon energies reflects that H unevenly affects the shape of the RA spectrum.

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In situ Raman spectroscopy was exploited to analyze the interaction between carbon and hydrogen during electrochemical hydrogen storage at cathodic conditions. Two different activated carbons were used and characterized by different electrochemical techniques in two electrolytes (6 M KOH and 0.5 M Na2SO4). The in situ Raman spectra collected showed that, in addition to the D and G bands associated to the graphitic carbons, two bands appear simultaneously at about 1110 and 1500 cm−1 under cathodic conditions, and then they disappear when the potential increases to more positive values. This indicates that carbon–hydrogen bonds are formed reversibly in both electrolytes during cathodic conditions. Comparing the two activated carbons, it was confirmed that, in both electrolytes, the hydrogenation of carbon atoms is produced more easily for the sample with lower amount of surface oxygen groups. In KOH medium, for the two samples, the formation of carbon–hydrogen bonds proceeds at more positive potential with respect to the thermodynamic potential value for hydrogen evolution. Furthermore, changes in the shape of the D band (due to an intensity increase of the D1 band) during the formation of carbon–hydrogen bonds suggest that hydrogenation of the carbon atoms increases the number of edge planes.

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The Logatchev hydrothermal vent field (14°45'N, Mid-Atlantic Ridge) is located in a ridge segment characterized by mantle-derived ultramafic outcrops. Compared to basalt-hosted vents, Logatchev high temperature fluids are relatively low in sulfide indicating that the diffuse, low temperature fluids of this vent field may not contain sufficient sulfide concentrations to support a chemosymbiotic invertebrate community. However, the high abundances of bathymodiolin mussels with bacterial symbionts related to free-living sulfur oxidizing bacteria suggested that bioavailable sulfide is present at Logatchev. To clarify if diffuse fluids above mussel beds of Bathymodiolus puteoserpentis provide the reductants and oxidants needed by their symbionts for aerobic sulfide oxidation, in situ microsensor measurements of dissolved hydrogen sulfide and oxygen were combined with simultaneous temperature measurements. High temporal fluctuations of all three parameters were measured above the mussel beds. H2S and O2 co-existed with mean concentrations between 9-31 µM (H2S) and 216-228 µM (O2). Temperature maxima (<= 7.4°C) were generally concurrent with H2S maxima (<= 156 µM) and O2 minima (>= 142 µM). Long-term measurements for 250 days using temperature as a proxy for oxygen and sulfide concentrations indicated that the mussels were neither oxygen- nor sulfide-limited. Our in situ measurements at Logatchev indicate that sulfide may also be bioavailable in diffuse fluids from other ultramafic-hosted vents along slow- and ultraslow-spreading ridges.

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In-situ, synchronous MS/XANES reveals the Pd catalyzed selective aerobic oxidation of crotyl alcohol is regulated by the balance between the oxidation state and reducibility. Dynamic XANES measurements provide a new, rapid method to determine redox kinetics of nanoparticles and identify important parameters to optimize catalyst design. © 2012 American Chemical Society.

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An account is given of the Central Laser Facility's work to produce a cryogenic hydrogen targetry system using a pulse tube cryocooler. Due to the increasing demand for low Z thin laser targets, CLF (in collaboration with TUD) have been developing a system which allows the production of solid hydrogen membranes by engineering a design which can achieve this remotely; enabling the gas injection, condensation and solidification of hydrogen without compromising the vacuum of the target chamber. A dynamic sealing mechanism was integrated which allows targets to be grown and then remotely exposed to open vacuum for laser interaction. Further research was conducted on the survivability of the cryogenic targets which concluded that a warm gas effect causes temperature spiking when exposing the solidified hydrogen to the outer vacuum. This effect was shown to be mitigated by improving the pumping capacity of the environment and reducing the minimum temperature obtainable on the target mount. This was achieved by developing a two-stage radiation shield encased with superinsulating blanketing; reducing the base temperature from 14 0.5 K to 7.2 0.2 K about the coldhead as well as improving temperature control stability following the installation of a high-performance temperature controller and sensor apparatus. The system was delivered experimentally and in July 2014 the first laser shots were taken upon hydrogen targets in the Vulcan TAP facility.