106,355 research outputs found
Physical oceanography measured on water bottle samples during Victor Bugaev cruise OCL_5127
No full textPhysical oceanography measured on water bottle samples during Victor Bugaev cruise OCL_512
Hydrochemistry measured on water bottle samples during several Victor Bugaev cruises in Victor_Bugaev_1976
No full textHydrochemistry measured on water bottle samples during several Victor Bugaev cruises in Victor_Bugaev_197
Physical oceanography measured on water bottle samples during several Victor Bugaev cruises in Victor_Bugaev_1975
No full textPhysical oceanography measured on water bottle samples during several Victor Bugaev cruises in Victor_Bugaev_197
In situ formation of hydrides and carbides in palladium catalyst: When XANES is better than EXAFS and XRD
No full textIn a number of hydrogenation reactions, palladium nanoparticles may undergo a transition to the hydride or the carbide phase, which affects the catalytic properties. In the current work, we determine the structural evolution of an industrial Pd/C catalyst in the presence of hydrogen and acetylene by means of in situ X-ray absorption spectroscopy and X-ray powder diffraction. We observe reversible hydride phase formation and irreversible formation of the carbide phase. The near-edge structure of the absorption spectra (XANES) plays the key role in distinguishing between hydride and carbide phases. We show that the presence of hydrogen and carbon atoms have a direct effect on the near-edge region which is reproduced by theoretical simulations performed in the Monte-Carlo approach
Hydride phase formation in carbon supported palladium hydride nanoparticles by in situ EXAFS and XRD
No full textIn the current work we present a detailed analysis of the hydride phase formation in industrial Pd/C nanocatalysts by means of combined in situ X-ray absorption spectroscopy (EXAFS), X-ray diffraction (XRD) and volumetric measurements for the temperatures from - 10 to 50 °C in the hydrogen pressure range from 0 to 1000 mbar. α- and β- hydride phases are clearly distinguished in XRD. For the first time, H/Pd atomic ratio were obtained by theoretical fitting of the near-edge region of the absorption spectra (XANES) and compared with volumetric measurements
Core-Shell Structure of Palladium Hydride Nanoparticles Revealed by Combined X-ray Absorption Spectroscopy and X-ray Diffraction
No full textWe report an in situ, temperature and H2 pressure-dependent, characterization of (2.6 ± 0.4) nm palladium nanoparticles supported on active carbon during the process of hydride phase formation. For the first time the core-shell structure is highlighted in the single-component particles on the basis of a different atomic structure and electronic configurations in the inner "core" and surface "shell" regions. The atomic structure of these particles is examined by combined X-ray powder diffraction (XRPD), which is sensitive to the crystalline core region of the nanoparticles, and by first shell analysis of extended X-ray absorption fine structure (EXAFS) spectra, which reflects the averaged structure of both the core and the more disordered shell. In the whole temperature range (0-85 °C), XRPD analysis confirms the existence of two well-separated α- and β-hydride phases with the characteristic flat plateau in the phase transition region of the pressure-lattice parameter isotherms. In contrast, first shell interatomic distances obtained from EXAFS exhibit a slope in the phase transition region, typical for nanostructured palladium. Such difference is explained by distinct properties of bulk "core" which has crystalline structure and sharp phase transition, and surface "shell" which is amorphous and absorbs hydrogen gradually without forming distinguishable α- and β-phases. Combining EXAFS and XRPD we extract, for the first time, the Pd-Pd first-shell distance in the amorphous shell of the nanoparticles, that is significantly shorter than in the bulk core and relevant in catalysis. The core/shell model is supported by the EXAFS analysis of the higher shells, in the frame of the multiple scattering theory, showing that the evolution of the third shell distance (ΔR3/R3) is comparable to the evolution of (Δa/a) obtained from XRPD since amorphous PdHx shell gives a negligible contribution in this range of distances. This operando structural information is relevant for the understanding of structure-sensitive reactions. Additionally, we demonstrate the differences in the evolution of the thermal parameters obtained from EXAFS and XRPD along the hydride phase formation
Study of the Structure and Composition of the Strained Epitaxial Layer in the InAlAs/GaAs(100) Heterostructure by Transmission Electron Microscopy
No full textThe results of electron microscopy studies of an epitaxial InAlAs layer on a GaAs(100) substrate are reported. It is established that there exist misfit dislocations at the interface between the materials and there are residual strains distorting the lattice in the layer. From the measurements of lattice parameters in the directions parallel and orthogonal to the growth direction away from misfit dislocations, the local nominal lattice parameter of the layer is calculated and the relative content of indium is determined
Evolution of Pt and Pd species in functionalized UiO-67 metal-organic frameworks
No full textFunctionalization of metal-organic frameworks (MOFs) with noble metals is a promising way for producing new versatile catalysts that will combine the outstanding porosity and specific surface area of MOFs with high catalytic activity of metals. Here, we present a comparative study of two metal-organic frameworks with UiO-67 topology, functionalized with palladium and platinum moieties. The initial structure of all studied samples contained palladium or platinum atoms grafted into MCl2bpydc (M = Pd, Pt) linkers of MOFs. The materials were further activated by heating in inert and H2-containing atmospheres. Both Pd- and Pt- functionalized materials exhibited high thermal stability upon heating in these atmospheres. The evolution of Pt and Pd species during the activation procedure was monitored by in situ time-resolved X-ray absorption near-edge structure (XANES) spectroscopy. We applied multivariate curve resolution alternating least squares (MCR-ALS) approach to XANES to unravel the intermediates which can be formed during the activation procedure. For UiO-67-Pd, only simple one-step transformation from PdCl2bpydc to Pd nanoparticles (NPs) was observed. For UiO-67-Pt, two additional intermediate states were observed, which behave differently depending on the activation procedure. Theoretical calculation of XANES spectra allowed us to suggest the 3D-atomic structures corresponding to each of the pure spectra determined by MCR-ALS. In addition, reaction enthalpies for different possible reaction routes were calculated within a density functional theory approach. Based on the experimental and theoretical results showed that Pd nanoparticles (NPs) tend to be formed in UiO-67-Pd samples irrespective of the activation procedure, while either Pt NPs or isolated PtII active sites, grafted in the MOF framework may be formed in UiO-67-Pt samples depending on the activation temperature and atmosphere
Progress in the Characterization of the Surface Species in Activated Carbons by means of INS Spectroscopy Coupled with Detailed DFT Calculations
No full textActivated carbons are materials with relevance in different industrial applications. Due to the inherent complexity and heterogeneity of their structures, an easy assignment of the species present on their surface has a challenging result. Only recently, with the possibility to collect well-resolved inelastic neutron spectra and to simulate by DFT methods more or less extended graphitic clusters, this task is starting to become feasible. Here we report our investigation on a steam activated carbon and we show that different vibrations in the region of out-of-plane C-H bending modes are specifically connected to hydrogen terminations belonging to extended and regular borders or to short and defective ones. Furthermore, simulations including heteroatoms such as oxygen allowed us to point out spectral regions with a contribution from carboxyl species
Core-Shell Structure of Palladium Hydride Nanoparticles Revealed by Combined X-ray Absorption Spectroscopy and X-ray Diffraction
No full textWe report an in situ, temperature and H2 pressure-dependent, characterization of (2.6 +/- 0.4) nm palladium nanoparticles supported on active carbon during the process of hydride phase formation. For the first time the core-shell structure is highlighted in the single-component particles on the basis of a different atomic structure and electronic configurations in the inner “core” and surface “shell” regions. The atomic structure of these particles is examined by combined X-ray powder diffraction (XRPD), which is sensitive to the crystalline core region of the nanoparticles, and by first shell analysis of extended X-ray absorption fine structure (EXAFS) spectra, which reflects the averaged structure of both the core and the more disordered shell. In whole temperature range (085 °C), XRPD the analysis confirms the existence of two well-separated α- and β- hydride phases with the characteristic flat plateau in the phase transition region of the pressure-lattice parameter isotherms. In contrast, first shell interatomic distances obtained from EXAFS exhibit a smoother behavior in the phase transition region, typical for nanostructured palladium. Such difference is explained by distinct properties of bulk “core” which has crystalline structure and sharp phase transition, and surface “shell” which is amorphous and absorbs hydrogen gradually without forming distinguishable α- and β- phases. Combining EXAFS and XRPD we extract, for the first time, the Pd-Pd first-shell distance in the amorphous shell of the nanoparticle, that is significantly shorter than in the bulk core and relevant in catalysis. The core/shell model is supported by the EXAFS analysis of the higher shells, in the frame of the multiple scattering theory, showing that the evolution of the third shell distance (DeltaR3/R3) is comparable to the evolution of (Deltaa/a) obtained from XRPD since amorphous PdHx shell gives a negligible contribution in this range of distances This operando structural information is relevant for the understanding of structure-sensitive reactions. Additionally, we demonstrate the differences in the evolution of the thermal parameters obtained from EXAFS and XRPD along the hydride phase formation
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