RESUMEN
The oxygen stoichiometry of hollandite, KxMnO2-δ, nanorods has been accurately determined from a quantitative analysis of scanning-transmission electron microscopy (STEM) X-Ray Energy Dispersive Spectroscopy (XEDS) experiments carried out in chrono-spectroscopy mode. A methodology combining 3D reconstructions of high-angle annular dark field electron tomography experiments, using compressed-sensing algorithms, and quantification through the so-called ζ-factors method of XEDS spectra recorded on a high-sensitivity detector has been devised to determine the time evolution of the oxygen content of nanostructures of electron-beam sensitive oxides. Kinetic modeling of O-stoichiometry data provided K0.13MnO1.98 as overall composition for nanorods of the hollandite. The quantitative agreement, within a 1% mol error, observed with results obtained by macroscopic techniques (temperature-programmed reduction and neutron diffraction) validate the proposed methodology for the quantitative analysis, at the nanoscale, of light elements, as it is the case of oxygen, in the presence of heavy ones (K, Mn) in the highly compromised case of nanostructured materials which are prone to electron-beam reduction. Moreover, quantitative comparison of oxygen evolution data measured at macroscopic and nanoscopic levels allowed us to rationalize beam damage effects in structural terms and clarify the exact nature of the different steps involved in the reduction of these oxides with hydrogen.
RESUMEN
A Ni/CeO2/ZrO2 catalyst with improved redox properties has been washcoated onto a honeycomb cordierite monolith in the form of a nonconventional alumina-catalyst layer, just a few nanometers thick. In spite of the very low active phase loading, the monolith depicts outstanding performance in dry reforming of methane, both in terms of activity, with values reaching the thermodynamic limit already at 750 °C, even under extreme Weight Hourly Space Velocities (WHSV 115-346 L·g-1·h-1), as well as in terms of stability during prolonged Time on Stream (TOS 24-48 h).
RESUMEN
Nano-structural and nano-analytical studies show that the dramatic difference in CO oxidation activity observed between two Au/Ce0.50Tb0.12Zr0.38O2-x samples prepared by deposition-precipitation with urea and further activated under oxidising or reducing conditions is due to the poisoning effect of a very thin layer of carbon grown on the pre-reduced catalyst.
RESUMEN
The relation between the physico-chemical properties of nanoparticles (NPs) and the degree of cellular uptake is incompletely elucidated. In this study, we investigated the influence on the cellular uptake of a wide range of fully characterized TiO2 NPs. L929 fibroblasts were exposed for 24 h to clinically relevant concentrations of nano-TiO2 and the degree of their association was assessed by ultrahigh resolution imaging microscopy (URI), scanning (SEM) and transmission (TEM) electron microscopy, as well as inductivity coupled plasma-mass spectroscopy (ICP-MS). The role of actin polymerization, a central feature of active internalization, was also studied and the results indicated that the internalization of TiO2 NPs involves a combination of actin-dependent uptake of large agglomerates as well as non actin-dependent uptake of small agglomerates. SEM and TEM revealed that the agglomerates of all NPs types were attached to the cellular membrane as well as internalized and confined inside cytoplasmic vesicles. URI and ICP-MS demonstrated that the particle association with cells was dose-dependent. The highest association was observed for spherical particles having mixed anatase-rutile crystallographic phase and the lowest for spindle-shaped rutile particles. ICP-MS revealed that the association was size-dependent in the order 5>10>40 nm for anatase spherical nanoparticles.
