National Institute Of Materials Physics - Romania

Facet 111 oriented Au nanoplatelets (20-40 nm wide, 3-4 nm height) grafted on graphene ((Au) over bar /fl-G) are about three orders of magnitude more efficient than Pd nanoparticles supported on graphene to promote Suzuki-Miyaura coupling. In contrast to Pd catalysis, it is shown here that the product yields in Suzuki-Miyaura coupling catalyzed by Au nanoparticles follow the order chlorobenzene > bromobenzene > iodobenzene. Kinetic studies show that this reactivity order is the result of the poisoning effect of halides for Au that is much higher for I- than Br- and much higher than for Cl-, due to adsorption. This strong iodide adsorption leading to Au catalyst deactivation was predicted by DFT calculations of Au clusters. (Au) over bar /fl-G are about one order of magnitude more efficient than small Au nanoparticles (4-6 nm) obtained by the polyol method supported on graphene. Our results can have impact in organic synthesis, showing the advantage of (Au) over bar /fl-G as catalyst for Suzuki-Miyaura couplings. (C) 2017 Elsevier Inc. All rights reserved.

We report on the fabrication of silicon-reinforced carbon (C: Si) structures by combinatorial pulsed laser deposition to search for the best design for a new generation of multi-functional coated implants. The synthesized films were characterized from the morphological, structural, compositional, mechanical and microbiological points of view. Scanning electron microscopy revealed the presence, on top of the deposited layers, of spheroid particulates with sizes in the micron range. No microcracks or delaminations were observed. Energy dispersive x-ray spectroscopy and grazing incidence x-ray diffraction pointed to the existence of aC to Si compositional gradient from one end of the film to the other. Raman investigation revealed a relatively high sp(3) hybridization of up to 80% at 40-48 mm a part from the edge with higher Ccontent. Si addition was demonstrated to significantly increase C: Si film bonding to the substrate, with values above the ISO threshold for coatings to be used in high-loading biomedical applications. Surface energy studies pointed to an increase in the hydrophilic character of the deposited structures along with Si content up to 52 m Nm(-1'). In certain cases, the Si-reinforced Ccoatings elicited an antimicrobial biofilm action. The presence of Si was proven to be benign to HEp-2 cells of human origin, without interfering with their cellular cycle. On this basis, reliable C: Si structures with good adherence to the substrate and high efficiency against microbial biofilms can be developed for implant coatings and other advanced medical devices.

In quantum field theory, Weyl fermions are relativistic particles that travel at the speed of light and strictly obey the celebrated Lorentz symmetry. Their low-energy condensed matter analogs are Weyl semimetals, which are conductors whose electronic excitations mimic the Weyl fermion equation of motion. Although the traditional (type I) emergent Weyl fermions observed in TaAs still approximately respect Lorentz symmetry, recently, the so-called type II Weyl semimetal has been proposed, where the emergent Weyl quasiparticles break the Lorentz symmetry so strongly that they cannot be smoothly connected to Lorentz symmetric Weyl particles. Despite some evidence of nontrivial surface states, the direct observation of the type II bulk Weyl fermions remains elusive. We present the direct observation of the type II Weyl fermions in crystalline solid lanthanum aluminum germanide (LaAlGe) based on our photoemission data alone, without reliance on band structure calculations. Moreover, our systematic data agree with the theoretical calculations, providing further support on our experimental results.

Reduced-activation steels such as Eurofer alloys are candidates for supporting plasma facing components into kamak-like nuclear fusion reactors. In order to investigate the impact of hydrogen/deuterium insertion in their crystalline lattice, annealing treatments in hydrogen atmosphere have been applied on Eurofer slabs. The resulting samples have been analyzed with respect to local structure and atomic configuration both before and after successive annealing treatments, by X-ray diffractometry (XRD), scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS) and conversion electron Mossbauer spectroscopy (CEMS). The corroborated data point out for a bcc type structure of the non-hydrogenated alloy, with an average alloy composition approaching Fe0.9Cr0.1 along a depth of about 100 nm. EDS elemental maps do not indicate surface inhomogeneities in concentration whereas the Mossbauer spectra prove significant deviations from a homogeneous alloying. The hydrogenation increases the expulsion of the Cr atoms toward the surface layer and decreases their oxidation, with considerable influence on the surface properties of the steel. The hydrogenation treatment is therefore proposed as a potential alternative for a convenient engineering of the surface of different Fe-Cr based alloys.(C) 2017 Elsevier B.V. All rights reserved.

The electronic structure of alpha-Sn (001) thin films strained compressively in-plane was studied both experimentally and theoretically. A new topological surface state (TSS) located entirely within the gapless projected bulk bands is revealed by ab initio-based tight-binding calculations as well as directly accessed by soft x-ray angle-resolved photoemission. The topological character of this state, which is a surface resonance, is confirmed by unravelling the band inversion and by calculating the topological invariants. In agreement with experiment, electronic structure calculations show the maximum density of states in the subsurface region, while the already established TSS near the Fermi level is strongly localized at the surface. Such varied behavior is explained by the differences in orbital composition between the specific TSS and its associated bulk states, i.e., their hybridization, respectively.

N-Containing graphenes obtained either by simultaneous amination and reduction of graphene oxide or by pyrolysis of chitosan under an inert atmosphere have been found to act as catalysts for the selective wet oxidation of glucose to succinic acid. Selectivity values over 60% at complete glucose conversion have been achieved by performing the reaction at 160 degrees C and 18 atm O-2 pressure for 20 h. This activity has been attributed to graphenic-type N atoms on graphene. The active N-containing graphene catalysts were used four times without observing a decrease in conversion and selectivity of the process. A mechanism having tartaric and fumaric acids as key intermediates is proposed.

The electronic structure of the SiO2/SiC (0001) interface, buried below SiO2 layers with a thickness from 2 to 4 nm, was explored using soft X-ray angle-resolved photoemission spectroscopy with photon energies between 350 and 1000 eV. The measurements have detected the characteristic k-dispersive energy bands of bulk Silicon Carbide (SiC) below the SiO2 layer without any sign of additional dispersive states, up to an estimated instrumental sensitivity of approximate to 5 x 10(9) cm 2 eV. This experimental result supports the physical picture that the large density of interface traps observed in macroscopic measurements results from dangling bonds randomized by the SiO2 rather than from Shockley-Tamm surface derived states extending into the bulk SiC. Published by AIP Publishing.

We report the structural, electronic and magnetic investigation using extended X-ray absorption fine structure spectroscopy (EXAFS), photoelectron microscopy, spin-resolved photoemission and magneto-optical Kerr effect on the properties of MnGe systems obtained by molecular beam epitaxy deposition of manganese on Ge(001) wafers annealed on temperatures between 50 and 450 C. Magnetic ordering can be achieved when the substrate temperature is higher than 250 C, when the manganese tends to diffuse into the Ge matrix and segregate in MnGe-like compounds, as proved by EXAFS. High spatial resolution photoelectron spectroscopy reveals Mn inhomogeneities in the 5-10 m range, even though Mn is found mostly in the same chemical state all over the surface.

The present work investigates the photocatalytical abatement of trichlorethylene (TCE) under simulated solar irradiation (AM 1.5). The employed catalytic materials, Au and Pd-Au nanoparticles supported on TiO2, were prepared by incipient wetness and by deposition-precipitation methods. It is found out that TCE is converted efficiently (>80%) to CI- and CO2 over all scrutinized catalysts. Typically, the metal addition enhances to some extent the photooxidation activity of TiO2 via photogenerated center dot OH radicals, electrons, and holes. The photocatalytic abatement of TCE over the same catalytic materials was examined in the presence of small amount of methanol. The idea was to convert TCE to Cl- and C-2 (ethane and ethylene) over Au and Pd-Au/TiO2 catalysts by the H-2 generated photocatalytically in situ. The experimental results evidenced that, over Pd-Au/TiO2 catalysts, hydrodechlorination (HDC) and photomineralization reactions of TCE occurs simultaneously. In contrast, Au/TiO2 is inactive to catalyze the hydrogenation of TCE. The results of TCE abatement by combined photooxidation/HDC reactions in presence of methanol are corroborated with H-2 photocatalytic generation results, over the same catalytic materials, from water/methanol mixture. A reaction mechanism is advanced in light of experimental results. The photo generated center dot OH radicals, electrons, and holes participate in a complex reaction pathway to formation of oxygenated organic intermediates, Cl-, CO2, and H-2. (C) 2016 Elsevier Inc. All rights reserved.

TiO2-based photocatalysts were obtained during previous years in order to limit pollution and to ease human daily living conditions due to their special properties. However, obtaining biocompatible photocatalysts is still a key problem, and the mechanism of their toxicity recently received increased attention. Two types of TiO2 nanoparticles co-doped with 1% of iron and nitrogen (TiO2-1% Fe-N) atoms were synthesized in hydrothermal conditions at pH of 8.5 (HT1) and 5.5 (HT2), and their antimicrobial activity and cytotoxic effects exerted on human pulmonary and dermal fibroblasts were assessed. These particles exhibited significant microbicidal and anti-biofilm activity, suggesting their potential application for microbial decontamination of different environments. In addition, our results demonstrated the biocompatibility of TiO2-1% Fe-N nanoparticles at low doses on lung and dermal cells, which may initiate oxidative stress through dose accumulation. Although no significant changes were observed between the two tested photocatalysts, the biological response was cell type specific and time- and dose-dependent; the lung cells proved to be more sensitive to nanoparticle exposure. Taken together, these experimental data provide useful information for future photocatalytic applications in the industrial, food, pharmaceutical, and medical fields.