National Institute Of Materials Physics - Romania

The "one-pot" hydrolyltic hydrogenation of cellulose towards C2-C6 sugar alcohols has been recognized as one of the most promising biomass valorization routes for the production of high added-value chemicals. In this work, we studied the performance of Ru and Pt catalysts supported on micro/mesoporous activated carbon, in the hydrolytic hydrogenation of microcrystalline and ball-milled cellulose, in neat water, at 180 C and at relatively low hydrogen pressure of 2 MPa. The impact of metal loading (1-5 wt.%), metal reduction method (H2 at 350 C or NaBH4) and acidification (sulfonation) of the AC support on cellulose conversion and selectivity to the various products were systematically addressed. It was shown that Pt is significantly more selective towards hexitols (sorbitol and mannitol) compared to Ru, in glucose rich reaction media, such as those offered by the easily hydrolyzed ball-milled cellulose. For example, the 5wt%PtIAC-SO3H catalyst afforded hexitols yield of 69.5 wt.% (at 96.1% conversion) compared to 10.9 wt.% (at 95.2% wt.% conversion) obtained by the corresponding Ru catalyst, the latter being also selective towards glycerol and propane-1,2-diol (propylene glycol). A relatively moderate metal loading, such as in 3 wt.%Ru/AC-SO3H, was more favorable for hexitols production (44.5 wt.% yield, at 94.8 wt.% conversion) with Ru catalysts. These results were also verified by glucose hydrogenation experiments that were conducted at the same experimental conditions. Both Pt and Ru exhibited relatively high glucose hydrogenation activity towards hexitols, versus retro-aldol reactions that lead directly to smaller C2-C4 compounds, while the difference in the final product yields between the two metals was attributed to the higher hexitols hydrogenolysis (C C cleavage) reactivity of Ru. HRTEM data showed the formation of metallic crystalline Pt and Ru nanoparticles (<= 4 nm, depending on loading) as well as of amorphous oxygen-rich M(O)(x)(delta+) phases, which were also confirmed by the XPS data. The presence of these phases which may be a source of acidity, as well as the bacisity of the parent AC used in this study, were mainly responsible for inducing isomerization, retro-aldol and dehydration reactions leading eventually to increased glycerol and propylene glycol selectivity, as was observed for both low-metal catalysts, i.e. 1 wt.% Pt or Ru/AC. (C) 2017 Elsevier B.V. All rights reserved.

Lowering the temperature of crystallization by deposition of thin films on a heated substrate represents the easiest way to find new means to develop and improve new working devices based on nanocrystals embedded in thin films. The improvements are strongly related with the increasing of operation speed, substantially decreasing the energy consumption and reducing unit fabrication costs of the respective semiconductor devices. This approach avoids major problems, such as those related to diffusion or difficulties in controlling nanocrystallites size, which appear during thermal treatments at high temperatures after deposition. This article reports on a significant progress given by structuring Ge nanocrystals (Ge-NCs) embedded in silicon dioxide (SiO2) thin films by heating the substrate at 400 degrees C during co-deposition of Ge and SiO2 by magnetron sputtering. As a proof-of-concept, a Si/Ge-NCs:SiO2 photo-sensitive structure was fabricated thereof and characterized. The structure shows superior performance on broad operation bandwidth from visible to near-infrared, as strong rectification properties in dark, significant current rise in the inversion mode when illuminated, high responsivity, high photo-detectivity of 10(14) Jones, quick response and significant conversion efficiency with peak value reaching 850% at -1 V and about 1000 nm. This simple preparation approach brings an important contribution to the effort of structuring Ge nanocrystallites in SiO2 thin films at a lower temperature for the purpose of using these materials for devices in optoelectronics, solar cells and electronics on flexible substrates.

The positions of the low energy electron diffraction (LEED) spots from ferroelectric single crystal films depend on its polarization state, due to electric fields generated outside of the sample. Onemay derive the surface potential energy, yielding the depth where the mobile charge carriers compensating the depolarization field are located (delta). On ferroelectric Pb(Zr, Ti)O-3(001) samples, surface potential energies are between 6.7 and 10.6 eV, and d values are unusually low, in the range of 1.8 +/- 0.4 angstrom. When delta is introduced in the values of the band bending inside the ferroelectric, a considerably lower value of the dielectric constant and/or of the polarization near the surface than their bulk values is obtained, evidencing either that the intrinsic 'dielectric constant' of the material has this lower value or the existence of a 'dead layer' at the free surface of clean ferroelectric films. The inwards polarization of these films is explained in the framework of the present considerations by the formation of an electron sheet on the surface. Possible explanations are suggested for discrepancies between the values found for surface potential energies from LEED experiments and those derived from the transition between mirror electron microscopy and low energy electron microscopy.

We propose a novel idea to improve the surface properties of carbon-based Pt-free electrocatalysts in Polymer Electrolyte Membranes (PEMs) and Alkaline Fuel Cells (AFCs). Our concept is based on the addition of oxygenophilic and hydrophobic ionic liquids (ILs) to form a thin passivating layer at the triple point between the electrocatalyst-electrolyte-gas interface where the Oxygen Reduction Reaction (ORR) takes place.

The stability of thin films of lead zirco-titanate (PZT) under intense soft X-ray beams is investigated by time-resolved photoelectron spectromicroscopy with a lateral resolution below 1 micrometer. Surface dissociation is observed when samples are irradiated with intense (5 x 10(23) photons per s per m(2)) soft X-rays, with promotion of reduced lead on the surface. On areas exhibiting outwards polarization (P(+)), the reduced lead is formed at the expense of P(+)-PZT. On areas presenting co-existing P(+) states with areas without out-of-plane polarization (P-(0)), the reduced lead is formed at the expense of the P-(0)-PZT component, while the P(+)-PZT remains constant. The main dissociation mechanism was found to be triggered by 'hot' electrons in the conduction band, with energies exceeding the surface dissociation energies. Dissociation occurs basically when the electron affinity is larger than the dissociation energy of PbO (for P(+) areas) or PbO- (for P-(0) areas). Such mechanisms may be adapted for dissociation of other molecules on surfaces of ferroelectric thin films or for quantifying the stability of ferroelectric surfaces interacting with other radiation, with applications in the fields of photocatalysis or photovoltaic devices.

Tuneable nitrogen doped carbogels have been synthesised by a simple one-pot hydrothermal carbonisation, followed by pyrolysis at 1000 degrees C, using highly available and low cost precursors such as glucose and ovalbumin. Different physical activation ratios of nitrogen/oxygen were used to demonstrate a sustainable and easy method for changing surface area, pore size and elemental composition in order to investigate their effect on the oxygen reduction reaction when used as electrocatalysts. A ratio of nitrogen mixed with 2% of oxygen was found to be most beneficial for enhancing the catalytic activity by creating a high surface area of 874 m(2) g(-1) as well as a favourable ratio of pyridinic to graphitic nitrogen. The influence of sulphur doping and/or boron on the carbogel structure was investigated. Incorporation of sulphur does not interfere with the structure formation, but decreases the surface area and nitrogen content resulting in diminished ORR performance. However, boron doping with boric acid results in a different carbogel structure by acting as a catalyst, creating an altered morphology, surface area, pore properties and higher nitrogen content by fully utilising ovalbumin as a nitrogen source instead of as a structure directing/surface stabilising agent. Nitrogen content is found to determine the limiting current, while the oxygen content has a small influence on the onset potential. An assumed synergistic effect between nitrogen and boron generates higher electron transfer numbers and lower hydrogen peroxide yields in boron nitrogen co-doped carbogels than those observed in purely nitrogen doped systems.

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.