National Institute Of Materials Physics - Romania

N-doped, defective graphene obtained by pyrolysis of chitosan at 900 degrees C under Ar exhibits catalytic activity for the Sabatier hydrogenation of CO2 to CH4 at temperatures about 500 degrees C with estimated turnover frequencies and activation energy values of 73.17s(-1) and 24.3 kcal x mol(-1), respectively. It has been found that this enhanced catalytic activity compared to other related doped defective graphenes derives from the presence of pyridinic N atoms that adsorbs CO2 forming carbamate-type adsorbates.

This is the first report on synthesis and photocatalytic activity for trichloroethylene (TCE) degradation under simulated solar light over RbLaTa2O7 layered perovskites with predominant nanowire or platelet morphologies. SEM images witnessed that the one step thermal treatment at 1200 degrees C lead to formation of RbLaTa2O7 nanowires with diameter of 80-320 nm and several microns in length associated in bundles and sharp-edged, merged platelets (minor phase). The two-step annealing at 950 degrees C and 1200 degrees C resulted in decrease of wires bundle population and increase in that of platelets merged in facetted particles. The RbLaTa2O7 nanowires are made of by well-aligned atomic rows with preferred orientation toward the c-axis, relatively free of defect. High density of hydroxyl groups on the sample calcined in mild conditions (RbLaTa_01) favors the photo mineralization of TCE. In contrast, the activity of RbLaTa_02 annealed in harsh conditions (950 and 1200 degrees C), poor in surface hydroxyl groups, remained modest. The weak surface basicity directed the reaction mainly to generation of intermediate chlorinated compounds. Pd and Au were supported on RbLaTa2O7 perovskites as an alternative strategy to boost the removal of chlorinated pollutants by combining photocatalytic (mineralization) and catalytic (hydrodechlorination, HDC) processes. The mineralization of TCE to Cl- was drastically hindered in presence of methanol due to quenching of -OH radicals by alcohol. The results suggested that the density of RbLaTa2O7 surface hydroxyl groups is essential for photo mineralization of TCE whereas the surface carbonate is beneficial for the formation of intermediate chlorinated product.

Spirobifluorene-based porous organic polymers (POP) were synthesized following two different protocols; the acetylenic coupling reaction conditions and the Sonogashira cross-coupling reaction. These were utilized as support for the hydrogenation of a series of species containing unsaturated C=C and C=O bonds (4-nitrostyrene, 4-bromobenzophenone, acetophenone, 7-nitro-1-tetralone and 1,2-naphtoquinone confirmed their efficiency). POP1 prepared via a copper-catalysis protocol was completely inactive, while POP2-4 containing residual Pd exhibited different activities in accordance to the accessibility of the substrates to the metal. Further deposition of 0.5wt% Pd led to active and stable catalysts. They were easily separated by filtration, and after re-dispersion, afforded the same performances for ten successive cycles. This study also evidenced the specific role of the support in these reactions by comparing the behavior of Pd/POP with that of a Pd/C catalyst with the same loading of palladium. The deposition of Pt on these supports led to sub-nanometric particles and, in accordance, to a different catalytic behavior reflected merely by differences in the selectivity.

Manganese is deposited at high temperature on (001) oriented ferroelectric lead zirco-titanate prepared in two different ways: sputter-annealed or just simply annealed in ultrahigh vacuum. Room temperature ferromagnetism (FM) is obtained for Mn deposited on sputter-annealed substrates, while for the other sample preparation a paramagnetic behaviour is obtained. Also, for the first case a clear inwards component of the polarization P( - ) is observed by X-ray photoelectron spectroscopy and piezoresponse force microscopy. Composition analysis evidenced formation of Pb vacancies in the case of FM - P(( - ) )sample, consistent with hole formation near the surface, needed both to stabilize the inwards polarization state and to intermediate ferromagnetism between Mn2+ ions. The indirect exchange ferromagnetism mediated by holes is stronger, most probably because the interaction energy is proportional with the carrier effective mass. Also, whereas in the case of unsputtered substrate a stable surface Mn oxide is formed, defect formation by sputtering seems to favor Mn migration inside the sample. This also induces the formation of a thin film where ferromagnetism and the orientation of ferroelectric polarization might have the same origin, i. e. holes accumulated near the outer surface.

Ferroelectric field effect transistors (FeFETs) based on lead zirconate titanate (PZT) ferroelectric material and amorphous-indium-gallium-zinc oxide (a-IGZO) were developed and characterized. The PZT material was processed by a sol-gel method and then used as ferroelectric gate. The a-IGZO thin films, having the role of channel semiconductor, were deposited by radio-frequency magnetron sputtering, at a temperature of similar to 50 degrees C. Characteristics of a typical field effect transistor with SiO2 gate insulator, grown on highly doped silicon, and of the PZT-based FeFET were compared. It was proven that the FeFETs had promising performances in terms of I-on/I-off ratio (i.e., 10(6)) and IDS retention behavior.

500 nm thick silver-zinc oxide (Ag-ZnO) films were grown by electron beam evaporation on 316 L stainless steel (SS) substrate and on 150 nm thick Inconel 600 (IN600) interlayer. The films were annealed in air at 500 degrees C for 1 h. The morphological and structural analyses confirmed smooth, uniform, homogeneous and crack-free surfaces with nanocrystalline grain size for all films. The elemental composition analysis yielded up to 0.6 wt% Ag in Ag-ZnO/IN600 films. The ultraviolet-visible spectroscopy and Raman spectroscopy along with mechanical and electrochemical tests revealed improved optical, scratch resistance and electrochemical properties of Ag-ZnO/IN600 films than Ag-ZnO films. Ag-ZnO/IN600 and Ag-ZnO films exhibited higher antibiofilm activity against Staphylococcus aureus, Pseudomonas aeruginosa and Candida albicans pathogens, comparatively with IN600 films and SS substrate. The superior functional properties of Ag-ZnO/IN600 films suggest their potential for practical applications as antimicrobial and robust coatings on SS surface-contacting medical devices with limited exposure.

Highly defected tubular SiO2 is found to outperform the activity of TiO2-P25 and the SiO2-TiO2 composite in photocatalytic H-2 generation from methanol-water solution under simulated solar light AM 1.5. The enhanced performances of SiO2 come from the particularities of the reaction mechanism and ROS (reactive oxygen species) generation. The SiO2 exposed to light generates solely O-1(2) (singlet oxygen). The TiO2-P25 produces uniquely large quantities of OH radicals whereas the formation of O-2(-) is evidenced only over SiO2-TiO2, along with small amounts of OH. The TiO2 works as a photocatalyst by intermediation of OH radicals. In contrast, the organic substrate is activated on the surface of SiO2 by the intra-band gap, isolated, surface quantum defects. Distinct reaction mechanisms, involving the participation of photogenerated charges and ROS, are proposed. The material-related ROS production can be of great practical importance in fields such as biology (germ inactivation), medicine (photodynamic therapy by O-1(2)), and synthesis of oxygenated organic compounds of great added value.

Chalcogenide amorphous materials, such as GeTe, are known to exhibit deposition dependent optical and structural properties. The formation of a single and homogeneous amorphous GeTe (a-GeTe) phase is questionable since the deposited films can be mixtures of monoelemental nanoclusters. In this work, we employed two deposition techniques, pulsed laser deposition from a polycrystalline GeTe target and co-sputtering from two distinct Ge and Te targets, respectively, to obtain a-GeTe films. To improve the homogeneity of the amorphous phase obtained by magnetron sputtering, the substrate temperature was varied from room temperature up to 180 degrees C. The samples were investigated by X-ray diffraction, X-ray reflectometry, X-ray photoelectron spectroscopy and spectroscopic ellipsometry. It was found that the film mass density, optical bandgap, refractive index and absolute reflectivity become progressively larger with increasing substrate temperature, due to the minimization of voids fraction and the number of dangling bonds in the amorphous structure. Moreover, X-ray photoelectron spectroscopy results prove the formation of Ge-Te bonds and therefore of the GeTe alloy at the optimal substrate temperature of 180 degrees C. This study reveals the importance of optimizing the deposition conditions for obtaining a specific amorphous phase, which enables the atomic rearrangements responsible for fast phase-change needed in memory applications.

Ru@MNP-MWCNT catalysts were obtained via functionalization of nanostructured carbon-based carriers (ie, MWCNT) with base molecules (ie, 2-aminophenol and ethylenediamine) followed by the complexation with RuCl3. These structures demonstrated a highly efficient behavior for the selective wet oxidation of levulinic acid and glucose to succinic acid. However, to ensure an easy recovery and high recyclability the MWCNTs nanotubes were modified by incorporation of super-paramagnetic Fe3O4 nanoparticles into porous structure. Besides the catalytic performances the resulted composites showed a good mechanical resistance.

Zinc- (Zn) doped hydroxyapatite (HAp) were prepared by sol-gel method. Zinc-doped hydroxyapatite (ZnHAp) and HAp were analyzed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Rietveld analysis revealed that the HAp and 7ZnHAp powders obtained by sol-gel method have a monophasic hydroxyapatite structure belonging to the P6(3/m) spatial group. The results obtained from the ultrasound characterization of HAp and ZnHAp are also presented in this study. The effect of zinc concentration on properties that were deduced from ultrasonic measurements are studied in the case of a significant zinc concentration (x(Zn) = 0.07). From the values of the ultrasonic waves velocities were determined by the pairs of elastic coefficients of the suspensions (Young modulus E, Poisson coefficient nu), which have proven to be similar to those determined by other authors.