National Institute Of Materials Physics - Romania
Nanoscale Condensed Matter Laboratory
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articles found
51. N-Doped Defective Graphene from Biomass as Catalyst for CO2 Hydrogenation to Methane
Authors:
Jurca, B; Bucur, C; Primo, A; Concepcion, P; Parvulescu, VI; Garcia, H
Published: FEB 6 2019, DOI: 10.1002/cctc.201801984
Abstract: 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.
52. Particularities of trichloroethylene photocatalytic degradation over crystalline RbLaTa2O7 nanowire bundles grown by solid-state synthesis route
Authors:
Raciulete, M; Papa, F; Kawamoto, D; Munteanu, C; Culita, DC; Negrila, C; Atkinson, I; Bratan, V; Pandele-Cusu, J; Balint, I
Published: FEB 2019, DOI: 10.1016/j.jece.2018.11.034
Abstract: 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.
53. Bimodal mesoporous NiO/CeO2-delta-YSZ with enhanced carbon tolerance in catalytic partial oxidation of methane-Potential IT-SOFCs anode
Authors:
Somacescu, S; Cioatera, N; Osiceanu, P; Calderon-Moreno, JM; Ghica, C; Neatu, F; Florea, M
Published: FEB 2019, DOI: 10.1016/j.apcatb.2018.09.065
Abstract: In the present study we report on the activity, selectivity and stability of the bimodal mesoporous NiO/CeO2-delta-YSZ anodes for IT-SOFCs applications. These materials present high concentration of C3+ ions stably retained in the lattice, which proved to be efficient for the catalytic partial oxidation of CH4 to syngas in the temperature range 600-800 degrees C. The excellent carbon tolerance was proved by a comprehensive XPS analysis, which monitored the amount of carbon before and after catalytic partial oxidation of methane (CPOM) tests. The mesoporous anodes templated by hexadecyltrimethylammonium bromide (CTAB) and tripropylamine (TPA) were obtained using a hydrothermal synthesis route. The effect of Ni and Ce incorporation on the yttria stabilized zirconia (YSZ) structure, texture, morphology and surface chemistry was discussed and correlated with catalytic and electrochemical behavior. The exhaustive characterization of the bulk and surface properties of the catalysts have been accomplished by means of complementary methods: XRD, SEM / EDX / HR TEM, TGA / TPR, XPS. The electrochemical and catalytic performance were improved when the surface contains more reduced ceria and NiO was formed as secondary phase. These features lead to a large number of vacancies and consequently a better oxygen migration, which facilitate the carbon removal.
54. Spirobifluorene-based Porous Organic Polymers as Efficient Porous Supports for Pd and Pt for Selective Hydrogenation
Authors:
Trandafir, MM; Pop, L; Hadade, ND; Hristea, I; Teodorescu, CM; Krumeich, F; van Bokhoven, JA; Grosu, I; Parvulescu, VI
Published: JAN 9 2019, DOI: 10.1002/cctc.201801247
Abstract: 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.
55. PHOTO-ELECTRICAL PROPERTIES OF THIN FILMS WITH GE NANOPARTICLES EMBEDDED IN TIO2 MATRIX
Abstract: We present photo-electrical properties of thin films formed of Ge nanoparticles in TiO2 correlated with structure and morphology. The films co-deposited on Si using magnetron sputtering were annealed in conventional oven at 550 degrees C. We performed structure investigations by X-ray diffraction, transmission electron microscopy and measured current-voltage characteristics in dark and under illumination at different temperatures. We show that the films are formed of cubic Ge nanoparticles in nanostructured anatase TiO2 matrix. Also, (TiGe)O-2 with rutile structure was observed. The films have high photosensitivity under white light as the ratio between photo- and dark currents (-1 V) is of similar to 10(2).
56. Room temperature ferromagnetism and its correlation to ferroelectricity of manganese embedded in lead zirco-titanate
Authors:
Bucur, IC; Apostol, NG; Abramiuc, LE; Tanase, LC; Tache, CA; Lungu, GA; Costescu, RM; Chirila, CF; Trupina, L; Pintilie, L; Teodorescu, CM
Published: JAN 1 2019, DOI: 10.1016/j.tsf.2018.11.018
Abstract: 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.
57. Functional properties improvement of Ag-ZnO thin films using Inconel 600 interlayer produced by electron beam evaporation technique
Authors:
Lungu, MV; Sobetkii, A; Sobetkii, AA; Patroi, D; Prioteasa, P; Ion, I; Negrila, CC; Chifiriuc, MC
Published: DEC 1 2018, DOI: 10.1016/j.tsf.2018.09.055
Abstract: 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.
58. Delayed Transition to Coherent Emission in Nanolasers with Extended Gain Media
Authors:
Lohof, F; Barzel, R; Gartner, P; Gies, C
Published: NOV 26 2018, DOI: 10.1103/PhysRevApplied.10.054055
Abstract: The realization of high-beta lasers is one of the prime applications of cavity QED promising ultra-low thresholds, integrability, and reduced power consumption in the field of green photonics. In such nanolasers, spontaneous emission can play a central role even above the threshold. By going beyond rate-equation approaches, we revisit the definition of a laser threshold in terms of the input-output characteristics and the degree of coherence of the emission. We demonstrate that there are new regimes of cavity-QED lasing, realized, e.g., in high-Q nanolasers with extended gain material, for which the two can differ significantly such that coherence is reached at much higher pump powers than required to observe the thresholdlike intensity jump. Against the common perception, such devices do not benefit from high-beta factors in terms of power reduction, as a significant amount of stimulated emission is required to quieten the spontaneous emission noise.
59. Optoelectric charging-discharging of Ge nanocrystals in floating gate memory
Authors:
Palade, C; Slav, A; Lepadatu, AM; Maraloiu, AV; Dascalescu, I; Iftimie, S; Lazanu, S; Ciurea, ML; Stoica, T
Published: NOV 19 2018, DOI: 10.1063/1.5039554
Abstract: Photo-induced effects on charging and discharging of nanocrystals (NCs) in capacitor memories with Ge NCs in an HfO2 matrix as a floating gate layer are studied. The sequence of layers HfO2/Ge-HfO2/ HfO2 was deposited on a p-Si substrate using magnetron sputtering. Well separated Ge NCs are obtained after rapid thermal annealing at 600 degrees C. The optoelectric capacitor memories were fabricated with a semi-transparent electrode on top of the structure and an Al electrode on the back side of the Si substrate. Light illumination effects on hysteresis curves were investigated using different operation modes. The hysteresis window increases by increasing the light exposure time. The spectral dependence of the hysteresis window shows the maximum contribution of the light in the wavelength range of 950-1000 nm, corresponding to both contributions from the Si substrate and from Ge NCs. The stored information about the electrical and optical pulses is also investigated in the regime of the flat band potential measurements (retention measurements). It is shown that in our memory structure, the photo-effect on the memory retention corresponds to a tunnelling transfer of negative charges from the Si substrate to Ge NCs, up to a mean value of 1.6 electrons per NC. Published by AIP Publishing.
60. Particularities of photocatalysis and formation of reactive oxygen species on insulators and semiconductors: cases of SiO2, TiO2 and their composite SiO2-TiO2
Authors:
Anastasescu, C; Negrila, C; Angelescu, DG; Atkinson, I; Anastasescu, M; Spataru, N; Zaharescu, M; Balint, I
Published: NOV 7 2018, DOI: 10.1039/c8cy00991k
Abstract: 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.
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