National Institute Of Materials Physics - Romania

A series of five Cu(x)CeMgAlO mixed oxides with different copper contents (x) ranging from 6 to 18 at. % with respect to cations, but with fixed 10 at. % Ce and Mg/Al atomic ratio of 3, were prepared by thermal decomposition of layered double hydroxide (LDH) precursors at 750 degrees C. The solid containing 15 at. % Cu, i.e. Cu (15)CeMgAlO, was also calcined at 550 and 650 degrees C. Powder XRD was used to characterize the crystalline structure and SEM-EDX was used to monitor the morphology and chemical composition of both as prepared and calcined materials. Additionally, the textural properties and the reducibility of the mixed oxide catalysts were studied by nitrogen adsorption/desorption and temperature programmed reduction with hydrogen (H-2-TPR) techniques, respectively. X-ray photoelectron spectroscopy (XPS) was used to determine the chemical state of the elements on the catalyst surface and the diffuse reflectance UV-vis spectroscopy, to obtain information about the stereochemistry and aggregation of copper in the Cu-containing mixed oxides. Their catalytic properties in the total oxidation of methane, used as a volatile organic compound (VOC) model molecule, were evaluated and compared with those of an industrial Pd/Al2O3 catalyst. Their catalytic behavior was explained in correlation with their physicochemical properties. Cu(15)CeMgAlO mixed oxide was shown to be the most active catalyst in this series, with a T-50 (temperature corresponding to 50% methane conversion) value of only ca. 45 degrees C higher than that of a commercial Pd/Al2O3 catalyst. This difference becomes as low as ca. 25 degrees C for the Cu(15)CeMgAlO system calcined at 550 degrees C. The influences of the contact time and of the methane concentration in the feed gas on the catalytic performances of the Cu(15)CeMgAlO catalyst have been investigated and its good stability on stream was evidenced.

Controlled deposition of g-C3N4 films, used as photoelectrodes in PEC water splitting is still considered a challenge. In this paper, nanosheets of g-C3N4 were deposited on FTO and FTO/TiO2 substrates via spray coating method. This method allows the preparation of g-C3N4 films with a better exposure of nanosheet edges to the solution and light, favoring the photocatalytic process. The morphology, chemical composition and optical properties of these films were investigated, their behavior as photoanodes in photoelectrochemical water splitting being also evaluated. The results evidenced the formation of g-C3N4 films with an enhanced visible light absorption and improved photocatalytic activity. The interaction of these films with TiO2 substrate consists in the insertion of nitrogen species in the TiO2 lattice. A significant increase in bulk donor densities value correlated with a longer lifetime of photogenerated electrons was observed for TiO2/g-C3N4 photoanode. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Mixtures of nitrogen-doped titanium dioxide (TiO2:N) with different concentrations of Ag and/or SiO2 particles (0.5, 1 and 2 wt.%) were prepared in solid state by mechanico-chemical interactions. Using UV-VIS spectroscopy, Raman scattering, photoluminescence (PL) and photoluminescence excitation (PLE), the influence of the particles on the host material is evaluated. UV-VIS spectroscopy studies indicate a TiO2:N band gap shift to the UV range with increasing concentrations of SiO2 and Ag particles. PL intensities decrease with increasing concentrations of Ag and/or SiO2 particles in the TiO2:N host matrix, which in turn could effectively restrict the electron and hole recombination. To explain these processes, the different de-excitation ways will be advanced, taking into account the energy levels diagram of TiO2:N/Ag, TiO2:N/SiO2 and TiO2:N/Ag/SiO2 systems. PLE spectra show a gradual decrease in their relative intensities after 165 min of continuous irradiation due to photosensitivity of TiO2:N. The plasmonic effect of Ag particles in the TiO2:N/Ag system is highlighted for the first time by PLE studies.

Multilayer structures comprising of SiO2/SiGe/SiO2 and containing SiGe nanoparticles were obtained by depositing SiO2 layers using reactive direct current magnetron sputtering (dcMS), whereas, Si and Ge were co-sputtered using dcMS and high-power impulse magnetron sputtering (HiPIMS). The as-grown structures subsequently underwent rapid thermal annealing (550-900 degrees C for 1 min) in N-2 ambient atmosphere. The structures were investigated using X-ray diffraction, high-resolution transmission electron microscopy together with spectral photocurrent measurements, to explore structural changes and corresponding properties. It is observed that the employment of HiPIMS facilitates the formation of SiGe nanoparticles (2.1 +/- 0.8 nm) in the as-grown structure, and that presence of such nanoparticles acts as a seed for heterogeneous nucleation, which upon annealing results in the periodically arranged columnar self-assembly of SiGe core-shell nanocrystals. An increase in photocurrent intensity by more than an order of magnitude was achieved by annealing. Furthermore, a detailed discussion is provided on strain development within the structures, the consequential interface characteristics and its effect on the photocurrent spectra.

Metal-organic frameworks (MOFs) capable of mobility and manipulation are attractive materials for potential applications in targeted drug delivery, catalysis, and small-scale machines. One way of rendering MOFs navigable is incorporating magnetically responsive nanostructures, which usually involve at least two preparation steps: the growth of the magnetic nanomaterial and its incorporation during the synthesis of the MOF crystals. Now, by using optimal combinations of salts and ligands, zeolitic imidazolate framework composite structures with ferrimagnetic behavior can be readily obtained via a one-step synthetic procedure, that is, without the incorporation of extrinsic magnetic components. The ferrimagnetism of the composite originates from binary oxides of iron and transition metals such as cobalt. This approach exhibits similarities to the natural mineralization of iron oxide species, as is observed in ores and in biomineralization.

New thermotropic lanthanidomesogens based on Eu(III), Sm(III) and Tb(III) with N-alkylated 4-pyridones mesogenic ligands, having two cyanobiphenyl groups attached via long alkoxy spacers, with 6, 9 and 10 carbons atoms in 3,5-positions of a benzyl unit, have been designed and investigated. The liquid crystal behavior was assessed by differential scanning calorimetry, the mesophases being assigned by polarized light microscopy based on their characteristic textures and confirmed by variable temperature X-ray powder diffraction analysis. The three N-alkylated 4-pyridones nematic ligands reacted with lanthanide nitrates to yield new lanthanidomesogens with a stable and reproducible smectic A phase up to 125 degrees C. The emission spectra of the complexes have shown the characteristic emission of the lanthanide trivalent ions, over the entire temperature range of SmA phase up to isotropic state. The dielectric spectroscopy measurements performed in the temperature range of existence of the liquid crystal phase, both in the low frequency (LF) domain 0.01-10 MHz and in the high frequency (HF) range, 1 MHz-3 GHz, revealed three dipolar relaxation processes. The characteristic times have been obtained by fitting the spectra of the dielectric loss with a two component Havriliak-Negami function. The activation constant/energy was determined from the Vogel-Fiilcher-Tammann law. (C) 2019 Elsevier B.V. All rights reserved.

We study the electronic transport through a pair of distant nanosystems (S-a and S-b) embedded in a single-mode cavity. Each system is connected to source and drain particle reservoirs and the electron-photon coupling is described by the Tavis-Cummings model. The generalized master equation approach provides the reduced density operator of the double system in the dressed-states basis. It is shown that the photon-mediated coupling between the two subsystems leaves a signature on their transient and steady-state currents. In particular, a suitable bias applied on subsystem S-b induces a photon-assisted current in the other subsystem S-a which is otherwise in the Coulomb blockade. We also predict that a transient current passing through one subsystem triggers a charge transfer between the optically active levels of the second subsystem even if the latter is not connected to the leads. As a result of backaction, the transient current through the open system develops Rabi oscillations (ROs) whose period depends on the initial state of the closed system.

Control of structural coupling at complex-oxide interfaces is a powerful platform for creating ultrathin layers with electronic and magnetic properties unattainable in the bulk. However, with the capability to design and control the electronic structure of such buried layers and interfaces at a unit-cell level, a new challenge emerges to be able to probe these engineered emergent phenomena with depth-dependent atomic resolution as well as element- and orbital selectivity. Here, we utilize a combination of core-level and valence-band soft x-ray standing-wave photoemission spectroscopy, in conjunction with scanning transmission electron microscopy, to probe the depth-dependent and single-unit-cell resolved electronic structure of an isovalent manganite superlattice [Eu0.7Sr0.3MnO3/La0.7Sr0.3MnO3] x 15 wherein the electronic-structural properties are intentionally modulated with depth via engineered oxygen octahedra rotations/tilts and A-site displacements. Our unit-cell resolved measurements reveal significant transformations in the local chemical and electronic valence-band states, which are consistent with the layer-resolved first-principles theoretical calculations, thus opening the door for future depth-resolved studies of a wide variety of heteroengineered material systems.

SiGe nanoparticles dispersed in a dielectric matrix exhibit properties different from those of bulk and have shown great potential in devices for application in advanced optoelectronics. Annealing is a common fabrication step used to increase crystallinity and to form nanoparticles in such a system. A frequent downside of such annealing treatment is the formation of insulating SiO2 layer at the matrix/SiGe interface, degrading the optical properties of the structure. An annealing process that could bypass this downside would therefore be of great interest. In this work, a short-time furnace annealing of a SiGe/TiO2 system is applied to obtain SiGe nanoparticles without formation of the undesired SiO2 layer between the dielectric matrix (TiO2) and SiGe. The structures were prepared by depositing alternate layers of TiO2 and SiGe films, using direct-current magnetron sputtering technique. A wide range spectral response with a response-threshold up to similar to 1300 nm was obtained, accompanied with an increase in photo-response of more than two-orders of magnitude. Scanning electron microscopy, transmission electron microscopy, energy-dispersive x-ray spectroscopy and grazing incidence x-ray diffraction were used to analyze the morphological changes in respective structures. Photoconductive properties were studied by measuring photocurrent spectra using applied dc-voltages at various temperatures.

Nanoclustered Pd (2 mol%) was used to decorate Zn doped SnO2 (10 mol% Zn) in order to increase its sensing performances. Zn doped SnO2 built from nanoparticles was prepared by a hydrothermal method using a nonionic surfactant -Brij52 and Tripropylamine (TPA) as co-templates. The presence of well-dispersed Zn2+ ions in the SnO2 matrix leads to a nonstoichiometric surface. Pd was deposited by subsequent wet impregnation using hydrazine as reducing agent. The as obtained powders were deposited as thick layers onto commercial substrates, in order to obtain the sensitive structures. The coexistence of a mixture of valence states (Pd-0, Pd2+ and Pd4+) was highlighted on the surface of the as prepared layers. Several aspects have been followed regarding the Zn and Pd dispersion into the SnO2 matrix: the large scale and low scale morphology (SEM and TEM/HRTEM) in relation with the synthesis route, the obtained crystallographic phases (XRD, SAED) and the way in which the Zn2+ ions are inserted into the SnO2 structure (XRD, XPS, EPR), the spatial distribution of the added chemical elements, Zn and Pd (SEM, STEM, EDS). All these morphological and structural aspects, as well as the Pd surface chemistry, have been correlated with the sensing properties of the nanostructured materials under controlled gas atmosphere. Through this study, we could harvest the specific role of the aforementioned loadings towards selective detection of low NO2 concentrations, between 350 ppb to 5 ppm, at low operating temperature of 100 degrees C, for infield conditions.