National Institute Of Materials Physics - Romania

In order to understand the role of ambient humidity on NO2 detection, electrical resistance and work function changes were recorded simultaneously on ZnO-Eu2O3 material. Thus, surface band bending and electron affinity could be evaluated, according to the Schottky model. The lack of electron affinity changes during NO2 exposure in dry air conditions, reveals that only the free charge concentration is affected. Exposure to NO2 in humid background leads to an increase in sensor signals and a significant change in the electron affinity as well. This effect suggests an interaction between NO2 and surface hydroxyl species; thereby additional charge carriers are involved in the overall sensing process. High resolution XPS analysis proves the presence of Eu solely in the 3(+) oxidation state before and after NO2 exposure. A gas-sensing interaction mechanism has been proposed. (C) 2013 Elsevier B.V. All rights reserved.

Nanocrystals (NCs) of II-VI semiconductors of few nanometers average size, called quantum dots (QDs), are now intensely investigated as radiation detectors. Besides the expected quantum confinement and influence of surface states, our electron paramagnetic resonance investigations of cZnS QDs doped with Mn2+ ions, correlated with structural data, underline that other properties should be also taken into consideration in developing the II VI semiconductor QDs as radiation detectors. Thus, the preferential localization of Mn2+ in the core of the cubic ZnS QDs at substitutional Zn2+ cation sites next to a stacking lattice defect is expected to lead, besides changes in the impurity energy levels, to specific aggregation properties. An outer shell of different composition can also influence the structural properties of the QDs core with effects on the optical properties as well. (C) 2013 Elsevier Ltd. All rights reserved.

Nanocomposites based on TiO2 aerogel and Ag nanoparticles have been successfully obtained through different synthesis methods and their specific surface areas have been determined by N-2 sorption (BET method). The photocatalytic potential for salicylic acid degradation has been evaluated. It was found that under visible light irradiation, all synthesized nanocomposites exhibit higher photocatalytic activity than the commercially available Aeroxide P25. By correlating the structural parameters with the photocatalytic performances, it has been found that the Ag nanoparticles and brookite phase presence alongside the anatase play important roles on the visible photocatalysts behavior. For the Ag containing samples with mixed anatase brookite phases, it has been observed that the visible photocatalytic performance decreases with the increase in brookite crystalline phase content. On the other hand, the addition of Ag nanoparticles results, as expected, in a clear enhancement of the visible photocatalytic activity. (C) 2013 Elsevier B.V. All rights reserved.

We report results of noncellular tests, revealing the occurrence of photocatalytic interactions between titanium dioxide (TiO2, titania) nanoparticles and the MTT [3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium-bromide] cytotoxicity indicator. These interactions induce the reduction of MTT and formation of purple formazan under biologically relevant conditions. Classical MU assays have been performed to evaluate the production of formazan in DMEM-F12 and RPMI-1640 cell culture media (containing 10% fetal bovine serum-FBS) treated with Degussa-P25 TiO2 nanoparticles, in the absence of cells. The colorimetric determinations revealed the noncellular MU to formazan transformation induced by TiO2 nanoparticles, under conditions commonly used for in vitro cytotoxicity testing of nanomaterials. The formazan precipitation was found to be proportional to the TiO2 concentration, being enhanced under laboratory daylight exposure. The photocatalytic nature of the studied effect was assessed under UV irradiation at 365 nm. The biological significance of the reported reaction was established with respect to cellular reference experiments performed on V79-4, HeLa and B16 cell lines. The results show false viability increases with up to 14% (for TiO2 concentrations generally higher than 50 mu g/ml), induced by the TiO2-MTT reaction. This type of artifacts may lead to underestimated toxicity or false proliferation results. (C) 2013 Elsevier Ltd. All rights reserved.

High aspect ratio nanowires of Ni-Cu alloys have been synthesized by potentiostatic electrochemical deposition in etched ion-track membranes. The nickel-to-copper ratio in the nanowires was controlled via the deposition potential and electrochemical bath composition. We present a detailed study of nanowire properties including morphology, composition, and magnetic behavior. We report the magnetic configurations measured as function of the nanowire composition and discuss domain formation, anisotropy aspects, and local easy axis distributions.

The growth of gold layers on Pb(Zr,Ti)O-3 (PZT) deposited on SrTiO3 is investigated by X-ray photoelectron spectroscopy in the Au thickness range 2-100 angstrom. Two phases are identified, with compositions close to nominal PZT. The 'standard' phase is represented by all binding energies (Pb 4f, Ti 2p, Zr 3d, O 1s) sensibly equal to the nominal values for PZT, whereas the 'charged' phase exhibits all core levels are shifted by similar to 1 eV toward higher binding energies. By taking into account also scanning probe microscopy images together with recent photoemission results, the 'charged' phase belongs to P(+) regions of PZT, whereas the 'normal' phase corresponds to regions with no net ferroelectric polarization perpendicular to the surface. Au deposition proceeds in a band bending of Phi(PZT) - Phi(Au) similar to 0.4-0.5 eV for both phases, identified as similar shifts toward higher binding energies of all Pb, Ti, Zr, O core levels with Au deposition. The Au 4f core level exhibits also an unusually low binding energy component 1 eV below the 'nominal' Au 4f binding energy position (metal Au). This implies the existence of negatively charged gold, or electron transfer from PZT to Au, although the 'normal' PZT phase have a higher work function, as it is derived from the band bending. Most probably this charge transfer occurs toward Au nanoparticles, which have even higher ionization energies. High resolution transmission electron microscopy evidenced the formation of such isolated nanoparticles. (C) 2013 Elsevier B.V. All rights reserved.

We investigated the influence of rare earth (RE) additions on the structural, dielectric, magnetic and magnetostrictive properties of cobalt ferrite bulk materials. Three lanthanide ions with different ionic radii and magnetic properties were used as dopants: Dy, Gd, La. The structural properties of the sintered samples were investigated using X-ray diffraction, Raman spectroscopy and scanning electron microscopy. The room temperature hysteresis loops were obtained using a vibrating sample magnetometer. The frequency dependence of dielectric permittivity and tangent loss was investigated in the 20 Hz-20 kHz range. The variation of the magnetoelectric response with applied dc magnetic field was analyzed. The insertion of rare earth elements influenced the structural characteristics of the samples (density, cell edge, porosity) and the magnetic and electric properties. An increase in coercive field and a decrease in saturation magnetization and magnetostriction coefficient were observed. These results can be partially explained by the weaker nature of the RE3+-Fe3+ interaction compared to Fe3+-Fe3+ interaction and to the antiferromagnetic alignment of the REFeO3 second phase observed in the diffraction patterns after sintering process. (C) 2012 Elsevier BY. All rights reserved.

Postsynthetic modification of [Cu2(mand)2(hmt)] (mand=mandelic acid, hmt=hexamethylenetetramine) with a chiral, dimeric chromium(III)salen complex led to a robust structure. Characterization of this new material showed that it perfectly preserved the textural and structural properties of the parent metalorganic framework (MOF). Although epoxidation of trans-methyl cinnamate with hydrogen peroxide led to copper leaching of 23%, experiments performed with N-methylmorpholine-N-oxide indicated no leaching, even after 72h of exposure. The obtained chiral MOF is an effective catalyst for the enantioselective epoxidation of trans-methyl cinnamate and leads to (2R,3S)-phenylglycidate with a high enantiomeric excess at room temperature.

Cobalt environment and magnetic defects nature in hydrothermal synthesized anatase CoxTi1-xO2 nanopowders (0 <= x <= 0.1) are investigated by x-ray diffraction and a variety of spectroscopic techniques. One shows that cobalt is partially inserted in the anatase lattice, as Co2+ ions located on substitutional and interstitial sites. The fraction of the diluted Co is limited to 3 at.% for x >= 0.05, while the rest of the Co atoms gather into Co3O4 clusters. As found by electron paramagnetic resonance, the Co doping brings about hole-and electron-excess defects. (C) 2013 AIP Publishing LLC [http://dx.doi.org/10.1063/1.4802819]

TiO2-Au aerogels containing different amounts of gold nanoparticles of different sizes (5 and 16 nm) were successfully synthesized using a sol-gel procedure, and were tested for salicylic acid photo-degradation under UV irradiation. The structure and morphology of the obtained materials were investigated using X-ray diffraction, transmission electron microscopy, and N-2 adsorption-desorption measurements. UV-Vis spectroscopy was used to study the optical properties. The effects of the gold nanoparticles on the TiO2 crystallization process were twofold, as follows: (i) the number of crystallized zones was strongly related to the concentration of the gold nanoparticles, and (ii) the smaller gold particles increased the time taken for the crystallization of the samples. It was found that the noble metal-doped samples exhibited higher degradation rates compared with bare titania. It was found that the most active photocatalyst in each studied system was the sample with the highest concentration of gold nanoparticles. Additionally, the highest degradation rate value was obtained with the smallest Au nanoparticles (46.4 x 10(-3) mu mol/(L.s). (C) 2013, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier By. All rights reserved.