National Institute Of Materials Physics - Romania

Hydrides have emerged as strong candidates for energy storage applications and their study has attracted wide interest in both the academic and industry sectors. With clear advantages due to the solid-state storage of hydrogen, hydrides and in particular complex hydrides have the ability to tackle environmental pollution by offering the alternative of a clean energy source: hydrogen. However, several drawbacks have detracted this material from going mainstream, and some of these shortcomings have been addressed by nanostructuring/nanoconfinement strategies. With the enhancement of thermodynamic and/or kinetic behavior, nanosized complex hydrides (borohydrides and alanates) have recently conquered new estate in the hydrogen storage field. The current review aims to present the most recent results, many of which illustrate the feasibility of using complex hydrides for the generation of molecular hydrogen in conditions suitable for vehicular and stationary applications. Nanostructuring strategies, either in the pristine or nanoconfined state, coupled with a proper catalyst and the choice of host material can potentially yield a robust nanocomposite to reliably produce H-2 in a reversible manner. The key element to tackle for current and future research efforts remains the reproducible means to store H-2, which will build up towards a viable hydrogen economy goal. The most recent trends and future prospects will be presented herein.

The iron oxide nanoparticles coated with different surface coatings were studied and characterized by multiple physicochemical and biological methods. The present paper aims at estimating the toxicity in vitro and in vivo of dextran coated iron oxide aqueous magnetic fluids. The in vitro studies were conducted by quantifying the viability of HeLa cells after their incubation with the samples (concentrations of 62.5-125-250-500 mu g/mL at different time intervals). The estimation of the toxicity in vivo of administering dextran coated iron oxide aqueous magnetic fluids (DIO-AMF) with hydrodynamic diameter of 25.73 +/- 4 nm to Male Brown Norway rats has been made. Different concentrations (62.5-125-250-500 mu g/mL) of dextran coated iron oxide aqueous magnetic fluids were administered for 7 consecutive days. Hematology and biochemistry of the Male Brown Norway rats assessment was performed at various time intervals (24-72 h and 21-28 days) after intra-peritoneal injection. The results showed that high concentrations of DIO-AMF (250 and 500 mu g/mL) significantly increased white blood cells, red blood cells, hemoglobin and hematocrit compared to the values obtained for the control group (p < 0.05). Moreover, following the administration of DIO-AMF, the levels of alkaline phosphatase and aspartate aminotransferase increased compared to the control group (p < 0.05). After DIO-AMF administration, no significant difference was observed in the levels of alanine aminotransferase, gamma-glutamyl transpeptidase, urea and creatinine compared to the control group (p < 0.05). The results of the present study showed that dextran coated iron oxide aqueous magnetic fluids in concentrations lower than 250 mu g/mL are reliable for medical and pharmaceutical applications.

Glassy nanocomposites containing Yb3+/Er3+-doped GdF3 and LiGdF4 nanocrystals have been prepared by controlled crystallization of the xerogel and the structural, up-conversion luminescence, and magnetic properties were analyzed and discussed. Structural and morphological analysis showed uniform distribution of both GdF3 and LiGdF4 nanocrystals (tens of nm size), embedded in silica glass matrix as the result of thermal decomposition of the trifluoracetates, revealed as a strong exothermic peak at about 300 degrees C; the Li-ions co-doping showed a strong influence on the GdF3 and LiGdF4 nanocrystalline fraction. The energy dispersive spectrometry mapping showed Gd, F and Yb, Er within the nanocrystals but not in the silica glass matrix. X-ray diffraction pattern analysis indicated the crystalline lattice distortion consistent with the Yb/Er incorporation in both fluoride nanocrystals. The "green" ((H-2(11/2), S-4(3/2)) -> I-4(15/2)) and "red" (F-4(9/2)-> I-4(15/2)) up-conversion luminescences at 525, 545, and 660 nm observed under 980 nm laser light pumping were assigned to the Er3+ ions deexcitation through a two-photon process. The magnetic properties of the nanocomposite are strongly temperature dependent. The magnetization hysteresis loops show a ferromagnetic behavior at low temperatures (5K) related to the rare-earth ions contribution and the saturation magnetization of 39 emu/g. At 300 K a paramagnetic behavior was observed that was ascribed to the non-interacting localized nature of the magnetic moment of the rare-earth ions. Hence, such novel, multifunctional magnetic and optical materials can allow the intertwining between magnetism and photonics and might offer new opportunities for new magneto-optical device development.

Featuring a high hydrogen storage content of up to 20 wt%, complex metal borohydrides remain promising solid state hydrogen storage materials, with the real prospect of reversible behavior for a zero-emission economy. However, the thermodynamic barriers and sluggish kinetics are still barriers to overcome. In this context, nanoconfinement has provided a reliable method to improve the behavior of hydrogen storage materials. The present work describes the thermodynamic and kinetic enhancements of LiBH4 nanoconfined in MFe2O4 (M=Co, Ni) ferrite-catalyzed graphene host. Composites of LiBH4-catalysts were prepared by melt infiltration and investigated by X-ray diffraction, TEM, STEM-EDS and TPD. The role of ferrite additives, metal precursor treatment (Ar, Ar/H-2) and the effect on hydrogen storage parameters are discussed. The thermodynamic parameters for the most promising composite LiBH4-graphene-NiFe2O4 (Ar) were investigated by Kissinger plot method, revealing an E-A = 127 kJ/mol, significantly lower than that of neat LiBH4 (170 kJ/mol). The reversible H-2 content of LiBH4-graphene-NiFe2O4 (Ar) after 5 a/d cycles was similar to 6.14 wt%, in line with DOE's target of 5.5 wt% storage capacity, while exhibiting the lowest desorption temperature peak of 349 degrees C. The composites with catalysts treated in Ar have lower desorption temperature due to better catalyst dispersion than using H-2/Ar.

We present the multifrequency measurements of the surface resistance of spark-plasma-sintered MgB2 performed through a dielectric loaded resonator operating at 16.5 and 26.7 GHz. By normally applying magnetic fields <= 1.2 T to the sample surface, we drove it in the mixed state. By means of data-rooted analysis, we found that the sample vortex dynamics could be fully described within a single-component approach. Pinning phenomena were present and characterized by a depinning frequency smaller than the measurement ones. The multiband nature of the superconductor emerged in the flux-flow resistivity, whose field dependence could be interpreted well within theoretical models. By exploiting them, the upper critical field was extracted in the low-temperature range, which exhibited a consistent temperature trend with the values obtained at the onset of the resistive transition near Tc, and was well in line with literature data on other polycrystalline samples.

The p-n junctions are the building blocks of nowadays electronic devices. The n- or p-type conductivity is obtained in classic semiconductors, like Si, by doping with atoms acting as donors or acceptors, respectively. Doping was used in ferroelectrics to influence the transition temperature, magnitude of some physical properties, but not necessarily conduction type. Therefore, comprehensive studies to obtain true ferroelectric p-n junctions by controlled doping are missing. Recently, it has been shown that Pb(Zr0.2Ti0.8)O-3 films doped with & AP;1% atomic Nb (n-type doping) or Fe (p-type doping) have different orientations of polarization in the as-grown state. Knowing that polarization orientation depends on doping type, the next step is to build ferroelectric p-n homojunctions and to study their properties in relation to ferroelectric polarization. p-n and n-p structures were grown for this purpose by successive deposition of Nb-doped and Fe-doped Pb(Zr,Ti)O-3 layers with different thicknesses. We find that these p-n homojunctions are ferroelectric, but the magnitude of the polarization and coercive field, as well as the dominant polarization orientation in the as-grown state, depend on the conduction type of the first grown layer. The I-V characteristics are quasi-linear, although the interfaces with the electrodes behaves as Schottky contacts. The resistance extracted from the I-V characteristics displays an exponential dependence on temperature, with an activation energy in the range of 0.14-0.17 eV. These results are explained assuming that the total current in the junction is the total of electron and hole injections at the electrode interfaces. It is shown that for relatively low doping concentrations, the current density contains a dominant term with a linear voltage dependence and an exponential temperature dependence, as observed experimentally, and a secondary (correction) term that is dependent on the free carrier density and can induce non-linear voltage dependence when this density is significant.

Cu2SnSe3 (CTSe) is a polyvalent material that can be used as an absorber layer for thin film solar cells or as a starting layer for the synthesis of CZTSe or CZTSSe compounds. Obtaining CTSe single phase films with opti-mized properties for thin film solar cells is a difficult task. A systematic study using both metallic and binary chalcogenides precursors for the formation of the CTSe phase was not performed. The films consisting of four different stacks (Sn\Cu, SnSe2\Cu, Sn\Cu2Se, and SnSe2\Cu2Se) were prepared by magnetron sputtering on soda lime glass (SLG) and molybdenum (Mo) coated SLG substrates, followed by annealing at 550 degrees C under Sn + Se atmosphere. X-ray diffraction and Raman spectroscopy results indicated the formation of a single CTSe phase in most of the stacks deposited on both substrates. Scanning electron microscopy images showed compact surfaces with large grains in the films deposited on Mo substrate, while the films on SLG have more voids on their sur-faces. The elemental analysis measured by energy dispersive spectroscopy revealed stoichiometric films on Mo, and copper and tin rich compositions on SLG substrates. The band gap values inferred by conventional spec-troscopy are between 0.81 and 1.95 eV. It was found that the SnSe2\Cu and Sn\Cu2Se stacks are preferred for the formation of a single CTSe phase, with dense surface morphology, a stoichiometric composition, and an optimal absorber layer band gap. This study opens the way to comprehend the formation reactions during the seleni-zation of metallic and binary chalcogenides precursors towards the optimization of kesterite absorber for photovoltaic device fabrication.

The objective of this study consisted of the development of new materials with antimicrobial properties at the nanometric scale that could lead to an increase in therapeutic efficacy and reduction of toxic side effects. This work focuses on obtaining and characterizing stable suspensions with narrow size distribution with antimicrobial properties. The stability of the suspensions obtained by an adapted co-precipitation method was evaluated by ultrasonic measurements. The size and size distribution of the particle populations were determined using scanning electron microscopy (SEM), and dynamic light scattering (DLS). Both methods of analysis showed a narrow distribution of particles. DLS gave a monomodal distribution with hydrodynamic diameters around 38 nm for ciprofloxacin embedded in silver doped hydroxyapatite (AgHA-C) and 45.7 nm for tetracycline embedded in silver doped hydroxyapatite (AgHA-T). The average diameters calculated from SEM were 17 nm for AgHA-C and 19 nm for AgHA-T. Both Ciprofloxacin and Tetracycline influenced the hydroxyapatite structure, which led to the appearance of new vibrational bands characteristic of the specific chemical composition in the FTIR spectrum. The antimicrobial properties of the AgHA-C and AgHA-T suspensions were assessed using the most common reference microbial strains Staphylococcus aureus ATCC 25923, Escherichia coli ATCC 25922, and Candida albicans ATCC 10231. The results of the in vitro antimicrobial assays determined that the AgHA-C and AgHA-T suspensions exhibited exceptional antimicrobial activity. Moreover, the data revealed that the antimicrobial activity increased with the increase of the incubation time.

Photocatalytic conversion of H2O, CO2 and N-2 represents one promising approach to harvest and store solar energy, for which efficient visible light responsive semiconductors are inevitable. Often, the presence of a small amount of an additional component called a "cocatalyst", is required to synergistically enhance the performance of the photocatalyst. Tremendous efforts were made in the past to identify inexpensive materials to be used as cocatalysts, for which metal oxides (MOs) are one of the traditional choices. Among alternative categories of materials investigated, the recently discovered MXenes display enormous potential owing to their unique 2D layered structure, tuneable composition, abundant surface functionalities and superior electronic conductivity. Specifically, MOs and MXenes encompass a variety of distinct as well as analogous characteristics that allows them to be tailored to different extents. Unfortunately, a comprehensive overview covering the synthetic, structural and photocatalytic aspects of MOs and MXenes is not available as of now. Herein, we intend to summarize the progress achieved so far in these two families of materials to be used as cocatalysts for the photoconversion of H2O, CO2 and N-2. Followed by a general introduction, we briefly outline the fundamental principles and the role of cocatalysts in photocatalytic reactions. A discussion regarding the use of MOs and MXenes as cocatalysts for the conversion of H2O, CO2 and N-2 is then provided in separate sections. Critical assessment regarding structure and morphology control, surface properties and stability concerns can not only help to recognize the challenges that limit further advancement, but can also highlight the future research directions of these materials for the effective transformation of H2O, CO2 and N-2.

In this work, Tungsten(W)-doped TiO2 nanoparticles were synthesized using the sol-gel method and were used as electrode materials in supercapacitor applications. The structural and morphological properties of the prepared samples were analyzed by means of XRD, STEM, TEM, and XPS. The analysis of the defect centers was carried out using EPR spectroscopy. The electrochemical analysis of the assembled supercapacitor was done using cyclic voltammetry, galvanostatic cycling with potential limitation technique, potentiostatic electrochemical impedance spectroscopy, and voltage-holding experiments. All the presented samples showed paramagnetic defects in the EPR analysis, while 0.5% W-doped TiO2 showed a maximum signal intensity. The supercapacitor performance from the synthesized electrode material showed highly encouraging results. The equivalent series resistance (R-s) value for all the designs showed values under "1 omega,' which reflects high conductivity. As the maximum EPR intensity comes from TiO2 doped with 0.5% W, the supercapacitor performance of this sample was tested with a newly designed five-electrode system. This design showed superior performance compared to any other used designs with a specific capacitance of 25.5 F g(-1), with an energy density of 14.16 Wh kg (-1 )at 302 kW kg (-1).