National Institute Of Materials Physics - Romania

Multifunctional materials integrating optical and electric properties into a composite or into a doped single-phase material have attracted much attention from scientists for future optoelectronic devices. In this work, polycrystalline Ba1-xTbxTiO3, x = 0.00, 0.01 and 0.05 materials were synthesized by hydrothermal route and their photoluminescence and dielectric properties were studied. The as-prepared powders showed a microstructure consisting of grains with the shape of cube; and average particle size ranging from 75 nm to 150 nm. The investigated temperature dependence of dielectric permittivity of Ba1-xTbxTiO3 ceramics revealed a decrease of the Curie temperature (Tc) with increasing terbium content, and a more pronounced degree of diffuseness of phase transition. The resistivity at room temperature was discussed in terms of positive temperature coefficient of resistance (PTRC) effect. UV-vis reflectance spectra of Ba1-xTbxTiO3 samples showed a decrease of the band gap energy with the increase of Tb amount, due to the band-gap narrowing effect. The photoluminescence spectra recorded for Tb doped BaTiO3 materials, at 80 K, evidenced the typical f-f luminescence lines of the Tb3+ accompanied the broad luminescence band at about 425 nm due to self-trapped exciton recombination. These results demonstrated that the terbium enhances the dielectric properties and photoluminescence simultaneously, being suitable for electronic applications. (C) 2021 Elsevier B.V. All rights reserved.

Structural and functional changes induced by TiO2 addition to spherical zinc selenide together with lysozyme adsorption lead to valuable bioinorganic catalysts with enhanced activity. Spherical zinc selenide and its composite with TiO2 were obtained by hydrothermal method and subsequently modified by lysozyme adsorption. Morphological, structural and functional characteristics of zinc selenide based materials (ZnSe, TiO2-ZnSe) and their hybrids with lysozyme (Lys/ZnSe, Lys/TiO2-ZnSe) were investigated. TiO2 addition to ZnSe results in significant changes of surface composition, electrochemical behavior and lysozyme retention capacity. The lysozyme modified ZnSe and TiO2-ZnSe surfaces doubles the biocatalysts efficiency for 4-Methylumbelliferyl p-D-N,N',N ''-triacetylchitotrioside hydrolysis reaction compared to free lysozyme.

Three-dimensional graphene foam (3D-GrFoam) is a highly porous structure and sustained lattice formed by graphene layers with sp(2) and sp(3) hybridized carbon. In this work, chemical vapor deposition (CVD)-grown 3D-GrFoam was nitrogen-doped and platinum functionalized using hydrothermal treatment with different reducing agents (i.e., urea, hydrazine, ammonia, and dihydrogen hexachloroplatinate (IV) hydrate, respectively). X-ray photoelectron spectroscopy (XPS) survey showed that the most electrochemically active nitrogen-doped sample (GrFoam3N) contained 1.8 at % of N, and it exhibited a 172 mV dec(-1) Tafel plot associated with the Volmer-Heyrovsky hydrogen evolution (HER) mechanism in 0.1 M KOH. By the hydrothermal process, 0.2 at % of platinum was anchored to the graphene foam surface, and the resultant sample of GrFoamPt yielded a value of 80 mV dec(-1) Tafel associated with the Volmer-Tafel HER mechanism. Furthermore, Raman and infrared spectroscopy analysis, as well as scanning electron microscopy (SEM) were carried out to understand the structure of the samples.

Preventing and controlling the spread of multidrug-resistant (MDR) bacteria implicated in healthcare-associated infections is the greatest challenge of the health systems. In recent decades, research has shown the need for passive antibacterial protection of surfaces in order to reduce the microbial load and microbial biofilm development, frequently associated with transmission of infections. The aim of the present study is to analyze the efficiency of photocatalytic antimicrobial protection methods of surfaces using the new photocatalytic paint activated by light in the visible spectrum. The new composition is characterized by a wide range of analytical methods, such as UV-VIS spectroscopy, electron microscopy (SEM), X-ray powder diffraction (PXRD) or X-ray photoelectron spectroscopy (XPS). The photocatalytic activity in the UV-A was compared with the one in the visible light spectrum using an internal method developed on the basis of DIN 52980: 2008-10 standard and ISO 10678-2010 standard. Migration of metal ions in the composition was tested based on SR EN1186-3: 2003 standard. The new photocatalytic antimicrobial method uses a type of photocatalytic paint that is active in the visible spectral range and generates reactive oxygen species with inhibitory effect against all tested microbial strains.

Zn-Fe-O nanoparticle systems (Z3F, Z20F and Z60F) were produced by changing the Zn:Fe ratio (0.97 : 0.03, 0.8 : 0.2 and 0.4 : 0.6 in at%, respectively) in Zn(ii)-Fe(iii)-carboxylate precursors. According to X-ray diffraction, Z60F is nearly single-phase ZnFe2O4 (5.9 nm crystallite size), Z20F is a ZnO/ZnFe2O4 nanocomposite consisting of 48.8% ZnFe2O4 (4.7 nm crystallite size), and Z3F is apparently pure ZnO (9.5 nm). We found evidence for a ZnFe2O4 spinel of high inversion degree (80-100%) and with superparamagnetic (SPM) behaviour at room temperature in all three samples by a remarkable correlation between HRTEM, FTIR, XPS, Mossbauer and magnetization analyses. Iron modifies the decomposition process of the precursor and enhances its viscosity, which appears to favour the separation of Zn- and Fe-rich phases. As a consequence, two-phase systems of individual nanocrystals/nanoparticles (ZnO and ZnFe2O4) are formed. The large anisotropy constant, 10(6)-10(7) erg cm(-3), of the ZnFe2O4 nanoparticles and the concentration dependence of their magnetic energy barrier are explained in terms of interparticle interactions interlinked with finite size effects and high inversion degree; these factors also control the other parameters of importance for applications, including the blocking temperature (13-111 K), saturation magnetization (1.08-17.7 emu g(-1) at 300 K, 4.6-44.8 emu g(-1) at 5 K) and coercivity (85.4-491 Oe at 5 K). Magnetic dynamic results, particularly modelled by the Neel-Brown and Vogel-Fulcher laws, yield fitting parameters which validate the presence of concentration-dependent dipole-like interactions between ZnFe2O4 nanoparticles. A fraction of iron was found in the Fe2+ state, presumably substituting for Zn2+ in zinc oxide; however, the samples behave like ZnFe2O4 SPM nanoclusters/nanoparticles dispersed in a nonmagnetic ZnO particle assembly, rather than Zn(Fe)O dilute magnetic semiconductors. The relevance of the properties of the investigated material for specific applications is highlighted throughout the manuscript.

The commercially ubiquitous liquid electrolytes for lithium-ion batteries have several shortcomings in terms of safety. Therefore, development of solid electrolytes, especially those that are glass-based, has been gaining increasing interest in recent times. However, the fundamental understanding of the changes in the glass structure and the corresponding changes in the properties due to the addition of dopants is necessary for the development of glasses. Therefore, here, we report a study on the role of vanadium on the glass structure, ionic conduction, crystallization behavior, and other properties of lithium silicate-based glasses (23Li(2)O-2.64K(2)O-2.64Al(2)O(3)-71.72SiO(2)) as a solid electrolyte for high-temperature Li-ion battery applications. Furthermore, we proposed a mathematical model to describe/quantify the ion-conducting channels' connectivity in glasses. The experimental glass structures were assessed using Si-29, V-51, Al-27 nuclear magnetic resonance, Fourier transform infrared, and ultraviolet-visible spectroscopy techniques. The ionic conductivity was measured by impedance spectroscopy, and the crystallization behavior was studied by optical microscopy and X-ray diffraction. Furthermore, molecular dynamics simulations were also used to gain structural insights of the glasses. In the designed compositions, the addition of vanadium decreased the overall concentration of Li+ ions. However, the results revealed that the ionic conductivity improved with the addition of vanadium in spite of a decrease in the number of charge carriers. This suggests that vanadium makes the pathways easier for the conducting ions. Thus, we conclude that vanadium modifies the conduction channels to promote better hoping of the ions from one site to another.

In this work, the photodegradation process of atorvastatin calcium (ATC) is reported as depending on: (1) the presence and the absence of excipients in the solid state; (2) the chemical interaction of ATC with phosphate buffer (PB) having pH equal to 7 and 8; and (3) hydrolysis reaction of ATC in the presence of aqueous solution of NaOH. The novelty of this work consists in the monitoring of the ATC photodegradation by photoluminescence (PL). The exposure of ATC in solid state to UV light induces the photo-oxygenation reactions in the presence of water vapors and oxygen from air. According to the X-ray photoelectron spectroscopic studies, we demonstrate that the photo-oxygenation reaction leads to photodegradation compounds having a high share of C=O bonds compared to ATC before exposure to UV light. Both in the presence of PB and NaOH, the photodegradation process of ATC is highlighted by a significant decrease in the intensity of the PL and photoluminescence excitation (PLE) spectra. According to PLE spectra, the exposure of ATC in the presence of NaOH to UV light leads to the appearance of a new band in the spectral range 340-370 nm, this belonging to the photodegradation products. Arguments concerning the chemical compounds, that resulted in this last case, are shown by Raman scattering and FTIR spectroscopy.

Graphene oxide (GO) and N-doped graphene [(N)G] graphenes were submitted to H-2 glow discharge under different discharge regimes, in both the negative glow and positive column plasma regions. The resulted catalysts were fully characterized using several techniques such as Raman, DRIFT and XPS spectroscopy, powder X-ray diffraction, H-2 pulse chemisorption and H-2-, CO2- and NH3-TPD experiments. Density functional theory calculations were performed taking a slab model of graphene sheet with an optimized C-C bond length (1.426 angstrom) and a 16 angstrom vacuum layer between sheets. An overview of these characterizations showed that the O/C atomic ratio of GO is influenced by the plasma regime, indicating the occurrence of O removal, as also predicted by DFT calculations. In the case of (N)G, the plasma treatment also removes pyridinic N with an increase of the C/N ratio. The efficiency of the plasma modification has been checked through catalytic tests in hydroisomerization of 1-octene and hydrogenation of alpha-methyl-styrene. Contrarily to classical thermal activation requiring high temperatures, the generation of the defects by treating with plasma occurs at voltages in the range of 2 5 kV. In consequence, the hydrogenation and isomerization of alkenes resulted with high yields and good selectivities. Graphene prepared from sodium alginate from brown algae was considered as reference in these investigations.

A series of PtCeTi-SBA-15 catalysts, with different concentrations of Pt (0.25 %, 0.5 %, 1.0 %), were synthesized. New Ti-SBA-15 material was obtained by direct synthesis and used as support in successive immobilization of Pt and Ce precursors, changing their order of addition. The characterization of the catalysts has been achieved taking an ensemble of techniques which showed preservation of the support porous structure, high dispersion of the amorphous metal oxides and Pt?, the formation of metal crystals for samples with 1wt% Pt and variation of Pt? content on surface in condition of ceria addition. The best conversion (100 %) was obtained in oxidation of hydrocarbons (CH4, C3H8 and C6H14) for the samples with 1% Pt and a significant diminish of activity was obtained for catalyst in which Ce was added on PtTi-SBA-15 sample. Differently of these, CO oxidation was totally irrespective of the catalyst composition.