National Institute Of Materials Physics - Romania

Metal-organic frameworks (MOFs) are a class of porous coordination networks extraordinarily varied in physicochemical characteristics such as porosity, morphologies, and compositions. These peculiarities make MOFs widely exploited in a large array of applications, such as catalysis, chemicals and gas sensing, drug delivery, energy storage, and energy conversion. MOFs can also serve as nanostructured precursors of metal oxides with peculiar characteristics and controlled shapes. In this work, starting from MIL125-(Ti), a 1,4-benzenedicarboxylate (BDC)-based MOF with Ti as metallic center, mesoporous TiO2 powders containing both anatase and rutile crystalline phases were produced. A challenging utilization of these porous MOF-derived Ti-based oxides is the optically-based quantitative detection of molecular oxygen (O-2) in gaseous and/or aqueous media. In this study, the photoluminescence (PL) intensity changes during O-2 exposure of two MOF-derived mixed-phase TiO2 powders were probed by exploiting the opposite response of rutile and anatase in VIS-PL and NIR-PL wavelength intervals. This result highlights promising future possibilities for the realization of MOF-derived doubly-parametric TiO2-based optical sensors.

Cation-substituted hydroxyapatite (HA), standalone or as a composite (blended with polymers or metals), is currently regarded as a noteworthy candidate material for bone repair/regeneration either in the form of powders, porous scaffolds or coatings for endo-osseous dental and orthopaedic implants. As a response to the numerous contradictions reported in literature, this work presents, in one study, the physico-chemical properties and the cytocompatibility response of single cation-doped (Ce, Mg, Sr or Zn) HA nanopowders in a wide concentration range (0.5-5 at.%). The modification of composition, morphology, and structure was multiparametrically monitored via energy dispersive X-ray, X-ray photoelectron, Fourier-transform infrared and micro-Raman spectroscopy methods, as well as by transmission electron microscopy and X-ray diffraction. From a compositional point of view, Ce and Sr were well-incorporated in HA, while slight and pronounced deviations were observed for Mg and Zn, respectively. The change of the lattice parameters, crystallite size, and substituting cation occupation factors either in the Ca(I) or Ca(II) sites were further determined. Sr produced the most important HA structural changes. The in vitro biological performance was evaluated by the (i) determination of leached therapeutic cations (by inductively coupled plasma mass spectrometry) and (ii) assessment of cell behaviour by both conventional assays (e.g., proliferation-3-(4,5-dimethyl thiazol-2-yl) 5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium assay; cytotoxicity-lactate dehydrogenase release assay) and, for the first time, real-time cell analysis (RTCA). Three cell lines were employed: fibroblast, osteoblast, and endothelial. When monophasic, the substituted HA supported the cells' viability and proliferation without signs of toxicity. The RTCA results indicate the excellent adherence of cells. The study strived to offer a perspective on the behaviour of Ce-, Mg-, Sr-, or Zn-substituted HAs and to deliver a well-encompassing viewpoint on their effects. This can be highly important for the future development of such bioceramics, paving the road toward the identification of candidates with highly promising therapeutic effects.

We present a detailed study regarding the bandgap dependence on diameter and composition of spherical Ge-rich GexSi1-x nanocrystals (NCs). For this, we conducted a series of atomistic density functional theory (DFT) calculations on H-passivated NCs of Ge-rich GeSi random alloys, with Ge atomic concentration varied from 50 to 100% and diameters ranging from 1 to 4 nm. As a result of the dominant confinement effect in the DFT computations, a composition invariance of the line shape of the bandgap diameter dependence was found for the entire computation range, the curves being shifted for different Ge concentrations by Delta E(eV)=0.651(1-x). The shape of the dependence of NCs bandgap on the diameter is well described by a power function 4.58/d(1.25) for 2-4 nm diameter range, while for smaller diameters, there is a tendency to limit the bandgap to a finite value. By H-passivation of the NC surface, the effect of surface states near the band edges is excluded aiming to accurately determine the NC bandgap. The number of H atoms necessary to fully passivate the spherical GexSi1-x NC surface reaches the total number atoms of the Ge+Si core for smallest NCs and still remains about 25% from total number of atoms for bigger NC diameters of 4 nm. The findings are in line with existing theoretical and experimental published data on pure Ge NCs and allow the evaluation of the GeSi NCs behavior required by desired optical sensor applications for which there is a lack of DFT simulation data in literature.

Gold nanoparticles (similar to 10 nm) were deposited on titanium dioxide nanoparticles (similar to 21 nm) and the material obtained was characterized using IR, UV-Vis, N-2 adsorption-desorption isotherm, DLS, EDS (EDX), TEM, XPS, and XRD techniques. It was found that the methylene blue dye is degraded in the presence of this material when using hydrogen peroxide as the oxidant. Tests were performed at 2, 4, 6, and 24 h, with hydrogen peroxide contents varying from 1 to 5 mg/mL. Longer exposure time and a higher content of oxidant led to the degradation of methylene blue dye at up to 90%. The material can be reused several times with no loss of activity.

Tuning the intrinsic structural and stoichiometric properties by different means is used for increasing the green energy production efficiency of complex oxide materials. Here, we report on the formation of self-assembled nanodomains and their effects on the photoelectrochemical (PEC) properties of LaFeO3 (LFO) epitaxial thin films as a function of layer's thickness. The variation with the film's thickness of the structural parameters such as in-plane and out-of-plane crystalline coherence length and the coexistence of different epitaxial orientation-SrTiO3// LFO, SrTiO3// LFO and [110] LFO//[10] STO, as well as the appearance of self-assembled nanodomains for film's thicknesses higher than 14 nm, is presented. LFO thin films exhibit different epitaxial orientations depending on their thickness, and the appearance of self-assembled nanopyramids-like domains after a thickness threshold value has proven to have a detrimental effect on the PEC functional properties. Using Nb:SrTiO3 as conductive substrate and 0.5 M NaOH aqueous solution for PEC measurements, the dependence of the photocurrent density and the onset potential vs. RHE on the structural and stoichiometric features exhibited by the LFO photoelectrodes are unveiled by the X-ray diffraction, high-resolution transmission electron microscopy, ellipsometry, and Rutherford backscattering spectroscopy results. The potentiodynamic PEC analysis has revealed the highest photocurrent density J(photocurrent) values (up to 1.2 mA/cm(2)) with excellent stability over time, for the thinnest LFO/Nb:SrTiO3 sample, both cathodic and anodic behavior being noticed. Noticeably, the LFO thin film shows unbiased hydrogen evolution from water, as determined by gas chromatography in aqueous 0.5 M NaOH solution under constant illumination.

NiO-loaded SnO2 powders were prepared involving two chemical procedures. The mesoporous SnO2 support was synthesized by a hydrothermal route using Brij 35 non-ionic surfactant as a template. The nickel loadings of 1 and 10 wt.%. NiO were deposited by the wet impregnation method. The H2S sensing properties of xNiO-(1-x)SnO2 (x = 0, 1, 10%) thick layers deposited onto commercial substrates have been investigated with respect to different potential interfering gases (NO2, CO, CO2, CH4, NH3 and SO2) over a wide range of operating temperatures and relative humidity specific for in-field conditions. Following the correlation of the sensing results with the morphological ones, 1wt.% NiO/SnO2 was selected for simultaneous electrical resistance and work function investigations. The purpose was to depict the sensing mechanism by splitting between specific changes over the electron affinity induced by the surface coverage with hydroxyl dipoles and over the band bending induced by the variable surface charge under H2S exposure. Thus, it was found that different gas-interaction partners are dependent upon the amount of H2S, mirrored through the threshold value of 5 ppm H2S, which from an applicative point of view, represents the lower limit of health effects, an eight-hour TWA.

Amorphous metal chalcogenides have good switching properties for resistive memories, but have low thermal stability. In this work, the response to rapid thermal stress, as high as 550 degrees C, of amorphous Cu-GeSe, Ag-GeSe, Cu-GeTe, Ag-GeTe thin films, is investigated. Metal-GeTe films, which are amorphous up to 280 degrees C, are the most stable. Metal-GeSe films start to crystallize at 190 degrees C and a Cu1.59Se phase, with 20.5% Cu vacancies and a structure similar to the c-Cu2-xSe superionic conductor, is formed. This might boost the performance of memory devices. Silver atoms migration is facilitated in Ag-GeSe by poor crystallization (below 5%, at all temperatures). Difussion of Ag is enhanced in Ag-GeTe, due to the crystallization of the cubic (Ag2Te)(4)-GeTe2 (Ag8GeTe6) phase, which has Ag+ vacancies. In Cu-GeTe, the formation of stoichiometric polycrystalline Cu0.67Ge0.33 Te might hinder diffusion. An unusual anisotropic behaviour (increase in thickness, simultaneously with contraction of surface) is observed at 100 degrees C in Cu-GeSe and Cu-GeTe thin films, which suggests the orientation of the amorphous clusters package along a preferential direction.

Structural and electrical properties of epitaxial Pb(Zr0.2Ti0.8)O-3 films grown by pulsed laser deposition from targets with different purities are investigated in this study. One target was produced in-house by using high purity precursor oxides (at least 99.99%), and the other target was a commercial product (99.9% purity). It was found that the out-of-plane lattice constant is about 0.15% larger and the a domains amount is lower for the film grown from the commercial target. The polarization value is slightly lower, the dielectric constant is larger, and the height of the potential barrier at the electrode interfaces is larger for the film deposited from the pure target. The differences are attributed to the accidental impurities, with a larger amount in the commercial target as revealed by composition analysis using inductive coupling plasma-mass spectrometry. The heterovalent impurities can act as donors or acceptors, modifying the electronic characteristics. Thus, mastering impurities is a prerequisite for obtaining reliable and reproducible properties and advancing towards all ferroelectric devices.

In this study, nano-BaTiO3 (BTO) powders were obtained via the solvothermal method at different reaction times and were investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy. The results were compared with those obtained for a larger crystallite size BTO powder (BTO-m). The sizes of the cuboid crystallites (as determined by XRD and TEM) ranged from about 18 to 24 nm, depending on the reaction time. The evolution with temperature of the structure parameters of nano-BTO was monitored by means of X-ray diffraction and Raman spectroscopy and no signs of phase transition were found up to 170 degrees C. Careful monitoring of the dependence of the XRD peak widths on the hkl indices showed that the effect of the cubic crystallite shape upon the XRD peak widths was buried by the effect of hidden tetragonal line splits and by anisotropic microstrain. The good correlation of the line widths with the tetragonal split amplitudes, observed especially for BTO-m above the transition temperature, indicates tetragonal deformations, as also revealed by Raman spectroscopy. The large anisotropic microstrain shown by the nano-powders, which had a maximum value in the directions, was considered evidence of the phenomenon of surface relaxation of cubic crystallites edged by {100} faces. The observed behavior of the nano-BTO structures with increasing temperature may suggest a correlation between the surface relaxation and tetragonal deformation in the nano-cubes. The experimental results for both nano-BTO and mezoscale-BTO are in agreement with the core-shell model.

Resveratrol (RES) is a naturally occurring product with numerous biological activities. Despite its potential benefits, its use is limited due to its low aqueous stability and solubility in its native form. The porous sol-gel silica materials which are able to entrap different organic molecules represent new studied release carriers. The aim of this work was to generate a solid matrix to encapsulate RES ensuring protection, increased solubility and release in solutions. A non-toxic ingredient, namely beta-cyclodextrin (beta-CD), able to form inclusion complexes (ICs) with RES has been used. Ecological formulations have been processed by entrapping the RES containing ICs in silica matrices obtained from a silica colloidal sol by the aqueous route of the sol-gel method. Characterization methods (DSC, FTIR, UV-Vis, fluorescence studies, SEM) have evidenced the presence of RES-beta-CD inclusion complex in the silica powder, RES stability in the matrix and its release in aqueous and organic solutions, and the morphology of the carrier. An evaluation of the antioxidant activity of RES in the present formulation was performed by the chemiluminescence assay and RES release profile in aqueous solutions was obtained by HPLC-MS. The resulted materials can find applications in different domains. Graphic abstract