National Institute Of Materials Physics - Romania

Two hybrid materials, based on 7-amino-4-(trifluoromethyl)coumarin and 7-amino-4-methyl-coumarin that attach covalently to graphene oxide (GO) have been synthesized in two steps: i) increasing the number of carboxyl groups required for functionalization with aminocoumarin derivatives by derivatization of the hydroxyls groups with chloroacetic acid, transforming GO into GO-COOH material; ii) activation of carboxylic groups using the carbodiimide-promoted reaction. The obtained composites were characterized by numerous methods that highlighted their successful obtaining. The antimicrobial activity was evaluated on resistant Mycobacterium tuberculosis strains, as well as on ESKAPE pathogens ((Enterococcus faecium, Staphylococcus aureus, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa, and Enterobacter spp.) in planktonic and biofilm growth states. The biocompatibility of the materials has been assayed using 3-(4, 5-dimethylthiazol-2-yl)2, 5-diphenyltetrazolium bromide assay as well as by measuring the level of nitric oxide/total reactive oxygen species and superoxide release in treated cells. The results have shown that materials exhibited improved inhibitory activity against resistant M. tuberculosis strains in comparison with GO, but also against planktonic and adherent strains. Also, the tested composites have been proved to be biocompatible on the MRC-5 fibroblast cells, demonstrating their promising potential to develop novel agents effective against multidrug resistant pathogens, including M. tuberculosis, as well as by the activation of a pro-inflammatory and of an oxidative response in the mammalian cells.

B doped as well as B and N co-doped highly reduced graphene oxide and multiwall carbon nanotubes/Ni oxide and Ni hydroxide nanohybrid layers were synthesized using a one-step laser technique. NiO nanoparticles, graphene oxide platelets, and multiwall carbon nanotubes were used as starting materials for the preparation of the composite layers. H3BO3 was used as B precursor and urea as well as NH3 as N precursors for B and N co -doping of the composite layers. The influence of the nature and concentration of the B and N precursors on the physico-chemical properties of the nanohybrid layers, chemical composition and chemical bonding states, crystalline structure, as well as charge transfer properties was systematically investigated. The relation between the physico-chemical properties and functional characteristics of the nanohybrid layers, photocatalytic removal of water contaminants under simulated sun irradiation conditions was studied, identifying the optimum con-centrations of the dopant precursor materials. The mechanism of the photodegradation process was explored, based of the band structure of the composites. The main intermediates, reactive oxygen species implied in the photocatalytic degradation processes of organic molecules, was investigated through the addition of scavengers to the organic dye test solutions. The highest photocatalytic activities were achieved for B and N co-doped samples synthesised using H3BO3 as B and urea as N precursors.

Dielectric spectroscopy is a well-known method to characterize different liquid or solid (nano) materials such as liquid crystals, polymers, composites, ceramics etc. More the material structure is complex, more the molecular dynamics are put in evidence with difficulty. In many such cases, the analysis of the spectra with the classic Havriliak-Negami (H-N) functions is hard to apply or even fails. Therefore, we propose a simple numerical approach (with two different procedures) for the deconvolution of complex spectra in dielectric spectroscopy (DS). The final goal is to obtain the frequency of maximum loss (fmax) depending on the temperatures, Arrhenius diagram, and the activation energy/energies. The developed procedures have as their starting point the "logarithmic derivative of the permittivity". To our knowledge, these procedures have not yet been presented in the literature. The proposed first numerical processing allows a better separation of the different relaxation processes, a decrease in the contribution of the electrical conductivity and a better localization of the frequencies where the dielectric loss has maximum values. The second of the procedures is applied in certain particular situations, and the other procedure is more general. Where the former can be applied, it is equivalent to using the classical H-N functions in terms of obtaining the fmax, but it is simpler to apply. The first procedure uses an "artificial" and simpler H-N function, in which the fewer fitting parameters have no physical meaning, but allow a good localization of the frequency of maximum dielectric loss. The proposed procedure was applied on experimental data of dielectric spectroscopy obtained on pristine materials (nematic mixture E7 and ZnO) and composites E7-ZnO, obtained by a "green technology". The complicated spectra of the dielectric permittivity presented by these samples represent the suitable test to highlight the advantages but also the limitations of our approach. Comparing the values of the activation energy obtained for the two procedures is the criterion for verifying their correctness. The volume of processed experimental data is large, for this reason we present only the results obtained based on numerical approaches. The differences between the results obtained with the two procedures are small. The procedures can be considered as alternatives to the application of fitting with H-N functions. One procedure replaces H-N by eliminating the use of functions with complex variables and the method of least squares and has the advantage that it can apply non-specialized software like Origin. The other allows a better analysis of spectra being an improved-modified H-N approach. Proposed procedures are

One of the new materials for next-generation thin film solar cells is Cu2ZnSnSe4 (CZTSe). However, achieving a single-phase CZTSe compound remains a challenge. This study describes the development of Cu2ZnSnSe4 thin films through the sequential deposition of stacked films of non-stoichiometric Cu2SnSe3 (CTSe) and ZnSe by magnetron sputtering. The structural, morphological, and electrical properties as well as the surface chemistry of the films were investigated and compared depending on the growth sequence of the thin films. By using Raman spectroscopy and grazing incidence X-ray diffraction, the tetragonal CZTSe structure was confirmed. Scanning electron microscopy and energy-dispersive spectroscopy measurements of the morphological and compositional properties indicated large grains and dense surfaces with an elemental composition close to the desired stoichiometry in SLG\SnSe2\Cu\ZnSe and SLG\SnSe2\Cu2Se\ZnSe stacks. To ascertain the surface chemistry and unique characteristics of the produced films, additional X-ray photoemission spectroscopy experiments were carried out. The optimal band gap values for the absorber layers were found using conventional spectroscopy, and they ranged from 0.88 to 1.47 eV. According to the electrical measurements, all the films were p-type and have high carrier concentrations between 1016 and 1020 cm-3. Our findings demonstrate that employing a sequential deposition approach and annealing in different atmospheres can yield CZTSe absorber layers with desirable properties, overcoming the challenge of non-stoichiometric CTSe precursors.

The development of new synthetic methods is paramount for the versatile production of complex multicompo-nent electrodes for supercapacitors with enhanced performance. The reactive inverse matrix assisted pulsed laser evaporation (RIMAPLE) technique shows promise for the deposition of complex functional nanocomposites in a facile way. In this work, hybrid supercapacitor electrodes constituted by reduced graphene oxide (rGO) and carbon nanotubes (CNTs) decorated with a myriad of cerium and manganese oxide nanoparticles were obtained by using GO sheets, CNTs, CeO2 nanoparticles and, for the first time, the (NH4)2[Mn2(C6H5O7)2(H2O)2] coor-dination compound as precursors in the RIMAPLE targets. Compositional and structural characterizations revealed that post-annealing treatments at mild conditions (150-250 degrees C) induce a further reduction of the rGO and CNTs, besides an oxidation of the Ce oxide phases (Ce3+ to Ce4+) and a reduction of the Mn oxides (Mn3+ to Mn2+). The substantial change of the carbon and metal oxide nanostructures causes an up to 8-fold increase of the capacitance of the electrodes (63 F/cm3 @ 10 mV/s). Finally, the generation of a high quantity of edge defects at 250 degrees C and long dwell time leads to the drop of the electrode's capacitance.

Herewith, we investigated the capacitive properties of hybrid nanometric architectures consisting of tungsten oxide nanoparticles deposited on graphite (WOx/G) and graphite coated with highly-porous carbon nanowall layers (WOx/CNW/G). The deposition of the nanostructured oxide was performed by a plasma-assisted sublimation, vapor transport and condensation technique. The samples containing the CNW interlayer show superior areal capacitances making this architecture and its fabrication route promising approaches for supercapacitor applications. Thus, areal capacitances of WOx/CNW/G and WOx/G, estimated from galvanostatic chargedischarge tests (GCD) at an applied density current of 1 mA cm-2, are 1247.2 mF cm-2 and 527.3 mF cm-2, respectively. From SEM and XPS investigations, it was observed that CNW promotes the formation of a high amount of small tungsten oxide particles, homogeneously distributed on electrode surface, and facilitates the formation of highly conductive tungsten nitride species, resulting in electrodes with remarkable charge-storage capacity.

Bulk MgB2 discs were prepared by an in situ route from mixtures of magnesium and boron powders. The boron powders were produced by two methods. The first one consisted of a self-propagating high tem-perature magnesiothermic synthesis (SHS) process followed by acid and fluorine cleaning and a heat treatment in inert atmosphere. This approach produced boron with purities between 86 % and 97 %, where the main impurity was Mg. Depending on the final heat treatment, these boron powders were amorphous or crystalline. In the second route, high purity nano powders (99 %) of boron were obtained by a diborane pyrolysis process. Bulks of MgB2 were characterized by structural, microstructural, and magnetic mea-surements. Critical current density, pinning force aspects and levitation force (including guiding force) details were assessed. Amorphous lower purity boron (86-97 %) obtained by the first processing route was found to promote the largest levitation forces of the MgB2 bulks and, among these samples, the best le-vitation results were recorded when using boron with a purity of 95-97 %. Use of a lower purity boron that decreases the cost of MgB2 promotes large scale production at industrial level of bulk MgB2 super-conducting magnets for levitation applications and enhances the applicability potential of MgB2 super-conductor. The relationship between levitation force and specific features of the samples such as pinning force details are discussed.& COPY; 2023 Elsevier B.V. All rights reserved.

Romula (today Resca, Dobrosloveni Village, Romania) was the largest urban and economic center of Dacia Inferior (Malvensis), a Roman province located in the north of the Lower Danube region. In this context, the city market included workshops for the production of ceramic, metal, stone, bone, and glass objects. In 2013, 2015, and 2018, during excavations of the former Roman city, two rectangular glass furnaces were discovered. One has only one chamber, the other has two chambers. A melted glass layer was found on the walls of furnace no. 1, as well as in one room of furnace no. 2. Broken fragments of glass were also found in both. The furnaces are located in the central area of the Roman city. The evidence suggests that the furnaces belong to secondary glass workshops. The glass may have arrived in raw form, where it was remelted and processed. The discovery of these furnaces contributes to the growing body of evidence for Roman glass production around the empire.1

In this work, applications of nanohybrid composites based on titanium dioxide (TiO2) with anatase crystallin phase and single-walled carbon nanohorns (SWCNHs) as promising catalysts for the photodegradation of amoxicillin (AMOX) are reported. In this order, TiO2/SWCNH composites were prepared by the solid-state interaction of the two chemical compounds. The increase in the SWCNH concentration in the TiO2/SWCNH composite mass, from 1 wt.% to 5 wt.% and 10 wt.% induces (i) a change in the relative intensity ratio of the Raman lines located at 145 and 1595 cm(-1), which are attributed to the E-g(1) vibrational mode of TiO2 and the graphitic structure of SWCNHs; and (ii) a gradual increase in the IR band absorbance at 1735 cm(-1) because of the formation of new carboxylic groups on the SWCNHs' surface. The best photocatalytic properties were obtained for the TiO2/SWCNH composite with a SWCNH concentration of 5 wt.%, when approx. 92.4% of AMOX removal was achieved after 90 min of UV irradiation. The TiO2/SWCNH composite is a more efficient catalyst in AMOX photodegradation than TiO2 as a consequence of the SWCNHs' presence, which acts as a capture agent for the photogenerated electrons of TiO2 hindering the electron-hole recombination. The high stability of the TiO2/SWCNH composite with a SWCNH concentration of 5 wt.% is proved by the reusing of the catalyst in six photodegradation cycles of the 98.5 mu M AMOX solution, when the efficiency decreases from 92.4% up to 78%.

Thick tungsten oxide layers were prepared electrophoretically in order to be used as photoanodes in photoelectrochemical water oxidation applications. The highest photocurrent density was obtained for a WO3 layer with thickness of similar to 900 nm. Additionally, WO3/BiVO4 and WO3/BiVO4/MIL-101(Fe) heterojunctions have been fabricated using WO3 layer as substrate. WO3/BiVO4 shows an increased value of the electrochemical active surface area indicating that more sites of this photoanode are activated through the formation of the heterojunction. The small V5+ signals observed in the V 2p XPS spectra of these heterojunctions were attributed to the substitution of V5+ atoms with W6+ atoms on the surface of BiVO4. Excessive W doping of the BiVO4 film determined the decrease of the photoelectrochemical performance of WO3/BiVO4 photoanode. The significant improvement of the photoconversion efficiency of the sample decorated with MIL-101(Fe) indicated that this cocatalyst provides sites more efficiently in the photoelectrochemical process. This performance was correlated with the reduced value of the charge transfer resistance at electrode/electrolyte interface obtained from electrochemical impedance spectroscopy investigation.