National Institute Of Materials Physics - Romania

Visible light-mediated photodegradation offers a sustainable and environmentally friendly solution for removing emerging contaminants from water sources. Herein, we report on the synergy effect between adsorption and visible-light-driven photo-degradation of 17 fl - estradiol using (Au)TiO 2 nanotubes-graphene composites. The graphene structures (graphene oxide - GO or thermally reduced graphene oxide - trGO) provide a platform for strong adsorption of 17 fl -estradiol molecules and facilitate the charge transfer between plasmonic Au nanoparticles and TiO 2 , leading to an improvement of the overall degradation process. To better understand the effect of Au nanoparticles and TiO 2 separately, three different concentrations of Au (1 %, 2.5 %, and 5 %) were prepared and characterized. The estrogenic molecules preferred GO over trGO, suggesting that hydrogen bonds govern the interaction between GO and 17 fl -estradiol. Consequently, a higher photocatalytic efficiency of GOcontaining composites was observed when removing estrogenic molecules. The role of adsorption proved crucial for capturing and retaining more contaminant molecules on the composite surface, thus increasing the odds of surface reactions with the photogenerated carriers. A total removal of 17 fl -estradiol has been obtained for Au (1 %, 2.5 %, and 5 %) TiO 2 nanotubes-GO. The mechanism behind the adsorption and photo-degradation processes has been discussed.

Considering the increasing need for sustainable and economical energy storage solutions, the integration of layered materials such as MoS2 into these systems represents an important step toward enhancing energy sustainability and efficiency. Exploring environmentally responsible fabrication techniques, this study assesses wrinkled MoS2 thin films synthesized from distinct Mo and MoS2 targets, followed by sulfurization conducted in a graphite box. We utilized magnetron sputtering to deposit precursor Mo and MoS2 films on Si substrates, achieving thicknesses below 20 nm. This novel approach decreases sulfur by up to tenfold during sulfurization due to the confined space technique, contributing also to avoiding the formation of toxic gases such as SO2 or the necessity of using H2S, aligning with sustainable materials development. Thinner MoS2 layers were obtained post-sulfurization from the MoS2 precursors, as shown by X-ray reflectometry. Raman spectroscopy and grazing X-ray diffraction analyses confirmed the amorphous nature of the as-deposited films. Post-sulfurization, both types of films exhibited crystalline hexagonal MoS2 phases, with the sulfurized Mo showing a polycrystalline nature with a (100) orientation and sulfurized MoS2 displaying a (00L) preferred orientation. The X-ray photoelectron spectroscopy results supported a Mo:S ratio of 1:2 on the surface of the films obtained using the MoS2 precursor films, confirming the stoichiometry obtained by means of energy dispersive X-ray spectroscopy. Scanning electron microscopy and atomic force microscopy images revealed micrometer-sized clusters potentially formed during rapid cooling post-sulfurization, with an increased average roughness. These results open the way for the further exploration of wrinkled MoS2 thin films in advanced energy storage technologies.

Bulk nanocrystalline La0.67Ba0.33_xKxMnO3 (with x = 0, 0.05, 0.1, and 0.2) manganites have been prepared by the modified sol-gel method (Pechini). The single-phase rhombohedral crystal structure with the R-3c (no. 167) space group was verified by X-ray diffraction (XRD) and sustained by Rietveld refinement. As follows from the results of XRD structural analyses, the increase in K-doping triggers an increase in the distortion of the MnO6 octahedra, which eventually causes the narrowing of the eg bandwidth. Mn is in a mixed valence state of Mn4+/ Mn3+ as inferred by X-ray photoelectron spectroscopy. Magnetic measurements confirm that the Curie tem-perature decreases from 348 K for La0.67Ba0.33MnO3 to 316 K for La0.67Ba0.13K0.20MnO3. The increasing of the Mn4+ ion concentration at the B-site sublattice and A-site ionic disorder (sigma 2) breaks up the double exchange interaction between the Mn3+ and Mn4+ ions. The ferromagnetic to paramagnetic second-order magnetic phase transition at TC is also confirmed by electron paramagnetic resonance. According to magnetic field-dependent magnetization isotherms at different temperatures, La0.67Ba0.13K0.20MnO3 shows a relatively large magneto -caloric effect (1400 mJ cm_ 3 K_ 1 at 316 K under 5 T applied magnetic field), which raises the possibility of using this material for room-temperature micro-scale magnetic cooling.

This work investigates the conduction mechanism of hydrothermally grown Gd2O3-sensitive material in order to explain its electrical resistance behaviour when exposed to increasing concentrations of CO2 under in-field conditions. To achieve this, the experimental investigation began with X-ray photoelectron spectroscopy of the Gd2O3 microstructure to verify the oxidation states of the surface. Subsequently, the impact of constant atmospheric factors such as oxygen and relative humidity on the electrical resistance of the Gd2O3 layer was examined. Finally, a progressive dosing of CO2 concentrations ranging from 400 to 3000 ppm was conducted. The DC electrical resistance measurements were performed using a computer-controlled Gas Mixing System operated under a dynamic gas flow regime. Experimental data was validated using the Boltzmann distribution statistics and the grain-to-grain Schottky barrier model. The results highlight the preservation of the n-type semiconductor behaviour of Gd2O3 irrespective of the background relative humidity and bring the oxidising character of CO2 to the fore.

In the quest for advanced materials suitable for next-generation electronic and optoelectronic applications, tungsten disulfide (WS2) ultrathin films have emerged as promising candidates due to their unique properties. However, obtaining WS2 directly on the desired substrate, eliminating the need for transfer, which produces additional defects, poses many challenges. This paper aims to explore the synthesis of WS2 ultrathin films via physical vapor deposition (PVD) followed by sulfurization in a confined space, addressing the challenge of film formation for practical applications. Precursor layers of tungsten and WS2 were deposited by RF magnetron sputtering. Subsequent sulfurization treatments were conducted in a small, closed, graphite box to produce WS2 films. The physical and chemical properties of these precursor and sulfurized layers were thoroughly characterized using techniques such as X-ray reflectometry (XRR), X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The findings reveal notable distinctions in film thickness, structural orientation, and chemical composition, attributable to the different precursor used. Particularly, the sulfurized layers from the tungsten precursor exhibited a preferred orientation of WS2 crystallites with their (00L) planes parallel to the substrate surface, along with a deviation from parallelism in a small angular range. This study highlights the necessity of precise control over deposition and sulfurization parameters to tailor the properties of WS2 films for specific technological applications.

In a milestone paper [F. D. M. Haldane, Phys. Rev. Lett. 61, 2015 (1988)], Haldane elaborated a model of graphene within the time -reversal symmetry breaking is achieved by next -nearest -neighbors imaginary counterrotating hopping, hence conferring topological properties. In recent years, the time -reversal symmetry turned out to be broken also by light irradiation in so-called Floquet topological insulators (FTIs). On the other hand, Kane and Mele introduced a spin -orbit coupling (SOC) model [C. L. Kane et al., Phys. Rev. Lett. 95, 226801 (2005)] inspired by the Haldane's mechanism. In this paper, we present the topological properties of a FTI possessing SOC, using graphene as the playground. It was found that the interplay between sublattice subspace and the spin one triggers interesting topological phase transitions. Basically, in a FTI with SOC, two topological phases may be excited: charge quantum Hall effect (CQHE) and, respectively, spin quantum Hall effect (SQHE) phases. Also, it was demonstrated that the CQHE and SQHE coexistence is forbidden by the topology of the system. As well, it was identified a special driving regime of spin filter (SF), in which only one spin state is topological and, consequently, will be filtered in quantum transport.

Ti-aluminosilicate gels were used as supports for the immobilization of Fe, Co, and Ni oxides (5%) by impregnation and synthesis of efficient photocatalysts for the degradation of beta-lactam antibiotics from water. Titanium oxide (1 and 2%) was incorporated into the zeolite network by modifying the gel during the zeolitization process. The formation of the zeolite Y structure and its microporous structure were evidenced by X-ray diffraction and N-2 physisorption. The structure, composition, reduction, and optical properties were studied by X-ray diffraction, H-2-TPR, XPS, Raman, photoluminescence, and UV-Vis spectroscopy. The obtained results indicated a zeolite Y structure for all photocatalysts with tetracoordinated Ti4+ sites. The second transitional metals supported by the post-synthesis method were obtained in various forms, such as oxides and/or in the metallic state. A red shift of the absorption edge was observed in the UV-Vis spectra of photocatalysts upon the addition of Fe, Co, or Ni species. The photocatalytic performances were evaluated for the degradation of cefuroxime in water under visible light irradiation. The best results were obtained for iron-immobilized photocatalysts. Scavenger experiments explained the photocatalytic results and their mechanisms. A different contribution of the active species to the photocatalytic reactions was evidenced.

The primary objective of this research was to develop efficient solid catalysts that can directly convert the lactic acid (LA) obtained from lignocellulosic biomass into alanine (AL) through a reductive amination process. To achieve this, various catalysts based on ruthenium were synthesized using different carriers such as multi-walled carbon nanotubes (MWCNTs), beta-zeolite, and magnetic nanoparticles (MNPs). Among these catalysts, Ru/MNP demonstrated a remarkable yield of 74.0% for alanine at a temperature of 200 degrees C. This yield was found to be superior not only to the Ru/CNT (55.7%) and Ru/BEA (6.6%) catalysts but also to most of the previously reported catalysts. The characterization of the catalysts and their catalytic results revealed that metallic ruthenium nanoparticles, which were highly dispersed on the external surface of the magnetic carrier, significantly enhanced the catalyst's ability for dehydrogenation. Additionally, the -NH2 basic sites on the catalyst further facilitated the formation of alanine by promoting the adsorption of acidic reactants. Furthermore, the catalyst could be easily separated using an external magnetic field and exhibited the potential for multiple reuses without any significant loss in its catalytic performance. These practical advantages further enhance its appeal for applications in the reductive amination of lactic acid to alanine.

The effect of the annealing temperature on 1% nitrogen-doped WO3 materials was studied, which were then used as electrode materials for high-performance supercapacitor (SC) devices. The supercapacitive performance of the proposed materials was strongly influenced by the doping element and the annealing temperature by directly changing the defect structure of the host material. The 1% N-doped WO3 materials annealed at different temperatures were thoroughly characterized through various characterization techniques, including electron paramagnetic resonance and photoluminescence spectroscopy, giving insight into the effect of N-doping on the defect structure and optical properties of WO3. When the WO3:N materials were used as electrode material in symmetric SCs, the doping element and the annealing temperature improved the electrochemical performance. No booster materials (such as carbon black) were used in the symmetric SC designs, showing increased specific capacitance (102 F/g) and energy density (14.6 W h/kg) values.

This study reports the development of a novel biocomposite for potential applications in the environmental remediation. The hydroxyapatite/sodium bicarbonate (HAp-SB) biocomposite obtained by a cheap method could offer promising characteristics to be used in environmental applications. The obtaining of HAp-SB ceramic composites was studied with the aim of increasing the adsorption efficiency of lead ions from contaminated waters. A composite material (HAp-SB) with good crystallinity that preserves the hexagonal structure of pure hydroxyapatite was obtained. For the powder recovered after decontamination of the lead solution (PbHAp-SB), the XRD model highlighted additional maxima belonging to Ca10(PO4)5(OH)2, Ca0.805Pb4.195(PO4)(OH) and PbH2P2O7. The FTIR spectra of PbHAp-SB are similar to those of HAp-SB composites showing a broadening of the vibration peaks and a slight shift. The XPS and EDS studies illustrated the purity of the HAp-SB sample. Moreover, the presence of lead in the powder recovered after decontamination was also highlighted by XPS and EDS studies. The efficiency of HAp-SB in the adsorption of Pb2+ ions from the contaminated solution was also highlighted by ultrasound studies using double-distilled water as the reference liquid. The adsorption kinetics were investigated with the aid of Langmuir and Freundlich theoretical models. The results demonstrated that the HAp-SB ceramic composite has a strong affinity for the adsorption of Pb2+ ions from contaminated solutions. The removal efficiency of Pb2+ ions was about 92% for the initial Pb2+ concentration above 50 mg/L. The results of the cell viability and cytotoxicity studies demonstrated that HAp-SB nanoparticles did not influence negatively the HeLa cell's viability and did not induce any significant changes of the morphological features of HeLa cells after 24 h of incubation. The batch adsorption results as well as the cytotoxicity assay results suggested that the HAp-SB powder could be successfully used for the removal of Pb2+ from contaminated water.