Publications

Despite being the lightest element in the periodic table, hydrogen poses many risks regarding its production, storage, and transport, but it is also the one element promising pollution-free energy for the planet, energy reliability, and sustainability. Development of such novel materials conveying a hydrogen source face stringent scrutiny from both a scientific and a safety point of view: they are required to have a high hydrogen wt.% storage capacity, must store hydrogen in a safe manner (i.e., by chemically binding it), and should exhibit controlled, and preferably rapid, absorption-desorption kinetics. Even the most advanced composites today face the difficult task of overcoming the harsh re-hydrogenation conditions (elevated temperature, high hydrogen pressure). Traditionally, the most utilized materials have been RMH (reactive metal hydrides) and complex metal borohydrides M(BH4)(x) (M: main group or transition metal; x: valence of M), often along with metal amides or various additives serving as catalysts (Pd2+, Ti4+ etc.). Through destabilization (kinetic or thermodynamic), M(BH4)(x) can effectively lower their dehydrogenation enthalpy, providing for a faster reaction occurring at a lower temperature onset. The present review summarizes the recent scientific results on various metal borohydrides, aiming to present the current state-of-the-art on such hydrogen storage materials, while trying to analyze the pros and cons of each material regarding its thermodynamic and kinetic behavior in hydrogenation studies.

This work presents the preparation of W and V co-doped TiO2 nanoparticles (W:TiO2 and W:V:TiO2) using laser pyrolysis technique subsequently modified with noble metals Pt or Pd using chemical impregnation method. By using well defined TiO2 nanoparticles, the enhancement of catalytic activity is expected mainly due to their higher surface area and density defects relative to bulk material. Structural, morphological and optical properties of the as-obtained nanopowders have been characterized by transmission electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, UV-VIS diffuse reflectance spectroscopy and photoluminescence techniques. The phase composition analysis reveals the preponderance of anatase (95%) in addition to ruffle phase, its particle average size ranging from 25 to 30 nm. The TiO 2 based nanomaterials were supplementary modified by noble metals deposition (Pt particles with dimensions of 3-4 nm and spherical Pd crystallites with a diameter between 3 and 9 nm) and their photocatalytic activity was tested in oxidative photo degradation of CH3OH, under simulated solar light. The metal modified samples displayed higher specific surface areas (3-6 times) and improved photocatalytic properties, the W:V:TiO2@Pt material showing better conversion efficiency of CH3OH to CH2O than the reference Degussa P25 sample (1.54 versus 0.90%).

In the last decade orthorhombic hafnia and zirconia films have attracted tremendous attention arising from the discovery of ferroelectricity at the nanoscale. However, an initial wake-up pre-cycling is usually needed to achieve a ferroelectric behaviour in these films. Recently, different strategies, such as microstructure tailoring, defect, bulk and interface engineering, doping, NH3 plasma treatment and epitaxial growth, have been employed to obtain wake-up free orthorhombic ferroelectric hafnia and zirconia films. In this work we review recent developments in obtaining polar hafnia and zirconia-based thin films without the need of any wake-up cycling. In particular, we discuss the rhombohedral phase of hafnia/ zirconia, which under a constrained environment exhibits wake-up-free ferroelectric behaviour. This phase could have a strong impact on the current investigations of ferroelectric binary oxide materials and pave the way toward exploiting ferroelectric behaviour for next-generation memory and logic gate applications. Crown Copyright (c) 2022 Published by Elsevier Ltd. All rights reserved.

Titanium dioxide nanoparticles (TiO2 NPs) are found in several products on the market that include paints, smart textiles, cosmetics and food products. Besides these, TiO2 NPs are intensively researched for their use in biomedicine, agriculture or installations to produce energy. Taking into account that several risks have been associated with the use of TiO2 NPs, our aim was to provide TiO2 NPs with improved qualities and lower toxicity to humans and the environment. Pure TiO2 P25 NPs and the same NPs co-doped with iron (1%) and nitrogen atoms (P25-Fe(1%)-N NPs) by hydrothermal treatment to increase the photocatalytic activity in the visible light spectrum were in vitro evaluated in the presence of human lung cells. After 24 and 72 h of incubation, the oxidative stress was initiated in a time- and dose-dependent manner with major differences between pure P25 and P25-Fe(1%)-N NPs as revealed by malondialdehyde and reactive oxygen species levels. Additionally, a lower dynamic of autophagic vacuoles formation was observed in cells exposed to Fe-N-doped P25 NPs compared to the pure ones. Therefore, our results suggest that Fe-N doping of TiO2 NPs can represent a valuable alternative to the conventional P25 Degussa particles in industrial and medical applications.

The role of Ag addition on the structural, dielectric, and mechanical harvesting response of 20%(xAg - (1 - x)BaTiO3) - 80%PVDF (x = 0, 2, 5, 7 and 27 vol.%) flexible composites is investigated. The inorganic fillers were realized by precipitating fine (similar to 3 nm) silver nanoparticles onto BaTiO3 nanoparticles (similar to 60 nm average size). The hybrid admixtures with a total filling factor of 20 vol.% were embedded into the PVDF matrix. The presence of filler enhances the amount of beta-PVDF polar phase and the BaTiO3 filler induces an increase of the permittivity from 11 to 18 (1 kHz) in the flexible composites. The addition of increasing amounts of Ag is further beneficial for permittivity increase; with the maximum amount (x = 27 vol.%), permittivity is three times larger than in pure PVDF (epsilon(r) similar to 33 at 1 kHz) with a similar level of tangent losses. This result is due to the local field enhancement in the regions close to the filler-PVDF interfaces which are additionally intensified by the presence of silver nanoparticles. The metallic addition is also beneficial for the mechanical harvesting ability of such composites: the amplitude of the maximum piezoelectric-triboelectric combined output collected in open circuit conditions increases from 0.2 V/cm(2) (PVDF) to 30 V/cm(2) for x = 27 vol.% Ag in a capacitive configuration. The role of ferroelectric and metallic nanoparticles on the increasing mechanical-electric conversion response is also been explained.

Owing to its unique biological and physicochemical properties, hydroxyapatite (HAp) represents one of the most extensively studied biomaterials for biomedical applications. It is well known that Candida is currently one of the fungi frequently involved in the onset and development of post-implant infections and, owing to the appearance of antifungal resistance, it is quite difficult to treat despite all the tremendous efforts made in this regard by the scientific world. Therefore, in this context, we report for the first time in this paper, the development and characterization of europium-doped thin films (5EuHAp, x(Eu) = 0.05) on a Si substrate by a spin-coating method. The results of ultrasound (US), zeta (zeta) potential, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Fourier-transform infrared spectroscopy (FTIR) studies are presented. The XRD studies conducted on 5EuHAp suspension revealed the nanometric dimensions of the particles and sample purity. In addition, a moderate stability of the 5EuHAp suspension was observed. XPS measurements revealed the presence of Eu 3d in the 5EuHAp thin films. In the SEM micrographs, the surface uniformity and the absence of the surface defects could be observed. Moreover, the results of the FTIR studies showed the presence of the vibrational bands specific to the HAp structure in the studied sample. The antifungal activity of the HAp and 5EuHAp suspensions and coatings was evaluated using the Candida albicans ATCC 10231 (C. albicans) fungal strain. The qualitative assays of the antifungal properties of HAp and 5EuHAp coatings were also visualized by SEM and CLSM. The antifungal studies revealed that both 5EuHAp suspensions and coatings exhibited noticeable antifungal activity against C. albicans cells.

Phosphate and tellurite glasses can be used in optics, optoelectronics, magneto-optics, and nuclear and medical fields. Two series of phosphate-tellurite glasses, (50-x)ZnO-10Al(2)O(3)-40P(2)O(5)-xTeO(2) and (40-x)Li2O-10Al(2)O(3)-5TiO(2)-45P(2)O(5)-xTeO(2) (x = 5, 10), were synthesized by a non-conventional wet-route, and the mechanical properties as key performance measures for their application in optoelectronics were investigated. X-ray Diffraction (XRD) measurements revealed the vitreous nature of the investigated materials. Instrumented indentation tests allowed the calculation of hardness (H) and Young's modulus (E) using the Oliver and Pharr model. The influence of increasing the TeO2 content, as well as the substitution of ZnO by Li2O-TiO2, on the variation of hardness, Young's modulus, penetration depth (PD), and fracture toughness (FT) was evaluated in both series. As a general trend, there is a decrease in the hardness and Young's modulus with increasing penetration depth. The addition of Li2O and TiO2 instead of ZnO leads to improved hardness and elastic modulus values. Regarding the H/E ratio, it was found that the samples with lower TeO2 content should be significantly more crack-resistant compared to the higher TeO2 content samples. The H-3/E-2 ratio, being lower than 0.01, revealed a poor resistance of these glasses to plastic deformation. At the same time, a decrease of the fracture toughness with increasing TeO2 content was noticed for each glass series. Based on dilatometry measurements, the thermal expansion coefficient as well as the characteristic temperatures of the glasses were measured. Field Emission Scanning Electron Microscopy-Energy Dispersive X-ray analysis (FESEM-EDX) revealed a uniform distribution of the elements in the bulk samples. The mechanical properties of these vitreous materials are important in relation to their application as magneto-optical Faraday rotators in laser cavities.

We report the mechanical behavior of a bulk boron ceramic prepared by spark plasma sintering of commercially available beta-boron powder. In order to fabricate polycrystalline boron ceramic, we used a protective tantalum foil reacted with carbon from the graphite die or graphite foil forming a thin layer of TaB2 and TaC covering the boron specimen. This is the first study to show the high-temperature flexural strength, toughness, and Young's moduli of boron up to 1400 degrees C. At 1600 degrees C and above, boron will react with testing environment forming an outer shell. The flexural strength and fracture toughness at room temperature reached an average of 340 MPa and 4.1 MPa m (1/2) , respectively. Despite showing clear signs of plastic deformation on the strain-stress curves, the yield strength of the monolithic boron ceramic exceed 1 GPa at 1200 degrees C. It was determined that fracture at elevated temperatures follows a quasi-transgranular mechanism, where the sub-grains of the boron fracture as plate-like structures. An interpretation for the observed fracture behavior was proposed.

Silver doped hydroxyapatite [AgHAp, Ca10-xAg(PO4)(6)(OH)(2)], due to its antimicrobial properties, is an advantageous material to be used for various coatings. The AgHAp thin films with x(Ag) = 0.05 and x(Ag) = 0.1 were achieved using the spin-coating method. The resulting samples were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). XRD analysis revealed that the particles of both samples are ellipsoidal. Also, in agreement with the results obtained by XRD measurements, the results of the SEM studies have shown that the particles shape is ellipsoidal. Optical properties of silver doped hydroxyapatite thin films deposited on Si substrate were investigated through Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. The results obtained by the two complementary techniques highlighted that the molecular structure of the studied samples is not influenced by the increase of the silver concentration in the samples. Our studies revealed that the surface morphology of the obtained samples consist of uniform and continuous layers. The biocompatibility of the obtained thin films was also evaluated with the aid of human osteosarcoma MG63 (ATCC CRL 1427) cell line. Moreover, the in vitro antifungal activity against Candida albicans fungal strain of the AgHAp thin films was studied and the obtained results revealed their antifungal effect. The results of the biological assays showed that the AgHAp thin films are a very promising material for biomedical applications.

MoO2-Fe2O3 nanoparticle systems were successfully synthesized by mechanochemical activation of MoO2 and alpha-Fe2O3 equimolar mixtures throughout 0-12 h of ball-milling. The role of the long-range ferromagnetism of MoO2 on a fraction of more defect hematite nanoparticles supporting a defect antiferromagnetic phase down to the lowest temperatures was investigated in this work. The structure and the size evolution of the nanoparticles were investigated by X-ray diffraction, whereas the magnetic properties were investigated by SQUID magnetometry. The local electronic structure and the specific phase evolution in the analyzed system versus the milling time were investigated by temperature-dependent Mossbauer spectroscopy. The substantially shifted magnetic hysteresis loops were interpreted in terms of the unidirectional anisotropy induced by pinning the long-range ferromagnetic order of the local net magnetic moments in the defect antiferromagnetic phase, as mediated by the diluted magnetic oxide phase of MoO2, to those less defect hematite nanoparticles supporting Morin transition. The specific evolutions of the exchange bias and of the coercive field versus temperature in the samples were interpreted in the frame of the specific phase evolution pointed out by Mossbauer spectroscopy. Depending on the milling time, a different fraction of defect hematite nanoparticles is formed. Less nanoparticles supporting the Morin transition are formed for samples exposed to a longer milling time, with a direct influence on the induced unidirectional anisotropy and related effects.