Publications

TiO2 nanoparticles were synthesized by laser pyrolysis from TiCl4 vapor in air in the presence of ethylene as sensitizer at different working pressures (250-850 mbar) with and without further calcination at 450 degrees C. The obtained powders were analyzed by energydispersive X-ray spectroscopy, X- ray photoelectron spectroscopy, X-ray diffractometry, and transmission electron microscopy. Also, specific surface area and photoluminescence with optical absorbance were evaluated. By varying the synthesis parameters (especially the working pressure), different TiO2 nanopowders were obtained, whose photodegradation properties were tested compared to a commercial Degussa P25 sample. Two series of samples were obtained. Series "a" includes thermally treated TiO2 nanoparticles (to remove impurities) that have different proportions of the anatase phase (41.12-90.74%) mixed with rutile and small crystallite sizes of 11-22 nm. Series "b" series represents nanoparticles with high purity, which did not require thermal treatment after synthesis (ca. 1 atom % of impurities). These nanoparticles show an increased anatase phase content (77.33-87.42%) and crystallite sizes of 23-45 nm. The TEM images showed that in both series small crystallites form spheroidal nanoparticles with dimensions of 40-80 nm, whose number increases with increasing the working pressure. The photocatalytic properties have been investigated regarding the photodegradation of ethanol vapors in Ar with 0.3% O2 using P25 powder as reference under simulated solar light. During the irradiation H-2 gas production has been detected for the samples from series "b", whereas the CO2 evolution was observed for all samples from series "a".

Two neutral copper(I) halide complexes ([Cu(BTU)(2)X], X = Cl, Br) were prepared by the reduction of the corresponding copper(II) halides (chloride or bromide) with a benzoylthiourea (BTU, N-(3,4-diheptyloxybenzoyl)-N '-(4-heptadecafluorooctylphenyl)thiourea) ligand in ethanol. The two copper(I) complexes show a very interesting combination of 2D supramolecular structures, liquid crystalline, emission, and 1D ionic conduction properties. Their chemical structure was ascribed based on ESI-MS, elemental analysis, IR, and NMR spectroscopies (H-1 and C-13), while the mesomorphic behavior was analyzed through a combination of differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and powder X-ray diffraction (XRD). These new copper(I) complexes have mesomorphic properties and exhibit a hexagonal columnar mesophase over a large temperature range, more than 100 K, as evidenced by DSC studies and POM observations. The thermogravimetric analysis (TG) indicated a very good thermal stability of these samples up to the isotropization temperatures and over the whole temperature range of the liquid crystalline phase existence. Both complexes displayed a solid-state emission with quantum yields up to 8% at ambient temperature. The electrical properties of the new metallomesogens were investigated by variable temperature dielectric spectroscopy over the entire temperature range of the liquid crystalline phase. It was found that the liquid crystal phases favoured anhydrous proton conduction provided by the hydrogen-bonding networks formed by the NH horizontal ellipsis X moieties (X = halide or oxygen) of the benzoylthiourea ligand in the copper(I) complexes. A proton conductivity of 2.97 x 10(-7) S.cm(-1) was achieved at 430 K for the chloro-complex and 1.37 x 10(-6) S.cm(-1) at 440K for the related bromo-complex.

Methanol (CH3OH) oxidation offers a promising avenue for transitioning to clean energy, particularly in the field of direct methanol fuel cells (DMFCs). However, the development of efficient and cost-effective catalysts for the methanol oxidation reaction (MOR) remains a critical challenge. Herein, we report the exceptional electrocatalytic activity and stability of Ni3Sn4 toward MOR in acidic media, achieving a performance comparable to that of commercial Pt/C catalysts. Our catalyst design incorporates Earth-abundant Ni and Sn elements, resulting in a material that is 1800 times more cost-effective than Pt/C. Density functional theory (DFT) modeling substantiates our experimental findings, shedding light on the favorable reaction mechanisms and kinetics on the Ni3Sn4 surface. Additionally, the as-synthesized Ni3Sn4 electrocatalyst demonstrates commendable durability, maintaining its electrocatalytic activity even after prolonged exposure to harsh acidic conditions.

Historically, titanium dioxide (TiO2) has been one of the most extensively studied metal oxide photocatalysts; however, it suffers from a large bandgap and fast charge recombination. We report the use of green, rapid, single-step continuous hydrothermal flow synthesis for the preparation of TiO2, and TiO2 hybrids with reduced graphene oxide (rGO) and/or N-doped carbon quantum dots (NCQDs) with significant enhancement in photocatalytic activity. Using a solar light generator under ambient conditions with no extra oxygen gas added, we observed the evolution reaction of the model pollutant (methylene blue) in real time. Tailoring of the light absorption to match that of the solar spectrum was achieved by a combination of materials of nano-TiO2 hybrids of nitrogen-doped carbon quantum dots and graphene in its reduced form with a photocatalytic rate constant of ca. 25 x 10(-5) s(-1). Using a diversity of state-of-the-art techniques including high-resolution transmission electron microscopy, transient photoluminescence, X-ray photoelectron spectroscopy and high accuracy, sophisticated hybrid density functional theory calculations we have gained substantial insight into the charge transfer and modulation of the energy band edges of anatase due to the presence of graphene or carbon dots, parameters which play a key role in improving drastically the photocatalytic efficiencies when compared to pristine titania. More importantly, we prove that a combination of features and materials displays the best photocatalytic behaviour. This performance is delivered in a greener synthetic process that not only produces photocatalytic materials with optimised properties and tailored visible light absorption and efficiency but also provides a path to industrialization.

We simulated numerically and demonstrated experimentally that the thermal emittance of a metasurface consisting of an array of rectangular metallic meta-atoms patterned on a layered periodic dielectric structure grown on top of a metallic layer can be tuned by changing several parameters. The resonance frequency, designed to be in the near-infrared spectral region, can be tuned by modifying the number of dielectric periods, and the polarization and incidence angle of the incoming radiation. In addition, the absorbance/emittance value at the resonant wavelength can be tuned by modifying the orientation of meta-atoms with respect to the illumination direction.

Zinc substituted nickel-cobalt ferrites, i.e., ZnxNi0.8-xCo0.2Fe2O4 (x = 0.0, 0.05, 0.10 and 0.20) with average crystallite size 100 nm were synthesized by citrate-gel auto-combustion method to investigate effects of Zn2+ substitution on the structural and dielectric properties. Both X-ray diffraction (XRD) and IR spectroscopy studies confirms the formation of pure cubic spinel structure. Variation of lattice parameter infers Vegard's law linear dependence with the addition of Zn2+ concentration. The temperature-dependent behavior of dielectric and modulus spectra has been studied within the frequency range 100 Hz-100 kHz for different temperatures between 100 K and 400 K. It was concluded that the dielectric responses of ZnxNi0.8-xCo0.2Fe2O4 are found to be frequency dependent and thermally activated. Also, In the Zn doped ferrites variations of dielectric loss (tan d) and the imaginary part of electric modulus (M") show the presence of the non-Debye type of dielectric relaxation. Rise in Zinc concentration leads to a decrease in dielectric constant (e (r)) due to the declining of Fe3+-O-M2+ conducting network (M is Co or Ni). Here, we report a low loss tangent factor of the order of 8x10-3 0.6Zn(0.2)Co(0.2)Fe(2)O(4) make this composition suitable for high frequency-applications at room temperature. The activation energy is calculated from electric modulus formalism and DC electrical conductivity and found to increase with further substitution of Zn2+ concentration.

Sub-stochiometric nickel oxide (NiOx) films were investigated as a hole selective contact option in silicon (Si) heterojunction solar cells. Numerical simulations were carried out to evaluate the impacts of the NiOx electronic properties variations and the NiOx/Si interface defect density (D-it) on device performance. Simulation data suggest that the best performance is achievable for wide bandgaps (E-g) and corresponding high valence band edge (E-VB) positions in the NiOx films. Overall, in simulations, the performance remains practically unchanged for the nickel vacancy concentrations [V-Ni] = 10(17)-10(21 )cm(-3), assuming high E-VB and low D-it. The experimental data measured using NiOx films prepared by radio-frequency magnetron sputtering reveal that the increase in [V-Ni] lifts the conductivity, concurrently decreasing E-g and E-VB. As a result, we concluded that the performance of the fabricated sputtered NiOx/Si heterojunction solar cell is limited by high D-it as well as narrow E-g and low E-VB.

A new approach for the stabilization of the ferroelectric orthorhombic ZrO2 films is demonstrated through nanosecond laser annealing (NLA) of as-deposited Si/SiOx/W(14 nm)/ZrO2(8 nm)/W(22 nm), grown by ion beam sputtering at low temperatures. The NLA process optimization is guided by COMSOL multiphysics simulations. The films annealed under the optimized conditions reveal the presence of the orthorhombic phase, as confirmed by X-ray diffraction, electron backscatter diffraction, and transmission electron microscopy. Macroscopic polarization-electric field hysteresis loops show ferroelectric behavior, with saturation polarization of 12.8 mu C cm(-2), remnant polarization of 12.7 mu C cm(-2) and coercive field of 1.2 MV cm(-1). The films exhibit a wake-up effect that is attributed to the migration of point defects, such as oxygen vacancies, and/or a transition from nonferroelectric (monoclinic and tetragonal phase) to the ferroelectric orthorhombic phase. The capacitors demonstrate a stable polarization with an endurance of 6.0 x 10(5) cycles, demonstrating the potential of the NLA process for the fabrication of ferroelectric memory devices with high polarization, low coercive field, and high cycling stability.

High density (99.5%) ceramic composite composed of titanium boride and boron carbide (70/30 vol%) was obtained by spark plasma sintering and was tested by 3-point bending test in Ar atmosphere at 1800 degrees C. Bending strength was high, around 1.1 GPa. The strength-strain curve presents a peculiar shape composed of three regions where elastic and plastic deformations are active with a different weight. Based on transmission electron microscopy observations we propose a process of mechanical energy absorption driven by shear stress in the boron carbide crystals: stacking faults with (1-11) and (011) stacking planes and twins with (1-11) twinning plane rearrange into nano-twins with (10-1) twinning planes, orthogonal but equivalent to the initial ones. This rearrangement mechanism provides in the first instance a plastic signature, but further contributes strengthening.

For practical applications of superconductors, understanding the vortex matter and dynamics is of paramount importance. An important issue in this context is the transition of the vortex glass, which is a true superconducting phase, into a vortex liquid phase having a linear dissipation. By using multi-harmonic susceptibility studies, we have investigated the vortex glass-vortex liquid phase transitions in CaKFe4As4 and BaFe2(As0.68P0.32)(2) single crystals. The principle of our method relates the on-set of the third-harmonic susceptibility response with the appearance of a vortex-glass phase in which the dissipation is non-linear. Similar to the high-critical temperature cuprate superconductors, we have shown that even in these iron-based superconductors with significant lower critical temperatures, such phase transition can be treated as a melting in the sense of Lindemann's approach, considering an anisotropic Ginzburg-Landau model. The experimental data are consistent with a temperature-dependent London penetration depth given by a 3D XY fluctuations model. The fitting parameters allowed us to extrapolate the vortex melting lines down to the temperature of liquid hydrogen, and such extrapolation showed that CaKFe4As4 is a very promising superconducting material for high field applications in liquid hydrogen, with a melting field at 20 K of the order of 100 T.