Publications

This contribution concerns the catalytic activity of functional layered double hydroxides (LDHs) for 1,4-addition of n-octanol to 2-propenonitrile aiming to investigate the influence of the organic interlayer anion nature on their physico-chemical and catalytic performances. Two series of functional LDHs, e.g. Mg2.5Al, and Zn2.5Al respectively, were synthesized by co-precipitation at pH 9.5 using a metal nitrates M2+ (NO3)(2)center dot 6H(2)O (M2+ = Mg, Zn), Al(NO3)(3)center dot 9H(2)O solution, an organic acid sodium salt (e.g. sodium dodecyl sulfate (NaDS), sodium laurate (NaL), or sodium stearate (NaS)) and NaOH solution for pH adjustment. XRD, DRIFTS and DR-UV-Vis-NIR characterizations indicated a better intercalation of DS in the interlayer region compared to L or S. The catalytic activity of these solids was related to both their organophilic character and basicity, Mg2.5Al-DS samples, which were more basic, showed a higher activity than Zn2.5Al-DS.

The crystallization mechanism of sol-gel-derived NaYF4:(Yb, Er) up-converting phosphors has been studied by differential scanning calorimetry analysis using both model-free and model fitting approaches. Structural and optical data have shown that the hexagonal NaYF4:(Yb, Er) phase crystallization process occurs at around 315 degrees C as a result of the thermal decomposition of the metal trifluoroacetates. As the annealing temperature increases, sphere-like microcrystals of about 1-2 mu m size (at 300 degrees C) break up into smaller ones (400-500 nm size) and finally collapse at higher temperatures (600 degrees C); the up-conversion luminescence signal intensity increases due to the crystallinity improvement and dehydration process. The crystallization process can be described as an autocatalytic-type reaction where the accompanying cubic NaYF4 phase played a catalytic role by reducing the energy barrier against the crystallization of the hexagonal NaYF4 phase, causing its fast self-accelerated crystallization. The energy resulting from the disintegration process of the initial NaYF4 microcrystals contributed to the growth and agglomeration processes and finally the collapse of the crystalline fragments with increasing temperature.

The exciton-phonon interaction, considered as a stimulated Raman scattering process, is studied in different semiconductor mixtures: PbI2/TiO2, PbI2/Si and CdS/Si. Raman spectra recorded at excitation wavelengths of 514.5 and 488 nm for PbI2 and CdS, respectively, reveal a strong enhancement of the Raman lines peaked at 97 and 305 cm(-1), evaluated by the ratio I-TK/I-300 (K) between the relative intensities of the spectra recorded in the temperature range of 88-300 K. It is found that PbI2 and CdS exhibit a decrease in the Raman intensity modes with decreasing temperature, while in TiO2 and Si an increase in the Raman lines intensities peaked at 138 and 520 cm(-1) is observed. This behavior can be explained by an energy transfer process from PbI2 or CdS towards TiO2 and Si. This explanation is supported by the schematic potential energy levels diagram obtained from the density of states, which is calculated using the density functional theory. According to this energy levels diagram, the electrons are expected to migrate directly from the conduction band (CB) energetic levels of the PbI2 and CdS towards the CB levels of TiO2 and Si.

The synthesis of Cu-0 nanoparticles on different supports and their activity in controlled living radical polymerization processes is presented. The type of support influences the final size of the copper nanoparticles as well as their adhesion to the support. These aspects have a direct influence on the characteristics of the polymers obtained. The best results were obtained for SiO2 particles, which afforded a good molecular weight distribution (Mw/Mn = 1.25). The activity, recovery and recycling of the catalyst was explored for ultrafast polymerization reaction of butyl acrylate. Further, the terminal bromine reactivity was used for the synthesis of a block poly(n butyl acrylate-block-styrene). The influence of ligand type on the control of the reaction was studied. Also, a straightforward polymerization procedure without any ligand afforded a polydispersity value of 1.38.

We propose a novel idea to improve the surface properties of carbon-based Pt-free electrocatalysts in Polymer Electrolyte Membranes (PEMs) and Alkaline Fuel Cells (AFCs). Our concept is based on the addition of oxygenophilic and hydrophobic ionic liquids (ILs) to form a thin passivating layer at the triple point between the electrocatalyst-electrolyte-gas interface where the Oxygen Reduction Reaction (ORR) takes place.

Graphene is widely used in nanotechnologies to amplify the photocatalytic activity of TiO2, but the development of TiO2/graphene composites imposes the assessment of their risk to human and environmental health. Therefore, reduced graphene oxide was decorated with two types of TiO2 particles co-doped with 1% iron and nitrogen, one of them being obtained by a simultaneous precipitation of Ti3+ and Fe3+ ions to achieve their uniform distribution, and the other one after a sequential precipitation of these two cations for a higher concentration of iron on the surface. Physico-chemical characterization, photocatalytic efficiency evaluation, antimicrobial analysis and biocompatibility assessment were performed for these TiO2-based composites. The best photocatalytic efficiency was found for the sample with iron atoms localized at the sample surface. A very good anti-inhibitory activity was obtained for both samples against biofilms of Gram-positive and Gram-negative strains. Exposure of human skin and lung fibroblasts to photocatalysts did not significantly affect cell viability, but analysis of oxidative stress showed increased levels of carbonyl groups and advanced oxidation protein products for both cell lines after 48 h of incubation. Our findings are of major importance by providing useful knowledge for future photocatalytic self-cleaning and biomedical applications of graphene-based materials.

We present an investigation consisting of single walled carbon nanotubes (SWCNTs) based cryogenic temperature sensors, capable of measuring temperatures in the range of 2-77 K. Carbon nanotubes (CNTs) due to their extremely small size, superior thermal and electrical properties have suggested that it is possible to create devices that will meet necessary requirements for miniaturization and better performance, by comparison to temperature sensors currently available on the market. Starting from SWCNTs, as starting material, a resistive structure was designed. Employing dropcast method, the carbon nanotubes were deposited over pairs of gold electrodes and in between the structure electrodes from a solution. The procedure was followed by an alignment process between the electrodes using a dielectrophoretic method. Two sensor structures were tested in cryogenic field down to 2 K, and the resistance was measured using a standard four-point method. The measurement results suggest that, at temperatures below 20 K, the temperature coefficient of resistance average for sensor 1 is 1.473%/K and for sensor 2 is 0.365%/K. From the experimental data, it can be concluded that the dependence of electrical resistance versus temperature can be approximated by an exponential equation and, correspondingly, a set of coefficients are calculated. It is further concluded that the proposed approach described here offers several advantages, which can be employed in the fabrication of a microsensors for cryogenic applications.

The specific dynamic magnetic response and magnetic relaxation phenomena in magnetite-based glass-ceramics by controlled crystallization of Fe-rich borosilicate glasses with 25 wt% Fe2O3, in the presence of two types of nucleating agents, Cr2O3 and P2O5, were investigated. The magnetic response is complex and shows contributions arising from two subsystems: a system with collective characteristics, superspin-glass like, and another one with single particle characteristics (superparamagnetic) with dipolar interaction. The nucleating agents have strong influence on the characteristic temperatures and anisotropy energy.

Epitaxial Pb(Zr0.2Ti0.8)O-3 (PZT) thin films were grown by pulsed laser deposition on two slightly different types of single crystal substrates, namely SrTiO3 (STO) buffered with a thin layer of conductive SrRuO3 (SRO), and SrTiO3 doped with 0.5% Nb (STON). Although self-poling effect was expected in both cases, due to the compressive strain imposed by the substrate, it was found that the pyroelectric response of as grown samples is with about two orders of magnitude larger for the PZT film deposited on SRO/STO compared to the one deposited on STON substrate. In order to explain the finding, the electrical properties were investigated and it was found that the quantities involved in the equation giving the magnitude of the pyroelectric signal, namely dielectric constant and electrical resistivity, have about the same values Therefore, the different pyroelectric response in the as-grown samples was explained by different structure of ferroelectric domains induced by the different carrier concentration in the two substrates: 90 degrees domains for PZT on SRO/STO and 180 degrees domains for PZT on STON. It appears that the resistivity of the substrate and its ability to compensate the depolarization field affect the domain structure, with impact on the pyroelectric response, although the strain conditions are similar in both cases. The trying to increase the pyroelectric response for the PZT film deposited on STON substrate by applying a poling process was not successful, as the 180 degrees domain structure restores shortly after removing the poling field. (C) 2017 Elsevier Ltd. All rights reserved.

The stability of thin films of lead zirco-titanate (PZT) under intense soft X-ray beams is investigated by time-resolved photoelectron spectromicroscopy with a lateral resolution below 1 micrometer. Surface dissociation is observed when samples are irradiated with intense (5 x 10(23) photons per s per m(2)) soft X-rays, with promotion of reduced lead on the surface. On areas exhibiting outwards polarization (P(+)), the reduced lead is formed at the expense of P(+)-PZT. On areas presenting co-existing P(+) states with areas without out-of-plane polarization (P-(0)), the reduced lead is formed at the expense of the P-(0)-PZT component, while the P(+)-PZT remains constant. The main dissociation mechanism was found to be triggered by 'hot' electrons in the conduction band, with energies exceeding the surface dissociation energies. Dissociation occurs basically when the electron affinity is larger than the dissociation energy of PbO (for P(+) areas) or PbO- (for P-(0) areas). Such mechanisms may be adapted for dissociation of other molecules on surfaces of ferroelectric thin films or for quantifying the stability of ferroelectric surfaces interacting with other radiation, with applications in the fields of photocatalysis or photovoltaic devices.