Publications

A rapidly-growing 3D printing technology is innovatively employed for the manufacture of a new class of heterogenous catalysts for the conversion of CO2 into industrially relevant chemicals such as cyclic carbonates. For the first time, directly printed graphene-based 3D structured nanocatalysts have been developed combining the exceptional properties of graphene and active CeZrLa mixed-oxide nano particles. It constitutes a significant advance on previous attempts at 3D printing graphene inks in that it does not merely explore the printability itself, but enhances the efficiency of industrially relevant reactions, such as CO2 utilisation for direct propylene carbonate (PC) production in the absence of organic solvents. In comparison to the starting powder, 3D printed GO-supported CeZeLa catalysts showed improved activity with higher conversion and no noticeable change in selectivity. This can be attributed to the spatially uniform distribution of nanoparticles over the 2D and 3D surfaces, and the larger surface area and pore volume of the printed structures. 3D printed GO-supported CeZeLa catalysts compared to unsupported 3D printed samples exhibited higher selectivity and yield owing to the great number of new weak acid sites appearing in the supported sample, as observed by NH3-TPD analysis. In addition, the catalyst's facile separation from the product has the capacity to massively reduce materials and operating costs resulting in increased sustainability. It convincingly shows the potential of these printing technologies in revolutionising the way catalysts and catalytic reactors are designed in the general quest for clean technologies and greener chemistry. 2019 Elsevier Ltd. All rights reserved.

Laser melting deposition is a 3D printing method usually studied for the manufacturing of machine parts in the industry. However, for the medical sector, although feasible, applications and actual products taking advantage of this technique are only scarcely reported. Therefore, in this study, Ti6Al4V orthopedic implants in the form of plates were 3D printed by laser melting deposition. Tuning of the laser power, scanning speed and powder feed rate was conducted, in order to obtain a continuous deposition after a single laser pass and to diminish unwanted blown powder, stuck in the vicinity of the printed elements. The fabrication of bone plates is presented in detail, putting emphasis on the scanning direction, which had a decisive role in the 3D printing resolution. The printed material was investigated by optical microscopy and was found to be dense, with no visible pores or cracks. The metallographic investigations and X-ray diffraction data exposed an unusual biphasic alpha+beta structure. The energy dispersive X-ray spectroscopy revealed a composition very similar to the one of the starting powder material. The mapping of the surface showed a uniform distribution of elements, with no segregations or areas with deficient elemental distribution. The in vitro tests performed on the 3D printed Ti6Al4V samples in osteoblast-like cell cultures up to 7 days showed that the material deposited by laser melting is cytocompatible.

Plasma assisted atomic oxygen deposition was used to grow polycrystalline ferroelectric Hf1-xZrxO2 (x = 0.5-0.7) on technologically important (100) Germanium substrates showing sharp crystalline interfaces free of interfacial amorphous layers and strong evidence for the presence of a predominately orthorhombic phase. The electrical properties, evaluated using metal-ferroelectric-semiconductor (MFS) capacitors, show symmetric and robust ferroelectric hysteresis with weak or no wake-up effects. The MFS capacitors with x = 0.58 show very large remanent polarization up to 34.4 mu C/cm(2) or 30.6 mu C/cm(2) after correction for leakage and parasitics, combined with good endurance reaching 10(5) cycles at a cycling field of 2.3 MV/cm. The results show good prospects for the fabrication of Ge ferroelectric field effect transistors (FeFETs) for use in 1 T FeFET embedded nonvolatile memory cells with improved endurance. (C) 2019 Author(s).

The research focuses on a few key points concerning the light-driven processes taking place on TiO2 anatase and sodium titanates with tubular morphology, such as the relationship between the morphology and activity for H-2 and CO2 production, density of surface hydroxyl groups, ROS (center dot OH and center dot O-2(-)) production and photocatalytic activity, and charge separation at the interface of semiconducting domains and enhancement of activity. One key point discussed is whether the materials with peculiar morphologies (i.e. tubular) are superior to the conventional ones. The experimental evidences show that the main advantage of the tubular morphology of sodium titanate is given by its significantly higher surface area compared to parental anatase. FTIR and XPS progressive analyses evidence that the density of surface hydroxyl groups decreases with the development of the tubular morphology. The radical trapping experiments show that the variation of surface hydroxyl density is, generally, followed by activities for center dot OH and center dot O-2(-) generation, as well as by the photocatalytic production of H-2 and CO2 from water/methanol mixture. Consequently, the ROS, formed by action of photogenerated electrons and holes on adsorbed O-2 and hydroxyl groups, respectively, play an important role in determining the photocatalytic activity of titania-based materials. The other major aspect revealed by this research is that the charge separation at the interfaces formed between anatase and sodium titanate crystalline phases has remarkable effect on the activity formation rates of H-2 and CO2.

Polycrystalline ruthenium-doped lithium-copper-ferrite (Ru - LiCuFe2O4)nanoparticles (NPs) are synthesized using a simple and cost-effective chemical co-precipitation method and annealed at different temperatures for increasing the crystallinity. The transmission and scanning electron microscopy images have confirmed the presence of soft agglomerations and cuboids for the samples annealed at 1100 degrees C. X-ray photoelectron results along with Raman spectra have collectively demonstrated the presence of Ru in the structure of Ru - LiCuFe2O4 NPs. The dielectric properties of as-synthesized Ru - LiCuFe2O4 NPs are investigated using LCR meter where the smaller NPs demonstrates a higher dielectric constant. Also, the results of magnetic measurements of annealed Ru - LiCuFe2O4 NPs have corroborated a soft magnetic nature due to the pinning sites that endow lower coercivity, remanence and saturation magnetization than that of the pristine one. The variation of permittivity and electrical resistivity with respect to frequency under humidity conditions suggested that this material has a potential to use as capacitive and resistive humidity sensor. The results of this study open the doors for utilization of metal-doped magnetic ferrites for humidity sensing applications.

The one-pot production of HMF from glucose was investigated in pure hot water and biphasic water/methyli-sobutylketone (MIBK) solvent using mesoporous Nb(0.02 and 0.05 mol%)-Beta zeolites obtained by a post synthesis methodology. The mesoporous Nb-Beta zeolites present residual framework Al-acid sites, extra-framework isolated Nb(V) and Nb2O5 pore-encapsulated clusters in which Nb(V) O-H exhibit moderate strength Bronsted acidity. After optimization, the dehydration of glucose onto the Nb-modified Beta-zeolites occurred with a selectivity of 84.3% in HMF for a glucose conversion of 97.4%. This result has been obtained in a biphasic water/ MIBK solvent and in the presence of NaCl, at 180 degrees C, after 12 h.

This study deals with the behavior of molybdenum-vanadium (Mo/V) mixed oxides catalysts in both disproportionation and selective oxidation of toluene. Samples containing different Mo/V ratios were prepared by a modified method using tetradecyltrimethylammonium bromide and acetic acid. The catalysts were characterized using several techniques: nitrogen adsorption-desorption isotherms, X-Ray diffraction (XRD), ammonia temperature-programmed desorption (TPD-NH3), temperature-programmed reduction by hydrogen (H-2-TPR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, Fourier-transform infrared-spectroscopy (FTIR) and ultraviolet-visible spectroscopies (UV-VIS). The XRD results evidenced the presence of orthorhombic -MoO3 and V2O5 phases, as well as monoclinic -MoO3 and V2MoO8 phases, their abundance depending on the Mo to V ratio, while the TPD-NH3 emphasized that, the total amount of the acid sites diminished with the increase of the Mo loading. The TPR investigations indicated that the samples with higher Mo/V ratio possess a higher reducibility. The main findings of this study led to the conclusion that the presence of strong acid sites afforded a high conversion in toluene disproportionation (Mo/V = 1), while a higher reducibility is a prerequisite to accomplishing high conversion in toluene oxidation (Mo/V = 2). The catalyst with Mo/V = 1 acquires the best yield to xylenes from the toluene disproportionation reaction, while the catalyst with Mo/V = 0.33 presents the highest yield to benzaldehyde.

In this work, we theoretically model the time-dependent transport through an asymmetric double quantum dot etched in a two-dimensional wire embedded in a far-infrared (FIR) photon cavity. For the transient and the intermediate time regimes, the current and the average photon number are calculated by solving a Markovian master equation in the dressed-states picture, with the Coulomb interaction also taken into account. We predict that in the presence of a transverse magnetic field the interdot Rabi oscillations appearing in the intermediate and transient regime coexist with slower non-equilibrium fluctuations in the occupation of states for opposite spin orientation. The interdot Rabi oscillation induces charge oscillations across the system and a phase difference between the transient source and drain currents. We point out a difference between the steady-state correlation functions in the Coulomb blocking and the photon-assisted transport regimes.

Photosensitive films based on finely dispersed semiconductor nanocrystals (NCs) in dielectric films have great potential for sensor applications. Here we report on preparation and characterization of photosensitive Si1-xGex NCs sandwiched between SiO2 matrix. A radio-frequency magnetron sputtering was applied to obtain a multilayer-structures (MLs) by depositing SiO2/SiGe/SiO2 films on Si (0 0 1) substrate. The Si1-xGex NCs were formed by a post-deposition annealing at 100-700 degrees C for 1-5 min. The effect of annealing temperature and time on MLs morphology and NCs size and density was studied using grazing incidence X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy and measurements of spectral distribution of photocurrent. It is demonstrated how the photoconductive properties of the MLs can be enhanced and tailored by controlling the NCs formation conditions and the presence of stress field in MLs and defects acting as traps and recombination centers. All these features can be adjusted/controlled by altering the annealing conditions (temperature and time). The MLs photosensitivity was increased of more than an order of magnitude by the annealing process. A mechanism, where a competition between crystallization process (NCs formation and evolution i.e. size and shapes) and stress field appearance determines the peak position in the photocurrent spectra, was identified.

A series of seven alkali-free silica-based bioactive glasses (SBG) with ZnO and/or SrO additives (in concentrations of 0-12 mol%) were synthesized by melt-quenching, aiming to delineate a candidate formulation possessing (i) a coefficient of thermal expansion (CTE) similar to the one of titanium (Ti) and its medical grade super alloys (crucial for the future development of mechanically adherent implant-type SBG coatings) and (ii) antibacterial efficiency, while (iii) conserving a good cytocompatibility. The SBGs powders were multi-parametrically evaluated by X-ray diffraction, Fourier transform infrared and micro-Raman spectroscopy, dilatometry, inductively coupled plasma mass spectrometry, antibacterial (against Staphylococcus aureus and Escherichia coli strains) suspension inhibition and agar diffusion tests, and human mesenchymal stem cells cytocompatibility assays. The results showed that the coupled incorporation of zinc and strontium ions into the parent glass composition has a combinatorial and additive benefit. In particular, the "Z6S4" formulation (mol%: SiO2-38.49, CaO-32.07, P2O5-5.61, MgO-13.24, CaF2-0.59, ZnO-6.0, SrO-4.0) conferred strong antimicrobial activity against both types of strains, minimal cytotoxicity combined with good stem cells viability and proliferation, and a CTE (similar to 8.7 x 10(-6) x degrees C-1) matching well those of the Ti-based implant materials.