National Institute Of Materials Physics - Romania

Polymer electrolyte membrane fuel cells require cheap and active electrocatalysts to drive the oxygen reduction reaction. Nitrogen-doped carbons have been extensively studied regarding their oxygen reduction reaction. The work at hand looks beyond the nitrogen chemistry and brings to light the role of oxygen. Nitrogen-doped nanocarbons were obtained by a radio-frequency plasma route at 0, 100, 250, and 350 W. The lateral size of the graphitic domain, determined from Raman spectroscopy, showed that the nitrogen plasma treatment decreased the crystallite size. Synchrotron radiation photoelectron spectroscopy showed a similar nitrogen chemistry, albeit the nitrogen concentration increased with the plasma power. Lateral crystallite size and several nitrogen moieties were plotted against the onset potential determined from oxygen reduction reaction curves. There was no correlation between the electrochemical activity and the sample structure, as determine from Raman and synchrotron radiation photoelectron spectroscopy. Near-edge X-ray absorption fine structure (NEXAFS) was performed to unravel the carbon and nitrogen local structure. A difference analysis of the NEXAFS spectra showed that the oxygen surrounding the pyridinic nitrogen was critical in achieving high onset potentials. The work shows that there were more factors at play, other than carbon organization and nitrogen chemistry.

Resveratrol (RES) is a naturally occurring product with numerous biological activities. Despite its potential benefits, its use is limited due to its low aqueous stability and solubility in its native form. The porous sol-gel silica materials which are able to entrap different organic molecules represent new studied release carriers. The aim of this work was to generate a solid matrix to encapsulate RES ensuring protection, increased solubility and release in solutions. A non-toxic ingredient, namely beta-cyclodextrin (beta-CD), able to form inclusion complexes (ICs) with RES has been used. Ecological formulations have been processed by entrapping the RES containing ICs in silica matrices obtained from a silica colloidal sol by the aqueous route of the sol-gel method. Characterization methods (DSC, FTIR, UV-Vis, fluorescence studies, SEM) have evidenced the presence of RES-beta-CD inclusion complex in the silica powder, RES stability in the matrix and its release in aqueous and organic solutions, and the morphology of the carrier. An evaluation of the antioxidant activity of RES in the present formulation was performed by the chemiluminescence assay and RES release profile in aqueous solutions was obtained by HPLC-MS. The resulted materials can find applications in different domains. Graphic abstract

In this work, amorphous tin oxide thin films were deposited by non-reactive radio frequency magnetron sputtering. A ceramic SnO2 target was used, while different working pressures were employed. The target to substrate distance was fixed to 17 cm, and the substrate was not intentionally heated. The properties of SnO2 (thickness, refractive index dispersion, optical band gap, resistivity, free carriers concentration, carriers mobility, carriers majority type and their scattering time) have been inferred from spectroscopic ellipsometry, conventional UV-Vis spectroscopy and specific Hall electrical measurements. Thickness and refractive index are slightly dependent on the deposition conditions, while the optical band gap, free carriers concentration and their mobilities are changing from sample to sample. The evolution of the optical band gap and carriers concentration is correlated to the active defects concentration. Amorphous SnO2 films grown at 0.4 Pa have the lowest resistivity of 0.86 Omega cm, a carrier concentration of 1.05x10(18)cm(-3) Vs. The average optical transmittance in visible spectrum is 76%.

A successful bone-graft-controlled healing entails the development of novel products with tunable compositional and architectural features and mechanical performances and is, thereby, able to accommodate fast bone in-growth and remodeling. To this effect, graphene nanoplatelets and Luffa-fibers were chosen as mechanical reinforcement phase and sacrificial template, respectively, and incorporated into a hydroxyapatite and brushite matrix derived by marble conversion with the help of a reproducible technology. The bio-products, framed by a one-stage-addition polymer-free fabrication route, were thoroughly physico-chemically investigated (by XRD, FTIR spectroscopy, SEM, and nano-computed tomography analysis, as well as surface energy measurements and mechanical performance assessments) after sintering in air or nitrogen ambient. The experiments exposed that the coupling of a nitrogen ambient with the graphene admixing triggers, in both compact and porous samples, important structural (i.e., decomposition of beta-Ca-3(PO4)(2) into alpha-Ca-3(PO4)(2) and alpha-Ca2P2O7) and morphological modifications. Certain restrictions and benefits were outlined with respect to the spatial porosity and global mechanical features of the derived bone scaffolds. Specifically, in nitrogen ambient, the graphene amount should be set to a maximum 0.25 wt.% in the case of compact products, while for the porous ones, significantly augmented compressive strengths were revealed at all graphene amounts. The sintering ambient or the graphene addition did not interfere with the Luffa ability to generate 3D-channels-arrays at high temperatures. It can be concluded that both Luffa and graphene agents act as adjuvants under nitrogen ambient, and that their incorporation-ratio can be modulated to favorably fit certain foreseeable biomedical applications.

In this study, nano-BaTiO3 (BTO) powders were obtained via the solvothermal method at different reaction times and were investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy. The results were compared with those obtained for a larger crystallite size BTO powder (BTO-m). The sizes of the cuboid crystallites (as determined by XRD and TEM) ranged from about 18 to 24 nm, depending on the reaction time. The evolution with temperature of the structure parameters of nano-BTO was monitored by means of X-ray diffraction and Raman spectroscopy and no signs of phase transition were found up to 170 degrees C. Careful monitoring of the dependence of the XRD peak widths on the hkl indices showed that the effect of the cubic crystallite shape upon the XRD peak widths was buried by the effect of hidden tetragonal line splits and by anisotropic microstrain. The good correlation of the line widths with the tetragonal split amplitudes, observed especially for BTO-m above the transition temperature, indicates tetragonal deformations, as also revealed by Raman spectroscopy. The large anisotropic microstrain shown by the nano-powders, which had a maximum value in the directions, was considered evidence of the phenomenon of surface relaxation of cubic crystallites edged by {100} faces. The observed behavior of the nano-BTO structures with increasing temperature may suggest a correlation between the surface relaxation and tetragonal deformation in the nano-cubes. The experimental results for both nano-BTO and mezoscale-BTO are in agreement with the core-shell model.

Thin AlN piezoelectric layers have been deposited on high resistivity Si and glass substrates by reactive RF magnetron sputtering, in order to manufacture one-port gigahertz operating surface acoustic wave (SAW)-type resonators to be used as temperature sensors. The growth morphology surface topography, crystallographic structure, and crystalline quality of the AlN layers have been analyzed. Advanced nanolithographic techniques have been used to manufacture structures having interdigitated transducers with fingers and finger interdigit spacing width in the range of 250-170 nm. High resonance frequency ensures the increase of the sensitivity, but also of its normalized value, the temperature coefficient of frequency (TCF). The resonance frequency shift versus temperature has been measured in the -267 degrees C-+150 degrees C temperature range, using a cryostat setup adapted for on wafer microwave measurements up to 50 GHz. The sensitivity and the TCF were determined in the 25 degrees C-150 degrees C temperature range.

Web-like architectures of ZnO and TiO2 nanotubes were fabricated based on a three-step process of templating polymer nanofibers produced by electrospinning (step 1). The electrospun polymer nanofibers were covered by radio-frequency magnetron sputtering with thin layers of semiconducting materials (step 2), with FESEM observations proving uniform deposits over their entire surface. ZnO or TiO2 nanotubes were obtained by subsequent calcination (step 3). XRD measurements proved that the nanotubes were of a single crystalline phase (wurtzite for ZnO and anatase for TiO2) and that no other crystalline phases appeared. No other elements were present in the composition of the nanotubes, confirmed by EDX measurements. Reflectance spectra and Tauc plots of Kubelka-Munk functions revealed that the band gaps of the nanotubes were lower than those of the bulk materials (3.05 eV for ZnO and 3.16 eV for TiO2). Photocatalytic performances for the degradation of Rhodamine B showed a large degradation efficiency, even for small quantities of nanotubes (0.5 mg/10 mL dye solution): similar to 55% for ZnO, and similar to 95% for TiO2.

Continuing growth in global energy consumption and the growing concerns regarding climate change and environmental pollution are the strongest drivers of renewable energy deployment. Solar energy is the most abundant and cleanest renewable energy source available. Nowadays, photovoltaic technologies can be regarded as viable pathways to provide sustainable energy generation, the achievement attained in designing nanomaterials with tunable properties and the progress made in the production processes having a major impact in their development. Solar cells involving hybrid nanocomposite layers have, lately, received extensive research attention due to the possibility to combine the advantages derived from the properties of both components: flexibility and processability from the organic part and stability and optoelectronics features from the inorganic part. Thus, this review provides a synopsis on hybrid solar cells developed in the last decade which involve composite layers deposited by spin-coating, the most used deposition method, and matrix-assisted pulsed laser evaporation, a relatively new deposition technique. The overview is focused on the hybrid nanocomposite films that can use conducting polymers and metal phthalocyanines as p-type materials, fullerene derivatives and non-fullerene compounds as n-type materials, and semiconductor nanostructures based on metal oxide, chalcogenides, and silicon. A survey regarding the influence of various factors on the hybrid solar cell efficiency is given in order to identify new strategies for enhancing the device performance in the upcoming years.

In this paper we report the results of a photoelectrochemical study performed on photoanodes based on hematite nanowire arrays and films prepared on fluoride-doped tin oxide coated glass (FTO) and FTO/TiO2 substrates, respectively by hydrothermal and spray pyrolysis methods. The hematite nanowires grown on FTO/TiO2 substrate are more stable mechanically, longer (1 ?m) and their density on substrate is higher. Hematite film obtained on FTO substrate has a thickness of 92 nm covering uniformly the substrate. X-ray photoelectron spectroscopy measurements showed that hematite samples synthesized on FTO/TiO2 substrate have lower content of oxygen vacancies. The photoelectrochemical performances of the prepared photoanodes are in close connection with the presence or absence of the TiO2 underlayer, with oxygen vacancies content and with their morphological characteristics. Electrochemical impedace spectroscopy was used to investigate the charge transfer kinetics at electrode/electrolyte interface and Mott-Schottky analysis was performed to estimate the flatband potential and the carrier density. TiO2 underlayer led to the formation of defects on the samples surface which induced a positive shift of the flatband potentials compared to that of the bare hematite film. The results showed that the best density photocurrent was obtained with a photoanode of hematite nanowires grown on FTO/TiO2 substrate.

Major research efforts are being carried out for the technological advancement to an energetically sustainable society. However, for the full commercial integration of electrochemical energy storage devices, not only materials with higher performance should be designed and manufactured but also more competitive production techniques need to be developed. The laser processing technology is well extended at the industrial sector for the versatile and high throughput modification of a wide range of materials. In this work, a method based on laser processing is presented for the fabrication of hybrid electrodes composed of graphene nanowalls (GNWs) coated with different transition-metal oxide nanostructures for electrochemical capacitor (EC) applications. GNW/stainless steel electrodes grown by plasma enhanced chemical vapor deposition were decorated with metal oxide nanostructures by means of their laser surface processing while immersed in aqueous organometallic solutions. The pseudocapacitive nature of the laser-induced crystallized oxide materials prompted an increase of the GNW electrodes' capacitance by 3 orders of magnitude, up to ca. 28 F/cm(3) at 10 mV/s, at both the positive and negative voltages. Finally, asymmetric aqueous and solid-state ECs revealed excellent stability upon tens of thousands of charge-discharge cycles.