National Institute Of Materials Physics - Romania

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.

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%.

Thin film metal-ferroelectric-metal capacitors with an equal mixture of hafnium oxide and zirconium oxide as the ferroelectric material are fabricated using iridium oxide as the electrode material. The influence of the oxygen concentration in the electrodes during crystallization anneal on the ferroelectric properties is characterized by electrical, chemical, and structural methods. Forming gas, O-2, and N-2 annealing atmospheres significantly change the ferroelectric performance. The use of oxygen-deficient electrodes improves the stabilization of the ferroelectric orthorhombic phase and reduces the wake-up effect. It is found that oxygen-rich electrodes supply oxygen during anneal and reduce the amount of oxygen vacancies, but the nonferroelectric monoclinic phase is stabilized with a negative impact on the ferroelectric properties.

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.

The presence of a metallic layer can influence the properties of high-temperature superconductors underneath. We investigate the influence of metallic structures deposited in form of nanoparticles or continuous layers by electron beam evaporation or ion beam sputtering on the properties of Y1Ba2Cu3O7-x (YBCO) thin films. To generally avoid diffusion of metal atoms an additional barrier layer is introduced. Detailed measurements of the magnetic moment of the superconductor as a function of temperature and magnetic field have been performed using SQUID magnetometry. It is found that the modification of the superconducting properties of coated YBCO strongly depends on the deposition method of the metal on top rather than the type of metal (Ni or Ag), its magnetic properties (ferromagnetic or paramagnetic) or its morphology (nanoparticles or thin film). The main result is a transient increase of the critical temperature T-c and critical current density J(c) that was observed for samples prepared by electron beam evaporation.

Niobia-based magnetic nanocomposites were prepared by covering magnetite nanoparticle cores (Fe3O4, MNP) with either Nb2O5 or Nb2O5-SiO2 shells using a two-step procedure. In the first step magnetite nanoparticles were prepared by the coprecipitation method. The second step involved their coverage with either Nb2O5 shells, through a precipitation method, or with Nb2O5-SiO2 shells, through a sol-gel protocol followed by precipitation in the presence of the CTAB surfactant. The obtained materials were exhaustively characterised by X-ray diffraction, Mossbauer spectroscopy, magnetic measurements, ICP-OES, DRIFT and Raman spectroscopy, and CO2 - and NH3-TPD measurements, and investigated for glucose dehydration to HMF. The catalytic performances were directly correlated to the nature of the supported niobia phases, which, in turn, has been dictated by the niobia content and the preparation route. The high selectivity to HMF was correlated with to the large pseudohexagonal niobium oxide (TT-Nb2O5) phase while the catalytic activity was directly correlated to the small nanoparticles size. A proper combination of these features led to an optimum catalytic system for the selective production of HMF through glucose dehydration. A third important feature making the developed catalyst promising is its magnetic property, ensured by the magnetite nanoparticles core. This allowed its easy separation from the reaction products.

In the present paper is presented an efficient strategy for synthesis of mesoporous TiO2 modified with different Ce concentrations through a sol-gel process in the presence of triblock Pluronic P123 as structure directing agent, integrated with evaporation-induced self- assembly (EISA) approach. The nanocomposite consisted mostly of small crystallite of anatase. The presence of a new crystal phase corresponding to cerium titanate was evidenced in Ce-modified powder samples. All materials were characterized by SEM and TEM microscopies, UV-vis, XPS and N-2 adsorption-desorption isotherms in order to examine the textural and structural characteristics and the chemical nature of their surface. Furthermore, the photoelectrochemical characterization evidenced the effect of the TiO2 mesoporous structure, the amount of cerium and the oxidation state of Ti and Ce in the new photocatalysts on the enhanced photovoltaic performance. The photocatalytic activity of the as-synthesized materials was evaluated for phenol photodegradation in aqueous media and the reactive species involved in photocatalytic process were established by using some radical scavengers in the photodegradation experiments. Based on the obtained results, these new Ce-modified mesoporous TiO2 photocatalysts could be considered for degradation of organic compounds from wastewaters by advanced oxidation processes or for photoanodes construction for efficient photoelectrochemical fuel cell (PFC) systems.

Carbon monoxide is adsorbed at room temperature on graphene formed on atomically clean Pt(001)-hex by chemical vapor deposition, starting with ethylene, in ultrahigh vacuum. The graphene formation is characterized in situ by high resolution photoelectron spectroscopy (HRPES), by low energy electron diffraction (LEED) and by near-edge X-ray absorption fine structure (NEXAFS). The formation of graphene destroys the hex reconstruction of Pt(001) and graphene exhibits totally in-plane sp(2) bonding. CO adsorption is characterized by HRPES and a rigid shift towards higher binding energies by about 96 meV is experienced by Pt 4f core levels, together with a shift towards lower binding energy by 36 meV of the C 1s level corresponding to graphene, while the amplitude analysis of carbon and platinum peaks suggests the intercalation of carbon oxide between graphene and the metal substrate. The presence of oxidized carbon is evidenced by a separate component in the C 1s spectrum (attributed to carbon bond to oxygen) and by the occurrence of the O 1s signal. The coverage expressed in terms of the ratio of the integral amplitudes of the carbon bond to oxygen to the amplitude of the carbon from graphene approaches 3 %, yielding a CO coverage of Pt(001) of about 0.12 monolayer. The derived atomic ratio (O 1s):(C 1s bond to O) is initially close to 1, then evolves in time towards values close to 2, which means that CO is progressively oxidized upon adsorption and irradiation with soft X-rays. The relative amount of oxygen and oxidized carbon decreases in time under irradiation with soft X-rays. Weakly bound graphene on incommensurate metal surfaces may be used as atomic scale nanoreactors for trapping and immediate oxidation of carbon monoxide.