National Institute Of Materials Physics - Romania

The objective of the present study is the valorization of natural resources and the recycling of vegetal wastes by converting them into novel plasmonic bio-active hybrids. Thus, a "green" approach was used to design pectin-coated bio-nanosilver. Silver nanoparticles were generated from two common garden herbs (Mentha piperitaandAmaranthus retroflexus), and pectin was extracted from lemon peels. The samples were characterized by the following methods: Ultraviolet-visible (UV-Vis) absorption spectroscopy, Fourier Transform Infrared (FT-IR), X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), dynamic light scattering (DLS), Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM)-Energy-dispersive X-ray Spectroscopy (EDX), and zeta potential measurements. Microscopic investigations revealed the spherical shape and the nano-scale size of the prepared biohybrids. Their bioperformances were checked in terms of antioxidant and antibacterial activity. The developed plasmonic materials exhibited a strong ability to scavenge short-life (96.1% divided by 98.7%) and long-life (39.1% divided by 91%) free radicals. Microbiological analyses demonstrated an impressive antibacterial effectiveness of pectin-based hybrids againstEscherichia coli. The results are promising, and the obtained biomaterials could be used in many bio-applications, especially as antioxidant and antimicrobial biocoatings.

Antibacterial cerium-doped hydroxyapatite (Ce-HAp) layers have been researched sparingly in recent years. The Ce-HAp powder, Ca10-xCex(PO4)(6)(OH()2)with x(Ce)= 0.05, was obtained by an adapted chemical co-precipitation method at room temperature. The target was prepared using the Ce-HAp (x(Ce)= 0.05) powder sintered in air at 600 degrees C. The coatings on the Ti substrate were generated in plasma using a radio frequency (RF) magnetron sputtering discharge in an Ar gas flow in a single run. To collect the most complete information regarding the antimicrobial activity of cerium-doped hydroxyapatite with x(Ce)= 0.05, (5Ce-HAp), antimicrobial studies were carried out both on the final suspensions and on the coated surfaces. The target was tested using ultrasound measurement, transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), glow-discharge optical emission spectroscopy (GDOES), and X-ray photoelectron spectroscopy (XPS). The present study exhibited for the first time results of the homogeneous coatings of hydroxyapatite doped with cerium using a radio frequency magnetron sputtering technique. In addition, this study highlighted for the first time the stability of the cerium-doped hydroxyapatite gels used in the creation of the coating. Ultrasound measurements on the concentrated suspension of 5Ce-HAp showed a good stability compared to double distilled, water which was chosen as the reference fluid. Particles with spherical shape were observed by both TEM and SEM analysis. The broadening of the IR bands in the IR spectrum of the 5Ce-HAp film in comparison with the IR spectrum of the precursor target indicate the formation of interlinked bonds into the layer bulk. XPS analysis revealed that the mixture of Ce(3+)and Ce(4+)ions in the hydroxyapatite (HAp) structure of the coatings could be due to the deposition process. The surface of 5Ce-HAp coatings was homogenous with particles having a spherical shape. A uniform distribution of all the constituent elements on the surface the 5Ce-HAp layer was revealed. The antimicrobial assays proved that both 5Ce-HAp suspensions and 5Ce-HAp coatings effectively inhibited the development of colony forming units (CFU) for all the tested microbial strains. Moreover, the antimicrobial assays emphasized that the 5Ce-HAp suspensions had a biocide effect against Escherichia coli (E. coli) andCandida albicans(C. albicans)microbial strains after 72 h of incubation.

We have explored an efficient strategy to enhance the overall photocatalytic performances of layered perovskites by increasing the density of hydroxyl group by protonation. The experimental procedure consisted of the slow replacement of interlayer Rb(+)cation of RbLaTa(2)O(7)Dion-Jacobson (DJ) perovskite by H(+)via acid treatment. Two layered perovskites synthesized by mild (1200 degrees C for 18 h) and harsh (950 and 1200 degrees C, for 36 h) annealing treatment routes were used as starting materials. The successful intercalation of proton into D-J interlayer galleries was confirmed by FTIR spectroscopy, thermal analyses, ion chromatography and XPS results. In addition, the ion-exchange route was effective to enlarge the specific surface area, thus enhancing the supply of photocharges able to participate in redox processes involved in the degradation of organic pollutants. HLaTa_01 protonated layered perovskite is reported as a efficient photocatalyst for photomineralization of trichloroethylene (TCE) to Cl(-)and CO(2)under simulated solar light. The enhanced activity is attributed to combined beneficial roles played by the increased specific surface area and high density of hydroxyl groups, leading to an efficiency of TCE mineralization of 68% moles after 5 h of irradiation.

A new composite base on reduced graphene oxide (RGO) and poly(5-amino-1-naphthol) (P5A1N) was synthesized by the electrochemical polymerization of 5-amino-1-naphthol (5A1N) in the presence of HClO(4)and H(4)SiW(12)O(40)onto the surface of Au electrode covered with the RGO sheets. The linear dependence of the current densities of the anodic and cathodic peaks with the scan rate of the potential range (0; 0.8) V vs. SCE, reported during electropolymerization of 5A1N, indicates an electron transfer that is controlled by diffusion. A covalent functionalization of the RGO sheets with P5A1N is argued by: (i) the simultaneous disappearance of the IR band at 1584 cm(-1)and the appearance of the new IR bands at 812, 976 and 3744 cm(-1), and (ii) the appearance of two Raman lines at 738 and 1428 cm(-1). An application of the RGO sheets covalently functionalized with P5A1N is demonstrated to support 1,4-phenylene diisothiocyanate (PDITC), a compound used as a cross-linking agent for various biological applications. The chemical adsorption of PDITC onto the RGO sheets covalently functionalized with P5A1N, which involves the appearance of new functional groups of the type thiourea, was proven by Raman scattering and IR spectroscopy.

To improve the catalytic performance of an active layered double hydroxide (LDH)-derived CuCeMgAlO mixed oxide catalyst in the total oxidation of methane, it was promoted with different transition-metal cations. Thus, two series of multicationic mixed oxides were prepared by the thermal decomposition at 750 degrees C of their corresponding LDH precursors synthesized by coprecipitation at constant pH of 10 under ambient atmosphere. The first series of catalysts consisted of four M(3)CuCeMgAlO mixed oxides containing 3 at.% M (M = Mn, Fe, Co, Ni), 15 at.% Cu, 10 at.% Ce (at.% with respect to cations), and with Mg/Al atomic ratio fixed to 3. The second series consisted of four Co(x)CuCeMgAlO mixed oxides withx= 1, 3, 6, and 9 at.% Co, while keeping constant the Cu and Ce contents and the Mg/Al atomic ratio. All the mixed oxides were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) coupled with X-ray energy dispersion analysis (EDX), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption at -196 degrees C, temperature-programmed reduction under hydrogen (H-2-TPR), and diffuse reflectance UV-VIS spectroscopy (DR UV-VIS), while thermogravimetric and differential thermal analyses (TG-DTG-DTA) together with XRD were used for the LDH precursors. The catalysts were evaluated in the total oxidation of methane, a test reaction for volatile organic compounds (VOC) abatement. Their catalytic performance was explained in correlation with their physicochemical properties and was compared with that of a reference Pd/Al(2)O(3)catalyst. Among the mixed oxides studied, Co(3)CuCeMgAlO was found to be the most active catalyst, with a temperature corresponding to 50% methane conversion (T-50) of 438 degrees C, which was only 19 degrees C higher than that of a reference Pd/Al(2)O(3)catalyst. On the other hand, this T(50)value was ca. 25 degrees C lower than that observed for the unpromoted CuCeMgAlO system, accounting for the improved performance of the Co-promoted catalyst, which also showed a good stability on stream.

This work involves the synthesis and characterization of Cu2ZnSnS4 (CZTS) layers. The films were prepared on Mo/glass substrates by single-step electrodeposition method followed by sulfurization at 500 degrees C under argon flow. The effect of boric acid concentration on the crystallographic structure, compositional and morphological properties of CZTS films was investigated, with the objective to understand the growth behavior and to enhance the film properties. Cyclic Voltammetry was used in order to estimate the adequate deposition potential for the CZT alloy. The x-ray diffraction analysis showed the formation of the kesterite phase in all the samples. The Raman and x-ray photoelectron spectroscopy studies confirmed the existence of the CZTS phase. The scanning electron microscopy was employed to inspect the films structure. The results indicated that increasing the concentration of boric acid affects the physico-chemical properties of the films.

The underlying mechanisms of the metal-insulator transition in correlated oxides are a rich source of interesting physics and a topic of long-standing investigation. Here, the authors use angle-resolved photoelectron spectroscopy to investigate changes in charge carrier properties and electron-phonon interactions as a function of Ce-doping across the metal-insulator transition in CaMnO3. Many transition metal oxides (TMOs) are Mott insulators due to strong Coulomb repulsion between electrons, and exhibit metal-insulator transitions (MITs) whose mechanisms are not always fully understood. Unlike most TMOs, minute doping in CaMnO3 induces a metallic state without any structural transformations. This material is thus an ideal platform to explore band formation through the MIT. Here, we use angle-resolved photoemission spectroscopy to visualize how electrons delocalize and couple to phonons in CaMnO3. We show the development of a Fermi surface where mobile electrons coexist with heavier carriers, strongly coupled polarons. The latter originate from a boost of the electron-phonon interaction (EPI). This finding brings to light the role that the EPI can play in MITs even caused by purely electronic mechanisms. Our discovery of the EPI-induced dichotomy of the charge carriers explains the transport response of Ce-doped CaMnO3 and suggests strategies to engineer quantum matter from TMOs.

Herein we report on novel multiferroic core shell nanostructures of cobalt ferrite (CoFe2O4) bismuth, sodium titanate doped with barium titanate (BNT-BT0.08), prepared by a two step wet chemical procedure, using the sol gel technique. The fraction of CoFe2O4 was varied from 1:0.5 to 1:1.5 = BNT-BT0.08/CoFe2O4 (molar ratio). X-ray diffraction confirmed the presence of both the spinel CoFe2O4 and the perovskite Bi0.5Na0.5TiO3 phases. Scanning electron microscopy analysis indicated that the diameter of the core shell nanoparticles was between 15 and 40 nm. Transmission electron microscopy data showed two phase composite nanostructures consisting of a BNT-BT0.08 core surrounded by a CoFe2O4 shell with an average thickness of 4-7 nm. Cole-Cole plots reveal the presence of grains and grain boundary effects in the BNT-BT0.08/CoFe2O4 composite. Moreover, the values of the dc conductivity were found to increase with the amount of CoFe2O4 semiconductive phase. Both X-ray photoelectron spectroscopy (XPS) and Mossbauer measurements have shown no change in the valence of the Fe3+, Co2+, Bi3+ and Ti4+ cations. This study provides a detailed insight into the magnetoelectric coupling of the multiferroic BNT-BT0.08/CoFe2O4 core shell composite potentially suitable for magnetoelectric applications.

EIS and XPS investigations on the interaction of hemin with p- and n-doped GaAs(100) electrodes in PBS solution revealed significant differences concerning both the adsorbed species and the mechanism of the redox process caused by dopant nature. XPS data show that hemin is adsorbed on p-GaAs(100) by its carboxyl groups and adopts a vertical position favorable to a polymeric film formation whereas on n-GaAs(100), the adsorbed hemin is monomeric and has a rather planar configuration involving mainly the OH groups of the organic molecule. Hemin gives rise to a reversible redox process at the p-GaAs(100) electrode whereas at n-GaAs(100), there is only one reduction wave of a considerably lower current density appearing at a more negative potential. The effects of the applied potential on the phase angle measured at p-GaAs(100) point out major changes not only in the insulating properties of the adsorbed layer, as found at n-GaAs(100), but also in the electronic properties of the semiconductor triggered by the hemin redox process. Analysis of the experimental data points to a mechanism of charge transfer through surface states, the observed differences being related to the location of the surface states with respect to the formal potential of the hemin redox couple.

We explore the cross coupling between the ferroelectric and ferromagnetic phases in Ni/BaTiO3(001) heterostructures and demonstrate the modulation of the magnetism and incidence of exchange bias in the ultrathin metallic Ni overlayer, depending on the ferroelectric state of the bottom layer. We establish that 5-nm-thick monocrystalline Ni film deposited on BaTiO3 with ferroelectric polarization pointing towards the surface (P+) favors the organization of Ni into uniform ferromagnetic domains. Ni grown on BaTiO3 with opposite ferroelectric polarization is featured by emerging exchange-bias coupling between the ferromagnetic Ni top layers and the antiferromagnetic reacted interface, as theoretically explained by first-principles calculations. We explicitly obtain the morphology of the magnetic domains of the crystalline Ni layer in atomic and magnetic force microscopy measurements (AFM/MFM). The resemblance of AFM and MFM images indicate that, although with radically different morphologies, in both cases all spins orient in the Ni plane. Consequently, the distinct signature of the ferroelectric-ferromagnetic coupling extracted from the magneto-optical Kerr effect measurements encodes all the information of sample magnetism. The peculiar magnetic coupling depending on the ferroelectric state indicates new ways of engineering the functionality of metal/ferroelectric interfaces.