National Institute Of Materials Physics - Romania

Microporous graphitic carbons obtained by pyrolysis of a-cyclodextrin have been conveniently doped with N and P elements by performing the thermal graphitization adding urea or phosphoric acid as source of these elements. Electron microscopy shows that doping does not influence the structure and dimensions of the micropores, while XPS reveals the distribution of these dopant elements in two main families corresponding to pyridinic and pryrrolic N atoms and to triphenylphosphine and triphenylphosphine oxide for P doping. Thermo-programmed desorption of H2, CO2 and NH3 indicates that the presence of dopant element is responsible for chemisorption of these gases and introduces basic and acid sites. These desorption measurements agree with the catalytic performance of the series of carbons for the chemo and stereo selective hydrogenation of internal aliphatic and aromatic alkynes to cis configured alkenes. N/P doped microporous carbons were found to be stable under the reaction conditions, according to the constant TOF values and XRD and XPS characterization of the materials after their use as catalysts. In addition microporosity appears to play a positive effect by comparing the activity of microporous carbons with the performance of analogous N/P-doped graphenes. (c) 2021 The Author(s). Published by Elsevier Inc. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Europium doped (0.1% and 1%) chlomborate BaO-B2O3-BaCl2 glass and glass-ceramic with embedded BaCl2 nanocrystals have been synthesised, investigated, and compared with the corresponding nanocrystalline powder. The structural analysis of the glass evidenced ionic bonds characteristic to the glass host structure and compositional changes during the melting. X-ray diffraction and transmission electron microscopy revealed the formation of orthorhombic BaCl2 nanocrystals of about tens on nm in size and a smaller amount of BaB2O4 nanocrystals. Structural analysis of the Eu2+-doped BaCl2 nanocrystals has shown a distortion of the crystalline cell assigned to the growth process, affected by defects and ionic impurities. Photoluminescence spectra of the glass-ceramic revealed Eu3+ and Eu2+ luminescent ion species, but only Eu2+ is incorporated within the BaCl2 nanocrystalline phase. Electron paramagnetic resonance measurements in X-band sustain the presence of Eu2+ ions. The EPR parameters (g values and hyperfine constants) resulting from the Q-band EPR spectra simulations recorded on glass-ceramic are similar to those in Eu2+-doped BaCl2 and confirmed the partial incorporation of Eu2+ ions within the BaCl2:Eu2+ nanocrystals in the glass-ceramics.

Piezoelectric hard/soft effects of multivalence co-dopants (Sb and Mn) in correlation with their location in the lattice, were investigated in PZT ceramics, prepared by conventional ceramic technology, with the following compositions: Pb0.98Sr0.02 ((Ti0.49Zr0.51)(1-0.015-x)Mn0.015Sbx)O-3 with x = 0, 0.005, 0.01, 0.02, 0.03, where antimony was initially assumed to substitute for Ti/Zr ions. The antimony valence state was found to be +3 in all samples by X-ray Photoelectron Spectroscopy investigations. The Electron Paramagnetic Resonance spectra evidenced a steep enhancement of the Mn2+ concentration upon increasing antimony doping level, explained by a charge compensation mechanism, between the Sb3+ ions substituting Pb2+ at the A-sites and the Mn2+ ions, localized at the B-sites. The incorporation of Sb3+ at the A-site of the PZT lattice is also supported by the variation of the lattice parameters, determined by X-ray Diffraction, with the increasing Sb concentration. The investigation of the dielectric, electromechanical and ferroelectric properties evidenced a hard piezoelectric behavior, mainly attributed to the presence of large sized Mn2+ ions, localized at B-sites. Our results prove that the piezoelectric hard/soft response is decisively influenced by the interplay between multiple valence states and locations of the co-dopants, on one hand, and the charge compensation mechanisms, on the other hand. This provides indirect information about the location of some co-dopants which can substitute for both cationic sites in the PZT based ceramics.

Hydroxyapatite (Ca-10(PO4)(6)(OH)(2), HAp), due to its high biocompatibility, is widely used as biomaterial. Doping with various ions of hydroxyapatite is performed to acquire properties as close as possible to the biological apatite present in bones and teeth. In this research the results of a study performed on thin films of hydroxyapatite co-doped with nitrogen and bromine (NBrHAp) are presented for the first time. The NBrHAp suspension was obtained by performing the adapted co-precipitation method using cetyltrimethylammonium bromide (CTAB). The thin layers of NBrHAp were obtained by spin-coating. The stability of the NBrHAp suspension was examined by ultrasound measurements. The thin layers obtained by the spin-coating method were examined by scanning electron microscopy (SEM), optical microscopy (OM), and metallographic microscopy (MM). The presence of nitrogen and bromine were highlighted by energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) studies. Fourier transform infrared spectroscopy (FTIR) was used to highlight the chemical status of nitrogen and bromine. In addition, the powder obtained from the NBrHAp suspension was analyzed by XRD. Moreover, the in vitro antimicrobial activity of the NBrHAp suspensions and coatings was investigated using the reference microbial strains Staphylococcus aureus ATCC 25923, Escherichia coli ATCC 25922, and Candida albicans ATCC 10231. The results highlighted the successful obtainment of N and Br co-doped hydroxyapatite suspension for the first time by an adapted co-precipitation method. The obtained suspension was used to produce pure NBrHAp composite thin films with superior morphological properties. The NBrHAp suspensions and coatings exhibited in vitro antimicrobial activity against bacterial and fungal strains and revealed their good antimicrobial activity.

Nanoscale thermometers with high sensitivity are needed in domains which study quantum and classical effects at cryogenic temperatures. Here, we present a micrometer sized and nanometer thick chromium selenide cryogenic temperature sensor capable of measuring a large domain of cryogenic temperatures down to tenths of K. Hexagonal Cr-Se flakes were obtained by a simple physical vapor transport method and investigated using scanning electron microscopy, energy dispersive X-ray spectrometry and X-ray photoelectron spectroscopy measurements. The flakes were transferred onto Au contacts using a dry transfer method and resistivity measurements were performed in a temperature range from 7 K to 300 K. The collected data have been fitted by exponential functions. The excellent fit quality allowed for the further extrapolation of resistivity values down to tenths of K. It has been shown that the logarithmic sensitivity of the sensor computed over a large domain of cryogenic temperature is higher than the sensitivity of thermometers commonly used in industry and research. This study opens the way to produce Cr-Se sensors for classical and quantum cryogenic measurements.

Multifunctional materials integrating optical and electric properties into a composite or into a doped single-phase material have attracted much attention from scientists for future optoelectronic devices. In this work, polycrystalline Ba1-xTbxTiO3, x = 0.00, 0.01 and 0.05 materials were synthesized by hydrothermal route and their photoluminescence and dielectric properties were studied. The as-prepared powders showed a microstructure consisting of grains with the shape of cube; and average particle size ranging from 75 nm to 150 nm. The investigated temperature dependence of dielectric permittivity of Ba1-xTbxTiO3 ceramics revealed a decrease of the Curie temperature (Tc) with increasing terbium content, and a more pronounced degree of diffuseness of phase transition. The resistivity at room temperature was discussed in terms of positive temperature coefficient of resistance (PTRC) effect. UV-vis reflectance spectra of Ba1-xTbxTiO3 samples showed a decrease of the band gap energy with the increase of Tb amount, due to the band-gap narrowing effect. The photoluminescence spectra recorded for Tb doped BaTiO3 materials, at 80 K, evidenced the typical f-f luminescence lines of the Tb3+ accompanied the broad luminescence band at about 425 nm due to self-trapped exciton recombination. These results demonstrated that the terbium enhances the dielectric properties and photoluminescence simultaneously, being suitable for electronic applications. (C) 2021 Elsevier B.V. All rights reserved.

Structural and functional changes induced by TiO2 addition to spherical zinc selenide together with lysozyme adsorption lead to valuable bioinorganic catalysts with enhanced activity. Spherical zinc selenide and its composite with TiO2 were obtained by hydrothermal method and subsequently modified by lysozyme adsorption. Morphological, structural and functional characteristics of zinc selenide based materials (ZnSe, TiO2-ZnSe) and their hybrids with lysozyme (Lys/ZnSe, Lys/TiO2-ZnSe) were investigated. TiO2 addition to ZnSe results in significant changes of surface composition, electrochemical behavior and lysozyme retention capacity. The lysozyme modified ZnSe and TiO2-ZnSe surfaces doubles the biocatalysts efficiency for 4-Methylumbelliferyl p-D-N,N',N ''-triacetylchitotrioside hydrolysis reaction compared to free lysozyme.

Three-dimensional graphene foam (3D-GrFoam) is a highly porous structure and sustained lattice formed by graphene layers with sp(2) and sp(3) hybridized carbon. In this work, chemical vapor deposition (CVD)-grown 3D-GrFoam was nitrogen-doped and platinum functionalized using hydrothermal treatment with different reducing agents (i.e., urea, hydrazine, ammonia, and dihydrogen hexachloroplatinate (IV) hydrate, respectively). X-ray photoelectron spectroscopy (XPS) survey showed that the most electrochemically active nitrogen-doped sample (GrFoam3N) contained 1.8 at % of N, and it exhibited a 172 mV dec(-1) Tafel plot associated with the Volmer-Heyrovsky hydrogen evolution (HER) mechanism in 0.1 M KOH. By the hydrothermal process, 0.2 at % of platinum was anchored to the graphene foam surface, and the resultant sample of GrFoamPt yielded a value of 80 mV dec(-1) Tafel associated with the Volmer-Tafel HER mechanism. Furthermore, Raman and infrared spectroscopy analysis, as well as scanning electron microscopy (SEM) were carried out to understand the structure of the samples.

Preventing and controlling the spread of multidrug-resistant (MDR) bacteria implicated in healthcare-associated infections is the greatest challenge of the health systems. In recent decades, research has shown the need for passive antibacterial protection of surfaces in order to reduce the microbial load and microbial biofilm development, frequently associated with transmission of infections. The aim of the present study is to analyze the efficiency of photocatalytic antimicrobial protection methods of surfaces using the new photocatalytic paint activated by light in the visible spectrum. The new composition is characterized by a wide range of analytical methods, such as UV-VIS spectroscopy, electron microscopy (SEM), X-ray powder diffraction (PXRD) or X-ray photoelectron spectroscopy (XPS). The photocatalytic activity in the UV-A was compared with the one in the visible light spectrum using an internal method developed on the basis of DIN 52980: 2008-10 standard and ISO 10678-2010 standard. Migration of metal ions in the composition was tested based on SR EN1186-3: 2003 standard. The new photocatalytic antimicrobial method uses a type of photocatalytic paint that is active in the visible spectral range and generates reactive oxygen species with inhibitory effect against all tested microbial strains.