National Institute Of Materials Physics - Romania

Palladium nanoparticles entrapped in porous aromatic frameworks (PAFs) or covalent organic frameworks may promote heterogeneous catalytic reactions. However, preparing such materials as active nanocatalysts usually requires additional steps for palladium entrapment and reduction. This paper reports as a new approach, a simple procedure leading to the self-entrapment of Pd nanoparticles within the PAF structure. Thus, the selected Sonogashira synthesis affords PAF-entrapped Pd nanoparticles that can catalyze the C-C Suzuki-Miyaura cross-coupling reactions. Following this new concept, PAFs were synthesized via Sonogashira cross-coupling of the tetraiodurated derivative of tetraphenyladamantane or spiro-9,9 '-bifluorene with 1,6-diethynylpyrene, then characterized them using powder X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, X-ray photoelectron spectroscopy, high-resolution scanning transmission electron microscopy, and textural properties (i.e., adsorption-desorption isotherms). The PAF-entrapped Pd nanocatalysts showed high catalytic activity in Suzuki-Miyaura coupling reactions (demonstrated by preserving the turnover frequency values) and stability (demonstrated by palladium leaching and recycling experiments). This new approach presents a new class of PAFs with unique structural, topological, and compositional complexities as entrapped metal nanocatalysts or for other diverse applications.

In this paper, we present a theoretical perspective concerning the scattering of electrons on a twisted light (TL) driven graphene quantum dot (GQD). Relatively recently discovered, TL is a novel type of electromagnetic field which carries a finite orbital angular momentum oriented on the propagation direction, besides its spin. This striking property of TL is due to its spatial structure. It is well known that the localization of electrons in a GQD is forbidden by the Klein tunneling, an effect that manifests by the perfect transmission of electrons through a potential barrier, regardless of its magnitude. Here we demonstrate that, for a suitable choice of the scattering regimes, there emerge scattering resonances characterized by trapping states of the incident electron inside the GQD for finite periods of time. The most interesting result is the prediction regarding the possibility to control the trapping times using a TL irradiation. Also, we mention that the investigation was performed for a frequency of the TL within the infrared spectrum.

A nanostructured samarium oxide electrode was constructed by electrodeposition onto the surface of a gold electrode on SiO2/Si wafer. The samarium oxides electrode's surface morphology was investigated by scanning electron microcopy showing a quasi-monodispersed nanoplatelets like structure. X-rays diffraction analysis demonstrated a mixture of monoclinic and hexagonal phases while the X-rays photoelectron spectroscopy indicated the co-existence of both Sm2+ and Sm3+ species in a 1:3 proportion. Cyclic voltammetry and electrochemical impedance spectroscopy were used to investigate the charge transfer processes at the surface of the samarium oxide electrode in the absence and in the presence of redox probes. A roughness factor of 2.5 was determined from the samarium oxide electrode while the charge transfer constant was almost double when compared to the planar gold electrode. Then, the samarium oxide electrode was used for the H2O2 detection by fixed potential amperometry at -0.20 V (vs. Ag/AgCl) with a linear region between 0.01 and 1.00 mM, a sensitivity of 153 mu A cm(-2) mM(-1) and a LoD = 2.70 mu M. Glucose oxidase was used as a model enzyme in order to test the capacity of the samarium oxides electrode for biosensing. The enzyme was immobilized by physical adsorption and the optimum conditions for glucose analysis investigated. The biosensor showed a linear range for glucose detection between 0.10 and 1.20 mM with a sensitivity of 8.40 mu A cm(-2) mM(-1) and a LoD = 8.00 mu M. Selectivity was tested toward common interfering species, and the results revealed the lack of biosensor response. The glucose biosensor on samarium oxides was tested for glucose detection in serum samples with a recovery factor of 90%, and the result validated with a commercial glucometer. (C) 2021 Elsevier Ltd. All rights reserved.

The green macroalga Ulva rigida represents a promising feedstock for biorefinary due to its fast growth and cosmopolitan distribution. The main component of the cell walls of U. rigida is a sulfated glucuronorhamnan polysaccharide known as ulvan. Herein it was found that due to the high (hydrogen)sulfate group content of ulvan, hydrothermal autohydrolysis at 130 degrees C renders a high percentage of rhamnose (78-79 % recovery from the initial content in the raw material), a rare sugar of high added value. In addition, acid catalysis by a triflate-based graphene oxide under oxygen-free conditions at 180 degrees C affords moderate amounts of tartaric acid (24-26 %). The same triflate-based graphene oxide catalyst under oxygen pressure yields remarkably high percentages of succinic acid (65 %). The catalyst preserves its activity for at least five consecutive reuses.

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.