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 tetraphenyl aLam an tan e 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.

Anode materials are key to determining the energy density, cyclability and of life recyclability for Li-ion energy storage systems. High surface area materials, such as MXenes, can be manufactured with improved electrochemical properties that remove the need for polymeric binders or hazardous chemicals that pose a challenge to recycle Li-ion batteries. However, there remains a challenge to produce Li-ion anode materials that are binder free and poses energy storage characteristics that match the current carbon-based electrodes. Here we show the synthesis of N-doped MXene-TiO2 hybrid anode materials using an aqueous route. N-doped TiO2-MXene was modified using a single step continuous hydrothermal process. Capacity tests indicate an improvement from the initial specific energy capacity of 305 mAhg(-1) to 369 mAhg(-1) after 100 cycles at a charge rate of 0.1 C and a Coulombic efficiency of 99.7%. This compares to 252 mAhg(-1) for the unmodified MXene which exhibited significant capacity fade to 140 mAhg(-1). The ability to manufacture a Li-ion anode that does not require toxic chemicals for processing into an electrode and exhibits good energy storage characteristics in a binder free system is a significant step forward for energy storage applications.

Detailed tests and analysis of ageing effects of high irradiation dose on Multi-Strip Multi-Gap Resistive Plate Counters (MSMGRPC) based on low resistivity glass electrodes, foreseen to be used for the most forward polar angles covered by the Time-of Flight (ToF) sub-detector of the Compressed Baryonic Matter (CBM) experiment at Facility for Antiprotons and Ion Research (FAIR) - Darmstadt are reported. The tests were performed at a multi-purpose irradiation facility of IFIN-HH based on( 60)Co source. MSMGRPC efficiency, cluster size, surface and volume resistivity of the glass electrodes after irradiation are measured and compared with their values before irradiation. The results of a comprehensive analysis of the composition and properties of the deposited layers on the glass electrodes, based on different methods, i.e. Scanning Electron Microscope (SEM), X-ray Photoelectron Spectroscopy (XPS), foil Elastic Recoil Detection Analysis (ERDA), Rutherford Backscattering Spectrometry (RBS), Atomic Force Microscopy (AFM) and Terahertz Time Domain Spectroscopy (THz-TDS), are presented.

Detailed tests and analysis of ageing effects of high irradiation dose on Multi-Strip Multi-Gap Resistive Plate Counters (MSMGRPC) based on low resistivity glass electrodes, foreseen to be used for the most forward polar angles covered by the Time-of Flight (ToF) sub-detector of the Compressed Baryonic Matter (CBM) experiment at Facility for Antiprotons and Ion Research (FAIR) - Darmstadt are reported. The tests were performed at a multi-purpose irradiation facility of IFIN-HH based on Co-60 source. MSMGRPC efficiency, cluster size, surface and volume resistivity of the glass electrodes after irradiation are measured and compared with their values before irradiation. The results of a comprehensive analysis of the composition and properties of the deposited layers on the glass electrodes, based on different methods, i.e. Scanning Electron Microscope (SEM), X-ray Photoelectron Spectroscopy (XPS), foil Elastic Recoil Detection Analysis (ERDA), Rutherford Backscattering Spectrometry (RBS), Atomic Force Microscopy (AFM) and Terahertz Time Domain Spectroscopy (THz-TDS), are presented.

Recently, a simple model was proposed for the microscopic energy associated to the ferroelectric phase, to be used in a statistical approach in order to derive the equations of state for a ferroelectric thin film [C. M. Teodorescu, Phys. Chem. Chem. Phys., 2021, 23, 4085-4093]. The stabilization energy for an elemental dipole in a polar thin film is the result of the interaction of this dipole with the field generated by charges accumulated at surfaces or interfaces of the thin film. An essential parameter of this interaction is the permittivity of the film, assumed to be a material constant, together with the maximum value of an elemental dipole and the density of the elemental dipoles. These can be connected to three experimental parameters which are the saturation polarization P-s, the coercive field at zero temperature E-c((0)) and the Curie temperature T-C. However, for a ferroelectric material both the global and the differential permittivity depend on the temperature and on the polarization. This raises the question whether such a non-constant permittivity should be used in the stabilization energy of the ferroelectric phase, and whether it can be identified self-consistently with the function resulting after applying the statistics based on the microscopic model. In such case, a mutual interdependence should exist between P-s, E-c((0)) and T-C. A model is built up, able to predict coercitivity, however E-c((0)) and T-C yield values several orders of magnitude higher than the experimental ones. Therefore, one has to introduce a background dielectric constant of several hundreds to accommodate the result of the model with the experimental data. The poling history of the film has to be taken into account, together with the presence of a small bias field. The model is able to predict self-consistently the equation of state of a ferroelectric, and in particular the linear decrease of the coercive field with temperature. The microscopic parameters, in particular the background dielectric constant and the density of elemental dipoles may be expressed directly from experimental quantities.

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/).