National Institute Of Materials Physics - Romania

Electronic structure of LaAlO3/SrTiO3 (LAO/STO) samples, grown at low oxygen pressure and post-annealed ex situ, was investigated by soft-x-ray ARPES focussing on the Fermi momentum (k (F)) of the mobile electron system (MES). X-ray irradiation of these samples at temperatures below 100 K creates oxygen vacancies (V(O)s) injecting Ti t (2g)-electrons into the MES. At this temperature the oxygen out-diffusion is suppressed, and the V(O)s should appear mostly in the top STO layer. The x-ray generated MES demonstrates, however, a pronounced three-dimensional (3D) behavior as evidenced by variations of its experimental k (F) over different Brillouin zones. Identical to bare STO, this behavior indicates an unexpectedly large extension of the x-ray generated MES into the STO depth. The intrinsic MES in the standard LAO/STO samples annealed in situ, in contrast, demonstrates purely two-dimensional (2D) behaviour. The relevance of our ARPES data analysis is supported by model calculations to compare the intensity vs gradient methods of the k (F) determination as a function of the energy resolution ratio to the bandwidth. Based on self-interaction-corrected DFT calculations of the MES induced by V(O)s at the interface and in STO bulk, we discuss possible scenarios of the puzzling 3D-ity. It may involve either a dense ladder of quantum-well states formed in a long-range interfacial potential or, more likely, x-ray-induced bulk metallicity in STO accessed in the ARPES experiment through a short-range interfacial barrier. The mechanism of this metallicity may involve remnant V(O)s and photoconductivity-induced metallic states in the STO bulk, and even more exotic mechanisms such as x-ray induced formation of Frenkel pairs.

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 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.

Carbon dots (CDs) are an emerging class of photoluminescent material. Their unique optical properties arise from the discrete energy levels in their electronic states, which directly relate to their crystalline and chemical structure. It is expected that when CDs go through structural changes via chemical reduction or thermal annealing, their energy levels will be altered, inducing unique optoelectronic properties such as solid-state photoluminescence (PL). However, the detailed structural evolution and how the optoelectronic characteristics of CDs are affected remain unclear. Therefore, it is of fundamental interest to understand how the structure of CDs prepared by hydrothermal carbonisation (HTC) rearranges from a highly functionalised disordered structure into a more ordered graphitic structure. In this paper, detailed structural characterisation and in situ TEM were conducted to reveal the structural evolution of CDs during the carbonisation process, which have demonstrated a growth in aromatic domains and reduction in oxidation sites. These structural features are correlated with their near-infrared (NIR) solid-state PL properties, which may find a lot of practical applications such as temperature sensing, solid-state display lighting and anti-counterfeit security inks.

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.

Catalytic activity of TiO2, 2%Re-TiO2 and 10%Re-TiO2 in the conversion of carbohydrates into levulinic acid under autoclave conditions was evaluated. These materials were prepared by aerogel method, for the first time to the best of our knowledge, and characterized by XPS, SEM-EDX, DRIFTS, DR UV-vis, Raman, N-2 adsorption/desorption isotherms, TGA and XRD. Further, the surface acidity was probed by NH3-TPD and pyridine-FT-IR where it was observed that increasing the amount of rhenium doped into TiO2 led to an increase in the total number of acid sites (Lewis + Bronsted) but with an overall lower strength. The presence of both Bronsted and Lewis acid sites led to the hypothesis that these materials may be well suited for conversion of carbohydrates into levulinic acid. Indeed a levulinic acid yield of 57% was reached over 10%Re-TiO2 for a low mass ratio catalyst to glucose (1 : 5). Moreover, the 10%Re-TiO2 catalyst was reused in the conversion of glucose for four catalytic cycles without a significant loss of the catalytic activity.

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.