National Institute Of Materials Physics - Romania

Sodium hexatitanate (Na2Ti6O13) nanoparticles have been synthesized by the hydrothermal method with microwave and conven-tional heating, after which their photocatalytic properties toward an azo dye pollutant degradation have been investigated. Insights into the dynamics and reactivity of the species involved in the photocatalytic mechanism of the (Na2Ti6O13) samples were precisely investigated, for the first time, by X-band electron paramagnetic resonance (EPR) spectroscopy under different experimental conditions. X-ray diffraction structural analysis revealed that all samples crystallized in a monoclinic C2/m structure, with different short-range structural order according to the employed heating, as indicated by Raman. Field-emission scanning electron microscopy and transmission electron microscopy results revealed the formation of rod-and fiber-like nanoparticles with different diameters and lengths. EPR measurements indicated the presence of different Ti3+ point defects and F centers in the samples. X-ray photoelectron spectroscopy analysis proved the presence of oxygen-related defects, but no Ti3+ was detected on the surface. Spin trapping experiments monitored the generation of hydroxyl (OH center dot) radicals over UV-irradiation time. Various parameters contribute to the photocatalytic activity of the samples; however, the type of defect and particle morphology appeared as key factors for enhanced efficiency. Our study provides significant information about paramagnetic defects in Na2Ti6O13 materials and their role in photocatalysis to design other Ti-based photocatalysts.

Sodium hexatitanate (Na2Ti6O13) nanoparticles have been synthesized by the hydrothermal method with microwave and conven-tional heating, after which their photocatalytic properties toward an azo dye pollutant degradation have been investigated. Insights into the dynamics and reactivity of the species involved in the photocatalytic mechanism of the (Na2Ti6O13) samples were precisely investigated, for the first time, by X-band electron paramagnetic resonance (EPR) spectroscopy under different experimental conditions. X-ray diffraction structural analysis revealed that all samples crystallized in a monoclinic C2/m structure, with different short-range structural order according to the employed heating, as indicated by Raman. Field-emission scanning electron microscopy and transmission electron microscopy results revealed the formation of rod-and fiber-like nanoparticles with different diameters and lengths. EPR measurements indicated the presence of different Ti3+ point defects and F centers in the samples. X-ray photoelectron spectroscopy analysis proved the presence of oxygen-related defects, but no Ti3+ was detected on the surface. Spin trapping experiments monitored the generation of hydroxyl (OH center dot) radicals over UV-irradiation time. Various parameters contribute to the photocatalytic activity of the samples; however, the type of defect and particle morphology appeared as key factors for enhanced efficiency. Our study provides significant information about paramagnetic defects in Na2Ti6O13 materials and their role in photocatalysis to design other Ti-based photocatalysts.

Herein, a new direct synthesis route leading to a mesoporous NiWO4 with crystalline framework and NiWO4 -graphene nanoplatelets (GNP) composite is reported. Ni and W assembled into a mesoporous tungstate type of symmetry by co-precipitation synthesis route and its composite with GNP were used as supports for electrocatalysts, with reduced Pt content (8 wt.%), in oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) in acidic medium. A comprehensive assessment of the modifications related to the crystalline and porous structures, morphological aspects as well as the surface chemistry aiming to explain the electrochemical properties was performed. It was found that the presence of GNP during the synthesis process leads, mainly, to the enhanced growth of NiWO4 nanocrystallites, as well as induces changes in the surface chemistry. The elec-trochemical results show that the introduction of GNPs into the NiWO4 composite support leads to a significant improvement in the activity of the Pt electrocatalyst in ORR and HOR compared to both initial NiWO4 and Pt/NiWO4 samples, as well as mechanical mixtures of these catalysts with carbon. Mass activity for hydrogen oxidation, determined in a mixed kinetic-diffusion controlled region, obtained on the 8 wt.% Pt/NiWO4-GNP catalyst was significantly higher compared to the commercial 20 wt.% Pt/C Quintech catalyst. Our comprehensive structural and surface chemistry assessments indicate this composite material as a viable electrocatalyst for PEMFCs using a broader type of fuels.& COPY; 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Photocatalytic conversion of H2O, CO2 and N-2 represents one promising approach to harvest and store solar energy, for which efficient visible light responsive semiconductors are inevitable. Often, the presence of a small amount of an additional component called a "cocatalyst", is required to synergistically enhance the performance of the photocatalyst. Tremendous efforts were made in the past to identify inexpensive materials to be used as cocatalysts, for which metal oxides (MOs) are one of the traditional choices. Among alternative categories of materials investigated, the recently discovered MXenes display enormous potential owing to their unique 2D layered structure, tuneable composition, abundant surface functionalities and superior electronic conductivity. Specifically, MOs and MXenes encompass a variety of distinct as well as analogous characteristics that allows them to be tailored to different extents. Unfortunately, a comprehensive overview covering the synthetic, structural and photocatalytic aspects of MOs and MXenes is not available as of now. Herein, we intend to summarize the progress achieved so far in these two families of materials to be used as cocatalysts for the photoconversion of H2O, CO2 and N-2. Followed by a general introduction, we briefly outline the fundamental principles and the role of cocatalysts in photocatalytic reactions. A discussion regarding the use of MOs and MXenes as cocatalysts for the conversion of H2O, CO2 and N-2 is then provided in separate sections. Critical assessment regarding structure and morphology control, surface properties and stability concerns can not only help to recognize the challenges that limit further advancement, but can also highlight the future research directions of these materials for the effective transformation of H2O, CO2 and N-2.

The paper presents a study concerning the role of ferroelectric filler size and clustering in the dielectric properties of 20%BaTiO3-80%PVDF and of 20% (2%Ag-98%BaTiO3)-PVDF hybrid nanocomposites. By finite element calculations, it was shown that using fillers with epsilon > 103 does not provide a permittivity rise in the composites and the effective dielectric constant tends to saturate to specific values determined by the filler size and agglomeration degree. Irrespective of the ferroelectric filler sizes, the addition of metallic ultrafine nanoparticles (Ag) results in permittivity intensification and the effect is even stronger if the metallic nanoparticles are connected to a higher degree with the ferroelectric particles' surfaces. When using coarse ferroelectric fillers, the probability of clustering is higher, thus favoring the permittivity increase by field concentration in small regions close to the interfaces separating dissimilar materials. The modeling results were validated by an experimental dielectric analysis performed in a series of PVDF-based thick films with the same amount of BaTiO3 fillers or with Ag-BaTiO3 hybrid fillers. Similar trends as predicted by simulations were found experimentally but with slightly higher permittivity values which were assigned to the modifications of the polymer phase composition due to the presence of nanofillers and the local sample inhomogeneity (the presence of clustering, in particular for coarse BaTiO3 grains), which create regions with enhanced local fields.

The paper presents a study concerning the role of ferroelectric filler size and clustering in the dielectric properties of 20%BaTiO3-80%PVDF and of 20% (2%Ag-98%BaTiO3)-PVDF hybrid nanocomposites. By finite element calculations, it was shown that using fillers with epsilon > 103 does not provide a permittivity rise in the composites and the effective dielectric constant tends to saturate to specific values determined by the filler size and agglomeration degree. Irrespective of the ferroelectric filler sizes, the addition of metallic ultrafine nanoparticles (Ag) results in permittivity intensification and the effect is even stronger if the metallic nanoparticles are connected to a higher degree with the ferroelectric particles' surfaces. When using coarse ferroelectric fillers, the probability of clustering is higher, thus favoring the permittivity increase by field concentration in small regions close to the interfaces separating dissimilar materials. The modeling results were validated by an experimental dielectric analysis performed in a series of PVDF-based thick films with the same amount of BaTiO3 fillers or with Ag-BaTiO3 hybrid fillers. Similar trends as predicted by simulations were found experimentally but with slightly higher permittivity values which were assigned to the modifications of the polymer phase composition due to the presence of nanofillers and the local sample inhomogeneity (the presence of clustering, in particular for coarse BaTiO3 grains), which create regions with enhanced local fields.

Photocatalytic conversion of H2O, CO2 and N-2 represents one promising approach to harvest and store solar energy, for which efficient visible light responsive semiconductors are inevitable. Often, the presence of a small amount of an additional component called a "cocatalyst", is required to synergistically enhance the performance of the photocatalyst. Tremendous efforts were made in the past to identify inexpensive materials to be used as cocatalysts, for which metal oxides (MOs) are one of the traditional choices. Among alternative categories of materials investigated, the recently discovered MXenes display enormous potential owing to their unique 2D layered structure, tuneable composition, abundant surface functionalities and superior electronic conductivity. Specifically, MOs and MXenes encompass a variety of distinct as well as analogous characteristics that allows them to be tailored to different extents. Unfortunately, a comprehensive overview covering the synthetic, structural and photocatalytic aspects of MOs and MXenes is not available as of now. Herein, we intend to summarize the progress achieved so far in these two families of materials to be used as cocatalysts for the photoconversion of H2O, CO2 and N-2. Followed by a general introduction, we briefly outline the fundamental principles and the role of cocatalysts in photocatalytic reactions. A discussion regarding the use of MOs and MXenes as cocatalysts for the conversion of H2O, CO2 and N-2 is then provided in separate sections. Critical assessment regarding structure and morphology control, surface properties and stability concerns can not only help to recognize the challenges that limit further advancement, but can also highlight the future research directions of these materials for the effective transformation of H2O, CO2 and N-2.

Due to the currently worldwide petrochemical feedstock shortage, the ethylene synthesis from renewable non-oil sources becomes of high interest. The catalysts were prepared in two steps: (i) formation of spheres containing the carbon-coated Mn core by hydrothermal method, (ii) formation of the Si-Zr oxide shell by sol-gel method. The prepared catalysts were characterized by N2 physisorption, SEM-EDX, XRD, XPS, and NH3-TPD. The catalytic results have shown that Fe, Zn or Ni modified Mn core exhibited superior activity compared to the catalysts containing only Mn in the core. With 75% yield and 98% ethanol conversion at 350 degrees C and WHSV of 1.4 h-1, MnNi@SiZr was the best catalyst. These results are due to an increased number of acid sites compared to the other materials and an optimal ratio of weak/medium acid sites. Our findings suggest new lines for developing active and stable catalysts for ethylene synthesis from ethanol.

TiO2-based mixed oxide-carbon composite supports have been suggested to provide enhanced stability for platinum (Pt) electrocatalysts in polymer electrolyte membrane (PEM) fuel cells. The addition of molybdenum (Mo) to the mixed oxide is known to increase the CO tolerance of the electrocatalyst. In this work Pt catalysts, supported on Ti1-xMoxO2-C composites with a 25/75 oxide/carbon mass ratio and prepared from different carbon materials (C: Vulcan XC-72, unmodified and functionalized Black Pearls 2000), were compared in the hydrogen oxidation reaction (HOR) and in the oxygen reduction reaction (ORR) with a commercial Pt/C reference catalyst in order to assess the influence of the support on the electrocatalytic behavior. Our aim was to perform electrochemical studies in preparation for fuel cell tests. The ORR kinetic parameters from the Koutecky-Levich plot suggested a four-electron transfer per oxygen molecule, resulting in H2O. The similarity between the Tafel slopes suggested the same reaction mechanism for electrocatalysts supported by these composites. The HOR activity of the composite-supported electrocatalysts was independent of the type of carbonaceous material. A noticeable difference in the stability of the catalysts appeared only after 5000 polarization cycles; the Black Pearl-containing sample showed the highest stability.

A series of cobalt-iron mixed oxides, CoxFe3-xO4 (x = 0; 0.05; 0.1; 0.15), were synthesized by coprecipitation and tested for oxidative decarboxylation of malic acid to pyruvic or malonic acid. The characterization of catalysts was performed by different techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFT) and Ultraviolet-visible spectroscopy (UV-Vis). Among studied catalysts, Co0.15Fe2.85O4 sample (denoted Co3Fe) showed the highest malic acid conversion in oxidative decarboxylation reaction as well as the highest pyruvic acid yield. This behavior can be due to the fact that this sample has the highest content of tetrahedral Co2+ that replaces Fe3+ from octahedral position that determine an increased number of defects that play a crucial role for the malic acid conversion.