National Institute Of Materials Physics - Romania

Two new families of zinc/cobalt/aluminum-based pigments, with a unique composition, were obtained through the polyol method. The hydrolysis process of a mixture of Co(CH3COO)(2), Zn(acac)(2) and Al(acac)(3) (acac(-) = acetylacetonate ion) in 1,4-butanediol afforded dark blue gels (wPZn(x)Co(1-x)Al), in the presence of a supplementary amount of water, and light green powders (PZnxCo1-xAl), respectively, for the water-free procedure (x = 0, 0.2, 0.4). The calcination of the precursors yielded dark green (wZn(x)Co(1-x)Al) and blue (ZnxCo1-xAl) products. XRD measurements and Rietveld refinement indicate the co-existence of three spinel phases, in different proportions: ZnxCo1-xAl2O4, Co3O4 and the defect spinel, ?-Al2.67O4. The Raman scattering and XPS spectra are in agreement with the compositions of the samples. The morphology of wZn(x)Co(1-x)Al consists of large and irregular spherical particle aggregates (ca. 5-100 mm). Smaller agglomerates (ca. 1-5 mm) with a unique silkworm cocoon-like hierarchical morphology composed of cobalt aluminate cores covered with flake-like alumina shells are formed for ZnxCo1-xAl. TEM and HR-TEM analyses revealed the formation of crystalline, polyhedral particles of 7-43 nm sizes for wZn(x)Co(1-x)Al, while for ZnxCo1-xAl, a duplex-type morphology, with small (7-13 nm) and larger (30-40 nm) particles, was found. BET assessment showed that both series of oxides are mesoporous materials, with different pore structures, with the water-free samples exhibiting the largest surface areas due, most likely, to the high percent of aluminum oxide. A chemical mechanism is proposed to highlight the role of the water amount and the nature of the starting compounds in the hydrolysis reaction products and, further, in the morpho-structural features and composition of the resulting spinel oxides. The CIE L*a*b* and C* colorimetric parameters indicate that the pigments are bright, with a moderate degree of luminosity, presenting an outstanding high blueness.

Iron-doped Co3O4 oxides prepared by a surfactant-assisted method exhibited good catalytic activity in malic acid conversion, and the oxygen defects associated with the presence of Co2+ played a key role in catalyst activation for pyruvic acid production. The most active catalyst, for which the malic acid conversion was 70% and the pyruvic acid yield was 24%, has an inverse spinel type structure (Fe3+ replaces Co2+ from tetrahedral sites, while Fe2+ replaces Co3+ from octahedral sites) as well as a small energy difference between the highest occupied orbital and the lowest unoccupied orbital (low band-gap, E-g). The catalyst with the highest Co2+ loading showed the highest yield of pyruvic acid.

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.

Replacing lead atoms in halide perovskite materials is of significant importance for the development of environmentally friendly perovskite solar cells. In this paper, we investigated the effect of doping the MAPbI(2.6)Cl(0.4) hybrid perovskite (MA-methyl ammonium) with non-toxic elements, such as alkaline earth metal ions (Mg2+) and transition metal ions (Zn2+). The structural, morphological, and optical properties of the prepared samples were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and UV-Vis. spectroscopy. Finally, the doped films were used as photoactive layers in solar devices in order to evaluate their photovoltaic performance. Zn proved to be more appropriate to replace partially Pb and films with higher quality were obtained. As a result, the MAPb1(-x)Zn(x)I(2.6)Cl(0.4) based solar cells have demonstrated a slight improvement of the photovoltaic performances, resulting in a uniform and narrower PCEs (power conversion efficiency) range, compared to pristine MAPbI(2.6)Cl(0.4) based devices.

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.

Light-emissive compounds able to transfer protons, either intra-or intermolecularly in the excited state, have increasingly attracted attention, especially by structural diversification of recognized fluorophores. We report herein synthesis and structural characterization of novel 1,3,4-oxadiazole-based compounds functionalised by salicylaldehyde or o-vanillin moieties. Solution absorption and emission spectroscopy performed on the resulted compounds indicated the essential influence of the established (intra and/or intermolecular) hydrogen bonds onto the optical properties. Theoretical calculations positively contributed to the effort of understanding the emissive behaviour of the compounds and the calculated data correlated very well to experiments. Occurrence of hydrogen bond interactions has been also observed in solid state and we discuss their molecular structures and the effects on the luminescent behaviour. The phenol groups in close proximity of the oxadiazole core were further exploited in cocrystallization experiments with pyridine-based co-partners. Hydrogen bonding were also found responsible for the supramolecular recognition between the two components. One type of the resulted co -crystals preserved the luminescence of the starting compound.

Electronic and stability properties of quasi-2D alkylammonium perovskites are investigated using density functional theory (DFT) calculations and validated experimentally on selected classes of compounds. Our analysis is focused on perovskite structures of formula (A)(2)(A ')(n-1)PbnX3n+1, with large cations A = butyl-, pentyl-, hexylammonium (BA, PA, HXA), small cations A ' = methylammonium, formamidinium, ethylammonium, guanidinium (MA, FA, EA, GA) and halogens X = I, Br, Cl. The role of the halogen ions is outlined for the band structure, stability and defect formation energies. Two opposing trends are found for the absorption efficiency versus stability, the latter being assessed with respect to possible degradation mechanisms. Experimental validation is performed on quasi-2D perovskites based on pentylammonium cations, namely: (PA)(2)PbX4 and (PA)(2)(MA)Pb2X7, synthesized by antisolvent-assisted vapor crystallization. Structural and optical analysis are inline with the DFT based calculations. In addition, the thermogravimetric analysis shows an enhanced stability of bromide and chloride based compounds, in agreement with the theoretical predictions.

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.

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.