National Institute Of Materials Physics - Romania

Publications

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142 articles found

1. Tuning the acidity by addition of transition metal to Mn modified hollow silica spheres and their catalytic activity in ethanol dehydration to ethylene

Authors: Florea, M; Bocirnea, A; Neatu, S; Kuncser, AM; Trandafir, MM; Neatu, F

Published: SEP 25 2022, APPLIED CATALYSIS A-GENERAL, 646, 118860, DOI: 10.1016/j.apcata.2022.118860

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.

2. Electrocatalytic Properties of Mixed-Oxide-Containing Composite-Supported Platinum for Polymer Electrolyte Membrane (PEM) Fuel Cells

Authors: Ayyubov, I; Talas, E; Salmanzade, K; Kuncser, A; Paszti, Z; Neatu, S; Mirea, AG; Florea, M; Tompos, A; Borbath, I

Published: MAY 2022, MATERIALS, 15, 3671, DOI: 10.3390/ma15103671

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.

3. A green way for pyruvic acid synthesis from biomass-derived L-malic acid on tetrahedral versus octahedral cobalt sites/hematite

Authors: Mitran, G; Urda, A; Pavel, OD; Neatu, S; Florea, M; Neatu, F

Published: MAR 2022, BIOMASS CONVERSION AND BIOREFINERY, DOI: 10.1007/s13399-022-02513-1

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.

4. Structural properties and near-infrared light from Ce3+/Nd3+-co-doped LaPO4 nanophosphors for solar cell applications

Authors: AitMellal, O; Oufni, L; Messous, MY; Tahri, M; Neatu, S; Florea, M; Neatu, F; Secu, M

Published: MAR 2022, JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 33, DOI: 10.1007/s10854-021-07615-6

To enhance the spectral response of solar cells, an experimental study on LaPO4:0.01Ce(3+)/xNd(3+) (x = 0, 2, 4 mol%) was carried out, where structural and morphological properties of the prepared samples were well characterized by the means of X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electronic microscope. Additionally, the photoluminescence behavior of phosphors in ultraviolet-visible (UV-VIS) and Near-infrared (NIR) regions were investigated to confirm the energy transfer (ET) from Ce3+ to Nd3+. Moreover, the quantum efficiency of Ce3+/Nd3+-co-doped samples was estimated as high as similar to 172% and the possible ET process was described. Accordingly, the LaPO4:Ce3+/Nd3+ phosphors can convert the UV light (275 nm) into NIR photons (approx. 1059 nm) through the possible two-pathway energy transfer processes from Ce3+ sensitizer ions to Nd3+ activators. Obtained NIR down-conversion emissions are suitable for improving the conversion efficiency of c-Si solar cells.

5. Increasing Permittivity and Mechanical Harvesting Response of PVDF-Based Flexible Composites by Using Ag Nanoparticles onto BaTiO3 Nanofillers

Authors: Horchidan, N; Ciomaga, CE; Curecheriu, LP; Stoian, G; Botea, M; Florea, M; Maraloiu, VA; Pintilie, L; Tufescu, FM; Tiron, V; Rotaru, A; Mitoseriu, L

Published: MAR 2022, NANOMATERIALS, 12, 934, DOI: 10.3390/nano12060934

The role of Ag addition on the structural, dielectric, and mechanical harvesting response of 20%(xAg - (1 - x)BaTiO3) - 80%PVDF (x = 0, 2, 5, 7 and 27 vol.%) flexible composites is investigated. The inorganic fillers were realized by precipitating fine (similar to 3 nm) silver nanoparticles onto BaTiO3 nanoparticles (similar to 60 nm average size). The hybrid admixtures with a total filling factor of 20 vol.% were embedded into the PVDF matrix. The presence of filler enhances the amount of beta-PVDF polar phase and the BaTiO3 filler induces an increase of the permittivity from 11 to 18 (1 kHz) in the flexible composites. The addition of increasing amounts of Ag is further beneficial for permittivity increase; with the maximum amount (x = 27 vol.%), permittivity is three times larger than in pure PVDF (epsilon(r) similar to 33 at 1 kHz) with a similar level of tangent losses. This result is due to the local field enhancement in the regions close to the filler-PVDF interfaces which are additionally intensified by the presence of silver nanoparticles. The metallic addition is also beneficial for the mechanical harvesting ability of such composites: the amplitude of the maximum piezoelectric-triboelectric combined output collected in open circuit conditions increases from 0.2 V/cm(2) (PVDF) to 30 V/cm(2) for x = 27 vol.% Ag in a capacitive configuration. The role of ferroelectric and metallic nanoparticles on the increasing mechanical-electric conversion response is also been explained.

6. Green Epoxidation of Olefins with ZnxAl/MgxAl-LDH Compounds: Influence of the Chemical Composition

Authors: Zavoianu, R; Cruceanu, A; Pavel, OD; Bradu, C; Florea, M; Birjega, R

Published: FEB 2022, CATALYSTS, 12, 145, DOI: 10.3390/catal12020145

This contribution concerns the effect of the chemical composition of the brucite-type layer of bi-cationic LDH materials ZnxAl and MgxAl (x = 2-5) and tri-cationic LDH MgyZnzAl (y + z = 4, y = 1, 2, 3) on their catalytic activity for olefin epoxidation with H2O2 in the presence of acetonitrile. LDH materials were prepared by the standard method of co-precipitation at constant pH 10, using an aqueous solution of the corresponding metal nitrates and a basic solution containing NaOH and Na2CO3. The fresh LDHs were calcined to yield the corresponding mixed oxides and then the recovery of the LDH structure by hydration of the mixed oxides was performed. The resulting samples were characterized by AAS, XRD, DRIFT, DR-UV-Vis, BET and determination of basic sites. The results of the catalytic tests for olefin epoxidation were well correlated with the basicity of the samples, which was in turn related to the M2+/Al3+ ratio and the electronegativity of different bivalent metals in the brucite-type layer.

7. Structural properties and near-infrared light from Ce3+/Nd3+-co-doped LaPO4 nanophosphors for solar cell applications

Authors: AitMellal, O; Oufni, L; Messous, MY; Tahri, M; Neatu, S; Florea, M; Neatu, F; Secu, M

Published: JAN 2022, JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, DOI: 10.1007/s10854-021-07615-6

8. Two are better than one-Synthesis of novel blue and green emissive hydroxy-oxadiazoles

Authors: Anghel, CC; Badescu, C; Mirea, AG; Paun, A; Hadade, ND; Madalan, AM; Matache, M; Popescu, CC

Published: JAN 2022, DYES AND PIGMENTS, 197, DOI: 10.1016/j.dyepig.2021.109927

We describe herein synthesis of novel hydroxy-bis-2,5-disubstituted-1,3,4-oxadiazoles and their ability to emit green light, through ESIPT mechanism. Unlike previous reports, our compounds exhibit very good quantum yields, most likely avoiding the presumed intramolecular fluorescence quenching in presence of the second oxadiazole moiety. Studies regarding behaviour of the compounds in polar and non-polar solvents are also described, indicating the possibility to modulate the emission according to the environment. The solid-state structural analysis, corroborated with fluorescence data, suggest the importance of the tert-butyl group in preservation of the luminescent properties. The corresponding benzyl-protected compounds, precursors to the target hydroxy-bis-2,5-disubstituted-1,3,4-oxadiazoles were also investigated for their optical properties and found to display very intense blue emission, with quantum yields values in dichloromethane (between 0.423 and 0.499) almost equal to the standard quinine sulfate.

9. Synthesis and Characterization of Graphite Oxide Derived TiO2-Carbon Composites as Potential Electrocatalyst Supports

Authors: Ayyubov, I; Borbath, I; Paszti, Z; Sebestyen, Z; Mihaly, J; Szabo, T; Illes, E; Domjan, A; Florea, M; Radu, D; Kuncser, A; Tompos, A; Talas, E

Published: OCT 2021 , TOPICS IN CATALYSIS, DOI: 10.1007/s11244-021-01513-1

TiO2-C (carbon) hybrid materials are promising electrocatalyst supports because the presence of TiO2 results in enhanced stability. Use of new types of carbonaceous materials such as reduced graphene oxide instead of traditional active carbon provides certain benefits. Although the rutile polymorph of TiO2 seems to have the most beneficial properties in these hybrid materials, the anatase type is more frequent in TiO2-rGO composites, especially in graphite oxide (GO) derived ones, as GO has several properties which may interfere with rutile formation. To explore and evaluate these peculiarities and their influence on the composite formation, we compared TiO2-C systems formulated with GO and Black Pearls (BP) carbon. Various physicochemical methods, such as attenuated total reflection infrared (ATR-IR)-, solid state NMR-, Raman- and X-ray photoelectron spectroscopy, X-ray powder diffraction (XRD), electron microscopy, etc. were used to characterize the samples from the different stages of our multistep sol-gel synthesis. Our experiments demonstrated that utilization of GO is indeed feasible for composite preparation, although its sodium contamination has to be removed during the synthesis. On the other hand, high temperature treatment and/or solvothermal treatment during composite synthesis resulted in decomposition of the functional groups of the GO and the functional properties of the final product were similar in case of both composites. However, Pt/TiO2-GO derived sample showed higher oxygen reduction reaction activity than Pt/TiO2-BP derived one. Based on the decrease of electrochemical surface area, the stability order was the following: Pt/C (commercial) < Pt/TiO2-BP derived C < Pt/TiO2-GO derived C.

10. Applications of MAX phases and MXenes as catalysts

Authors: Chirica, IM; Mirea, AG; Neatu, S; Florea, M; Barsoum, MW; Neatu, F

Published: SEP 21 2021, JOURNAL OF MATERIALS CHEMISTRY A, 9, 19612, DOI: 10.1039/d1ta04097a

MAX phases and MXenes are important materials that have recently gained great popularity due to their special properties, which render them particularly useful in many applications, including catalytic ones. This can be seen in the large number of publications that appear annually on these materials and their applications. This review aims to evaluate MAX phases and MXenes as materials for heterogeneous, non-electrocatalytic, catalytic applications. The review begins with a brief introduction to the MAX phase and MXene properties that recommend them as potential materials for heterogeneous catalytic applications, followed by four sections grouped according to the processes in which they have already proven effective. These include supports to activate the C-H or C-O bonds in applications such as dehydrogenation of light or aromatic alkanes, methanol formation from CH4, dry reforming, and CO oxidation or the water gas shift reaction (Section 2), and their use in fine chemical reactions (Section 3) and in chemical degradation (Section 4). The last section deals with photocatalytic applications (Section 5). The review ends by highlighting the huge potential of these materials for a wide range of heterogeneous catalytic applications as well as the challenges ahead.