Dr. Stefan NEATU
Scientific Researcher II
Laboratory of Catalytic Materials and Catalysis
stefan[DOT]neatu[AT]infim[DOT]roEducation
2005 - 2010 PhD in Chemistry at University of Bucharest, Faculty of Chemistry, Bucharest, Romania / “Photocatalytic degradation of vesicant and neurotoxic compounds using catalytic systems based on titanium dioxide”
2003 - 2005 Master in Catalysis and Catalytic Processes at University of Bucharest, Faculty of Chemistry, Department of Chemical Technology and Catalysis, Bucharest, Romania / “Isobutane dehydrogenation over Cr2O3/Al2O3 modified catalysts”
1995 - 2003 Graduate in Chemistry, University of Chemistry, Faculty of Chemistry, Department of Organic Chemistry, Bucharest, Romania / “The synthesis of pyrrolo [1,2-b] pyridazine through 1,3-dipolar cycloaddition reactions”
Positions
April 2018 onwards: Scientific Researcher II at National Institute of Materials Physics, Magurele, Romania
July 2014 - April 2018: Scientific Researcher III at National Institute of Materials Physics, Magurele, Romania
July 2014 - September 2017: Scientific Researcher at S.C. Stimpex S.A., Bucharest, Romania
July 2010 - May 2012: Chemistry Expert at S.C. Cromatec Plus S.R.L., Bucharest, Romania
June 2007 - December 2009: Research assistant at University of Bucharest, Catalysis and Catalytic Processes Research Centre, Bucharest, Romania
Fellowships:
November 2012 - November 2014: Marie Curie IEF postdoctoral fellowship at the Instituto de Tecnologia Quimica, Technical University of Valencia, Valencia, Spain
October 2011 - December 2012: Postdoctoral fellowship at the University Politehnica of Bucharest, Bucharest, Romania
June 2008 - September 2008: NATO fellowship–Chemist researcher at the Instituto de Tecnología Química, Technical University of Valencia, Valencia, Spain
January 2007 - March 2007: NATO fellowship–Chemist researcher at University of Ottawa, Ontario, Ottawa, Canada
May 2006 - August 2006: NATO fellowship–Chemist researcher at the Dipartimento di Chimica IFM and NIS-Centre of Excellence, University of Turin, Turin, Italy
Research interests
Heterogeneous photocatalysis
Heterogeneous catalysis
Expertize
Specialized in the use of several materials characterization techniques (PXRD, SEM, textural measurements), spectral techniques (FTIR, DRIFT, FTNIR, UV-Vis-NIR, DR-UV-Vis, Raman, XPS, AAS, AES, ICP-OES, ICP-MS, TAS), thermal analysis (DSC, TG-DTA, DMA, TMA, STA), hyphenated techniques (DSC-Raman, TG-IR, TG-MS, TG-GC/MS), elemental analysis (CHNS/O) and chromatographic analysis (GC, GC-MS, HPLC).
Links:
Books
A. Primo, S. Neatu, H. Garcia, "Photocatalytic CO2 reduction", Advanced Materials for Clean Energy, 2015, 421–444; DOI: 10.1201/b18287; ISBN: 978-1-4822-0580-0; 978-1-4822-0578-7
Projects
1. MXene-semiconductor composites for hydrogen production by photocatalytic water splitting reaction
Project Type: PCE, Start Date: 2022-06-02 End Date: 2024-12-31
3. Integrated nanosystems for solar fuel generation
Project Type: TE, Start Date: 2015-10-01 End Date: 2017-11-30
Publications
1. A comparative overview of MXenes and metal oxides as cocatalysts in clean energy production through photocatalysis
Authors:
Nair, MM; Iacoban, AC; Neatu, F; Florea, M; Neatu, S
Published: JUN 20 2023, JOURNAL OF MATERIALS CHEMISTRY A, 11, DOI: 10.1039/d2ta08983a
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.
2. Iron-doped Co3O4 catalysts prepared by a surfactant-assisted method as effective catalysts for malic acid oxidative decarboxylation
Authors:
Mitran, G; Neatu, S; Pavel, OD; Urda, A; Mirea, AG; Florea, M; Neatu, F
Published: JUL 31 2023, CATALYSIS SCIENCE & TECHNOLOGY, 13, DOI: 10.1039/d3cy00121k
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.
3. A comparative overview of MXenes and metal oxides as cocatalysts in clean energy production through photocatalysis
Authors:
Nair, MM; Iacoban, AC; Neatu, F; Florea, M; Neatu, S
Published: JAN 2023, JOURNAL OF MATERIALS CHEMISTRY A, DOI: 10.1039/d2ta08983a
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.
4. Design of electrocatalysts with reduced Pt content supported on mesoporous NiWO4 and NiWO4-graphene nanoplatelets composite for oxygen reduction and hydrogen oxidation in acidic medium
Authors:
Somacescu, S; Osiceanu, P; Moreno, JMC; Culita, DC; Neatu, F; Trandafir, MM; Neatu, S; Kuncser, A; Szijjártó, GP; Tálas, E; Tompos, A; Borbáth, I; Florea, M
Published: FEB 22 2023, INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, 48, DOI: 10.1016/j.ijhydene.2022.04.270
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.
5. Photo-stable, 1D-nanofilaments TiO2-based lepidocrocite for photocatalytic hydrogen production in water-methanol mixtures
Authors:
Badr, HO; Natu, V; Neatu, S; Neatu, F; Kuncser, A; Rostas, AM; Racey, M; Barsoum, MW; Florea, M
Published: SEP 6 2023, MATTER, 6, DOI: 10.1016/j.matt.2023.05.026
Water and sunlight are the cleanest, most renewable, and abundant resources on Earth. Developing inexpensive, scalable photocatalysts that are highly stable for hydrogen (H-2) production has long been a cherished dream of humanity. Herein, we report on one-dimensional lepidocrocite-based sub-nanofilaments (NFs), approximate to 5 x 7 & Aring;(2) in cross-section, that generate H-2 from 80:20 v/v water/methanol mixtures when illuminated by simulated sunlight. The NFs were stable in the mixtures for times >4,300 h, 300 h of which were under irradiation. Apparent quantum yields as high as 11.7% were obtained. Based on deuterated water results, we conclude that water is the H-2 source. Further, no carbon dioxide (CO2) due to photocatalytic degradation of methanol was detected. Therefore, the NFs have strong green credentials and lucrative economic prospects for large scale up. We expect these NFs will lead to new lines for developing cheap and ultra-stable materials to produce H-2 photochemically for a long time.
6. A comparative overview of MXenes and metal oxides as cocatalysts in clean energy production through photocatalysis
Authors:
Nair, MM; Iacoban, AC; Neatu, F; Florea, M; Neatu, S
Published: 2023 JAN 16 2023, JOURNAL OF MATERIALS CHEMISTRY A, DOI: 10.1039/d2ta08983a
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.
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
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.
8. 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.
9. 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.
10. 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.
11. 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.
12. Accidental Impurities in Epitaxial Pb(Zr0.2Ti0.8)O-3 Thin Films Grown by Pulsed Laser Deposition and Their Impact on the Macroscopic Electric Properties
Authors:
Boni, GA; Chirila, CF; Stancu, V; Amarande, L; Pasuk, I; Trupina, L; Istrate, CM; Radu, C; Tomulescu, A; Neatu, S; Pintilie, I; Pintilie, L
Published: MAY 2021, NANOMATERIALS, 11, DOI: 10.3390/nano11051177
Structural and electrical properties of epitaxial Pb(Zr0.2Ti0.8)O-3 films grown by pulsed laser deposition from targets with different purities are investigated in this study. One target was produced in-house by using high purity precursor oxides (at least 99.99%), and the other target was a commercial product (99.9% purity). It was found that the out-of-plane lattice constant is about 0.15% larger and the a domains amount is lower for the film grown from the commercial target. The polarization value is slightly lower, the dielectric constant is larger, and the height of the potential barrier at the electrode interfaces is larger for the film deposited from the pure target. The differences are attributed to the accidental impurities, with a larger amount in the commercial target as revealed by composition analysis using inductive coupling plasma-mass spectrometry. The heterovalent impurities can act as donors or acceptors, modifying the electronic characteristics. Thus, mastering impurities is a prerequisite for obtaining reliable and reproducible properties and advancing towards all ferroelectric devices.
13. Effect of strain and stoichiometry on the ferroelectric and pyroelectric properties of the epitaxial Pb(Zr0.2Ti0.8)O-3 films deposited on Si wafers
Authors:
Chirila, C; Boni, GA; Filip, LD; Husanu, M; Neatu, S; Istrate, CM; Le Rhun, G; Vilquin, B; Trupina, L; Pasuk, I; Botea, M; Pintilie, I; Pintilie, L
Published: APR 2021, MATERIALS SCIENCE AND ENGINEERING B-ADVANCED FUNCTIONAL SOLID-STATE MATERIALS, 266, DOI: 10.1016/j.mseb.2021.115042
Properties of epitaxial PbZr0.2Ti0.8O3 (PZT) films deposited on Si substrates were investigated for integration in the present CMOS technology. Polarization is downward oriented, in association with the presence of an internal electric field, and has a lower value compared to the PZT films deposited on single crystal perovskite SrTiO3 (STO) substrates (40 mu C/cm(2) versus 80 mu C/cm(2)), while the dielectric constant is larger (180 versus 120). Large value for the pyroelectric coefficient was also found, 1.22 x 10(-3)C/m(2)K, as for PZT grown on single crystal STO. The macroscopic ferroelectric and pyroelectric properties appear to be affected by the structural quality and stoichiometry of the PZT film. The changes in the electric properties are an effect of the strain gradients induced by the large difference between the thermal expansion coefficients of PZT and Si substrate, leading in turn to Pb oxidation and antisite defect formation compared to PZT films deposited on STO substrates.
14. Enhancing stability of hybrid perovskite solar cells by imidazolium incorporation
Authors:
Tomulescu, AG; Leonat, LN; Neatu, F; Stancu, V; Toma, V; Derbali, S; Neatu, S; Rostas, AM; Besleaga, C; Patru, R; Pintilie, I; Florea, M
Published: AUG 1 2021, SOLAR ENERGY MATERIALS AND SOLAR CELLS, 227, DOI: 10.1016/j.solmat.2021.111096
Hybrid perovskites based solar cells have demonstrated high conversion efficiency but poor long-term stability. This study reports on the results obtained after doping the CH3NH3PbI2.6Cl0.4 mixed halide perovskite with imidazolium (C3N2H5+, denoted IM) on the "A site" position of a perovskite, to improve photovoltaic performances and stability of hybrid perovskite solar cells. The perovskite films were investigated exhaustively by different characterization techniques: X-ray diffraction, Atomic Force Microscopy, Scanning Electron Microscopy, UV-Vis, X-ray Photoelectron Electron Paramagnetic Resonance spectroscopies, Impedance Spectroscopy and Incident Photon-to-Electron Conversion Efficiency. The photovoltaic parameters were determined by measuring the IV curves of the corresponding solar cells. The amount of IM inserted in the perovskite play a key role on the film properties. The calculated new tolerance factors according to the "globularity factor" are experimentally proved and thus at doping concentrations greater than 20% for CH3NH3PbI2.6Cl0.4 perovskite the 3D structure is no longer obtained. However, below this value, the IM substituted perovskite film possesses an improved film quality and crystallinity as compared to the pristine film. Substituting MA+ with IM+ provides a favorable way to reduce recombination processes and shows great potential to achieve high stability, and an improved charge generation, resulting in increased PCE values. We find that the optimal percentage of imidazolium incorporation to achieve better stability of solar cells is 6%.
15. Comparative investigation of structural, EPR, optical and photoluminescence properties of nanostructured LaPO4:Ce/RE/Me and LaPO4:Yb/Er phosphors prepared by co-precipitation method
Authors:
AitMellal, O; Oufni, L; Messous, MY; Trandafir, MM; Chirica, IM; Florea, M; Neatu, S; Rostas, AM; Secu, M; Neatu, F
Published: SEP 2021, JOURNAL OF SOLID STATE CHEMISTRY, 301, DOI: 10.1016/j.jssc.2021.122310
In this work, the structural, thermal, vibrational, morphological, magnetic and optical properties of LaPO4:Ce/RE/Me (RE=Nd3+, Tb3+; Me-Cr3+, Mn2+) and LaPO4:Yb3+/Er3+ phosphors prepared by the co-precipitation method are presented. The obtained materials crystallized in monoclinic structure with the P2(1)/n space group and the particles were of nanorod shape with about 200 nm in length and the diameter approximately 19 nm. The presence of dopant ions was confirmed by both electron paramagnetic resonance (EPR) and UV-visible spectroscopies. In addition, the down-conversion (DC) and up-conversion (UC) of the LaPO4 nanophosphors via the 275 and 980 nm excitations, respectively, were considered, and a wide range of electronic transitions was observed. Based on the photoluminescence (PL) spectra, there is an efficient energy transfer (ET) process from Ce3+ donors to Nd3+ and Tb3+ acceptors, and the computed ET efficiency was 70% and 88%, respectively. The Ce3+/Cr3+ and Ce3+/Mn2+ doped LaPO4 showed weak far-red and green luminescence with much smaller ET efficiency of about 3.7 and 0.4%, respectively. LaPO4:Yb3+/Er3+ showed UC luminescence under the 980 nm laser radiation, and the resulted red and green light was attributed to the Er3+ transitions.
16. Structural Details of BaTiO3 Nano-Powders Deduced from the Anisotropic XRD Peak Broadening
Authors:
Pasuk, I; Neatu, F; Neatu, S; Florea, M; Istrate, CM; Pintilie, I; Pintilie, L
Published: MAY 2021, NANOMATERIALS, 11, DOI: 10.3390/nano11051121
In this study, nano-BaTiO3 (BTO) powders were obtained via the solvothermal method at different reaction times and were investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy. The results were compared with those obtained for a larger crystallite size BTO powder (BTO-m). The sizes of the cuboid crystallites (as determined by XRD and TEM) ranged from about 18 to 24 nm, depending on the reaction time. The evolution with temperature of the structure parameters of nano-BTO was monitored by means of X-ray diffraction and Raman spectroscopy and no signs of phase transition were found up to 170 degrees C. Careful monitoring of the dependence of the XRD peak widths on the hkl indices showed that the effect of the cubic crystallite shape upon the XRD peak widths was buried by the effect of hidden tetragonal line splits and by anisotropic microstrain. The good correlation of the line widths with the tetragonal split amplitudes, observed especially for BTO-m above the transition temperature, indicates tetragonal deformations, as also revealed by Raman spectroscopy. The large anisotropic microstrain shown by the nano-powders, which had a maximum value in the directions, was considered evidence of the phenomenon of surface relaxation of cubic crystallites edged by {100} faces. The observed behavior of the nano-BTO structures with increasing temperature may suggest a correlation between the surface relaxation and tetragonal deformation in the nano-cubes. The experimental results for both nano-BTO and mezoscale-BTO are in agreement with the core-shell model.
17. Recent progress in electrocatalysts and electrodes for portable fuel cells
Authors:
Neatu, S; Neatu, F; Chirica, IM; Borbath, I; Talas, E; Tompos, A; Somacescu, S; Osiceanu, P; Folgado, MA; Chaparro, AM; Florea, M
Published: AUG 28 2021, JOURNAL OF MATERIALS CHEMISTRY A, 9, 17128, DOI: 10.1039/d1ta03644k
Fuel cells are devices that transform efficiently the chemical energy of hydrogen or another fuel into clean electricity. The fuel cell technology is attractive for its high-energy efficiency and expanded fuel flexibility and it became very relevant in the last decade. Moreover, the utilization of fuel cells for portable electronic devices has seen remarkable increase in the last few years. Performances of fuel cells, among others, strongly depend on the types of electrocatalysts and membrane, anion exchange or cation exchange, used in the system. Therefore, a status report about the latest advances in electrocatalysts and electrodes for portable fuel cells is the objective of this review paper. Herein, the recent progress in designing electrocatalysts for producing high performance fuel cells with truly potential applicability to be used in portable devices is highlighted.
18. Structural and Optical Investigations of Ce3+/Mn2+-Doped LaPO4 Phosphors
Authors:
Aitmellal, O; Oufni, L; Messous, MY; Neatu, F; Florea, M; Neatu, S; Rostas, AM; Secu, M
Published: APR 2021, JOURNAL OF ELECTRONIC MATERIALS, 50, 2147, DOI: 10.1007/s11664-020-08678-7
Lanthanum orthophosphate (LaPO4) and La0.95-xCe0.05MnxPO4 (x = 0.00, 0.03, 0.10) phosphors were synthesized by a simple and cost-efficient co-precipitation method and the formation of LaPO4 nanorods with a monoclinic P21/n crystal structure was observed. X-ray diffraction pattern analysis indicated a slight distortion of the LaPO4 crystalline structure and an increase of the lattice strain as a consequence of the Mn2+ and Ce3+ dopants incorporation in the host matrix. Scanning electron microscopy revealed that the microstructure of all powders consists of agglomerations of nanorods, which are around 17 +/- 3 nm in diameter and length ranging from 100 nm to 300 nm. Electron paramagnetic resonance measurements have indicated the presence of Mn2+ in isolated species, but also as agglomerates. Ce3+ and Mn2+ doping of LaPO4 resulted also in a decrease of the band gap up to 4.70 eV compared to the un-doped sample. Because of an energy transfer effect from Ce3+ to Mn2+ ions, green emission of Mn2+ ions at around 550 nm was observed upon 275 nm excitation.
19. 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.
20. Degenerated TiO(2)Semiconductor Modified with Ni and Zn as Efficient Photocatalysts for the Water Splitting Reaction
Authors:
Neatu, F; Abramiuc, LE; Trandafir, MM; Negrea, RF; Florea, M; Teodorescu, CM; Neatu, S
Published: SEP 17 2020, CHEMCATCHEM, 12, DOI: 10.1002/cctc.202000691
The development of robust, safe, cost-effective and efficient photocatalytic systems for water splitting should take into account the presence of a proper and powerful photon absorber and an efficient, low-cost and earth-abundant electrocatalyst to perform the reaction at high conversions. In this study, Ni-Zn/TiO(2)ternary composites with high photocatalytic activity for water splitting under UV irradiation were successfully prepared via a simple and low-cost deposition-precipitation route. Thus, different Ni : Zn molar ratios (1 : 0, 1 : 1, 3 : 1, 6 : 1, 9 : 1, and 0 : 1) were deposited on TiO(2)in order to reach a total metal loading of 50 wt. %. The obtained composites were characterized using several techniques, such as: X-ray diffraction, UV-Vis spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. The most active synthesized composite, namely Ni-Zn/TiO2(9 : 1), exhibits H(2)generation rate above 17 mmols g(-1) h(-1), which is nearly one thousand times higher than that obtained with TiO(2)Evonik P25. Our study demonstrates that TiO(2)becomes a degenerated semiconductor in the presence of Ni and ZnO, with remarkable photocatalytic properties. Thus, the obtained results can open new opportunities in the preparation of very active materials for hydrogen production based on the optimization of three-component structures.
21. Degenerated TiO2 Semiconductor Modified with Ni and Zn as Efficient Photocatalysts for the Water Splitting Reaction
Authors:
Neatu, F; Abramiuc, LE; Trandafir, MM; Negrea, RF; Florea, M; Teodorescu, CM; Neatu, S
Published: SEP 17 2020, CHEMCATCHEM, 12, 4651, DOI: 10.1002/cctc.202000691
The development of robust, safe, cost-effective and efficient photocatalytic systems for water splitting should take into account the presence of a proper and powerful photon absorber and an efficient, low-cost and earth-abundant electrocatalyst to perform the reaction at high conversions. In this study, Ni-Zn/TiO(2)ternary composites with high photocatalytic activity for water splitting under UV irradiation were successfully prepared via a simple and low-cost deposition-precipitation route. Thus, different Ni : Zn molar ratios (1 : 0, 1 : 1, 3 : 1, 6 : 1, 9 : 1, and 0 : 1) were deposited on TiO(2)in order to reach a total metal loading of 50 wt. %. The obtained composites were characterized using several techniques, such as: X-ray diffraction, UV-Vis spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. The most active synthesized composite, namely Ni-Zn/TiO2(9 : 1), exhibits H(2)generation rate above 17 mmols g(-1) h(-1), which is nearly one thousand times higher than that obtained with TiO(2)Evonik P25. Our study demonstrates that TiO(2)becomes a degenerated semiconductor in the presence of Ni and ZnO, with remarkable photocatalytic properties. Thus, the obtained results can open new opportunities in the preparation of very active materials for hydrogen production based on the optimization of three-component structures.
22. CeO2:Mn3O4 Catalytic Micro-Converters Tuned for CH4 Detection Based on Catalytic Combustion under Real Operating Conditions
Authors:
Simion, CE; Florea, OG; Florea, M; Neatu, F; Neatu, S; Trandafir, MM; Stanoiu, A
Published: MAY 2020, MATERIALS, 13, DOI: 10.3390/ma13092196
Mesoporous CeO2:Mn3O4 materials (3:7 and 7:3 molar ratio) were prepared by co-precipitation and deposited as porous thick films over alumina (Al2O3) planar substrate provided with Pt meander. The aim was oriented towards detecting low levels methane (CH4) at moderate operating temperatures. Herein we demonstrated that the sensitivity of catalytic micro-converters (CMCs) towards a given peak of CH4 concentration corresponds to specific gas-surface interaction phenomena. More precisely, a transition from thermal conductivity to combustion rate is likely to occur when CMCs are operated under real atmospheric conditions (normal pressure, presence of relative humidity, and constant operating temperature). The response to CH4 was analyzed over different gas flows and different gas concentrations under the same operating regime. The materials were fully characterized by adsorption-desorption isotherms, H-2-Temperature Programmed Reduction (H-2-TPR), X-ray Diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), and Raman spectroscopies. Thus, the applicative aspect of using CeO2:Mn3O4 as moderate temperature CMC for CH4 detection is brought to the fore.
23. Undoped SnO2 as a Support for Ni Species to Boost Oxygen Generation through Alkaline Water Electrolysis
Authors:
Neatu, S; Neatu, F; Diculescu, VC; Trandafir, MM; Petrea, N; Somacescu, S; Krumeich, F; Wennmacher, JTC; Knorpp, AJ; van Bokhoven, JA; Florea, M
Published: APR 22 2020, ACS APPLIED MATERIALS & INTERFACES, 12, 18420, DOI: 10.1021/acsami.9b19541
In this study, the synergistic behavior of Ni species and bimodal mesoporous undoped SnO2 is investigated in oxygen evolution reactions (OERs) under alkaline conditions without any other modification of the compositional phases or using noble metals. An efficient and environmentally friendly hydrothermal method to prepare bimodal mesoporous undoped SnO2 with a very high surface area (>130 m(2) g(-1)) and a general deposition-precipitation method for the synthesis of well-dispersed Ni species on undoped SnO2 are reported. The powders were characterized by adsorption-desorption isotherms, TG-DTA, XRD, SEM, TEM, Raman, TPRH2, and XPS. The best NiSn composite generates, under certain experimental conditions, a very high TOF value of 1.14 s(-1) and a mass activity higher than 370 A g(-1), which are remarkable results considering the low amount of Ni deposited on the electrode (3.78 ng). Moreover, in 1 M NaOH electrolyte, this material produces more than 24 mA cm(-2) at an overpotential value of approximately +0.33 V, with only 5 wt % Ni species. This performance stems from the dual role of undoped SnO2, on the one hand, as a support for active and well-dispersed Ni species and on the other hand as an active player through the oxygen vacancies generated upon Ni deposition.
24. Exploring the effect of aliovalent substitution of Pb2+ by Eu3+ on structural, morphological and optical properties of CH3NH3PbI3 perovskite films
Authors:
Derbali, S; Nouneh, K; Florea, M; Neatu, F; Neatu, S; Leonat, LN; Secu, M; Tomulescu, AG; Stancu, V; Pintilie, L; Touhami, ME; Galca, AC
Published: APR 2020, PHYSICA SCRIPTA, 95, DOI: 10.1088/1402-4896/ab5baa
In this work, the effect of aliovalent substitution of Pb2+ by Eu3+ on structural, morphological and optical properties of CH3NH3PbI3 (MAPbI(3)) was studied, aiming to improve the properties of perovskite films used in solar cells application. The surface morphology, the microstructure and the optical properties of the obtained films containing different Europium (Eu) concentrations were characterized by atomic force microscopy, x-ray photoelectron spectroscopy, x-ray diffraction, UV-vis spectroscopy and photoluminescence spectroscopy.
25. Highly Efficient Ultralow Pd Loading Supported on MAX Phases for Chemoselective Hydrogenation
Authors:
Trandafir, MM; Neatu, F; Chirica, IM; Neatu, S; Kuncser, AC; Cucolea, EI; Natu, V; Barsoum, MW; Florea, M
Published: MAY 15 2020, ACS CATALYSIS, 10, 5908, DOI: 10.1021/acscatal.0c00082
Palladium is one of the most efficient metals for the hydrogenation of organic compounds. However, when molecules, such as nitroaromatics, with several reducible functionalities, are hydrogenated, Pd, like any other very active metal, such as nickel or platinum, often behaves unselectively. One strategy to render Pd more selective is to choose the proper support. Herein, we show that MAX phase powders of Ti3SiC2, Ti2AlC, or Ti3AlC2 can chemoselectively hydrogenate 4-nitrostyrene to 4-aminostyrene, with 100% selectivity, at around 3-4% conversion. To boost the latter, we loaded Ti3SiC2 with 0.0005 wt % Pd and increased the conversion to 100% while maintaining the 4-AS selectivity at >90%. By optimizing the Pd loading, we were also able to increase the turnover frequency 100-fold relative to previous literature results. The identification of this highly efficient and chemoselective system has broad implications for the design of cost-effective, earth-abundant, nontoxic, metal catalysts, with ultralow noble metal loadings.
26. Methane Combustion Using Pd Deposited on CeOx-MnOx/La-Al2O3 Pellistors
Authors:
Florea, OG; Stanoiu, A; Gheorghe, M; Cobianu, C; Neatu, F; Trandafir, MM; Neatu, S; Florea, M; Simion, CE
Published: NOV 2020, MATERIALS, 13, DOI: 10.3390/ma13214888
Pd deposited on CeOx-MnOx/La-Al2O3 has been prepared as a sensitive material for methane (CH4) detection. The effect of different amounts (1.25%, 2.5% and 5%) of Pd loading has been investigated. The as prepared materials were deposited on Pt microcoils using a drop-coating method, as a way of developing pellistors operated using a Wheatstone bridge configuration. By spanning the operating temperature range between 300 degrees C and 550 degrees C, we established the linearity region as well as the maximum sensitivity towards 4900 ppm of CH4. By making use of the sigmoid dependence of the output voltage signal from the Wheatstone bridge, the gas surface reaction and diffusion phenomena have been decoupled. The pellistor with 5% Pd deposited on CeOx-MnOx/La-Al2O3 exhibited the highest selective-sensitivity in the benefit of CH4 detection against threshold limits of carbon monoxide (CO), sulfur dioxide (SO2) and hydrogen sulfide (H2S). Accordingly, adjusting the percent of Pd makes the preparation strategies of pellistors good candidates towards CH4 detection.
27. VAlPOs as Efficient Catalysts for Glycerol Conversion to Methanol
Authors:
Mitran, G; Neatu, F; Neatu, S; Trandafir, MM; Florea, M
Published: JUL 2020, CATALYSTS, 10, DOI: 10.3390/catal10070728
The catalytic activity of a series of vanadium aluminophosphates catalysts prepared by sol-gel method followed by combustion of the obtained gel was evaluated in glycerol conversion towards methanol. The materials were characterized by several techniques such as X-ray diffraction (XRD), UV-vis, Fourier-transform infrared (FTIR), Raman and X-ray photoelectron (XPS) spectroscopies. The amount of vanadium incorporated in aluminophosphates framework played an important role in the catalytic activity, while in the products distribution the key role is played by the vanadium oxidation state on the surface. The sample that contains a large amount of V(4+)has the highest selectivity towards methanol. On the sample with the lowest vanadium loading the oxidation path to dihydroxyacetone is predominant. The catalyst with higher content of tetrahedral isolated vanadium species, such V5APO, is less active in breaking the C-C bonds in the glycerol molecule than the one containing polymeric species.
28. Bulk Versus Surface Modification of Alumina with Mn and Ce Based Oxides for CH4 Catalytic Combustion
Authors:
Neatu, S; Trandafir, MM; Stanoiu, A; Florea, OG; Simion, CE; Leonat, LN; Cobianu, C; Gheorghe, M; Florea, M; Neatu, F
Published: JUN 1 2019, MATERIALS, 12, DOI: 10.3390/ma12111771
This study presents the synthesis and characterization of lanthanum-modified alumina supported cerium-manganese mixed oxides, which were prepared by three different methods (coprecipitation, impregnation and citrate-based sol-gel method) followed by calcination at 500 degrees C. The physicochemical properties of the synthesized materials were investigated by various characterization techniques, namely: nitrogen adsorption-desorption isotherms, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and H-2-temperature programmed reduction (TPR). This experimental study demonstrated that the role of the catalytic surface is much more important than the bulk one. Indeed, the incipient impregnation of CeO2-MnOx catalyst, supported on an optimized amount of 4 wt.% La2O3-Al2O3, provided the best results of the catalytic combustion of methane on our catalytic micro-convertors. This is mainly due to: (i) the highest pore size dimensions according to the Brunauer-Emmett-Teller (BET) investigations, (ii) the highest amount of Mn4+ or/and Ce4+ on the surface as revealed by XPS, (iii) the presence of a mixed phase (Ce2MnO6) as shown by X-ray diffraction; and (iv) a higher reducibility of Mn4+ or/and Ce4+ species as displayed by H-2-TPR and therefore more reactive oxygen species.
29. La0.75Sr0.25XO3 (X = Fe, Mn or Cr) with coking tolerance for CH4/H2O reaction: effect of H2S on catalytic performance
Authors:
Florea, M; Somacescu, S; Postole, G; Urda, A; Neatu, F; Neatu, S; Massin, L; Gelin, P
Published: MAY 7 2019, CATALYSIS SCIENCE & TECHNOLOGY, 9, 2366, DOI: 10.1039/c9cy00065h
The influence of the B type cation from the ABO(3) perovskite formulation La0.75Sr0.25XO3 (LSX, where X is Fe, Mn or Cr) on the C and H2S tolerance and its catalytic activity for the methane/water reaction has been studied. The samples were prepared by a simple and cost-efficient citrate method. The exhaustive characterization of the bulk and surface properties of the catalysts has been accomplished by means of complementary methods: nitrogen adsorption-desorption isotherm measurements, XRD, TPR and XPS. Their catalytic properties in CH4/H2O reactions (CH4/H2O molar ratios of 10 and 1) were studied in the presence and absence of H2S in order to evaluate their potential use as anode materials in solid oxide fuel cells operated on natural gas. Before addition and upon suppression of H2S, the activity varied in the following order: LSF > LSM >> LSC. This correlates with the oxygen mobility determined by TPR. A strong promoting effect of H2S on the catalytic activity is observed for LSC, which makes this sample the most active of the series, while H2S has a weak influence on the other perovskites. The oxygen vacancies and the presence of S2- were identified as being responsible for the enhanced catalytic activity upon H2S addition.
30. The Cu- and Zn-complex-catalyzed methanolysis of the chemical warfare nerve agents soman, sarin, and VX
Authors:
Petrea, N; Petre, R; Pretorian, A; Toader, C; Somoghi, V; Neatu, F; Florea, M; Neatu, S
Published: MAR-APR 2018, COMPTES RENDUS CHIMIE, 21, 345, DOI: 10.1016/j.crci.2017.08.006
The catalytic methanolysis of the chemical warfare nerve agents soman, sarin, and VX was investigated by using Cu or Zn complexes. Although VX withstood decontamination, the decomposition yield being around 96%, the soman and sarin deposited on different surfaces were almost fully destroyed under ambient conditions. The catalytic tests performed on a wide range of contaminated surfaces confirm the activity of the investigated catalytic systems, these complexes being suitable, from an economical point of view, for use in the formulation of a possible decomposition kit with military or civilian applicability. (C) 2017 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.
31. Potential application of Ni and Co stabilized zirconia as oxygen reduction reaction catalyst
Authors:
Neatu, F; Trandafir, MM; Marcu, M; Preda, L; Calderon-Moreno, JM; Neatu, S; Somacescu, S; Florea, M
Published: APR 2017, CATALYSIS COMMUNICATIONS, 93, 42, DOI: 10.1016/j.catcom.2016.12.026
A new facile template method for the preparation of Ni, Co doped ZrO2 self-assembled electrocatalysts for oxygen reduction reaction was employed. The effect of the Ni and Co incorporation into ZrO2 lattice on the structural, texturaL surface chemistry and its activity on ORR was emphasized. As X-ray diffraction reveals, the pseudo-cubic lattice of the tetragonal ZrO2 polymorph (t-ZrO2) is stabilized when Ni and Co are co-doping ZrO2. The results indicate that the synergetic effects arisen from the intimate electronic interaction of the mixed oxides present in the lattice of the zirconia phase, i.e. Nil-xCoxO (or NiO and CoO) in NCZ enhance the electrocatalytic activity of the catalyst. (C) 2017 Elsevier B.V. All rights reserved.
32. The combined action of methanolysis and heterogeneous photocatalysis in the decomposition of chemical warfare agents
Authors:
Petrea, N; Petre, R; Epure, G; Somoghi, V; Tanase, LC; Teodorescu, CM; Neatu, S
Published: 2016, CHEMICAL COMMUNICATIONS, 52, 12959, DOI: 10.1039/c6cc07551g
We report the applicability of a hybrid system comprising a La3+-based catalyst and an Au/TiO2 photocatalyst in the decomposition of chemical weapons. This system is able to perform complete degradation of soman, sarin and VX in less than 1 minute under low basic conditions and visible light irradiation.
33. Unusual Behavior of a Novel Heterogeneous Chiral Dimer Cr(III)-Salen Complex in the Epoxidation/Epoxide Ring-Opening Reaction of trans-Methylcinnamate Ester
Authors:
Protesescu, L; Tudorache, M; Neatu, S; Grecu, MN; Kemnitz, E; Filip, P; Parvulescu, VI; Coman, SM
Published: FEB 3 2011, JOURNAL OF PHYSICAL CHEMISTRY C, 115, 1122, DOI: 10.1021/jp106281z
A dimer chromium(III)-salen complex immobilized on modified silica is an effective catalyst for the epoxidation/epoxide ring-opening reaction of trans-methylcinnamate ester and gave significantly high ee in methyl (2R,3S)-2,3-dihydroxy-3-phenylpropionate. For the first time, it is shown that a donor ligand (e.g., Et3N) can be involved into the enantioselective mechanism of the product configuration. It is suggested that the additive is interacting with the reaction intermediate in a manner that prolongs its lifetime, thus affording a free rotation of the C-C single bond in this species and a selective collapse to the cis-epoxide product. In the presence of water, this epoxide led to methyl (2S,3R)-2,3-dihydroxy-3-phenylpropionate. Alternatively, the donor additives may give rise to a new chromium-based oxidant that effects epoxidation and its consecutive ring opening to diols via an unusual pathway.
34. Structural and Optical Investigations of Ce3+/Mn2+-Doped LaPO4 Phosphors
Authors:
Aitmellal, O; Oufni, L; Messous, MY; Neatu, F; Florea, M; Neatu, S; Rostas, AM; Secu, M
Published: , JOURNAL OF ELECTRONIC MATERIALS, DOI: 10.1007/s11664-020-08678-7
Lanthanum orthophosphate (LaPO4) and La0.95-xCe0.05MnxPO4 (x = 0.00, 0.03, 0.10) phosphors were synthesized by a simple and cost-efficient co-precipitation method and the formation of LaPO4 nanorods with a monoclinic P21/n crystal structure was observed. X-ray diffraction pattern analysis indicated a slight distortion of the LaPO4 crystalline structure and an increase of the lattice strain as a consequence of the Mn2+ and Ce3+ dopants incorporation in the host matrix. Scanning electron microscopy revealed that the microstructure of all powders consists of agglomerations of nanorods, which are around 17 +/- 3 nm in diameter and length ranging from 100 nm to 300 nm. Electron paramagnetic resonance measurements have indicated the presence of Mn2+ in isolated species, but also as agglomerates. Ce3+ and Mn2+ doping of LaPO4 resulted also in a decrease of the band gap up to 4.70 eV compared to the un-doped sample. Because of an energy transfer effect from Ce3+ to Mn2+ ions, green emission of Mn2+ ions at around 550 nm was observed upon 275 nm excitation.
36. 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
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.
37. Applications of MAX phases and MXenes as catalysts
Authors:
Chirica, IM; Mirea, AG; Neatu, S; Florea, M; Barsoum, MW; Neatu, F
Published: , JOURNAL OF MATERIALS CHEMISTRY A, DOI: 10.1039/d1ta04097a
38. 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: , JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, DOI:
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.
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