301
Synthesis and Characterization of Graphite Oxide Derived TiO2-Carbon Composites as Potential Electrocatalyst Supports
Ayyubov, I; Borbáth, I; Pászti, Z; Sebestyén, Z; Mihály, J; Szabó, T; Illés, E; Domján, A; Florea, M; Radu, D; Kuncser, A; Tompos, A; Tálas, E
NOV 2024, TOPICS IN CATALYSIS, 67
DOI: 10.1007/s11244-021-01513-1
Show abstract
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.
302 Open Access
CO2 Interaction Mechanism of SnO2-Based Sensors with Respect to the Pt Interdigital Electrodes Gap
Stanoiu, A; Iacoban, AC; Mihalcea, CG; Dinu, IV; Florea, OG; Vlaicu, ID; Simion, CE
NOV 2024, CHEMOSENSORS, 12, 238
DOI: 10.3390/chemosensors12110238
Show abstract
The tuning sensitivity towards CO2 detection under in-field-like conditions was investigated using SnO2-sensitive material deposited onto Al2O3 substrates provided with platinum electrodes with interdigital gaps of 100 mu m and 30 mu m. X-ray diffraction, low-magnification and high-resolution transmission electron microscopy, and electrical and contact potential difference investigations were employed to understand the sensing mechanism involved in CO2 detection. The morpho-structural analysis revealed that the SnO2 nanoparticles exhibit well-defined facets along the (110) and (101) crystallographic planes. Complex phenomenological investigations showed that moisture significantly affects the gas sensing performance. The experimental results corroborated the literature evidence, highlighting the importance of Pt within the interdigital electrodes subsequently reflected in the increase in the CO2 sensing performance with the decrease in the interdigital gap. The catalytic efficiency is explained by the distribution of platinum at the gas-Pt-SnO2 three-phase boundary, which is critical for enhancing the sensor performance.
303 Open Access
Bioactive Hybrids Containing Artificial Cell Membranes and Phyto-Gold-Silver Chloride Bio-Nanoparticles
Barbinta-Patrascu, ME; Nichita, C; Enculescu, M; Maraloiu, VA; Bacalum, M; Ungureanu, C; Negrila, CC; Zgura, I
NOV 2024, INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES, 25, 11929
DOI: 10.3390/ijms252211929
Show abstract
This research targets the need for eco-friendly strategies in the synthesis of bioactive materials, addressing the importance of valorization of vegetal waste. This study focuses on developing biohybrids containing biomimetic lipid vesicles and phytosynthesized gold-silver chloride nanoparticles (AuAgCl NPs) derived from Achillea millefolium L. extract. By leveraging the natural antioxidant and antimicrobial properties of the plant, the research proposes a sustainable approach to creating materials with potential biomedical applications. The biomimetic membranes were loaded with chlorophyll a, a natural spectral marker. Three types of bioactive materials (biohybrids) were developed by varying the lipid vesicle/AuAgCl NP ratio. Optical (UV-Vis, fluorescence emission, FTIR), structural (XRD), elemental (EDX, XPS), and morphological (TEM) studies were performed to characterize the bio-developed materials. The hydrophobic/hydrophilic characteristics of the samples were investigated by measuring the water contact angle, and their size was estimated by DLS and TEM. Zeta potential measurements were used to evaluate the physical stability of phyto-developed particles. Antioxidant properties of phyto-particles were investigated through the chemiluminescence technique. The obtained biomaterials exhibited high antioxidant activity and antiproliferative activity against HT-29 and B-16 cancer cells. Therapeutic index values were calculated for each biohybrid. Additionally, the bio-prepared hybrids revealed biocidal action against Staphylococcus aureus and Enterococcus faecalis. The phyto-developed biomaterials are promising in biomedical applications, particularly as adjuvants in cancer therapy.
304 Open Access
MAPLE-Deposited Perylene Diimide Derivative Based Layers for Optoelectronic Applications
Breazu, C; Girtan, M; Stanculescu, A; Preda, N; Rasoga, O; Costas, A; Catargiu, AM; Socol, G; Stochioiu, A; Popescu-Pelin, G; Iftimie, S; Petre, G; Socol, M
NOV 2024, NANOMATERIALS, 14, 1733
DOI: 10.3390/nano14211733
Show abstract
Nowadays, the development of devices based on organic materials is an interesting research challenge. The performance of such devices is strongly influenced by material selection, material properties, design, and the manufacturing process. Usually, buckminsterfullerene (C60) is employed as electron transport material in organic photovoltaic (OPV) devices due to its high mobility. However, considering its low solubility, there have been many attempts to replace it with more soluble non-fullerene compounds. In this study, bulk heterojunction thin films with various compositions of zinc phthalocyanine (ZnPc), a perylene diimide derivative, or C60 were prepared by matrix-assisted pulsed laser evaporation (MAPLE) technique to assess the influence of C60 replacement on fabricated heterostructure properties. The investigations revealed that the optical features and the electrical parameters of the organic heterostructures based on this perylene diimide derivative used as an organic acceptor were improved. An increase in the JSC value (4.3 x 10-4 A/cm2) was obtained for the structures where the perylene diimide derivative acceptor entirely replaced C60 compared to the JSC value (7.5 x 10-8 A/cm2) for the heterostructure fabricated only with fullerene. These results are encouraging, demonstrating the potential of non-fullerene compounds as electron transport material in OPV devices.
305 Open Access
Magnetic Memory Effects in BaFe2(As0.68P0.32)2 Superconducting Single Crystal
Badea, AM; Ivan, I; Miclea, CF; Crisan, DN; Galluzzi, A; Polichetti, M; Crisan, A
NOV 2024, MATERIALS, 17, 5340
DOI: 10.3390/ma17215340
Show abstract
Among many iron-based superconductors, isovalently substituted BaFe2(As1-xPx)2 displays, for x approximate to 0.3, apart from the quite usual Second Magnetization Peak (SMP) in the field dependence of the critical current density, an unusual peak effect in the temperature dependence of the critical current density in the constant field, which is related to the rhombic-to-square (RST) structural transition of the Bragg vortex glass (BVG). By using multi-harmonic AC susceptibility investigations in three different cooling regimes-field cooling, zero-field cooling, and field cooling with measurements during warming up-we have discovered the existence of a temperature region in which there is a pronounced magnetic memory effect, which we attributed to the direction of the structural transition. The observed huge differences in the third harmonic susceptibility at low and high AC frequencies indicates the difference in the time-scale of the structural transition in comparison with the timescale of the vortex excitations. Our findings show that the RST influence on the vortex dynamics goes beyond the previously observed influence on the onset of the SMP.
306 Open Access
Investigation of the Effect of the Third Cation M (M = Mg, Al, Mn, and Fe) on the Properties and Catalytic Behavior in Ethane Oxidative Dehydrogenation of M-NiNbO Mixed Oxides
Ivan, SB; Trandafir, MM; Papa, F; Negrila, CC; Loridant, S; Florea, M; Popescu, I; Marcu, IC
OCT 25 2024, INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 63
DOI: 10.1021/acs.iecr.4c02682
Show abstract
This work examines the effect of incorporating a third cation M (M = Mg, Al, Mn, or Fe) into Nb-promoted NiO catalysts (Ni0.85Nb0.15O) on their physicochemical properties and catalytic performance in the oxidative dehydrogenation (ODH) of ethane into ethylene. Therefore, a series of mixed oxides with the composition Ni0.765Nb0.135M0.1O was synthesized, characterized, and analyzed for catalytic behavior. The addition of the third cation markedly modified the redox and semiconductive properties of the catalysts, thus affecting their ODH performance. The selectivity toward ethylene was strongly dependent on the cation modifier, as it modulated the density of nonselective sites on the catalyst surface. In the low-temperature region, Mn-NiNbO demonstrated the highest conversion rates but with the lowest ethylene selectivity, whereas Fe-NiNbO, despite being less active than the undoped NiNbO, exhibited the highest ethylene selectivity. Overall, undoped NiNbO emerged as the best catalyst in terms of both activity and selectivity at isoconversion. All catalysts underwent partial reduction under reaction conditions, with the degree of reduction inversely correlated with the specific reaction rates. Although none of the catalysts remained stable at 400 degrees C, Al-NiNbO showed the least deactivation over time. The deactivation was linked to a reduction in p-type conductivity and a loss of redox functionality during operation.
307 Open Access
Crystallization processes of rare-earth doped GdF3 nanocrystals in silicate glass matrix: Dimorphism and photoluminescence properties
Secu, CE; Bartha, C; Radu, C; Secu, M
OCT 15 2024, CERAMICS INTERNATIONAL, 50
DOI: 10.1016/j.ceramint.2024.06.335
Show abstract
Rare-earth doped GdF3 nanocrystals embedded in silica glassy matrix have been prepared by controlled crystallization of the xerogel; the influence of rare-earth ion (Pr, Sm, Eu, Tb, Dy, Er, Yb) and additional Li-codopant on structural and optical properties was discussed. The precipitation of RE-doped GdF3 nanocrystalline phase is the result of Gd-trifluoracetate thermolysis revealed as a strong exothermic peak at around 300 degrees C. Structural analysis of RE-doped SiO2-GdF3 glass-ceramic sample calcined at 525 degrees C showed the occurrence of GdF3 nanocrystals of about 25 nm size, showing hexagonal or orthorombic structure depending on the RE-ion. Under UV-light excitation at 273 nm of Gd3+ ions (S-8(7/2) -> I-6(13/2,15/2) transition), photoluminescence spectra showed characteristic RE3+ luminescence due to the non-radiative energy transfer between the excited Gd3+ and acceptor RE ions; the highest energy transfer (congruent to 80 %) was observed for Tb3+ and lowest (congruent to 21 %) for Sm3+.
308
Insights into Large-Scale Synthesis of Benfotiamine
Hanganu, A; Maximov, M; Maximov, OC; Popescu, CC; Sandu, N; Florea, M; Mirea, AG; Gârbea, C; Matache, M; Funeriu, DP
OCT 14 2024, ORGANIC PROCESS RESEARCH & DEVELOPMENT, 28
DOI: 10.1021/acs.oprd.4c00351
Show abstract
There has been increased interest in the synthesis of benfotiamine during the past few years, most likely as a direct consequence of growing market demand. It has much higher bioavailability than thiamine (vitamin B1) and therefore is more suitable for therapeutic purposes, especially in oral form. We report herein our research in an academic-private R&D project in which we investigate all aspects of the process on small and large scales. The procedure involves two labor-intensive steps, starting from thiami3ne chloride hydrochloride with the key intermediate thiamine monophosphate phosphate (TMP-the phosphate ester of thiamine monophosphate). We obtained the crystalline form of benfotiamine directly from the synthesis in the crystalline form required on the market, as proven by XRD powder spectroscopy, IR, and RAMAN.
309 Open Access
Spin asymmetry of O 2p-related states in SrTiO3(001)
Popescu, DG; Nicolaev, A; Costescu, RM; Borcan, LE; Lungu, GA; Tache, CA; Husanu, MA; Teodorescu, CM
OCT 1 2024, PHYSICA SCRIPTA, 99, 105925
DOI: 10.1088/1402-4896/ad732c
Show abstract
Atomically clean SrTiO3(001) is characterized by low energy electron diffraction, core level and valence band photoelectron spectroscopy, the latter also with spin resolution. Samples prepared by a sputtering-annealing procedure exhibited in-gap states in the valence band spectra, Ti3+ components in Ti 2p core level spectra and a noticeable spin asymmetry in the 3-9 eV binding energy range, which corresponds to valence states of mainly O 2p character. Upon annealing in oxygen, the spin asymmetry vanishes, accompanied by the intensity decrease of the contribution of titanium low ionization states and of in-gap states, indicating that these three phenomena are mutually connected. The observed spin asymmetry may be generated by indirect exchange mediated by the in-gap states between O 2p orbitals, or by the partial Ti 3d character of these states, which acquire non-zero spin in case of incomplete oxygen coordination.
310
Optimizing photocurrent intensity in layered SiGe heterostructures
Sultan, MT; Ciurea, ML; Stavarache, I; Thórarinsdóttir, KA; Arnalds, UB; Teodorescu, ; Manolescu, A; Ingvarsson, S; Svavarsson, HG
OCT 1 2024, SEMICONDUCTOR SCIENCE AND TECHNOLOGY, 39, 105007
DOI: 10.1088/1361-6641/ad70d4
Show abstract
We study the dependence of photo-spectral intensity on tri- and multilayers of SiO2/[SiGe [ dSiGe]/SiO2]N with repetitions N = 1 to 10 and thicknesses dSiGe=5-100 nm. Photocurrent analysis reveals a bimodal spectral feature. A comparison of the photocurrent analysis between tri- and multilayers shows that in the multilayer structures, the photo-spectral intensity increases with increasing repetition N. The change in intensity could then be further tuned by changing the thickness of the SiGe layers dSiGe. We attribute the change in intensity to an increase in tensile strain, along with increased Ge atomic concentration and reduced SiGe-nano cluster size.