371 Open Access
Abundant Catalytic Edge Sites in Few-Layer Horizontally Aligned MoS2 Nanosheets Grown by Space-Confined Chemical Vapor Deposition
Velea, A; Buruiana, AT; Mihai, C; Matei, E; Tite, T; Sava, F
JUN 2024, CRYSTALS, 14, 551
DOI: 10.3390/cryst14060551
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Recently, a smart strategy for two-dimensional (2D) materials synthesis has emerged, namely space-confined chemical vapor deposition (CVD). Its extreme case is the microreactor method, in which the growth substrate is face-to-face stacked on the source substrate. In order to grow 2D transition metal dichalcogenides by this method, transition metal oxides, dispersed in very small amounts on the source substrate, are used as source materials in most of the published reports. In this paper, a colloidal dispersion of MoS2 in saline solution is used and MoS2 nanosheets with various shapes, sizes (between 5 and 60 mu m) and thicknesses (2-4 layers) have been synthesized. Small MoS2 flakes (regular or defective) are present on the surface of the nanosheets. Catalytic sites, undercoordinated atoms located at the edges of MoS2 flakes and nanosheets, are produced in a high number by a layer-plus-island (Stranski-Krastanov) growth mechanism. Several double-resonance Raman bands (at 147, 177, 187, 225, 247, 375 cm(-1)) are assignable to single phonon processes in which the excited electron is elastically scattered on a defect. The narrow 247 cm(-1) peak is identified as a topological defect-activated peak. These findings highlight the potential of defect engineering in material property optimization, particularly for solar water splitting applications.
372 Open Access
Adsorption-catalysis synergy in the visible-light-driven removal of 17 β-estradiol by (Au)TiO 2 nanotubes-graphene composites
Cosma, DV; Rosu, MC; Socaci, C; Rostas, AM; Urda, A; Radu, T; Turza, A; Dan, MNC; Costescu, R; Gustavsen, KR; Dobroliubov, O; Wang, KY
JUN 2024, JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING, 12, 112885
DOI: 10.1016/j.jece.2024.112885
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Visible light-mediated photodegradation offers a sustainable and environmentally friendly solution for removing emerging contaminants from water sources. Herein, we report on the synergy effect between adsorption and visible-light-driven photo-degradation of 17 fl - estradiol using (Au)TiO 2 nanotubes-graphene composites. The graphene structures (graphene oxide - GO or thermally reduced graphene oxide - trGO) provide a platform for strong adsorption of 17 fl -estradiol molecules and facilitate the charge transfer between plasmonic Au nanoparticles and TiO 2 , leading to an improvement of the overall degradation process. To better understand the effect of Au nanoparticles and TiO 2 separately, three different concentrations of Au (1 %, 2.5 %, and 5 %) were prepared and characterized. The estrogenic molecules preferred GO over trGO, suggesting that hydrogen bonds govern the interaction between GO and 17 fl -estradiol. Consequently, a higher photocatalytic efficiency of GOcontaining composites was observed when removing estrogenic molecules. The role of adsorption proved crucial for capturing and retaining more contaminant molecules on the composite surface, thus increasing the odds of surface reactions with the photogenerated carriers. A total removal of 17 fl -estradiol has been obtained for Au (1 %, 2.5 %, and 5 %) TiO 2 nanotubes-GO. The mechanism behind the adsorption and photo-degradation processes has been discussed.
373 Open Access
MAPLE deposition of hybrid PLGA-Fe3O4-Cypress-PEDOT: PSS coatings
Stefan, N; Visan, AI; Grumezescu, V; Kuncser, V; Kuncser, A; Iacob, N; Schinteie, G; Socol, M; Florica, C; Zgura, I; Popescu, RC; Holban, AM; Socol, G
JUN 2024, GIANT, 18, 100250
DOI: 10.1016/j.giant.2024.100250
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We report on the Matrix Assisted Pulsed Laser Evaporation, laser technology for depositing biocompatible, antimicrobial, hydrophilic, and biodegradable complex hybrid polymeric system loaded with essential cypress-oil and magnetite nanoparticles as resorbable implants, capable of targeting possible hyperthermia applications, an anticancer moderate field heating therapy. Magnetite nanoparticles based on iron oxide (Fe3O4) coated with Cypress essential oil (denoted: Fe3O4- Cypress) and embedded in PLGA (poly(lactic-co-glycolic acid) (denoted: PLGA-Fe3O4- Cypress-) and PLGA - poly(3,4ethylene dioxythiophene) doped with poly(styrene sulfonate) anions) (PEDOT: PSS) mixture (denoted: PLGA-Fe3O4- Cypress- PEDOT: PSS) were used as MAPLE targets. The controlled drug delivery of the active Cypress oil, an antimicrobial therapeutic agent from Fe3O4- Cypress nanoparticles could be possible by applying an external radio frequency (RF) magnetic field. The Fe3O4-Cypress-based powders as well as the final hybrid coatings have been characterized in terms of stoichiometry, morphology, magnetic, antimicrobial properties, biocompatibility, and response to external physical stimuli. FTIR analyses confirmed the quasi-stoichiometric laser transfer of organic compounds while the XRD evidenced the semicrystalline structure of deposited thin films. SEM and AFM images evidence that conductive polymer addition led to the films' relief flattening and a decrease in the coatings' thickness and roughness by changing the polymeric packaging. The samples containing conductive polymer exhibited 3 times higher current and corrosion rate values. All coatings are hydrophilic and revealed enhanced cellular viability when cultured with osteoblast-like MG-63 cells. The composite structures exhibited significant antimicrobial activity against Gram-positive (Staphylococcus aureus), and Gram -negative (Escherichia coli ) bacteria, as well as to the opportunistic yeast Candida albicans.
374
Downscaling grain size toward the nanometre range - A key-factor for tuning the crystalline structure, phase transitions, dielectric and ferroelectric behaviour in Ba 0.8 Sr 0.2 TiO 3 ceramics
Patru, RE; Stanciu, CA; Surdu, VA; Soare, EM; Trusca, RD; Vasile, BS; Nicoara, AI; Trupina, L; Pasuk, I; Botea, M; Horchidan, N; Mitoseriu, L; Pintilie, L; Pintilie, I; Ianculescu, AC
JUN 2024, PROGRESS IN SOLID STATE CHEMISTRY, 74, 100457
DOI: 10.1016/j.progsolidstchem.2024.100457
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The present study aims to describe the role of the grain size on the properties of submicron- and nano-structured Ba0.8Sr0.2TiO3 (BST) ceramics. Dense (1 - 2% porosity) ceramics with average grain sizes in the range of (77 234) nm were consolidated under different spark plasma sintering conditions starting from nanopowders with a mean particle size of 70 nm, synthesized via the acetate variant of the sol-gel method. The structural analysis based on XRD data revealed a mixture of cubic and tetragonal modifications at room temperature for the precursor powders and for all the investigated ceramics. The structural heterogeneity of the individual ceramic grains with coexistence of cubic and tetragonal polymorphs was confirmed by HR-TEM investigations. Accordingly, a "brick-wall" model with cubic grain boundary regions and tetragonal grain cores is proposed. By increasing the grain size, from 77 to 234 nm, a decrease of the phase transitions diffuseness accompanied by an increase of the permittivity maxima (from 650 to 4500) and dielectric losses (from 5 to 7.5%, at 100 Hz), was detected by broadband dielectric spectroscopy. No variation of the Curie temperature in the investigated Ba0.8Sr0.2TiO3 ceramics was detected, unlike typically reported for BaTiO3 ceramics with similar grain sizes. The Curie-Weiss temperature and the Curie constant decrease when grain size is diminished, indicating an overall reduction of the ferroelectric active volume, as a scaling effect. The ferroelectric switching was demonstrated for all the selected fine-grained BST ceramics, either at nanoscale or macroscopically, with an increased ferroelectric character for the coarser submicron-structured ceramics, with respect to the nanocrystalline one. The observed properties of the fine-grained Ba0.8Sr0.2TiO3 ceramics are explained in the frame of multiphase coexistence and ferroelectricity "dilution" due to the increasing role of non-ferroelectric grain boundaries when reducing grain size and complete the knowledge on the scale-dependent properties of dense fine-grained BaTiO3-based ceramics.
375
In vitro and in vivo investigations of citric acid functionalized magnetic iron oxide nanoparticles for intra-tumoral melanoma treatment
Sima, L; Toderascu, LI; Tudor, M; Florian, P; Icriverzi, M; Ionita, F; Maraloiu, V; Iacob, N; Kuncser, V; Antohe, I; Stanciu, G; Trif, M; Roseanu, A; Coman, C; Socol, G
JUN 2024, FEBS OPEN BIO, 14
376 Open Access
Exploring FAST Technique for Diffusion Bonding of Tungsten to EUROFERE97 in DEMO First Wall
Sánchez, M; de Prado, J; Izaguirre, I; Galatanu, A; Ureña, A
JUN 2024, MATERIALS, 17, 2624
DOI: 10.3390/ma17112624
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The European Fusion Reactor (DEMO, Demonstration Power Plant) relies significantly on joining technologies in its design. Current research within the EUROfusion framework focuses on developing materials for the first wall and divertor applications, emphasizing the need for suitable joining processes, particularly for tungsten. The electric field-assisted sintering technique (FAST) emerges as a promising alternative due to its high current density, enabling rapid heating and cooling rates for fast sintering or joining. In this study, FAST was employed to join tungsten and EUROFERE97 steel, the chosen materials for the first wall, using 50-mu m-thick Cu foils as interlayers. Three distinct joining conditions were tested at 980 degrees C for 2, 5, and 9 min at 41.97 MPa to optimize joint properties and assess FAST parameters influence. Hardness measurements revealed values around 450 HV0.1 for tungsten, 100 HV0.1 for copper, and 390 HV0.1 for EUROFER97 under all joining conditions. Increasing bonding time improved joint continuity along the EUROFER97/Cu and W/Cu interfaces. Notably, the 5 min bonding time resulted in the highest shear strength, while the 9 min sample exhibited reduced strength, possibly due to Kirkendall porosity accumulation at the EUROFER97/Cu interface. This porosity facilitated crack initiation and propagation, diminishing interfacial adhesion properties.
377
Microwave post-treated activated carbons for capacitance boosted non-aqueous supercapacitors
Fasahat, S; Khosravi, M; Dini, G; del Pino, AP; Logofatu, C
MAY 15 2024, JOURNAL OF ALLOYS AND COMPOUNDS, 984, 173948
DOI: 10.1016/j.jallcom.2024.173948
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Herein, as a novel idea, a microwave (MW) post-treatment strategy is proposed to modify the structure and surface characteristics of already prepared activated carbons (ACs) for application in non-aqueous Electric Double-Layer Capacitors. Pistachio nutshell-derived carbon is first KOH-activated and then subjected to MW irradiation for 0, 2, 5, and 10 minutes. X-ray Diffraction and Raman analyses show that MW post-treatment leads to structural modifications, and FTIR and XPS analyses reveal relative elimination of surface functional groups which results in subsequent enhancement in water contact angle and renders more favorable surface wetting of carbon by non-aqueous organic electrolyte. The performance characteristics of symmetrical non-aqueous supercapacitors incorporated with the prepared ACs show a significant positive effect of MW irradiation in such a way that 0 and 10-minute-irradiated ACs demonstrate 152 and 392 F g-1 capacities, respectively, at 1.75 A g-1, with the corresponding specific energies and powers of 340 Wh kg-1 and 11 kW kg-1 for AC-10, respectively. This remarkable enhancement in the electrochemical performance is attributed to the effective role of the MW post-treatment in modifying the AC structure as well as providing AC surfaces that have better wettability with less polar non-aqueous electrolyte. Moreover, this strategy is additionally applicable to make hydrophobic activated carbons for other applications as the absorption of less polar contaminants from liquid or gaseous environments.
378 Open Access
Stacking model of a three-dimensional second-order topological insulator manifesting quantum anomalous Hall effect
Ostahie, B; Aldea, A
MAY 14 2024, PHYSICAL REVIEW RESEARCH, 6, 023168
DOI: 10.1103/PhysRevResearch.6.023168
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We investigate the transport and energy spectrum properties of a three-dimensional high-order topological structure formed by stacking two-dimensional square diatomic Chern insulator lattices. Electron-hole symmetry and the energy spectrum degeneracy at individual points in the semimetallic phase are proven to be due to chiral and antiunitary symmetries in the periodic system. Additionally, we explore the influence of boundary conditions in a slab system with varying surface atom connectivity, and we demonstrate analytically the presence of zero-energy surface states in specific configurations. Moreover, we describe the emergence of two chiral hinge states driven by a perpendicular phase in the nanowire geometry. Next, the quantum Hall resistance is computed in the cross-configuration of a four-lead device. In this paper, we demonstrate that the trajectories of hinge states, determined by the number of layers in parallelepiped finite structure, give rise to fractional Hall plateaus.
379
Structural and magneto-optical investigations of citrate sol-gel derived barium hexaferrite nanocrystalline powder
Secu, M; Secu, CE; Matei, E; Negrilla, C; Turchenko, V; Radu, C; Polosan, S
MAY 5 2024, JOURNAL OF ALLOYS AND COMPOUNDS, 983, 173897
DOI: 10.1016/j.jallcom.2024.173897
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Magneto-optical measurements enable the identification of Fe2+ and Fe3+ in the R and S blocks of BaFe12O19 Mhexaferrite powder obtained by sol -gel processing, followed by thermal annealing at 900 C for 3 hours. The ferromagnetic phase is evidenced by the spin-majority configuration (Fe3+) due to their unpaired electrons between d -d orbitals, while the Fe2+ in the low spin possesses diamagnetic behavior strongly dependent on the surrounded crystal field. Additionally, the irradiation with gamma rays changes the ratio between Fe2+/Fe3+, mainly on the surface of BaFe12O19 nanocrystals. These changes were confirmed by X-ray Photoelectron Spectroscopy measurements, in which the concentration of Fe2+ increased from 69% to 82%, while the one of Fe3+ decreased from 31% to 18%. he thermoluminescent measurements reveal the same changes of Fe3+ in Fe2+ by electron capturing during irradiation, which is released as a red emission after recombination processes. The changes are explained by the increasing of some Fe-O bonds along the c-axis, mainly due to breaking a part of these bonds. The X-ray analysis confirms the changing of the parameters for the BaFe12O19 hexagonal structure.
380 Open Access
The Influence of Cyclic Thermal Shocks at High Temperatures on the Microstructure, Hardness and Thermal Diffusivity of the Rene 41 Alloy
Arva, ERU; Negrea, DA; Galatanu, A; Galatanu, M; Moga, SG; Anghel, DC; Branzei, M; Stoica, L; Jinga, AI; Petrescu, MI; Munteanu, C; Abrudeanu, M
MAY 2024, MATERIALS, 17, 2262
DOI: 10.3390/ma17102262
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The precipitation-hardenable nickel-based superalloy Rene 41 exhibits remarkable mechanical characteristics and high corrosion resistance at high temperatures, properties that allow it to be used in high-end applications. This research paper presents findings on the influence of thermal shocks on its microstructure, hardness, and thermal diffusivity at temperatures between 700 and 1000 degrees C. Solar energy was used for cyclic thermal shock tests. The samples were characterized using microhardness measurements, optical microscopic analysis, scanning electron microscopy coupled with EDS elemental chemical analysis, X-ray diffraction, and flash thermal diffusivity measurements. Structural transformations and the variation of properties were observed with an increase in the number of shocks applied at the same temperature and with temperature variation for the same number of thermal shocks.