Transmission Electron Microscopy Energy-dispersive X-ray Research Articles

Hybrid plasma catalysis-thermal system for non-oxidative coupling of methane to ethylene and hydrogen

We report a two-stage hybrid plasma catalysis-thermal system for non-oxidative coupling of methane (NOCM) to ethylene (C2H4) and hydrogen (H2), achieving 66 % C2H4 selectivity and 60 % H2 selectivity with 28 % CH4 conversion. This corresponds to a C2H4 yield of 18 %, which is one of the highest reported in literature. The system consists of the first plasma catalysis stage (stage 1) and the second thermal cracking stage (stage 2). Comprehensive analyses using in-situ mass spectrometry (MS) and gas chromatography (GC) reveal that the combination of plasma and Pt/ZrO2 catalyst in stage 1 predominantly facilitates the conversion of methane to ethane. Characterizations employing X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy-scanning transmission electron microscopy-energy dispersive X-ray (HRTEM-STEM-EDX) mapping, and hydrogen temperature-programmed reduction (H2-TPR), indicate that the coordinatively unsaturated site of Pt could be the active sites for C–H bond cracking to generate abundant CH3 radicals (CH3·), enhancing the C2 selectivity by inhibiting the non-selective formation of coke and higher hydrocarbons. Subsequently, the products from stage 1 (especially C2H6) undergo pyrolysis reactions at 880 °C in stage 2, which further boosts the C2H4 selectivity and yield. Based on the reaction performance, catalyst characterization, optical emission spectroscopy (OES), and in-situ Fourier transform infrared spectroscopy (FTIR) results, we reveal the reaction mechanism within the hybrid two-stage plasma catalysis-thermal system for converting CH4 to C2H4 and H2.

Structural, morphological, and chemical composition of ternary ZrHfN thin films deposited by reactive co-magnetron sputtering

This study focuses on a deposited ternary zirconium hafnium nitride (ZrHfN) thin film prepared using the reactive co-magnetron sputtering technique. The effect of the nitrogen (N2) flow rate on the films' structural, morphological, and chemical composition was investigated. The gracing-incidence X-ray diffraction (GIXRD) showed that all ZrHfN thin films exhibited a crystalline face-centered cubic structure with a strong (111) orientation. With increasing the N2 flow rate, the film's crystallography changed based on thermodynamic theory. The films demonstrated uniformity and homogeneity in their ternary nitride composition, as confirmed by transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDS) mapping and electron probe microanalyzer (EPMA). Chemical state analysis using X-ray photoelectron spectroscopy (XPS) indicated the presence of both nitride and oxynitride species in all samples. Notably, the atomic concentration of the main elements (Zr, Hf, and N) remained relatively stable over the controlled N2 flow rate range. However, the N2 flow rate played a crucial role in forming hafnium nitride and oxynitride chemical states, whereas it did not significantly influence the Zr phases, dominated by Zr oxides. Additionally, the hardness of the ternary ZrHfN thin films exhibited enhancement comparable to typical ternary nitrides.

Contrasting shell thickness-dependent magnetic behaviors of CoFe2O4@Fe3O4 and Fe3O4@CoFe2O4 core/shell nanoparticles

The magnetic properties of bi-magnetic core/shell nanoparticles (NPs) have been a subject of extensive investigation. Yet, the role of shell thickness in hard/soft and soft/hard core/shell NPs, corresponding to conventional and inverse structures, remains incompletely elucidated. In this study, we synthesized two sets of core/shell NPs, namely Fe3O4@CoFe2O4 (IF@CF) and CoFe2O4@Fe3O4 (CF@IF), featuring a fixed core diameter of approximately 11 nm and varying shell thicknesses up to 5 nm. These NPs were synthesized via a seed-mediated particle growth approach. The formation of the core/shell configuration of typical NPs in both sets was directly verified through scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDS) imaging. Notably, the saturation magnetization (MS) of IF@CF NPs exhibited a significant increase compared to that of the IF core across all shell thickness variations, whereas it remained largely unchanged for CF core and CF@IF NPs. Conversely, the coercivity (HC) showed an opposite trend in the two structures with increasing shell thickness. We observed the emergence of a transition from constricted to smooth hysteresis loops in the conventional structure when the shell thickness reached 5 nm. The systematic evolution of hysteresis loops with escalating shell thickness in both structures closely correlates with distinct magnetic reversal mechanisms, influenced significantly by interparticle interactions. Our study presents a pathway for modulating the magnetic properties of bi-magnetic core/shell NPs, thereby opening avenues for advanced applications in magnetic imaging, sensing, drug delivery, and magnetic hyperthermia.

Pt/C and PtRu/C Catalysts Prepared by Modified Sulfite Complex Routes for Fuel Cell Applications

In-house 30 wt.% Pt and 50 wt.% Pt1Ru1 catalysts supported on high-surface area carbon (Ketjenblack, abbreviated as KB) were synthesized by the sulfite complex route. Two different procedures involving either a direct mixing of Pt-sulfite and Ru-sulfite complexes or Pt-sulfite preparation and subsequent impregnation of Ru precursor were adopted for the bimetallic species. In both cases, an impregnation of the formed metal oxides onto KB was adopted to increase the electronic conductivity of the samples. Finally, a carbothermal treatment at 600°C in He atmosphere was carried out for the reduction of the metal oxides to metallic PtRu/C compounds. The Pt1Ru1 ratio was calculated and revealed by X-ray fluorescence (XRF) analysis whereas the carbon percentage was calculated by weight loss. 50 mg of sample was treated in air at 550°C for 2 h and, after cooling, the weight corresponded to 25 mg, confirming a carbonaceous matrix percentage of 50 wt.%. In a similar way, the 30 wt.% Pt/C was determined. X-ray diffraction (XRD) revealed that the samples showed face centered cubic (fcc) structure for Pt nanoparticles. It appears that two distinct crystallographic phases of Pt and Ru nanoparticles were encountered after the synthesis conducted by Ru impregnation. In contrast, only a single fcc phase is visible when the Pt and Ru sulfite precursors were mixed, confirming the formation of an alloy. Furthermore, Scanning Transmission Electron Microscopy-Energy dispersive X-ray spectroscopy (S/TEM-EDX) and X-ray Photoelectron Spectroscopy (XPS) were used to characterize the differences in morphology and surface characteristics of the catalysts.For the electrochemical measurements, rotating disc electrode (RDE) technique under acid and alkaline conditions was employed to investigate the half cell reactions. The catalysts were also deposited at the anode and cathode of fuel cells to evaluate the activity, performance, and short-term durability. Acknowledgement “This research was funded by the European Union – EIT Raw Materials in the framework of the following project: LYDIA- Recycling Critical Metals from Fuel Cells (G.A. 22019)”

The Effect of ZnO Nanoparticles Functionalized with Glutamine and Conjugated with Thiosemicarbazide on Triggering of Apoptosis in the Adenocarcinoma Gastric Cell Line.

Gastric carcinoma is the fourth most common malignancy worldwide. Conjugation of metal nanoparticles with thiosemicarbazones has shown considerable anti-cancer potential. Zinc oxide nanoparticles (ZnO NPs) were synthesized, functionalized by glutamine, and conjugated with thiosemicarbazide (ZnO@Gln-TSC). Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy imaging, energy-dispersive X-ray, DLS, and zeta potential were used to characterize the NPs. The toxicity of ZnO NPs, TSC, ZnO@Gln-TSC NPs, and oxaliplatin in AGS cells and ZnO NPs and ZnO@Gln-TSC NPs in HEK293 cells was investigated by MTT assay. Cell apoptosis was evaluated by flow cytometry, caspase-3 activity, and Hoechst staining assays. The intra-cellular reactive oxygen species level and expression level of the CASP3 gene in AGS cells treated with ZnO@Gln-TSC NPs were evaluated. The NPs were in the size range of 20 to 70 nm. The DLS and zeta potential were 374 nm and -31.7 mV, respectively. In MTT, the IC50 of ZnO, TSC, oxaliplatin, and ZnO@Gln-TSC NPs for AGS cells were 130, 80.5, 67.7, and 9.8 μg/mL, respectively, and the IC50 of ZnO and ZnO@Gln-TSC NPs for HEK293 cells were 215 and 150.5 μg/mL, respectively. Flow cytometry showed higher apoptosis in the cell treated with the NPs and TSC. Apoptotic features, including cell shrinkage, were recognized. A significant increase of 5.9 folds in the level of ROS was noticed. The activity of caspase-3 and the expression level of the CASP3 gene were increased by1.83 and 1.6 folds after exposure to ZnO@Gln-TSC NPs, respectively. This study revealed the anti-cancer potential of ZnO@Gln-TSC NPs to be used for gastric cancer treatment after further in vitro and in vivo assays.

Leveraging Ligand Steric Demand to Control Ligand Exchange and Domain Composition in Stratified Metal-Organic Frameworks.

Incorporating diverse components into metal-organic frameworks (MOFs) can expand their scope of properties and applications. Stratified MOFs (sMOFs) consist of compositionally unique concentric domains (strata), offering unprecedented complexity through partitioning of structural and functional components. However, the labile nature of metal-ligand coordination handicaps achieving compositionally distinct domains due to ligand exchange reactions occurring concurrently with secondary strata growth. To achieve complex sMOF compositions, characterizing and controlling the competing processes of new strata growth and ligand exchange are vital. This work systematically examines controlling ligand exchange in UiO-67 sMOFs by tuning ligand sterics. We present quantitative methods for assessing and visualizing the outcomes of strata growth and ligand exchange that rely on high-angle annular dark-field images and elemental mapping via scanning transmission electron microscopy-energy dispersive X-ray spectroscopy. In addition, we leverage ligand sterics to create 'blocking layers' that minimize ligand exchange between strata which are particularly susceptible to ligand exchange and inter-strata ligand mixing. Finally, we evaluate strata compositional integrity in various solvents and find that sMOFs can maintain their compositions for >12 months in some cases. Collectively, these studies and methods enhance understanding and control over ligand placement in multi-domain MOFs, factors that underscore careful tunning of properties and function.

Nanoscale study on the initial stages of the interdiffusion across the amorphous/crystalline interface of poly(methyl methacrylate)/poly(vinylidene fluoride) (PMMA/PVDF) via STEM plus EDX/EELS

Interdiffusion across the interface of poly(methyl methacrylate)/poly(vinylidene fluoride) (PMMA/PVDF) was investigated thoroughly by scanning transmission electron microscopy (STEM) plus electron energy-loss spectroscopy (EELS) and energy-dispersive X-ray spectrometry (EDX) and further with the assistance of laser-Raman spectroscopy. The factors of the annealing temperature and the time on the interfacial widths and the concentration profiles of PMMA and PVDF across the interface of PMMA/PVDF have been considered in detail. It was found that the concentration profiles of PMMA and PVDF were determined by the crystallization of PVDF, especially at the high annealing temperature (220 °C) in the PMMA part of the interface. Under the influence of the PVDF crystallization, the concentration profiles of F (from PVDF) and O (from PMMA) monitored by STEM-EDX/EELS changed gradually from parabola-shape to linear-shape in the PMMA part. The activation energy for the interdiffusion across the interface of PMMA/PVDF was calculated to be 51.0 kJ/mol, lower than the other reported pairs like poly(vinyl chloride)/poly(ε-caprolactone) (PVC/PCL) (69.8 kJ/mol) and poly(styrene-ran-acrylonitrile)/poly(methyl methacrylate) (SAN-29/PMMA) (175 ± 15 kJ/mol).

Effect of proteins as constituents of island-nanomatrix structure on vulcanization of natural rubber

Effect of proteins, constituents of the island-nanomatrix structure, on dispersion of zinc to natural rubber was investigated by transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDX) and focused ion beam-scanning electron microscopy-energy dispersive X-ray spectroscopy (FIB-SEM-EDX). Films of natural rubber and deproteinized natural rubber (DPNR) prepared with urea were embedded in a mixture of ZnO, vulcanization accelerator and sulfur, and they were heated at 150 °C for 5 h. Migration of Zn from surface to inside of the films was observed by FIB-SEM-EDX. The Zn migrated from the surface to 14 μm for natural rubber, but not for DPNR. The optimum vulcanization time for natural rubber was short, i.e., about 4 min, whereas it was long for DPNR, i.e., about 15 min. To confirm the effect of the proteins, a latex-mixed rubber compound was prepared by mixing the latex with sulfur, ZnO and vulcanization accelerator followed by drying with a hotplate at 150 °C for 45 s since the proteins are segregated on the surface of natural rubber particles in the latex stage. Vulcanization was accelerated for the latex-mixed natural rubber compared with mechanically mixed natural rubber compound that was prepared by mixing natural rubber with ZnO, vulcanization accelerator and sulfur with a two-roll mill. The resulting latex-mixed natural rubber vulcanizate was superior in mechanical properties to the mechanically mixed natural rubber vulcanizate. It was found by rubber-state NMR spectroscopy that the difference in mechanical properties was attributed to the difference in the cis-1,4-average sequence length of the vulcanizates, which came from the difference in the dispersion of Zn.

Leaching kinetics of ash impurities from aphanitic graphite by combining dual-ultrasound and hydrochloric acid–potassium hydrogen fluoride

The hydrochloric acid-fluoride salt is useful for purifying graphite. Ultrasonic-assisted technique can significantly reduce the leaching time and improve the leaching efficiency. Compared with single-frequency, dual-frequency ultrasound has the advantages of high energy efficiency and wide cavitation area. In this study, the combination of a dual-frequency ultrasound-assisted technique and hydrochloric acid–potassium hydrogen fluoride leaching agent was proposed for the leaching of aphanitic graphite to remove impurity minerals. First, the effects of probe-type ultrasonic power, tank-type ultrasonic power, temperature, HCl concentration, ultrasonication time, and KHF2 concentration on the purification efficiency of impurities from aphanitic graphite with the assistance of dual-frequency ultrasound were investigated. It was found that the combination of dual-frequency ultrasound and hydrochloric acid–potassium hydrogen fluoride can reduce the ash content of aphanitic graphite from 13.02 % to 1.02 % with an ash removal rate of 94.17 %. Second, volumetric reaction models and unreacted shrinkage nucleation models were used to fit the kinetics of impurities from aphanitic graphite with dual-frequency ultrasound-assisted HCl-KHF2 leaching. Kinetic analysis shows that the volumetric reaction model with chemical control was better to fit the leaching process. This is consistent with the calculation results of the activation energy of the reaction (Ea = 58.13 kJ/mol). Finally, laser particle size analyzer, X-ray diffraction (XRD), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), X-ray fluorescence spectroscopy (XRF), transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDS) were used to analyze the fugacity of impurity minerals during the process of dual-frequency ultrasound-assisted HCl-KHF2 leaching. It was revealed that combining ultrasonic cavitation fragmentation with chloric acid–potassium fluoride generated SiF4 with high solubility, thereby removing silica-bearing impurities more efficiently. The challenges in further reducing ash content from 1.02 % in the leached concentrate of aphanitic graphite could be attributed to the existence of titanium-bearing mineral impurities on the surface of graphite particles and the presence of silica-bearing minerals between graphite carbon layers.

Development and characterization of lipid nanocapsules loaded with iron oxide nanoparticles for magnetic targeting to the blood–brain barrier

Brain drug delivery is severely hindered by the presence of the blood–brain barrier (BBB). Its functionality relies on the interactions of the brain endothelial cells with additional cellular constituents, including pericytes, astrocytes, neurons, or microglia. To boost brain drug delivery, nanomedicines have been designed to exploit distinct delivery strategies, including magnetically driven nanocarriers as a form of external physical targeting to the BBB. Herein, a lipid-based magnetic nanocarrier prepared by a low-energy method is first described. Magnetic nanocapsules with a hydrodynamic diameter of 256.7 ± 8.5 nm (polydispersity index: 0.089 ± 0.034) and a ξ-potential of -30.4 ± 0.3 mV were obtained. Transmission electron microscopy-energy dispersive X-ray spectroscopy analysis revealed efficient encapsulation of iron oxide nanoparticles within the oily core of the nanocapsules. Both thermogravimetric analysis and phenanthroline-based colorimetric assay showed that the iron oxide percentage in the final formulation was 12 wt.%, in agreement with vibrating sample magnetometry analysis, as the specific saturation magnetization of the magnetic nanocapsules was 12% that of the bare iron oxide nanoparticles. Magnetic nanocapsules were non-toxic in the range of 50–300 μg/mL over 72 h against both the human cerebral endothelial hCMEC/D3 and Human Brain Vascular Pericytes cell lines. Interestingly, higher uptake of magnetic nanocapsules in both cell types was evidenced in the presence of an external magnetic field than in the absence of it after 24 h. This increase in nanocapsules uptake was also evidenced in pericytes after only 3 h. Altogether, these results highlight the potential for magnetic targeting to the BBB of our formulation.Graphical

Aminosilane assisted deposition of gold nanoparticles on Zn(OH)2 nanosheets and their application in electrochemical sensor

A facile and efficient method for systematical deposition of gold nanoparticles (AuNPs) on Zn(OH)2 nanosheets (NS) with different Zn and Au ratios was established in the presence of N-[3-(trimethoxysilyl)propyl]diethylenetriamine (TPDT silane), without adding any external reducing agents, at room temperature. Here, TPDT silane behaves as both a stabilizing and reducing agent. UV–vis absorption spectroscopy, transmission electron microscopy, high-angle annular dark-field scanning transmission electron microscopy-energy dispersive X-ray spectroscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy were used to confirm the formation of AuNPs on Zn(OH)2 NS. As the concentration of AuNPs increased, a proportional increase in both the number and size of deposited AuNPs on Zn(OH)2 NS was observed. To understand how the variation in the number and size of AuNPs affects their catalytic activity, the electrocatalytic activity of different composition ratios of Zn(OH)2-Au NS toward nitrite ions was studied using cyclic voltammetry and amperometric technique. The TPDT-stabilized Zn(OH)2-Au NS showed high electrocatalytic activity, attributed to the effective electron transfer from Zn(OH)2 NS to AuNPs, creating a synergistic effect that enhances the overall activity. The optimal Zn(OH)2-Au NS modified electrode showed an amperometric sensitivity of 5.72 nA/µM and a limit of detection of 1.2 µM for nitrite ions in water sample well below the guideline value of WHO. This demonstrates the practical applicability of this method for real-world water analysis.

Atomic-level investigation of structure and formation process of Y3Al5O12 with super-high content of Ce emitting anomalous orange-red emissions

Ce-doped yttrium aluminum garnet (YAG:Ce, Y3Al5O12:Ce) is the most commonly used yellow phosphor in white light-emitting diodes. Recently, we found that (Y1–xCex)3Al5O12:Ce with a super-high content of Ce (x = 0.11–0.21) can be prepared by a polymerized complex method and exhibits anomalous orange–red emission. To understand the nature of this anomalous behavior from the atomic level, we applied high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and scanning transmission electron microscopy–energy dispersive X-ray spectroscopy (STEM-EDS), a state-of-the-art technique that enables analysis of the atomic-level elemental distributions of Al, Y, and Ce. STEM-EDS images on the atomic level were successfully obtained for YAG:Ce. It was found that Ce in Y site has spatially uneven for few nanometers. Ce–K edge extended X-ray absorption fine structure (EXAFS) analysis was also conducted, which revealed a high level of asymmetry around Ce. By combining the STEM-EDS and EXAFS results, a dynamic model for the red emission was proposed. STEM-EDS also revealed that CeO2 nanocrystals were firstly formed with low-temperature annealing and that the reaction of Y with the CeO2 nanocrystals subsequently yielded YAG:Ce, unlike in the conventional one-step high-temperature synthesis.

Evaluation of extremely thin polycrystalline germanium films and their TFT performance fabricated at 400 °C by Cu-induced crystallization on a glass substrate

Germanium (Ge) has high mobility and is more suitable for low-temperature device processes than silicon (Si); thus, it has attracted attention as an upper-layer transistor for monolithic three-dimensional (M3D) integration. We evaluated in detail the crystalline quality of extremely thin polycrystalline-Ge (poly-Ge) thin films thinner than 15 nm fabricated by metal-induced crystallization using copper (Cu-MIC) at 400 °C using micro-Raman scattering, in-plane X-ray diffraction, transmission electron microscopy (TEM), TEM energy dispersive X-ray spectroscopy, and TEM electron diffraction. Additionally, the films were applied to p-ch double-gate (DG) poly-Ge thin-film transistors (TFTs), and their performance was evaluated. As a result, a high I on/I off ratio of 2.8 × 103 was realized by crystallization at 400 °C with a ratio equal to that of crystallization at 500 °C. This study demonstrated the feasibility of Cu-MIC DG poly-Ge TFTs for M3D applications.

Trivalent lanthanum and ytterbium doped meso-silica/ceria abrasive systems toward chemical mechanical polishing (CMP) and ultraviolet irradiation-assisted photochemical mechanical polishing (PCMP)

Ceria (CeO2)-based abrasives are widely utilized in ultra-precision grinding and chemical mechanical polishing (CMP) applications over silica materials due to their unique physicochemical properties. Both mechanical and chemical contributions to polishing processes are highly affected by the size, shape, structure, component, defect of CeO2 abrasives. Herein, the composites involved mesoporous silica (mSiO2) cores and La- or Yb-doped CeO2 shells were synthesized and characterized in terms of X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, scanning transmission electron microscopy–energy dispersive X-ray mapping methods. The polishing effectiveness of the proposed composites toward quartz glass was experimentally evaluated under both CMP and ultraviolet irradiation-assisted photochemical mechanical polishing (PCMP) conditions. The polishing results indicated that the low-modulus mSiO2 cores strongly exerted the cushion effects for the friction and abrasion to substrates. Consequently, the heterostructured mSiO2/La-CeO2 and mSiO2/Yb-CeO2 abrasive systems offered nearly non-damage and ultra-smooth surfaces with angstrom-level roughness compared to conventional rigid abrasives. The enriched Ce3+ and oxygen vacancy defects at La- and Yb- doped CeO2 surfaces were responsible for the improvements of tribochemical and photochemical activities, thus allowing evidently enhanced removal efficiency with the assistance of ultraviolet irradiation. A possible polishing mechanism on the multi-component abrasive systems was also proposed.

Comparative Study of Exsolved and Impregnated Ni Nanoparticles Supported on Nanoporous Perovskites for Low-Temperature CO Oxidation.

This study investigated the redox exsolution of Ni nanoparticles from a nanoporous La0.52Sr0.28Ti0.94Ni0.06O3 perovskite. The characteristics of exsolved Ni nanoparticles including their size, population, and surface concentration were deeply analyzed by environmental scanning electron microscopy (ESEM), transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDX) mapping, and hydrogen temperature-programmed reduction (H2-TPR). Ni exsolution was triggered in hydrogen as early as 400 °C, with the highest catalytic activity for low-temperature CO oxidation achieved after a reduction step at 500 °C, despite only a 10% fraction of Ni exsolved. The activity and stability of exsolved nanoparticles were compared with their impregnated counterparts on a perovskite material with a similar chemical composition (La0.65Sr0.35TiO3) and a comparable specific surface area and Ni loading. After an aging step at 800 °C, the catalytic activity of exsolved Ni nanoparticles at 300 °C was found to be 10 times higher than that of impregnated ones, emphasizing the thermal stability of Ni nanoparticles prepared by redox exsolution.

A robust Ni/Au process and mechanism for p-type ohmic contact applied to GaN p-FETs

In this study, a new robust ohmic contact preparation process for GaN p-FETs application is developed on p-GaN/AlGaN/GaN, which excluded the commonly used descum step. A specific contact resistivity of approximately 2.0×10–3 Ω·cm2 is obtained based on Ni/Au metal stack. X-ray photoelectron spectroscopy (XPS) analysis revealed that the p-GaN surface underwent oxidation by O2 plasma in the descum step, forming Ga2O3 as a barrier layer between the metal and p-GaN. The resulting Ga2O3 could not be completely removed using a hydrochloric acid solution, resulting in a Schottky contact. Moreover, the Ni/Au ohmic contact mechanism was revealed for the first time by varying the O2 content in the annealing atmosphere. The X-ray transmission electron microscopy–energy-dispersive X-ray spectroscopy and XPS results proved that the Ni (III) oxide or Ni2O3 present at the metal/p-GaN interface and the Ga vacancies formed on the p-GaN surface played a crucial role in facilitating the formation of ohmic contacts.

Room temperature synthesis of 3D-nanocrystalline graphitic carbon from biomass-derived sugars, alcohols, and polyphenolic compounds.

Nanocrystalline carbon materials exhibit promising potential for sustainable and high-performance applications in electronics, energy storage, and environmental technologies. While sugars are abundant and renewable, converting them to graphitic carbon usually requires high temperature treatment. Here, we present a groundbreaking approach for synthesizing nanocrystalline carbon from readily available sugars such as glucose, fructose, and sucrose at ambient pressure and temperature. This novel method involves electrochemical reduction on a negatively charged Ag surface coupled with intermolecular dehydration between the organic precursors. By applying relatively low potentials ranging from -1.2 to -1.6 V vs. Ag/AgCl, and with the presence of hydrogen peroxide, oxygenic carbon precursors are efficiently transformed into nanocrystalline hybrid carbon structures. The role of hydrogen peroxide is pivotal in expediting hydrogen abstraction and facilitating the formation of 3D-nanostructured carbon allotropes. Characterization results based on Raman spectroscopy, transmission electron microscopy-energy dispersive X-ray spectroscopy-selected area electron diffraction (TEM-EDX-SAED), X-ray photoelectron spectroscopy (XPS), and grazing incidence-X-ray diffraction (GI-XRD) confirm the presence of mixed nanocrystalline sp2-sp3 hybridization in the resulting carbon materials. Moreover, this method's versatility extends beyond sugars to include alcohols, polyols, and polyphenolic compounds like ethanol, glycerol, and tannic acid, broadening its potential for biomass valorization.

Atomic-scale investigation of precipitate phases in QE22 Mg alloy

Precipitation-hardenable commercial Mg alloy QE22 (Mg-2.5Ag-2.0Nd-0.7Zr, wt.%) has excellent mechanical properties, but precipitates in this alloy have not been well understood. In this work, precipitate phases γ'', γ, and δ formed during the isothermal ageing process at 150, 200, 250, and 300 °C have been characterized using atomic-resolution high-angle annular dark-field scanning transmission electron microscopy and atomic-scale energy-dispersive X-ray spectroscopy. The morphology, crystal structure, and orientation relationship of these precipitate phases have been determined. Domain boundaries usually exist in a single γ particle, which can be characterized by a separation vector of [11¯01]α. The δ phase forms in situ from its precursor γ phase, consequently leading to the formation of three different variants within a single δ particle. The nucleation of the δ phase is strongly related to the domain boundaries of the γ phase. The formation of the γ phase may be promoted by its precursor γ'' phase. The similarities in atomic structures of the γ'', γ, and δ phases are described and discussed, indicating that transformations between these precipitate phases can be accomplished through the diffusion of added alloying elements.

Selenium-Fortified Kombucha-Pollen Beverage by In Situ Biosynthesized Selenium Nanoparticles with High Biocompatibility and Antioxidant Activity.

Biogenic selenium nanoparticles (SeNPs) have been shown to exhibit increased bioavailability. Fermentation of pollen by a symbiotic culture of bacteria and yeasts (SCOBY/Kombucha) leads to the release of pollen content and enhances the prebiotic and probiotic effects of Kombucha. The aim of this study was to fortify Kombucha beverage with SeNPs formed in situ by Kombucha fermentation with pollen. Response Surface Methodology (RSM) was used to optimize the biosynthesis of SeNPs and the pollen-fermented Kombucha beverage. SeNPs were characterized by Transmission electron microscopy energy-dispersive X-ray spectroscopy (TEM-EDX), Fourier-transform infrared spectroscopy (FTIR), Dynamic light scattering (DLS), and Zeta potential. The pollen-fermented Kombucha beverage enriched with SeNPs was characterized by measuring the total phenolic content, antioxidant activity, soluble silicon, saccharides, lactic acid, and the total content of Se0. The polyphenols were identified by liquid chromatography-mass spectrometry (LC-MS). The pollen and the bacterial (nano)cellulose were characterized by scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX), FTIR, and X-Ray diffraction (XRD). We also assessed the in vitro biocompatibility in terms of gingival fibroblast viability and proliferation, as well as the antioxidant activity of SeNPs and the pollen-fermented Kombucha beverage enriched with SeNPs. The results highlight their increased biological performance in this regard.

Flexoelectric Catalysts Based on Hierarchical Wrinkling Surface of Centrosymmetric High-Entropy Oxide.

A high-entropy oxide nanocomposite with Ag(CuZn)(AlCr)2O4 and CuO phases is fabricated to form an abundantly hierarchical wrinkled surface. Application of a mechanical force to the nanocomposite resulted in a nonhomogeneous strain gradient at the interface between the Ag(CuZn)(AlCr)2O4 and CuO phases, changing the local charge distribution and creating flexoelectric polarization that delayed electron/hole recombination. Transmission electron microscopy energy-dispersive X-ray spectroscopy mapping revealed that the Ag, Cu, Zn, Al, Cr, and O elements were highly distributed throughout the nanocomposite. The nanocomposite produced 2116 μmol·g-1 h-1 of H2 without external light irradiation, which is 980% higher than the H2 produced by the same nanocomposite under the photocatalytic process. A strong electrical field is observed at the interface between the Ag(CuZn)(AlCr)2O4 and CuO phases, demonstrating that a flexoelectric potential (flexopotential) is established at the structural boundaries because the strain gradient is localized at these interfaces. The nanocomposite is a promising approach for environmentally friendly energy production.