High-angle Annular Dark-field Microscopy Research Articles

Evaluation and associated mechanism of mitigating Cr depletion by vanadium in modified 9Cr-1Mo steel: Experiment and phase-field modelling

The 9Cr-1Mo steel is extensively utilized in nuclear heat exchangers due to its exceptional corrosion resistance properties. The Chromium (Cr) element plays a pivotal role in enhancing the corrosion resistance. The Cr accumulates at grain boundaries (GBs) where defects and mismatches are located during long-term usage, leading to the depletion of Cr within the grain interior. This results in the Cr-rich carbide precipitates form along GBs, with a corresponding the depletion zone residing in the adjacent regions. In this study, we employed aberration-corrected high-resolution electron microscopy in high-angle annular dark field microscopy (HAADF) mode, equipped with energy dispersive spectroscopy (EDS), to analyse carbides formation along GBs and obtain elemental distribution information. Our investigation reveals that the Cr-rich carbide promotes the formation of chromium-depletion zone (CDZ) by consuming the surrounding Cr in the matrix, and the presence of vanadium-rich carbide inhibits the formation of (CDZ) from atomic scale.A phase-field modelling approach is employed to investigate the diffusive formation process in a polycrystalline system. Our modelling results are consistent with experimental observations. Cr preferentially diffuses towards grain boundaries (GBs) and accumulates, facilitating the formation of Cr-rich phases by consuming adjacent Cr in the surrounding region. The bilateral region of GBs serves as a source for supplying Cr to these newly formed phases while depleting Cr content, ultimately leading to the development of CDZ.By employing experimental techniques and phase-field method, this research provides valuable insights into the role of Cr, carbide precipitates, influence of vanadium, and CDZ formation.

Isomorphic substitution behavior of Pt on synthetic vernadite (δ-MnO2):A model reaction to elucidate the mechanism of Pt enrichment in marine ferromanganese crust

Marine ferromanganese crusts are considered to be the potential Pt deposits, and recent studies report a strong association between Pt and vernadite in these crusts. However, there are still uncertainties regarding the molecular processes involved in the enrichment of Pt by vernadite. This study investigates the adsorption behavior and molecular-scale immobilization mechanisms of Pt at water/vernadite interfaces through a combination of batch adsorption and desorption experiments, X-ray absorption fine structure (XAFS) analyses, and atomic resolution chemical imaging. Our findings suggest that the Pt enrichment on vernadite is attributed to an isomorphic substitution of Mn by Pt. The extended X-ray absorption fine structure (EXAFS) analysis reveals that Pt undergoes ligand exchange reactions during the enrichment process, and provides a comprehensive explanation of how Pt penetrates into the vernadite structure starting from the surface. Scanning transmission electron microscopy high-angle annular dark field (STEM-HAADF) observations visually confirm the infiltration of Pt atoms into the crystal structure of vernadite. Additionally, we demonstrate that the Pt enrichment in vernadite is a multi-stage chemical process. X-ray absorption near edge structure (XANES) analysis shows that Pt is initially rapidly adsorbed onto the surface of vernadite and then slowly oxidized. Our study provides a detailed understanding of the molecular-scale mechanisms involved in the adsorption of Pt onto vernadite and its subsequent structural incorporation. This knowledge is valuable for gaining insights into the Pt enrichment in marine ferromanganese crusts.

Oxygen-defects evolution to stimulate continuous capacity increase in Co-free Li-rich layered oxides

Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes, the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the involvement of oxygen redox. Herein, a Co-free Li-rich layered oxide Li1.286Ni0.071Mn0.643O2 has been prepared by a co-precipitation method to systematically investigate the undefined effects of the oxygen defects. A significant O2 release and the propagation of oxygen vacancies were detected by operando differential electrochemical mass spectroscopy (DEMS) and electron energy loss spectroscopy (EELS), respectively. Scanning transmission electron microscopy-high angle annular dark field (STEM-HAADF) reveals the oxygen vacancies fusing to nanovoids and monitors a stepwise electrochemical activation process of the large Li2MnO3 domain upon cycling. Combined with the quantitative analysis conducted by the energy dispersive spectrometer (EDS), existed nano-scale oxygen defects actually expose more surface to the electrolyte for facilitating the electrochemical activation and subsequently increasing available capacity. Overall, this work persuasively elucidates the function of oxygen defects on oxygen redox in Co-free Li-rich layered oxides.

Dynamic Tracking of NiFe Smart Catalysts using In Situ X-Ray Absorption Spectroscopy for the Dry Methane Reforming Reaction

The exsolution of nanoparticles from perovskite precursors has been explored as a route to synthesize catalysts with sinter or coke resistance. The characteristics of these exsolved nanoparticles are highly dynamic depending on the redox nature of the environment to which they are subjected. To develop their properties for thermo- and electrocatalytic applications, it is necessary to track the states and behavior of exsolved catalysts with in situ and ex situ characterization. In this study, we conduct in situ X-ray absorption spectroscopy (XAS) along with ex situ scanning transmission electron microscopy high-angle annular dark-field (STEM-HAADF) and energy-dispersive X-ray spectroscopy analysis of the parent perovskite oxide precursor, LaFe0.8Ni0.2O3, as its structure forms bimetallic NiFe nanoparticles and evolves in oxidative, reductive, and dry methane reforming environments. We develop a theory that NiFe exsolution is a function of the reduction potential where LaFe0.8Ni0.2O3 transforms to NiFe alloy supported on LaOx-LaFeOx. The Ni starts to exsolve at 268 °C, while most Fe exsolves at 700 °C. During dry methane reforming conditions, most of the Fe is oxidized by CO2 during the reaction and re-enters the perovskite as LaFeO3, while Ni remains on the surface as nanoparticles in the metallic state. During the oxidative regeneration phase, most of the Fe re-enters the bulk perovskite phase, while Ni is partially regenerated with a small percentage oxidized to large NiO nanoparticles. This study sheds light on the exsolution and regeneration of bimetallic alloy nanoparticles and the influence of the reaction conditions on their catalyst performance.

3D Nanoprinting of All-Metal Nanoprobes for Electric AFM Modes.

3D nanoprinting via focused electron beam induced deposition (FEBID) is applied for fabrication of all-metal nanoprobes for atomic force microscopy (AFM)-based electrical operation modes. The 3D tip concept is based on a hollow-cone (HC) design, with all-metal material properties and apex radii in the sub-10 nm regime to allow for high-resolution imaging during morphological imaging, conductive AFM (CAFM) and electrostatic force microscopy (EFM). The study starts with design aspects to motivate the proposed HC architecture, followed by detailed fabrication characterization to identify and optimize FEBID process parameters. To arrive at desired material properties, e-beam assisted purification in low-pressure water atmospheres was applied at room temperature, which enabled the removal of carbon impurities from as-deposited structures. The microstructure of final HCs was analyzed via scanning transmission electron microscopy-high-angle annular dark field (STEM-HAADF), whereas electrical and mechanical properties were investigated in situ using micromanipulators. Finally, AFM/EFM/CAFM measurements were performed in comparison to non-functional, high-resolution tips and commercially available electric probes. In essence, we demonstrate that the proposed all-metal HCs provide the resolution capabilities of the former, with the electric conductivity of the latter onboard, combining both assets in one design.

Molybdenum trioxide hybridized kaempferol: double-powered nanosystem for salvaging oxidative stress and electrochemical immunoprobing of interleukin-6

Intracellular reactive oxygen species (iROS) are the culprit in inflammation-linked diseases. Excessive radical generation triggers an inflammation cascade involving interleukin-6 (IL-6) and other cytokines release, causing oxidative stress to cells. Developing healthcare materials with dual-functionality controlling iROS and diagnosing IL-6 would be extremely beneficial for chronic inflammatory disease management. Herein, molybdenum trioxide hybridized kaempferol nanoparticles (MoHK NPs) have been synthesized with iROS scavenging and in situ electrochemical redox property for immunoassay of IL-6. Physicochemical integrity of nanosystem comprising MoHK NPs is characterized by X-ray absorption/photoelectron, Raman, and fourier transform infrared (FT-IR) spectroscopy as well as scanning transmission electron microscopy–high-angle annular dark field microscopic analysis. In vitro radical scavenging mechanism of MoHK NPs was studied by electron paramagnetic spectroscopy. Distinctly, these MoHK NPs exhibit a clinically significant antioxidant function and cytocompatibility with RAW 264.7 macrophage cell line. Bioaffinity layer–assisted monoclonal antibodies of IL-6 immobilized on MoHK electrode enable superior selectivity, electrochemical signal transduction (sensitivity 0.63 μA/fM/cm2), and rapid analytical response time even at ultralow IL-6 concentrations (detection limit 0.91 fM). This work demonstrates that hybridizing redox-active and antioxidant-rich phytochemical on metal oxide nanosystem can be a promising strategy for multifunctional theranostics.

Beauveria bassiana assisted remediation of chromium and indanthane blue

The presence of toxic pollutants in wastewater is a matter of great concern, posing risk to environment and health. Generally, dyes and heavy metals are concomitant pollutants of wastewaters, associated with multiple diseases in humans. Various physical and chemical approaches of removing these contaminants have been in use, however biological approach, utilizing microorganisms has been identified as an advantageous option. The present study utilized the potential of fungus, Beauveria bassiana for the removal of Chromium (Cr) and Indanthane blue, individually and simultaneously. Results showed that maximum Cr removal of 61% was observed at 30 mg L−1 with 3.8 mg g−1 of specific metal uptake. Further, 99.6% removal of dye (Indanthane blue) was observed at 200 mg L− 1 of initial dye concentration. The results of simultaneous removal of Cr and dye mixture highlighted the higher potential of B. bassiana for dye removal in comparison to Cr uptake. Moreover, the temperature of 30 °C with pH value of 7, accounts for maximum removal efficacy by B. bassiana. The analytical techniques, such as Atomic force microscopy (AFM) and Transmission electron microscopy high-angle annular dark field (TEM HAADF) were employed to study the morphological characteristics of B. bassiana in presence of Cr and dye. AFM highlighted the increase in surface roughness of B. Bassiana cells, further TEM HAADF clearly indicated the localization of heavy metals within the cells of B. bassiana.

Extended B-Site Vacancy Content Range and Cation Ordering in Twinned Hexagonal Perovskites Ba8Cr4-xTa4+0.6xO24.

The new 8-layer twinned hexagonal solid solution Ba8Cr4-xTa4+0.6xO24 (x = 0.0-3.0) was isolated through the aliovalent substitution of Ta5+ for Cr3+ in Ba2CrTaO6, showing the widest B-site vacancy content range among the 8-layer twinned hexagonal perovskites. Ba8Cr4-xTa4+0.6xO24 forms a simple 8-layer hexagonal perovskite structure within 0.0 ≤ x < 2.4 and a tripled 8-layer hexagonal perovskite superstructure within 2.4 ≤ x ≤ 3.0. The latter shows expanded a and b axes by times in comparison to the simple 8-layer hexagonal perovskite structure owing to the partial face-sharing octahedral (FSO) B cation ordering along the ab plane. The B-cation and vacancy distributions in the tripled superstructure were characterized by neutron and X-ray powder diffraction and further confirmed by a scanning transmission electron microscopy-high angle annular dark field imaging and intensity profile analysis. The formation of 8-layer twinned hexagonal perovskites Ba8Cr4-xTa4+0.6xO24 in an extended solid solution range can be attributed to the presence of both covalent B-B and B-O-B bonding and B-site vacancies in the FSO sites. This work provides an effective way of combining covalent B-B and B-O-B bonding and vacancy creation as well as the cationic ordering in the FSO sites to reduce electrostatic repulsion, which could further enable the stabilization of new hexagonal perovskite compounds.

LiYF4-nanocrystal-embedded glass ceramics for upconversion: glass crystallization, optical thermometry and spectral conversion.

Glass ceramics (GCs) can perfectly integrate nanocrystals (NCs) into bulk materials. Herein, GCs containing LiYF4 NCs were fabricated via a traditional melt-quenching method and subsequent glass crystallization. Structural characterization was carried out via X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and scanning transmission electron microscopy high-angle annular dark-field (STEM-HAADF) analysis, suggesting the precipitation of LiYF4 NCs from a glass matrix. Taking Eu3+ as a structural probe, the spectrographic features provide compelling evidence for the partition of dopants. In particular, intense upconversion (UC) emission was achieved when co-doped with Yb3+ and Er3+. Temperature-dependent UC emission behaviour was also established based on the fluorescence intensity ratio (FIR) of Er3+, to study its properties for optical thermometry. Furthermore, spectral conversion was attained through cross relaxation (CR) between Ce3+ and Ho3+, tuning from green to red with various Ce3+ doping concentrations. There is evidence that LiYF4 NC-embedded GCs were favorable for UC, which may be extremely promising for optical thermometry and spectral conversion applications. This work may open up new avenues for the exploration of GC materials for expansive applications.

Synthesis of a zinc–imidazole metal–organic framework (ZIF-8) using ZnO rods grown on cotton fabrics as precursors: arsenate absorption studies

A Zn-imidazolate metal–organic framework, ZIF-8, was synthesized using ZnO nanorods grown on cotton fibers as precursors. We monitored the synthesis path via X-ray diffraction, scanning electron microscopy, and thermogravimetric analysis. The fibers were evaluated by their capacity to absorb arsenate from aqueous solutions and we used scanning transmission electron microscopy–high angle annular dark-field (STEM–HAADF) imaging to observe the transport gradient of arsenate across the ZIF layer and the ZnO interface. The uptake of arsenate in the fibers coated with ZIF-8 on top of the ZnO rods, at pH 7, was of 70% while the uptake of the fibers coated only with ZnO rods was 38%. In addition to the enhanced uptake capacity, the fibers containing ZIF-8 also exhibited lower amounts of Zn leaching into the arsenate solutions. These results provide insights on the synthesis of Zn-imidazole metal–organic frameworks and confirm the potential use of ZIF-8 in the removal of arsenate from contaminated water streams.

Effect of Gold Electronic State on the Catalytic Performance of Nano Gold Catalysts in n-Octanol Oxidation.

This study aims to identify the role of the various electronic states of gold in the catalytic behavior of Au/MxOy/TiO2 (where MxOy are Fe2O3 or MgO) for the liquid phase oxidation of n-octanol, under mild conditions. For this purpose, Au/MxOy/TiO2 catalysts were prepared by deposition-precipitation with urea, varying the gold content (0.5 or 4 wt.%) and pretreatment conditions (H2 or O2), and characterized by low temperature nitrogen adsorption-desorption, X-ray powder diffraction (XRD), energy dispersive spectroscopy (EDX), scanning transmission electron microscopy-high angle annular dark field (STEM HAADF), diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy of CO adsorption, temperature-programmable desorption (TPD) of ammonia and carbon dioxide, and X-ray photoelectron spectroscopy (XPS). Three states of gold were identified on the surface of the catalysts, Au0, Au1+ and Au3+, and their ratio determined the catalysts performance. Based on a comparison of catalytic and spectroscopic results, it may be concluded that Au+ was the active site state, while Au0 had negative effect, due to a partial blocking of Au0 by solvent. Au3+ also inhibited the oxidation process, due to the strong adsorption of the solvent and/or water formed during the reaction. Density functional theory (DFT) simulations confirmed these suggestions. The dependence of selectivity on the ratio of Brønsted acid centers to Brønsted basic centers was revealed.

Observation of unexpected uniaxial magnetic anisotropy in La2/3Sr1/3MnO3 films by a BaTiO3 overlayer in an artificial multiferroic bilayer.

We studied in detail the in-plane magnetic properties of heterostructures based on a ferroelectric BaTiO3 overlayer deposited on a ferromagnetic La2/3Sr1/3MnO3 film grown epitaxially on pseudocubic (001)-oriented SrTiO3, (LaAlO3)0.3(Sr2TaAlO6)0.7 and LaAlO3 substrates. In this configuration, the combination of both functional perovskites constitutes an artificial multiferroic system with potential applications in spintronic devices based on the magnetoelectric effect. La2/3Sr1/3MnO3 single layers and BaTiO3/La2/3Sr1/3MnO3 bilayers using the pulsed-laser deposition technique. We analyzed the films structurally through X-ray reciprocal space maps and high-angle annular dark field microscopy, and magnetically via thermal demagnetization curves and in-plane magnetization versus applied magnetic field loops at room temperature. Our results indicate that the BaTiO3 layer induces an additional strain in the La2/3Sr1/3MnO3 layers close to their common interface. The presence of BaTiO3 on the surface of tensile-strained La2/3Sr1/3MnO3 films transforms the in-plane biaxial magnetic anisotropy present in the single layer into an in-plane uniaxial magnetic anisotropy. Our experimental evidence suggests that this change in the magnetic anisotropy only occurs in tensile-strained La2/3Sr1/3MnO3 film and is favored by an additional strain on the La2/3Sr1/3MnO3 layer promoted by the BaTiO3 film. These findings reveal an additional mechanism that alters the magnetic behavior of the ferromagnetic layer, and consequently, deserves further in-depth research to determine how it can modify the magnetoelectric coupling of this hybrid multiferroic system.

Revealing the Doping Effect in Stabilizing Layered Cathode Materials for Sodium-Ion Battery

Energy storage devices allow us to use energy in a flexible, high efficient and eco-benign way, which has profoundly shaped our everyday life. The most successful energy storage device is lithium-ion battery (LIB), which has dominated the portable electronic devices and are now penetrating deep into vehicle markets. However, the limited reserves of lithium and cobalt in the earth crust cannot fulfill the huge demand gap of electrochemical energy storage, and the fast expansion of LIB industry has already led to accelerated cost rising. Therefore, worldwide research programs strategically encourage the development of energy storage devices beyond LIB, among of which, sodium ion battery (SIB) is a very attractive one. Sodium is much more natural abundance and more importantly SIB industry can share facilities and technologies from LIB because of the similarities of physical and chemical properties between Li and Na. To achieve superior performance of SIB, high performance cathode material plays a critical role. Among of variety of cathode candidates, layered NaxTMO2 (TM refers to transition metal) oxides are promising and widely studied, which can be grouped into two families, P2-type and O3-type structures. However, one critical drawback for both P2-type and O3-type layered oxides is the multi-phase-transition reactions during charge/discharge, which leads to the annoying multi-voltage-plateaus in voltage-capacity profiles. Various ordering processes (TM ordering, charge ordering and Na-vacancy ordering) and structure transitions (P2-O2, O3-P3, et al) have been identified previously. The structural ordering will result in sluggish Na-ion transportation kinetics and it can further couple with the structural transformation to collectively cause structural instability, significantly plaguing the cycling performance. Therefore, many efforts have been taken to suppress the structural ordering and transformation, namely eliminating the multi-voltage-plateaus in the charge/discharge profile. Particularly for P2-Na2/3Ni1/3Mn2/3O2 (NNM), doping electrochemically inactive elements (Li, Mg, Cu or Zn) is proven to be an effective approach to suppress the P2-O2 phase transition and Na-vacancy ordering to achieve improved electrochemical performance. In this work, by virtue of variety of analytical tools, such as X-ray diffraction (XRD), focused ion beam/scanning electron microscopy (FIB/SEM), transmission electron microscopy (TEM) and scanning transmission electron microscopy-high angle annular dark field (STEM-HAADF) imaging, we conduct systematic investigations on the degradation mechanisms of P2-NNM and find that P2-O2 phase transition induced grain cracking is the main cause of performance decay. Our further investigations on the role of dopant on P2-Na0.67Ni0.33-xMn0.67MgxO2 (x=0, 0.05, 0.1) (P2-NMMx) and find that doping electrochemically inactive elements can suppress intragranular cracking to improve cycle stability of P2-NM. we show that dopants segregation is more effectively to suppress intragranular crack and improve cycling stability than dopant uniform distribution in TM layer. By virtue of variety of analytical tools and simulation, dopant segregation have been characterized comprehensively and come up a new strategy, precipitation strengthening mechanism, to alleviate electrochemomechanical degradation and enhance stability of layered cathode operating at high voltage.

Enhancement of Electrical Conduction and Phonon Scattering in Ga2O3(ZnO)9-In2O3(ZnO)9 Compounds by Modification of Interfaces at the Nanoscale

The Ga2O3(ZnO)9 and In2O3(ZnO)9 homologous phases have attracted attention as thermoelectric (TE) oxides due to their layered structures. Ga2O3(ZnO)9 exhibits low thermal conductivity, while In2O3(ZnO)9 possesses higher electrical conductivity. The TE properties of the solid solution of Ga2O3(ZnO)9-In2O3(ZnO)9 were explored and correlated with changes in the crystal structure. High-quality (1−x)Ga2O3(ZnO)9-(ZnO)9 (x = 0.0 to 1.0) ceramics were prepared by the solid-state route using B2O3 and Nd2O3 as additives. The crystal structures were analysed by x-ray diffraction, high-resolution transmission electron microscopy and atomic resolution scanning transmission electron microscopy–high-angle annular dark field imaging–energy dispersive x-ray spectroscopy (STEM–HAADF–EDS) techniques. A layered superstructure with compositional modulations was observed in all samples in the (1−x)Ga2O3(ZnO)9-xIn2O3(ZnO)9 system. All the ceramics exhibited nanoscale structural features identified as Ga- and In-rich inversion boundaries (IBs). Substitution of 20 mol.% In (x = 0.2) in the Ga2O3(ZnO)9 compounds generated basal and pyramidal indium IBs typically found in the In2O3(ZnO)m system. The (Ga0.8In0.2)2O3(ZnO)9 compound does not exhibit the structural features of the $$ Cmcm $$CmcmGa2O3(ZnO)9 compound, which is formed by a stacking of Ga-rich IBs along the pyramidal plane of the wurtzite ZnO, but features that resemble the crystal structure exhibited by the $$ R\overline{3} m $$R3¯mIn2O3(ZnO)m with basal and pyramidal indium IBs. The structural changes led to improved TE performance. For example, (Ga0.8In0.2)2O3(ZnO)9 showed a low thermal conductivity of 2 W/m K and a high power factor of 150 μW/m K2 giving a figure of merit (ZT) of 0.07 at 900 K. This is the highest ZT for Ga2O3(ZnO)9-based homologous compounds and is comparable with the highest ZT reported for In2O3(ZnO)9 homologous compounds.

Atomic scale analyses of {\bb Z}-module defects in an NiZr alloy.

Some specific structures of intermetallic alloys, like approximants of quasicrystals, have their unit cells and most of their atoms located on a periodic fraction of the nodes of a unique {\bb Z}-module [a set of the irrational projections of the nodes of a (N > 3-dimensional) lattice]. Those hidden internal symmetries generate possible new kinds of defects like coherent twins, translation defects and so-called module dislocations that have already been discussed elsewhere [Quiquandon et al. (2016). Acta Cryst. A72, 55-61; Sirindil et al. (2017). Acta Cryst. A73, 427-437]. Presented here are electron microscopy observations of the orthorhombic phase NiZr - and its low-temperature monoclinic variant - which reveal the existence of such defects based on the underlying {\bb Z}-module generated by the five vertices of the regular pentagon. New high-resolution electron microscopy (HREM) and scanning transmission electron microscopy high-angle annular dark-field (STEM-HAADF) observations demonstrate the agreement between the geometrical description of the structure in five dimensions and the experimental observations of fivefold twins and translation defects.

Selective Oxidation of Veratryl Alcohol over Au-Pd/Ce0.62Zr0.38O₂ Catalysts Synthesized by Sol-Immobilization: Effect of Au:Pd Molar Ratio.

The selective oxidation of veratryl alcohol (VA), a model compound of lignin, with oxygen molecules to produce veratraldehyde (VAld) was studied over monometallic Au, Pd, and bimetallic Au:Pd nanoparticles supported on a Ce0.62Zr0.38O2 mixed oxide for the first time. These bimetallic Au-Pd catalysts with Au:Pd molar ratios from 0.4 to 4.3 were synthesized by the sol-immobilization method. Furthermore, all the catalysts were characterized by inductively coupled plasma-atomic emission spectroscopy (ICP-AES), N2 physisorption, X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy-high angle annular dark field (STEM-HAADF) imaging, energy dispersive X-ray spectroscopy (EDXS), and temperature programmed reduction (TPR) techniques. A synergistic effect between gold and palladium was observed over all the bimetallic catalysts in a wide range of studied Au:Pd ratios. Remarkably, the optimum Au:Pd ratio for this reaction was 1.4 with a turnover frequency of almost six times larger than for the monometallic gold and palladium catalysts. Selectivity to veratraldehyde was higher than 99% for the monometallic Au, Pd, and all the bimetallic Au-Pd catalysts, and stayed constant during the reaction time.

Formation of the Conducting Filament in TaO x-Resistive Switching Devices by Thermal-Gradient-Induced Cation Accumulation.

The distribution of tantalum and oxygen ions in electroformed and/or switched TaO x-based resistive switching devices has been assessed by high-angle annular dark-field microscopy, X-ray energy-dispersive spectroscopy, and electron energy-loss spectroscopy. The experiments have been performed in the plan-view geometry on the cross-bar devices producing elemental distribution maps in the direction perpendicular to the electric field. The maps revealed an accumulation of +20% Ta in the inner part of the filament with a 3.5% Ta-depleted ring around it. The diameter of the entire structure was approximately 100 nm. The distribution of oxygen was uniform with changes, if any, below the detection limit of 5%. We interpret the elemental segregation as due to diffusion driven by the temperature gradient, which in turn is induced by the spontaneous current constriction associated with the negative differential resistance-type I- V characteristics of the as-fabricated metal/oxide/metal structures. A finite-element model was used to evaluate the distribution of temperature in the devices and correlated with the elemental maps. In addition, a fine-scale (∼5 nm) intensity contrast was observed within the filament and interpreted as due phase separation of the functional oxide in the two-phase composition region. Understanding the temperature-gradient-induced phenomena is central to the engineering of oxide memory cells.

Thickness-dependent humidity sensing by poly(vinyl alcohol) stabilized Au-Ag and Ag-Au core-shell bimetallic nanomorph resistors.

We herein report a simple chemical route to prepare Au–Ag and Ag–Au core–shell bimetallic nanostructures by reduction of two kinds of noble metal ions in the presence of a water-soluble polymer such as poly(vinyl alcohol) (PVA). PVA was intentionally chosen as it can play a dual role of a supporting matrix as well as stabilizer. The simultaneous reduction of metal ions leads to an alloy type of structure. Ag(c)–Au(s) core–shell structures display tendency to form prismatic nanostructures in conjunction with nanocubes while Au(c)–Ag(s) core–shell structures show formation of merely nanocubes. Although UV–visible spectroscopy and X-ray photoelectron spectroscopy analyses of the samples typically suggest the formation of both Ag(c)–Au(s) and Au(c)–Ag(s) bimetallic nanostructures, the definitive evidence comes from high-resolution transmission electron microscopy–high-angle annular dark field elemental mapping in the case of Au(c)–Ag(s) nanomorphs only. The resultant nanocomposite materials are used to fabricate resistors on ceramic rods having two electrodes by drop casting technique. These resistors are examined for their relative humidity (RH) response in the range (2–93% RH) and both the bimetallic nanocomposite materials offer optimized sensitivity of about 20 Kohm/% RH and 300 ohm/% RH at low and higher humidity conditions, respectively, which is better than that of individual nanoparticles.

First 14-Layer Twinned Hexagonal Perovskite Ba14Mn1.75Ta10.5O42: Atomic-Scale Imaging of Cation Ordering

Formation of hexagonal perovskite with mixed cubic and hexagonal stacking of AO3 layers becomes more and more difficult when the number of layers in the stacking repeating unit increases. So far, the highest number of layers reported for twinned hexagonal perovskite is 12, with alternative 5 consecutive cubic layers and one hexagonal layer in the (ccccch)2 sequence. Here, we present the unexpected formation of a 14-layer twinned hexagonal perovskite with a stacking sequence (cccccch)2 for the BaO3 layers on the Ba14Mn1.75Ta10.5O42 (Ba8MnTa6O24) composition, the first example of twinned hexagonal perovskite with a periodicity exceeding 12-layers. The B-cation and vacancy distributions are characterized by multiple efficient and complementary techniques including neutron and synchrotron powder diffraction, scanning transmission electron microscopy-high angle annular dark field (STEM-HAADF) imaging, and electron energy loss spectroscopy (EELS) and X-ray energy dispersive spectroscopy (EDS) elemental mapping....

Synergistic effect of bimetallic Au-Pd supported on ceria-zirconia mixed oxide catalysts for selective oxidation of glycerol

A series of bimetallic Au-Pd catalysts supported on Ce0.62Zr0.38O2 mixed oxide has been synthesized using a simultaneous deposition-precipitation method. Different Au:Pd ratios were obtained maintaining Au loadings constant and varying Pd content. Elemental analysis, X-ray diffraction, N2 physisorption, X-ray photoelectron spectroscopy, scanning transmission electron microscopy-high angle annular dark field (STEM-HAADF) and X-ray energy dispersive spectroscopy (XEDS) techniques have been employed to characterize these catalysts. The catalytic activities for selective oxidation of glycerol over these bimetallic catalysts have been evaluated, a synergistic effect being observed. Thus, the bimetallic Au-Pd catalyst with the lowest Pd content was the one exhibiting the highest catalytic activity among all the prepared catalysts. Oxidation at 700°C of the bimetallic 2.2AuPd/Ce0.62Zr0.38O2 catalyst led to an increase of the catalytic activity for the selective oxidation of glycerol, which seemed to be due to the formation of a larger fraction of bimetallic Au-Pd alloy-type nanoparticles after oxidation at higher temperatures.