Exploring Reversible Redox Behavior in the 6H-BaFeO3-δ (0 < δ < 0.4) System: Impact of Fe3+/Fe4+ Ratio on CO Oxidation.

This work is devoted to evaluating the relationship between the oxygen content and catalytic activity in the CO oxidation process of the 6H-type BaFeO3-δ system. Strong evidence is provided about the improvement of catalytic performance with increasing Fe average oxidation state, thus suggesting the involvement of lattice oxygen in the catalytic process. The compositional and structural changes taking place in both the anionic and cationic sublattices of the catalysts during redox cycles have been determined by temperature-resolved neutron diffraction. The obtained results evidence a structural transition from hexagonal (P63/mmc) to orthorhombic (Cmcm) symmetry. This transition is linked to octahedra distortion when the Fe3+ concentration exceeds 40% (δ values higher than 0.2). The topotactical character of the redox process is maintained in the δ range 0 < δ < 0.4. This suggests that the cationic framework is only subjected to slight structural modifications during the oxygen exchange process occurring during the catalytic cycle.

Extremely long-range, high-temperature Josephson coupling across a half-metallic ferromagnet.

The Josephson effect results from the coupling of two superconductors across a spacer such as an insulator, a normal metal or a ferromagnet to yield a phase coherent quantum state. However, in junctions with ferromagnetic spacers, very long-range Josephson effects have remained elusive. Here we demonstrate extremely long-range (micrometric) high-temperature (tens of kelvins) Josephson coupling across the half-metallic manganite La0.7Sr0.3MnO3 combined with the superconducting cuprate YBa2Cu3O7. These planar junctions, in addition to large critical currents, display the hallmarks of Josephson physics, such as critical current oscillations driven by magnetic flux quantization and quantum phase locking effects under microwave excitation (Shapiro steps). The latter display an anomalous doubling of the Josephson frequency predicted by several theories. In addition to its fundamental interest, the marriage between high-temperature, dissipationless quantum coherent transport and full spin polarization brings opportunities for the practical realization of superconducting spintronics, and opens new perspectives for quantum computing.

Large intrinsic anomalous Hall effect in SrIrO3 induced by magnetic proximity effect.

The anomalous Hall effect (AHE) is an intriguing transport phenomenon occurring typically in ferromagnets as a consequence of broken time reversal symmetry and spin-orbit interaction. It can be caused by two microscopically distinct mechanisms, namely, by skew or side-jump scattering due to chiral features of the disorder scattering, or by an intrinsic contribution directly linked to the topological properties of the Bloch states. Here we show that the AHE can be artificially engineered in materials in which it is originally absent by combining the effects of symmetry breaking, spin orbit interaction and proximity-induced magnetism. In particular, we find a strikingly large AHE that emerges at the interface between a ferromagnetic manganite (La0.7Sr0.3MnO3) and a semimetallic iridate (SrIrO3). It is intrinsic and originates in the proximity-induced magnetism present in the narrow bands of strong spin-orbit coupling material SrIrO3, which yields values of anomalous Hall conductivity and Hall angle as high as those observed in bulk transition-metal ferromagnets. These results demonstrate the interplay between correlated electron physics and topological phenomena at interfaces between 3d ferromagnets and strong spin-orbit coupling 5d oxides and trace an exciting path towards future topological spintronics at oxide interfaces.

Modified Synthesis Strategies for the Stabilization of low n Tin O2n-1 Magnéli Phases.

Titanium reduced oxides TiO2-x occupy, since long time, a prominent place on the landscape of binary metal oxides because of their intriguing ability to form extended defects that affect both the formation of new superlattices and different electronic behaviours. Related to these features, a wide range of practical applications has been achieved. Moved by the conviction of the great potential of understanding the influence of the reactivity, compositional variations and size effects on their functional properties, the aim of this personal account is the optimization of a recently developed strategy for the stabilization of low n Tin O2n-1 terms. In particular, we will focus on the Ti4 O7 composition as well as the incorporation of transition metals, like Mn, in order to deal with new reduced Magnéli phases.

Silicon surface passivation by PEDOT: PSS functionalized by SnO2 and TiO2 nanoparticles.

In this paper, we present a study of silicon surface passivation based on the use of spin-coated hybrid composite layers. We investigate both undoped poly(3,4-ethylenedioxythiophene)/poly-(styrenesulfonate) (PEDOT:PSS), as well as PEDOT:PSS functionalized with semiconducting oxide nanomaterials (TiO2 and SnO2). The hybrid compound was deposited at room temperature by spin coating-a potentially lower cost, lower processing time and higher throughput alternative compared with the commonly used vacuum-based techniques. Photoluminescence imaging was used to characterize the electronic properties of the Si/PEDOT:PSS interface. Good surface passivation was achieved by PEDOT:PSS functionalized by semiconducting oxides. We show that control of the concentration of semiconducting oxide nanoparticles in the polymer is crucial in determining the passivation performance. A charge carrier lifetime of about 275 µs has been achieved when using SnO2 nanoparticles at a concentration of 0.5 wt.% as a filler in the composite film. X-ray diffraction (XRD), scanning electron microscopy, high resolution transmission electron microscopy (HRTEM), energy dispersive x-ray in an SEM, and µ-Raman spectroscopy have been used for the morphological, chemical and structural characterization. Finally, a simple model of a photovoltaic device based on PEDOT:PSS functionalized with semiconducting oxide nanoparticles has been fabricated and electrically characterized.

Atomically Resolved Short-Range Order at the Nanoscale in the Ca-Mn-O System.

The elucidation of the reaction mechanisms involving redox processes in functional transition-metal oxides, which usually start in areas of very few nanometers in size, is yet a challenge to be satisfactorily achieved. Atomically resolved HAADF and EELS have provided both chemical and structural information at the nanoscale, which reveal the preservation of short-range cationic order in areas of 2-3 nm length as the driving force behind the reversibility of the Ca2Mn3O8-Ca2Mn3O5 redox process. Oxygen evolution is accommodated by cationic diffusion along the Ca and Mn layers of the cation-deficient Ca2Mn3O8 delafossite related structure, whereas Mn remains octahedrally coordinated.

The wet synthesis and quantification of ligand-free sub-nanometric Au clusters in solid matrices.

The synthesis of ligand-free sub-nanometric metal clusters on a large scale suffers typically from very low yields (<5% yield) and needs very high dilutions. Here we show that Au clusters can be prepared with ethylene-vinyl alcohol copolymers (EVOH), charcoal, and different metal oxides (CeO2, Al2O3, TiO2 and ZnO) in >15% yields, as unambiguously determined using a very simple and extremely sensitive analytical reaction test.

Electron microscopy for inorganic-type drug delivery nanocarriers for antitumoral applications: what does it reveal?

The use of nanoparticles with the ability to transport drugs in a selective and controllable manner directly to diseased tissues and cells has improved the therapeutic arsenal for addressing unmet clinical situations. In recent years, a vast number of nanocarriers with inorganic, organic, hybrid and even biological nature have been developed especially for their application in the oncology field. The exponential growth in the field of nanomedicine would not have been possible without the also-rapid expansion of electron microscopy techniques, which allow a more precise observation of nanometric objects. The use of these techniques provides a better understanding of the key parameters which rule the nanoparticles' synthesis and behavior. In this review, the recent advances made in the application of inorganic nanoparticles to clinical uses and the role which electron microscopy has played are presented.

Light-emitting-diodes based on ordered InGaN nanocolumns emitting in the blue, green and yellow spectral range.

The growth of ordered arrays of InGaN/GaN nanocolumnar light emitting diodes by molecular beam epitaxy, emitting in the blue (441 nm), green (502 nm), and yellow (568 nm) spectral range is reported. The device active region, consisting of a nanocolumnar InGaN section of nominally constant composition and 250 to 500 nm length, is free of extended defects, which is in strong contrast to InGaN (planar) layers of similar composition and thickness. Electroluminescence spectra show a very small blue shift with increasing current (almost negligible in the yellow device) and line widths slightly broader than those of state-of-the-art InGaN quantum wells.

The dissolution and biological effects of silver nanoparticles in biological media.

Silver ions and silver nanoparticles have a well-known biological effect that typically occurs in biological or environmental media of complex composition. Silver nanoparticles release silver ions if oxidizing species like molecular oxygen or hydrogen peroxide are present. The presence of glucose as a model for reducing sugars has only a small effect on the dissolution rate. In the presence of chloride ions, precipitation of silver chloride nanoparticles occurs. At physiological salt concentrations, no precipitation of silver phosphate occurs as the precipitation of silver chloride always occurs first. If the surface of a silver nanoparticle is passivated by cysteine, the dissolution is quantitatively inhibited. Upon immersion of silver nanoparticles in pure water for 8 months, leading to about 50% dissolution, no change in the surface was observed by transmission electron microscopy. A model for the dissolution was derived from immersion and dissolution experiments in different media and from high-resolution transmission electron microscopy. A literature survey on the available data on the dissolution of silver nanoparticles showed that only qualitative trends can be identified as the nature of the nanoparticles and of the immersion medium are practically never comparable. The dissolution effects were confirmed by cell culture experiments (human mesenchymal stem cells and neutrophil granulocytes) where silver nanoparticles that were stored under argon had a clearly lower cytotoxicity than those stored under air. They also led to a less formation of reactive oxygen species (ROS). This underscores that silver ions are the toxic species.

Surprising resistivity decrease in manganites with constant electronic density.

A decrease of eight orders of magnitude in the resistance of (La0.5Ca0.5)zMnO3 has been detected when the electronic density is kept constant while the calcium content is modified by introducing cationic vacancies. This effect is related to the disappearance of the charge ordering state and the emergence of an antiferromagnetic­ferromagnetic transition. Moreover, high values of the colossal magnetoresistance above room temperature are attained.

Poly(methyl methacrylate) coating of soft magnetic amorphous and crystalline Fe,Co-B nanoparticles by chemical reduction.

The structural and magnetic properties of a collection of nanoparticles coated by Poly(methyl methacrylate) through a wet chemical synthesis have been investigated. The particles display either an amorphous (M = Fe, Co) M-B arrangement or a mixed structure bcc-Fe and fcc-Co + amorphous M-B. Both show the presence of a metal oxi-hydroxide formed in aqueous reduction. The organic coating facilitates technological handling. The cost-effective synthesis involves a reduction in a Poly(methyl methacrylate) aqueous solution of iron(II) or cobalt(II) sulphates (< 0.5 M) by sodium borohydride (< 0.5 M). The particles present an oxidized component, as deduced from X-ray diffraction, Mössbauer and Fe- and Co K-edge X-ray absorption spectroscopy and electron microscopy. For the ferrous alloys, this Fe-oxide is alpha-goethite, favoured by the aqueous solution. The Poly(methyl methacrylate) coating is confirmed by Fourier transform infrared spectroscopy. In pure amorphous core alloys there is a drastic change of the coercivity from bulk to around 30 Oe in the nanoparticles. The mixed structured alloys also lie in the soft magnetic regime. Magnetisation values at room temperature range around 100 emu/g. The coercivity stems from multidomain particles and their agglomeration, triggering the dipolar interactions.

Magnetic properties of ZnO nanoparticles.

We experimentally show that it is possible to induce room-temperature ferromagnetic-like behavior in ZnO nanoparticles without doping with magnetic impurities but simply inducing an alteration of their electronic configuration. Capping ZnO nanoparticles ( approximately 10 nm size) with different organic molecules produces an alteration of their electronic configuration that depends on the particular molecule, as evidenced by photoluminescence and X-ray absorption spectroscopies and altering their magnetic properties that varies from diamagnetic to ferromagnetic-like behavior.

Crystallochemistry, textural properties, and in vitro biocompatibility of different silicon-doped calcium phosphates.

Three silicon-doped calcium phosphates (Si-CaPs) were synthesized by heating precipitated silicon-doped apatite via different thermal treatments. Temperatures of 700 degrees C, 900 degrees C, and 1100 degrees C led to an apatite-glass biphasic material, nanocrystalline Si-doped apatite (SiHA), and Si-doped apatite-alpha tricalcium phosphate biphasic material, respectively. Structure, microstructure, textural properties, and chemical differences were determined for the three bioceramics. Biocompatibility tests were carried out by seeding osteblast-like cells onto the three substrates. Si-CaP treated at 700 degrees C and 900 degrees C led to Ca decrease in the culture media, partially impeding the cell proliferation over them. However, the proliferation capability is restored when additional culture medium is added. Finally, cytotoxicity results indicated that cell damage is much lower in osteblast-like cells seeded onto SiHA and SiHA-alpha tricalcium phosphate samples than in plastic culture control.

Interface double-exchange ferromagnetism in the Mn-Zn-O system: new class of biphase magnetism.

In this Letter, we experimentally show that the room temperature ferromagnetism in the Mn-Zn-O system recently observed is associated with the coexistence of Mn(3+) and Mn(4+) via a double-exchange mechanism. The presence of the ZnO around MnO(2) modifies the kinetics of MnO(2)-->Mn(2)O(3) reduction and favors the coexistence of both Mn oxidation states. The ferromagnetic phase is associated with the interface formed at the Zn diffusion front into Mn oxide, corroborated by preparing thin film multilayers that exhibit saturation magnetization 2 orders of magnitude higher than bulk samples.

Ferromagnetism in fcc twinned 2.4 nm size Pd nanoparticles.

The onset of ferromagnetism has been experimentally observed in small Pd particles of average diameter 2.4 nm. High-resolution studies reveal that a high percentage of the fcc particle exhibits single and multiple twinning boundaries. The spontaneous magnetization close to 0.02 emu/g seems to indicate that only a small fraction of atoms holds a permanent magnetic moment and contributes to ferromagnetism. The possible origin of ferromagnetism is briefly discussed according to different models recently reported.

Structural elucidation of microporous and mesoporous catalysts and molecular sieves by high-resolution electron microscopy.

Twenty years ago, one of us embarked (Bursill, L. A.; Lodge, E. A.; Thomas, J. M. Zeolitic structures as revealed by high-resolution electron microscopy. Nature 1980, 286, 111-113) on the study of zeolites (renowned for their electron-beam sensitivity) by high-resolution transmission electron microscopy (HRTEM). In the ensuing years, high-resolution imaging aided by optical diffractometry has yielded details of the open framework structures of a number of new aluminosilicate and aluminophosphate molecular sieves and catalysts. The nature of intergrowth and recurrently twinned structures, as well as new types of structural imperfection in hitherto uncharacterized materials, has also been elucidated. With continued improvements in instrumental development, encompassing higher accelerating voltages, better objective lenses and vacua, computational advances, and the arrival of slow-scan CCD detectors, electron crystallographic methods and HRTEM imaging now enable the ab initio three-dimensional structures of micro- and mesoporous solids, with their occluded structure-directing organic species, to be determined. High-resolution scanning transmission electron microscopy using subnanometric probes provides supplementary structural and ultramicro analytical information and electron spectroscopic imaging (at the attogram level). In its high-angle annular dark-field mode, it is capable of locating and determining the composition of individual nanoparticle catalysts (consisting of just a few atoms) supported on porous hosts.

Transition from the layered Sr2RhO4 to the monodimensional Sr4RhO6 phase.

Study of the structural changes occurring during the reduction process of the Sr2RhO4+delta, (214), n=1 term of the Ruddlesden and Popper series, shows that for delta <0.02 values, this material dissociates into the Sr4RhO6 (416) monodimensional phase, alpha = infinity, beta = 0 compound of the (A3B2O6)alpha-(A3B3O9)beta family, and Rh metal. During the first stage, this process occurs by the formation of an intergrowth between the (214) and (416) materials which can be only detected by high resolution electron microscopy and is easily interpreted on the basis of the structural relationship established between them. Further reduction allows the segregation of both phases as separated entities, which coexist with Rh metal. The dissociation process is reversible and, under oxidizing conditions, a layered material with anionic composition delta =0.06 is always obtained. This behaviour seems to be a general way of accommodating the compositional changes in layered A2BO4 phases where the B cation is always in a octahedral environment. The structural mechanism of this transformation is proposed, and the structural relationship between these two low-dimensional oxides is established.

Structural study and stability of hydroxyapatite and beta-tricalcium phosphate: two important bioceramics.

The stability of hydroxyapatite (OHAP) and beta-tricalcium phosphate (beta-TCP) ceramics depends on the temperature of preparation and the partial pressure of water in the reaction atmosphere. In bioceramics used in the study of biomaterials, these two phosphates often coexist in distinct proportions; therefore, structural characterization of the individual phases is hindered. The structure of these two individual calcium phosphates have been studied using X-ray diffraction, and mainly by high-resolution electron microscopy. Whereas the X-ray diffraction profile of OHAP has been refined in the space group P6(3)/m, the HREM images oriented along the [001] direction at the edges of the crystal show a threefold symmetry. The X-ray diffraction pattern of beta-TCP has been refined in the space group R3c and the HREM image oriented along [0001] zone axis shows regular contrast. Both these calcium phosphate ceramics are unstable to the electron beam for a prolonged exposure time, and show areas of decomposition in HREM images of thin regions of the crystal. The regions of decomposition in the beta-TCP crystal show the presence of CaO as one of the major phases.