Method for the production of pure and C-doped nanoboron powders tailored for superconductive applications.

The present paper describes the improvement of the performances of boron powder obtained applying the freeze-drying process (FDP) for the nanostructuration and doping of B2O3, which is here used as boron precursor. After the nanostructuration process, B2O3 is reduced to elemental nanoboron (nB) through magnesiothermic reaction with Mg. For this work, the usefulness of the process was tested focusing on the carbon-doping (C-doping), using Cblack, inulin and haemoglobin as C sources. The choice of these molecules, their concentration, size and shape, aims at producing improvements in the final compound of boron: in this case the superconductive magnesium diboride, which has been prepared and characterized both as powder and wire. The characteristics of B2O3, B and MgB2 powder, as well as MgB2 wire were tested and compared with that obtained using the best commercial precursors: H. C. Starck micrometric boron and Pavezyum nanometric boron. Both the FDP and the magnesiothermic reaction were carried out with simplicity and a great variety of doping sources, i.e. elements or compounds, which can be organic or inorganic and soluble or insoluble. The FDP allows to produce nB suitable for numerous applications. This process is also very competitive in terms of scalability and production costs if compared to the via gas technique adopted by nanoboron producers currently available on the world market.

From Anhydrous Zinc Oxide Nanoparticle Powders to Aqueous Colloids: Impact of Water Condensation and Organic Salt Adsorption on Free Exciton Emission.

Variations in the composition and structure of ZnO nanoparticle interfaces have a key influence on the materials' optoelectronic properties and are responsible for high number of discrepant results reported for ZnO-based nanomaterials. Here, we conduct a systematic study of the room-temperature photoluminescence of anhydrous ZnO nanocrystals, as synthesized in the gas phase and processed in water-free atmosphere, and of their colloidal derivatives in aqueous dispersions with varying amounts of organic salt admixtures. A free exciton band at hν = 3.3 eV is essentially absent in the anhydrous ZnO nanocrystal powders measured in vacuum or in oxygen atmosphere. Surface hydration of the nanoparticles during colloid formation leads to the emergence of the free exciton band at hν = 3.3 eV and induces a small but significant release in lattice strain as detected by X-ray diffraction. Most importantly, admixture of acetate or citrate ions to the aqueous colloidal dispersions not only allows for the control of the ζ-potential but also affects the intensity of the free exciton emission in a correlated manner. The buildup of negative charge at the solid-liquid interface, as produced by citrate adsorption, increases the free exciton emission. This effect is attributed to the suppression of electron trapping in the near-surface region, which counteracts nonradiative exciton recombination. Using well-defined ZnO nanoparticles as model systems for interface chemistry studies, our findings highlight water-induced key effects that depend on the composition of the aqueous solution shell around the semiconducting metal oxide nanoparticles.

Crystallographic and electronic evolution of lanthanum strontium ferrite (La0.6Sr0.4FeO3-δ) thin film and bulk model systems during iron exsolution.

We study the changes in the crystallographic phases and in the chemical states during the iron exsolution process of lanthanum strontium ferrite (LSF, La0.6Sr0.4FeO3-δ). By using thin films of orthorhombic LSF, grown epitaxially on NaCl(001) and rhombohedral LSF powder, the materials gap is bridged. The orthorhombic material transforms into a fluorite structure after the exsolution has begun, which further hinders this process. For the powder material, by a combination of in situ core level spectroscopy and ex situ neutron diffraction, we could directly highlight differences in the Fe chemical nature between surface and bulk: whereas the bulk contains Fe(iv) in the fully oxidized state, the surface spectra can be described perfectly by the sole presence of Fe(iii). We also present corresponding magnetic and oxygen vacancy concentration data of reduced rhombohedral LSF that did not undergo a phase transformation to the cubic perovskite system based on neutron diffraction data.

Reactive metal-support interaction in the Cu-In2O3 system: intermetallic compound formation and its consequences for CO2-selective methanol steam reforming.

The reactive metal-support interaction in the Cu-In2O3 system and its implications on the CO2 selectivity in methanol steam reforming (MSR) have been assessed using nanosized Cu particles on a powdered cubic In2O3 support. Reduction in hydrogen at 300 °C resulted in the formation of metallic Cu particles on In2O3. This system already represents a highly CO2-selective MSR catalyst with ~93% selectivity, but only 56% methanol conversion and a maximum H2 formation rate of 1.3 µmol gCu -1 s-1. After reduction at 400 °C, the system enters an In2O3-supported intermetallic compound state with Cu2In as the majority phase. Cu2In exhibits markedly different self-activating properties at equally pronounced CO2 selectivities between 92% and 94%. A methanol conversion improvement from roughly 64% to 84% accompanied by an increase in the maximum hydrogen formation rate from 1.8 to 3.8 µmol gCu -1 s-1 has been observed from the first to the fourth consecutive runs. The presented results directly show the prospective properties of a new class of Cu-based intermetallic materials, beneficially combining the MSR properties of the catalyst's constituents Cu and In2O3. In essence, the results also open up the pathway to in-depth development of potentially CO2-selective bulk intermetallic Cu-In compounds with well-defined stoichiometry in MSR.

Thin water films and particle morphology evolution in nanocrystalline MgO.

A key question in the field of ceramics and catalysis is how and to what extent residual water in the reactive environment of a metal oxide particle powder affects particle coarsening and morphology. With X-ray Diffraction (XRD) and Transmission Electron Microscopy (TEM), we investigated annealing-induced morphology changes on powders of MgO nanocubes in different gaseous H2O environments. The use of such a model system for particle powders enabled us to describe how adsorbed water that originates from short exposure to air determines the evolution of MgO grain size, morphology, and microstructure. While cubic nanoparticles with a predominant abundance of (100) surface planes retain their shape after annealing to T = 1173 K under continuous pumping with a base pressure of water p(H2O) = 10-5 mbar, higher water partial pressures promote mass transport on the surfaces and across interfaces of such particle systems. This leads to substantial growth and intergrowth of particles and simultaneously favors the formation of step edges and shallow protrusions on terraces. The mass transfer is promoted by thin films of water providing a two-dimensional solvent for Mg2+ ion hydration. In addition, we obtained direct evidence for hydroxylation-induced stabilization of (110) faces and step edges of the grain surfaces.

Hydroxylation Induced Alignment of Metal Oxide Nanocubes.

Water vapor is ubiquitous under ambient conditions and may alter the shape of nanoparticles. How to utilize water adsorption for nanomaterial functionality and structure formation, however, is a yet unexplored field. Herein, we report the use of water vapor to induce the self-organization of MgO nanocubes into regularly staggered one-dimensional structures. This transformation evolves via an initial alignment of the MgO cubes, the formation of intermediate elongated Mg(OH)2 structures, and their reconversion into MgO cubes arranged in staggered structures. Ab initio DFT modelling identifies surface-energy changes associated with the cube surface hydration and hydroxylation to promote the uncommon staggered stacked assembly of the cubes. This first observation of metal oxide nanoparticle self-organization occurring outside a bulk solution may pave novel routes for inducing texture in ceramics and represents a great test-bed for new surface-science concepts.

Porphyrin Metalation at MgO Surfaces: A Spectroscopic and Quantum Mechanical Study on Complementary Model Systems.

We show that both single-crystalline and nanostructured MgO surfaces convert free-base tetraphenyl porphyrin (2HTPP) into magnesium tetraphenyl porphyrin (MgTPP) at room temperature. The reaction can be viewed as an ion exchange between the two aminic protons of the 2HTPP molecule with a Mg(2+) ion from the surface. The driving force for the reaction is the strong stability of the formed hydroxyl groups along the steps and at defects on the MgO surface. We have used an integrated characterization approach that includes UV/Vis diffuse reflectance measurements on nanostructured powders, X-ray photoelectron spectroscopic investigation of atomically clean MgO(100) single-crystalline thin films, and density functional theory (DFT) calculations on model systems. The DFT calculations demonstrate that MgTPP formation is strongly exothermic at the corners, edges and steps, but slightly endothermic on terrace sites. This agrees well with the UV/Vis diffuse reflectance, which upon adsorption of 2HTPP shows a decrease in the absorption band associated with corner and edge sites on MgO nanocube powders.

Changing interfaces: Photoluminescent ZnO nanoparticle powders in different aqueous environments.

We transformed vapor phase grown ZnO nanoparticle powders into aqueous ZnO nanoparticle dispersions and studied the impact of associated microstructure and interface property changes on their spectroscopic properties. With photoluminescence (PL) spectroscopy, we probed oxygen interstitials O i 2 - in the near surface region and tracked their specific PL emission response at hvEM = 2.1 eV during the controlled conversion of the solid-vacuum into the solid-liquid interface. While oxygen adsorption via the gas phase does affect the intensity of the PL emission bands, the O2 contact with ZnO nanoparticles across the solid-liquid interface does not. Moreover, we found that the near band edge emission feature at hvEM = 3.2 eV gains relative intensity with regard to the PL emission features in the visible light region. Searching for potential PL indicators that are specific to early stages of particle dissolution, we addressed for aqueous ZnO nanoparticle dispersions the effect of formic acid adsorption. In the absence of related spectroscopic features, we were able to consistently track ZnO nanoparticle dissolution and the concomitant formation of sol- vated Zinc formate species by means of PL and FT-IR spectroscopy, dynamic light scattering, and zeta potential measurements. For a more consistent and robust assessment of nanoparticle properties in different continuous phases, we discuss characterization challenges and potential pitfalls that arise upon replacing the solid-gas with the solid-liquid interface.

Pt-B System Revisited: Pt2B, a New Structure Type of Binary Borides. Ternary WAl12-Type Derivative Borides.

On the basis of a detailed study applying X-ray single-crystal and powder diffraction, differential scanning calorimetry, and scanning electron microscopy analysis, it was possible to resolve existing uncertainties in the Pt-rich section (≥65 atom % Pt) of the binary Pt-B phase diagram above 600 °C. The formation of a unique structure has been observed for Pt2B [X-ray single-crystal data: space group C2/m, a = 1.62717(11) nm, b = 0.32788(2) nm, c = 0.44200(3) nm, ß = 104.401(4)°, RF2 = 0.030]. Within the homogeneity range of "Pt3B", X-ray powder diffraction phase analysis prompted two structural modifications as a function of temperature. The crystal structure of "hT-Pt3B" complies with the hitherto reported structure of anti-MoS2 [space group P63/mmc, a = 0.279377(2) nm, c = 1.04895(1) nm, RF = 0.075, RI = 0.090]. The structure of the new "[Formula: see text]T-Pt3B" is still unknown. The formation of previously reported Pt∼4B has not been confirmed from binary samples. Exploration of the Pt-rich section of the Pt-Cu-B system at 600 °C revealed a new ternary compound, Pt12CuB6-y [X-ray single-crystal data: space group Im3̅, a = 0.75790(2) nm, y = 3, RF2 = 0.0129], which exhibits the filled WAl12-type structure accommodating boron in the interstitial trigonal-prismatic site 12e. The isotypic platinum-aluminum-boride was synthesized and studied. The solubility of copper in binary platinum borides has been found to attain ∼7 atom % Cu for Pt2B but to be insignificant for "[Formula: see text]T-Pt3B". The architecture of the new Pt2B structure combines puckered layers of boron-filled and empty [Pt6] octahedra (anti-CaCl2-type fragment) alternating along the x axis with a double layer of boron-semifilled [Pt6] trigonal prisms interbedded with a layer of empty tetrahedra and tetragonal pyramids (B-deficient α-T[Formula: see text]I fragment). Assuming boron vacancies ordering (space group R3), the Pt12CuB6-y structure exhibits serpentine-like columns of edge-connected boron-filled [Pt6] trigonal prisms running infinitely along the z axis and embedding the icosahedrally coordinated Cu atom. Pt2B, (Pt1-yCuy)2B (y = 0.045), and Pt12CuB6-y (y = 3) behave metallically, as revealed by temperature-dependent electrical resistivity measurements.

Cation diffusion in La(0.6)Sr(0.4)CoO(3-δ) below 800 °C and its relevance for Sr segregation.

Cation diffusion was investigated in La0.6Sr0.4CoO3-δ (LSC) thin films on (100) yttria stabilized zirconia in the temperature range 625-800 °C. Isotopic ((86)Sr) and elemental tracers (Fe, Sm) were used to establish diffusion profiles of the cations in bi- and multi-layered thin films. The profiles were analyzed by time of flight-secondary ion mass spectrometry (ToF-SIMS). Grain and grain boundary diffusion coefficients of the cations were determined for LSC thin films with columnar grains - diffusion along grain boundaries is shown to be about three orders of magnitude faster than in grains. This could be verified for thin films with different grain size. A- and B-site cations showed very similar temperature dependencies with activation energies of ∼3.5 eV for bulk and ∼4.1 eV for grain boundary diffusion. The importance of cation diffusivities for surface segregation of Sr and thus for a major degradation mechanism of LSC cathodes in solid oxide fuel cells is discussed.

Electrochemical properties of La0.6Sr0.4CoO3 - δ thin films investigated by complementary impedance spectroscopy and isotope exchange depth profiling.

The oxygen exchange and diffusion properties of La0.6Sr0.4CoO3 - Î´ thin films on yttria stabilized zirconia were analyzed by impedance spectroscopy and 18O tracer experiments. The investigations were performed on the same thin film samples and at the same temperature (400 °C) in order to get complementary information by the two methods. Electrochemical impedance spectroscopy can reveal resistive and capacitive contributions of such systems, but an exact interpretation of the spectra of complex oxide electrodes is often difficult from impedance data alone. It is shown that additional isotope exchange depth profiling can significantly help interpreting impedance spectra by giving reliable information on the individual contribution and exact location of resistances (surface, electrode bulk, interface). The measurements also allowed quantitative comparison of electrode polarization resistances obtained by different methods.

Defect-Rich CuZn Nanoparticles for Model Catalysis Produced by Femtosecond Laser Ablation.

Femtosecond laser ablation of Cu0.70Zn0.30 targets in ethanol led to the formation of periodic surface nanostructures and crystalline CuZn alloy nanoparticles with defects, low-coordinated surface sites, and, controlled by the applied laser fluence, different sizes and elemental composition. The Cu/Zn ratio of the nanoparticles was determined by energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and selected area electron diffraction. The CuZn nanoparticles were about 2-3 nm in size, and Cu-rich, varying between 70 and 95%. Increasing the laser fluence from 1.6 to 3.2 J cm-2 yielded larger particles, more stacking fault defects, and repeated nanotwinning, as evident from high-resolution transmission electron microscopy, aided by (inverse) fast Fourier transform analysis. This is due to the higher plasma temperature, leading to increased random collisions/diffusion of primary nanoparticles and their incomplete ordering due to immediate solidification typical of ultrashort pulses. The femtosecond laser-synthesized often nanotwinned CuZn nanoparticles were supported on highly oriented pyrolytic graphite and applied for ethylene hydrogenation, demonstrating their promising potential as model catalysts. Nanoparticles produced at 3.2 J cm-2 exhibited lower catalytic activity than those made at 2.7 J cm-2. Presumably, agglomeration/aggregation of especially 2-3 nm sized nanoparticles, as observed by postreaction analysis, resulted in a decrease in the surface area to volume ratio and thus in the number of low-coordinated active sites.

Titanium Oxycarbide as Platinum-Free Electrocatalyst for Ethanol Oxidation.

The compound material titanium oxycarbide (TiOC) is found to be an effective electrocatalyst for the electrochemical oxidation of ethanol to CO2. The complete course of this reaction is one of the main challenges in direct ethanol fuel cells (DEFCs). While TiOC has previously been investigated as catalyst support material only, in this study we show that TiOC alone is able to oxidize ethanol to acetaldehyde without the need of expensive noble metal catalysts like Pt. It is suggested that this behavior is attributed to the presence of both undercoordinated sites, which allow ethanol to adsorb, and oxygenated sites, which facilitate the activation of water. This is a milestone in DEFC research and development and opens up innovative possibilities for the design of catalyst materials for intermediate temperature fuel cells.

Urethane functions can reduce metal salts under hydrothermal conditions: synthesis of noble metal nanoparticles on flexible sponges applied in semi-automated organic reduction.

We report an additive-free one-pot hydrothermal synthesis of Au, Ag, Pd, and alloy AuPd nanoparticles (NPs) anchored on commercial polyurethane (PU) foams. While unable to reduce the precursor metal salts at room temperature, PU is able to serve as a reducing agent under hydrothermal conditions. The resulting NP@PU sponge materials perform comparably to reported state-of-the-art reduction catalysts, and are additionally very well suited for use in semi-automated synthesis: the NP anchoring is strong enough and the support flexible enough to be used as a 'catalytic sponge' that can be manipulated with a robotic arm, i.e., be repeatedly dipped into and drawn out of solutions, wrung out, and re-soaked.

Se Nanopowder Conversion into Lubricious 2D Selenide Layers by Tribochemical Reactions.

Transition metal dichalcogenide (TMD) coatings have attracted enormous scientific and industrial interest due to their outstanding tribological behavior. The paradigmatic example is MoS2 , even though selenides and tellurides have demonstrated superior tribological properties. Here, an innovative in operando conversion of Se nanopowders into lubricious 2D selenides, by sprinkling them onto sliding metallic surfaces coated with Mo and W thin films, is described. Advanced material characterization confirms the tribochemical formation of a thin tribofilm containing selenides, reducing the coefficient of friction down to below 0.1 in ambient air, levels typically reached using fully formulated oils. Ab initio molecular dynamics simulations under tribological conditions reveal the atomistic mechanisms that result in the shear-induced synthesis of selenide monolayers from nanopowders. The use of Se nanopowder provides thermal stability and prevents outgassing in vacuum environments. Additionally, the high reactivity of the Se nanopowder with the transition metal coating in the conditions prevailing in the contact interface yields highly reproducible results, making it particularly suitable for the replenishment of sliding components with solid lubricants, avoiding the long-lasting problem of TMD-lubricity degradation caused by environmental molecules. The suggested straightforward approach demonstrates an unconventional and smart way to synthesize TMDs in operando and exploit their friction- and wear-reducing impact.

Reaction Modes on a Single Catalytic Particle: Nanoscale Imaging and Micro-Kinetic Modeling.

The kinetic behavior of individual Rh(hkl) nanofacets coupled in a common reaction system was studied using the apex of a curved rhodium microcrystal (radius of 0.65 µm) as a model of a single catalytic particle and field electron microscopy for in situ imaging of catalytic hydrogen oxidation. Depending on the extent of interfacet coupling via hydrogen diffusion, different oscillating reaction modes were observed including highly unusual multifrequential oscillations: differently oriented nanofacets oscillated with differing frequencies despite their immediate neighborhood. The transitions between different modes were induced by variations in the particle temperature, causing local surface reconstructions, which create locally protruding atomic rows. These atomic rows modified the coupling strength between individual nanofacets and caused the transitions between different oscillating modes. Effects such as entrainment, frequency locking, and reconstruction-induced collapse of spatial coupling were observed. To reveal the origin of the different experimentally observed effects, microkinetic simulations were performed for a network of 105 coupled oscillators, modeling the individual nanofacets communicating via hydrogen surface diffusion. The calculated behavior of the oscillators, the local frequencies, and the varying degree of spatial synchronization describe the experimental observations well.

Performance modulation through selective, homogenous surface doping of lanthanum strontium ferrite electrodes revealed by in situ PLD impedance measurements.

Accelerating the oxygen reduction kinetics of solid oxide fuel cell (SOFC) cathodes is crucial to improve their efficiency and thus to provide the basis for an economically feasible application of intermediate temperature SOFCs. In this work, minor amounts of Pt were doped into lanthanum strontium ferrite (LSF) thin film electrodes to modulate the material's oxygen exchange performance. Surprisingly, Pt was found to be incorporated on the B-site of the perovskite electrode as non metallic Pt4+. The polarization resistance of LSF thin film electrodes with and without additional Pt surface doping was compared directly after film growth employing in situ electrochemical impedance spectroscopy inside a PLD chamber (i-PLD). This technique enables observation of the polarization resistance of pristine electrodes unaltered by degradation or any external contamination of the electrode surface. Moreover, growth of multi-layers of materials with different compositions on the very same single crystalline electrolyte substrate combined with in situ impedance measurements allow excellent comparability of different materials. Even a 5 nm layer of Pt doped LSF (1.5 at% Pt), i.e. a Pt loading of 80 ng cm-2, improved the polarization resistance by a factor of about 2.5. In addition, p(O2) and temperature dependent impedance measurements on both pure and Pt doped LSF were performed in situ and obtained similar activation energies and p(O2) dependence of the polarization resistance, which allow us to make far reaching mechanistic conclusions indicating that Pt4+ introduces additional active sites.

Microbeam bending of hydrated human cortical bone lamellae from the central region of the body of femur shows viscoelastic behaviour.

Bone is a biological tissue with unique mechanical properties, owing to a complex hierarchical structure ranging from the nanoscale up to the macroscale. To better understand bone mechanics, investigation of mechanical properties of all structural elements at every hierarchical level and how they interact is necessary. Testing of bone structures at the lower microscale, e.g. bone lamellae, has been least performed and remains a challenge. Focused ion beam (FIB) milling is an attractive technique for machining microscopic samples from bone material and performing mechanical testing at the microscale using atomic force microscopy (AFM) and nanoindentation setups. So far, reported studies at this length scale have been performed on bone samples of animal origin, mostly in a dehydrated state, except for one study. Here we present an AFM-based microbeam bending method for performing bending measurements in both dehydrated and rehydrated conditions at the microscale. Single lamella bone microbeams of four human donors, aged 65-94 yrs, were machined via FIB and tested both in air and fully submerged in Hank's Balanced Salt Solution (HBSS) to investigate the effect of (de)hydration and to a certain extent, of age, on bone mechanics. Bending moduli were found to reduce up to 5 times after 2 h of rehydration and no trend of change in bending moduli with respect to age could be observed. Mechanical behavior changed from almost purely elastic to viscoelastic upon rehydration and a trend of lower dissipated energy in samples from older donors could be observed in the rehydrated state. These results confirm directly the importance of water for the mechanical properties of bone tissue at the microscale. Moreover, the trend of lowered capability of energy dissipation in older donors may contribute to a decrease of fracture toughness and thus an increase in bone fragility with age.

Surface Anchoring and Active Sites of [Mo3S13]2- Clusters as Co-Catalysts for Photocatalytic Hydrogen Evolution.

Achieving light-driven splitting of water with high efficiency remains a challenging task on the way to solar fuel exploration. In this work, to combine the advantages of heterogeneous and homogeneous photosystems, we covalently anchor noble-metal- and carbon-free thiomolybdate [Mo3S13]2- clusters onto photoactive metal oxide supports to act as molecular co-catalysts for photocatalytic water splitting. We demonstrate that strong and surface-limited binding of the [Mo3S13]2- to the oxide surfaces takes place. The attachment involves the loss of the majority of the terminal S2 2- groups, upon which Mo-O-Ti bonds with the hydroxylated TiO2 surface are established. The heterogenized [Mo3S13]2- clusters are active and stable co-catalysts for the light-driven hydrogen evolution reaction (HER) with performance close to the level of the benchmark Pt. Optimal HER rates are achieved for 2 wt % cluster loadings, which we relate to the accessibility of the TiO2 surface required for efficient hole scavenging. We further elucidate the active HER sites by applying thermal post-treatments in air and N2. Our data demonstrate the importance of the trinuclear core of the [Mo3S13]2- cluster and suggest bridging S2 2- and vacant coordination sites at the Mo centers as likely HER active sites. This work provides a prime example for the successful heterogenization of an inorganic molecular cluster as a co-catalyst for light-driven HER and gives the incentive to explore other thio(oxo)metalates.

Who Does the Job? How Copper Can Replace Noble Metals in Sustainable Catalysis by the Formation of Copper-Mixed Oxide Interfaces.

Following the need for an innovative catalyst and material design in catalysis, we provide a comparative approach using pure and Pd-doped LaCu x Mn1-x O3 (x = 0.3 and 0.5) perovskite catalysts to elucidate the beneficial role of the Cu/perovskite and the promoting effect of Cu y Pd x /perovskite interfaces developing in situ under model NO + CO reaction conditions. The observed bifunctional synergism in terms of activity and N2 selectivity is essentially attributed to an oxygen-deficient perovskite interface, which provides efficient NO activation sites in contact with in situ exsolved surface-bound monometallic Cu and bimetallic CuPd nanoparticles. The latter promotes the decomposition of the intermediate N2O at low temperatures, enhancing the selectivity toward N2. We show that the intelligent Cu/perovskite interfacial design is the prerequisite to effectively replace noble metals by catalytically equally potent metal-mixed-oxide interfaces. We have provided the proof of principle for the NO + CO test reaction but anticipate the extension to a universal concept applicable to similar materials and reactions.