Promoting Polysulfide Redox Reactions through Electronic Spin Manipulation.

Catalytic additives able to accelerate the lithium-sulfur redox reaction are a key component of sulfur cathodes in lithium-sulfur batteries (LSBs). Their design focuses on optimizing the charge distribution within the energy spectra, which involves refinement of the distribution and occupancy of the electronic density of states. Herein, beyond charge distribution, we explore the role of the electronic spin configuration on the polysulfide adsorption properties and catalytic activity of the additive.

Implementing magnetically-active Sn-based nanocomposites in hexavalent chromium removal from drinking water.

A novel nanocomposite consisting of FeO-loaded tin oxyhydroxy-chloride is demonstrated as an efficient adsorbent for the removal of hexavalent chromium in compliance to the new drinking water regulation. This study introduces a continuous-flow production of the nanocomposite through the separate synthesis of (i) 40 nm FeO nanoparticles and (ii) multilayered spherical arrangements of a tin hydroxy-chloride identified as abhurite, before the application of a wet-blending process. The homogeneous distribution of FeO nanoparticles on the abhurite's morphology, features nanocomposite with magnetic response whereas the 10 % loaded nanocomposite preserves a Cr(VI) uptake capacity of 7.

Enhanced Oxygen Evolution and Zinc-Air Battery Performance via Electronic Spin Modulation in Heterostructured Catalysts.

Beyond optimizing electronic energy levels, the modulation of the electronic spin configuration is an effective strategy, often overlooked, to boost activity and selectivity in a range of catalytic reactions, including the oxygen evolution reaction (OER). This electronic spin modulation is frequently accomplished using external magnetic fields, which makes it impractical for real applications. Herein, spin modulation is achieved by engineering Ni/MnFeO heterojunctions, whose surface is reconstructed into NiOOH/MnFeOOH during the OER.

Electronic Spin Alignment within Homologous NiS/NiSe Heterostructures to Promote Sulfur Redox Kinetics in Lithium-Sulfur Batteries.

The catalytic activation of the Li-S reaction is fundamental to maximize the capacity and stability of Li-S batteries (LSBs). Current research on Li-S catalysts mainly focuses on optimizing the energy levels to promote adsorption and catalytic conversion, while frequently overlooking the electronic spin state influence on charge transfer and orbital interactions. Here, hollow NiS/NiSe heterostructures encapsulated in a nitrogen-doped carbon matrix (NiS/NiSe@NC) are synthesized and used as a catalytic additive in sulfur cathodes.

Evaluation of Sputtering Processes in Strontium Iridate Thin Films.

The growth of epitaxial thin films from the Ruddlesden-Popper series of strontium iridates by magnetron sputtering is analyzed. It was found that, even using a non-stoichiometric target, the films formed under various conditions were consistently of the perovskite-like n = ∞ SrIrO phase, with no evidence of other RP series phases. A detailed inspection of the temperature-oxygen phase diagram underscored that kinetics mechanisms prevail over thermodynamics considerations.

Tuning the superconducting performance of YBaCuO films through field-induced oxygen doping.

The exploration of metal-insulator transitions to produce field-induced reversible resistive switching effects has been a longstanding pursuit in materials science. Although the resistive switching effect in strongly correlated oxides is often associated with the creation or annihilation of oxygen vacancies, the underlying mechanisms behind this phenomenon are complex and, in many cases, still not clear. This study focuses on the analysis of the superconducting performance of cuprate YBaCuO (YBCO) devices switched to different resistive states through gate voltage pulses.

Tin Oxide Nanoparticles via Solar Vapor Deposition for Hexavalent Chromium Remediation.

Tin oxide nanoparticles optimized to capture low concentrations of hexavalent chromium from water were developed through a facile, scalable, and low-cost one-step solar vapor deposition methodology. Considering the preservation of high electron donation capacity as the key to support the reduction of mobile Cr(VI) into insoluble forms, the growth of SnO nanoparticles was favored by the co-evaporation of SnO with Fe powders at various mass ratios. Characterization techniques indicated that the percentage and the stability of SnO is proportional to the Fe content in the target with a requirement of at least 50% wt to inhibit the formation of a passive SnO surface layer.

Identifying the Role of the Cationic Geometric Configuration in Spinel Catalysts for Polysulfide Conversion in Sodium-Sulfur Batteries.

An ABX spinel structure, with tetrahedral A and octahedral B sites, is a paradigmatic class of catalysts with several possible geometric configurations and numerous applications, including polysulfide conversion in metal-sulfur batteries. Nonetheless, the influence of the geometric configuration and composition on the mechanisms of catalysis and the precise manner in which spinel catalysts facilitate the conversion of polysulfides remain unknown. To enable controlled exposure of single active configurations, herein, Co and Co in CoO catalysts for sodium polysulfide conversion are in large part replaced by Fe and Fe, respectively, generating FeCoO and CoFeO.

Spin-to-Charge Conversion in All-Oxide LaSrMnO/SrIrO Heterostructures.

Spin injection and spin-charge conversion processes in all-oxide LaSrMnO/SrIrO (LSMO/SIO) heterostructures with different SIO layer thickness and interfacial features have been studied. Ferromagnetic resonance (FMR) technique has been used to generate pure spin currents by spin pumping (SP) in ferromagnetic (FM) half-metallic LSMO. The change of the resonance linewidth in bare LSMO layers and LSMO/SIO heterostructures suggests a successful spin injection into the SIO layers.

Sulfate-Decorated Amorphous-Crystalline Cobalt-Iron Oxide Nanosheets to Enhance O-O Coupling in the Oxygen Evolution Reaction.

The electrochemical oxygen evolution reaction (OER) plays a fundamental role in several energy technologies, which performance and cost-effectiveness are in large part related to the used OER electrocatalyst. Herein, we detail the synthesis of cobalt-iron oxide nanosheets containing controlled amounts of well-anchored SO anionic groups (CoFeO-SO). We use a cobalt-based zeolitic imidazolate framework (ZIF-67) as the structural template and a cobalt source and Mohr's salt ((NH)Fe(SO)·6HO) as the source of iron and sulfate.

Artificial Graphene Spin Polarized Electrode for Magnetic Tunnel Junctions.

2D materials offer the ability to expose their electronic structure to manipulations by a proximity effect. This could be harnessed to craft properties of 2D interfaces and van der Waals heterostructures in devices and quantum materials. We explore the possibility to create an artificial spin polarized electrode from graphene through proximity interaction with a ferromagnetic insulator to be used in a magnetic tunnel junction (MTJ).

X-ray Absorption Spectroscopy Study of Thickness Effects on the Structural and Magnetic Properties of PrNiMnO Double Perovskite Thin Films.

In this work, we report a systematic study of the influence of film thickness on the structural and magnetic properties of epitaxial thin films of PrNiMnO (PNMO) double perovskite grown on top of two different (001)-SrTiO and (001)-LaAlO substrates by RF magnetron sputtering. A strong dependence of the structural and magnetic properties on the film thickness is found. The ferromagnetic transition temperature () and saturation magnetization (s) are found to decrease when reducing the film thickness.

Spin Effect to Promote Reaction Kinetics and Overall Performance of Lithium-Sulfur Batteries under External Magnetic Field.

Lithium-sulfur batteries (LSBs) are still limited by the shuttle of lithium polysulfides (LiPS) and the slow Li-S reaction. Herein, we demonstrate that when using cobalt sulfide as a catalytic additive, an external magnetic field generated by a permanent magnet can significantly improve the LiPS adsorption ability and the Li-S reaction kinetics. More specifically, the results show both experimentally and theoretically how an electron spin polarization of Co ions reduces electron repulsion and enhances the degree of orbital hybridization, thus resulting in LSBs with unprecedented performance and stability.

Optimization of the Growth Process of Double Perovskite PrNiMnO Epitaxial Thin Films by RF Sputtering.

Epitaxial thin films of PrNiMnO (PNMO) double perovskite were grown on (001)-oriented SrTiO substrates by RF magnetron sputtering. The influence of the growth parameters (oxygen pressure, substrate temperature, and annealing treatments) on the structural, magnetic and transport properties, and stoichiometry of the films was thoroughly investigated. It is found that high-quality epitaxial, insulating, and ferromagnetic PNMO thin films can only be obtained in a narrow deposition parameter window.

Suppression of spin rectification effects in spin pumping experiments.

Spin pumping (SP) is a well-established method to generate pure spin currents allowing efficient spin injection into metals and semiconductors avoiding the problem of impedance mismatch. However, to disentangle pure spin currents from parasitic effects due to spin rectification effects (SRE) is a difficult task that is seriously hampering further developments. Here we propose a simple method that allows suppressing SRE contribution to inverse spin Hall effect (ISHE) voltage signal avoiding long and tedious angle-dependent measurements.

Hydrotalcite-Embedded Magnetite Nanoparticles for Hyperthermia-Triggered Chemotherapy.

A magnetic nanocomposite, consisting of FeO nanoparticles embedded into a Mg/Al layered double hydroxide (LDH) matrix, was developed for cancer multimodal therapy, based on the combination of local magnetic hyperthermia and thermally induced drug delivery. The synthesis procedure involves the sequential hydrolysis of iron salts (Fe, Fe) and Mg/Al nitrates in a carbonate-rich mild alkaline environment followed by the loading of 5-fluorouracil, an anionic anticancer drug, in the interlayer LDH space. Magnetite nanoparticles with a diameter around 30 nm, dispersed in water, constitute the hyperthermia-active phase able to generate a specific loss of power of around 500 W/g-Fe in an alternating current (AC) magnetic field of 24 kA/m and 300 kHz as determined by AC magnetometry and calorimetric measurements.

Formation of Nickel Oxide Nanocuboids in Ferromagnetic LaNiMnO.

The control of the spontaneous formation of nanostructures at the surface of thin films is of strong interest in many different fields, from catalysts to microelectronics, because surface and interfacial properties may be substantially enhanced. Here, we analyze the formation of nickel oxide nanocuboids on top of LaNiMnO double perovskite ferromagnetic thin films, epitaxially grown on SrTiO (001) substrates by radio-frequency (RF) magnetron sputtering. We show that, by annealing the films at high temperature under high oxygen partial pressure, the spontaneous segregation of nanocuboids is enhanced.

Spontaneous in-flight assembly of magnetic nanoparticles into macroscopic chains.

Knowing the interactions controlling aggregation processes in magnetic nanoparticles is of strong interest in preventing or promoting nanoparticles' aggregation at wish for different applications. Dipolar magnetic interactions, proportional to the particle volume, are identified as the key driving force behind the formation of macroscopic aggregates for particle sizes above about 20 nm. However, aggregates' shape and size are also strongly influenced by topological ordering.

The use of Sn(II) oxy-hydroxides for the effective removal of Cr(VI) from water: Optimization of synthesis parameters.

The development of a novel adsorbent based on Sn(II) oxy-hydroxide nanoparticles and the optimization of main synthesis parameters was examined for the efficient removal of hexavalent chromium at low residual concentration levels. The aqueous hydrolysis of Sn(II) salts in a continuous-flow process was evaluated as an effective method to synthesize an appropriate material able to operate both as an electron donor for Cr(VI) reduction, and provide a suitable crystal structure that favors strong complexation with the formed Cr(III) species. Experimental results revealed that the main hydrolysis parameters, such as pH value and tin origin/source, can be used to determine the chemical formula of the produced materials and thereby, eventually improve their uptake capacity for Cr(VI).

One-Step Route to Iron Oxide Hollow Nanocuboids by Cluster Condensation: Implementation in Water Remediation Technology.

The fabrication procedure of hollow iron oxide nanoparticles with a large surface to volume ratio by a single-step gas condensation process at ambient temperature is presented. Fe clusters formed during the sputtering process are progressively transformed into hollow cuboids with oxide shells by the Kirkendall mechanism at the expense of oxygen captured inside the deposition chamber. TEM and Raman spectroscopy techniques point to magnetite as the main component of the nanocuboids; however, the magnetic behavior exhibited by the samples suggests the presence of FeO as well.

Self-Arranged Misfit Dislocation Network Formation upon Strain Release in La0.7Sr0.3MnO3/LaAlO3(100) Epitaxial Films under Compressive Strain.

Lattice-mismatched epitaxial films of La0.7Sr0.3MnO3 (LSMO) on LaAlO3 (001) substrates develop a crossed pattern of misfit dislocations above a critical thickness of 2.

Macroscopic evidence of nanoscale resistive switching in La2/3Sr1/3MnO3 micro-fabricated bridges.

In this work we report on a combined macro, micro and nanoscale investigation where electronic transport properties through La⅔Sr⅓MnO3 (LSMO) microfabricated bridges, in which nano-sized resistive states are induced by using a conducting scanning probe microscope (C-SPM), are analyzed. The strategy intentionally avoids the standard capacitor-like geometry, thus allowing the study of the electronic transport properties of the locally modified region, and approaches the integration of functional oxides in low dimensional devices while providing macroscopic evidence of nanoscale resistive switching (RS). The metallic and ferromagnetic LSMO is locally modified from its low resistance state (LRS) to a high resistance state (HRS) when a bias voltage is applied on its surface through the conducting tip, which acts as a mobile electrode.

Competing misfit relaxation mechanisms in epitaxial correlated oxides.

Strain engineering of functional properties in epitaxial thin films of strongly correlated oxides exhibiting octahedral-framework structures is hindered by the lack of adequate misfit relaxation models. Here we present unreported experimental evidence of a four-stage hierarchical development of octahedral-framework perturbations resulting from a progressive imbalance between electronic, elastic, and octahedral tilting energies in La(0.7)Sr(0.

Spontaneous formation of hollow cobalt oxide nanoparticles by the Kirkendall effect at room temperature at the water-air interface.

We observe the spontaneous formation of hollow cobalt oxide nanoparticles at room temperature, indicating an enhancement of the solid-state diffusion at the nanoscale. Single crystal cobalt nanoparticles covered by a hydrophobic organic layer were transformed spontaneously into CoO hollow nanoparticles when deposited on the water-air interface in a matter of a few hours. The presence of water modifies the reactivity on the nanoparticle surface favoring the formation of the hollow structure; otherwise Co-CoO core-shell nanoparticles are obtained.

Thermal, dielectrical and mechanical response of α and β-poly(vinilydene fluoride)/Co-MgO nanocomposites.

Nanocomposites of the self-forming core-shell Co-MgO nanoparticles, which were of approximately 100 nm in diameter, and poly(vinylidene fluoride) (PVDF) polymer have been prepared. When the polymer is crystallized in the α-phase, the introduction of the nanoparticles leads to nucleation of the γ-phase of PVDF, increasing also the melting temperature of the polymer. With the introduction of the Co-MgO particles, the dielectric constant of the material slightly increases and the storage modulus decreases with respect to the values obtained for the pure polymer.