Electronic Spin Alignment within Homologous NiS2/NiSe2 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 NiS2/NiSe2 heterostructures encapsulated in a nitrogen-doped carbon matrix (NiS2/NiSe2@NC) are synthesized and used as a catalytic additive in sulfur cathodes. The NiS2/NiSe2 heterostructure promotes the spin splitting of the 3d orbital, driving the Ni3+ transformation from low to high spin. This high spin configuration raises the electronic energy level and activates the electronic state. This accelerates the charge transfer and optimizes the adsorption energy, lowering the reaction energy barrier of the polysulfides conversion. Benefiting from these characteristics, LSBs based on NiS2/NiSe2@NC/S cathodes exhibit high initial capacity (1458 mAh·g⁻1 at 0.1C), excellent rate capability (572 mAh·g⁻1 at 5C), and stable cycling with an average capacity decay rate of only 0.025% per cycle at 1C during 500 cycles. Even at high sulfur loadings (6.2 mg·cm⁻2), high initial capacities of 1173 mAh·g⁻1 (7.27 mAh·cm⁻2) are measured at 0.1C, and 1058 mAh·g⁻1 is retained after 300 cycles.

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 = ∞ SrIrO3 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. The analysis of the angular distribution of sputtered iridium and strontium species indicated clearly different spatial distribution patterns. Additionally, significant backsputtering was detected at elevated temperatures. Thus, it is assumed that the interplay between these two kinetic phenomena is at the origin of the preferential nucleation of the SrIrO3 phase. In addition, strategies for controlling cation stoichiometry off-axis have also been explored. Finally, the long-term stability of the films has been demonstrated.

Tuning the superconducting performance of YBa2Cu3O7-δ 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 YBa2Cu3O7-δ (YBCO) devices switched to different resistive states through gate voltage pulses. The goal is to evaluate the effect of field-induced oxygen diffusion on the magnetic field and angular dependence of the critical current density and identify the role of induced defects in the switching performance. Transition electron microscopy measurements indicate that field-induced transition to high resistance states occurs through the generation of YBa2Cu4O7 (Y124) intergrowths with a large amount of oxygen vacancies, in agreement with the obtained critical current density dependences. These results have significant implications for better understanding the mechanisms of field-induced oxygen doping in cuprate superconductors and their role on the superconducting performance.

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 SnO2 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 SnO2 surface layer. The produced particles were evaluated regarding their efficiency to capture Cr(VI) under conditions similar to water treatment for drinking purposes (pH 7). It was revealed that passivation-free SnO nanoparticles deliver significant improvement in the adsorption capacity corresponding to the residual concentration of 25 µg/L, reaching a value of 1.74 mg/g for the sample prepared with 50% wt Fe in the target. The increase of water acidity was found responsible for the activation of more reduction sites on the particle surface, as reflected through the elevation of efficiency by more than 20% at pH 6.

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

An AB2X4 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, Cotd2+ and Cooh3+ in Co3O4 catalysts for sodium polysulfide conversion are in large part replaced by Fetd2+ and Feoh3+, respectively, generating FeCo2O4 and CoFe2O4. Through an examination of electrochemical activation energies, the characterization of symmetric cells, and theoretical calculations, we determine that Cooh3+ serves as the active site for the breaking of S-S bonds, while Cotd2+ functions as the active site for the formation of S-Na bonds. The current study underlines the subtle relationship between activity and geometric configurations of spinel catalysts, providing unique insights for the rational development of improved catalysts by optimizing their atomic geometric configuration.

Spin-to-Charge Conversion in All-Oxide La2/3Sr1/3MnO3/SrIrO3 Heterostructures.

Spin injection and spin-charge conversion processes in all-oxide La2/3Sr1/3MnO3/SrIrO3 (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. However, low values of the spin mixing conductance, compared to more traditional permalloy (Py)/Pt or yttrium iron garnet (YIG)/Pt systems, are found. A thorough analysis of the interfaces by high-resolution scanning transmission electron microscopy (HR-STEM) imaging suggests that they are structurally clean and atomic sharp, but a compositional analysis by energy-dispersive X-ray spectroscopy (EDS) reveals the interdiffusion of La, Ir, and Mn atomic species in the first atomic layers close to the interface. Inverse spin Hall effect (ISHE) measurements evidence that interfacial features play a very relevant role in controlling the effectiveness of the spin injection process and low transversal ISHE voltage signals are detected. In addition, it is found that larger voltage signals are detected for the lowest SIO layer thickness highlighting the role of the spin diffusion length (λsd)/SIO layer thickness ratio. The values of ISHE voltage are rather low but allow us to determine the spin Hall angle of SIO (θSH ≈ 1.12% at T = 250 K), which is remarkably similar to that obtained for the well-known Py/Pt system, therefore suggesting that SIO could be a promising spin-Hall material.

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). Ferromagnetic insulator/graphene artificial electrodes were fabricated and integrated in MTJs based on spin analyzers. Evidence of the emergence of spin polarization in proximitized graphene layers was observed through the occurrence of tunnel magnetoresistance. We deduced a spin dependent splitting of graphene's Dirac band structure (∼15 meV) induced by the proximity effect, potentially leading to full spin polarization and opening the way to gating. The extracted spin signals illustrate the potential of 2D quantum materials based on proximity effects to craft spintronics functionalities, from vertical MTJs memory cells to logic circuits.

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 SO42- anionic groups (CoFexOy-SO4). We use a cobalt-based zeolitic imidazolate framework (ZIF-67) as the structural template and a cobalt source and Mohr's salt ((NH4)2Fe(SO4)2·6H2O) as the source of iron and sulfate. When combining the ZIF-67 with ammonium iron sulfate, the protons produced by the ammonium ion hydrolysis (NH4+ + H2O = NH3·H2O + H+) etch the ZIF-67, dissociating its polyhedron structure, and form porous assemblies of two-dimensional nanostructures through a diffusion-controlled process. At the same time, iron ions partially replace cobalt within the structure, and SO42- ions are anchored on the material surface by exchange with organic ligands. As a result, ultrathin CoFexOy-SO4 nanosheets are obtained. The proposed synthetic procedure enables controlling the amount of Fe and SO4 ions and analyzing the effect of each element on the electrocatalytic activity. The optimized CoFexOy-SO4 material displays outstanding OER activity with a 10 mA cm-2 overpotential of 268 mV, a Tafel slope of 46.5 mV dec-1, and excellent stability during 62 h. This excellent performance is correlated to the material's structural and chemical parameters. The assembled nanosheet structure is characterized by a large electrochemically active surface area, a high density of reaction sites, and fast electron transportation. Meanwhile, the introduction of iron increases the electrical conductivity of the catalysts and provides fast reaction sites with optimum bond energy and spin state for the adsorption of OER intermediates. The presence of sulfate ions at the catalyst surface modifies the electronic energy level of active sites, regulates the adsorption of intermediates to reduce the OER overpotential, and promotes the surface charge transfer, which accelerates the formation of oxygenated intermediates. Overall, the present work details the synthesis of a high-efficiency OER electrocatalyst and demonstrates the introduction of nonmetallic anionic groups as an excellent strategy to promote electrocatalytic activity in energy conversion technologies.

X-ray Absorption Spectroscopy Study of Thickness Effects on the Structural and Magnetic Properties of Pr2-δNi1-xMn1+xO6-y 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 Pr2-δNi1-xMn1+xO6-y (PNMO) double perovskite grown on top of two different (001)-SrTiO3 and (001)-LaAlO3 substrates by RF magnetron sputtering. A strong dependence of the structural and magnetic properties on the film thickness is found. The ferromagnetic transition temperature (TC) and saturation magnetization (Ms) are found to decrease when reducing the film thickness. In our case, the thinnest films show a loss of ferromagnetism at the film-substrate interface. In addition, the electronic structure of some characteristic PNMO samples is deeply analyzed using X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) measurements and compared with theoretical simulations. Our results show that the oxidation states of Ni and Mn ions are stabilized as Ni2+ and Mn4+, thus the ferromagnetism is mainly due to Ni2+-O-Mn4+ superexchange interactions, even in samples with poor ferromagnetic properties. XMCD results also make evident large variations on the spin and orbital contributions to the magnetic moment as the film's thickness decreases.

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. Under an external magnetic field, LSBs with 0.0084 % per cycle decay rate at 2 C during 8150 cycles are produced. Overall, this work not only demonstrates an effective strategy to promote LiPS adsorption and electrochemical conversion in LSBs at no additional energy cost but also enriches the application of the spin effect in the electrocatalysis fields.

Optimization of the Growth Process of Double Perovskite Pr2-δNi1-xMn1+xO6-y Epitaxial Thin Films by RF Sputtering.

Epitaxial thin films of Pr2-δNi1-xMn1+xO6-y (PNMO) double perovskite were grown on (001)-oriented SrTiO3 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. It is shown that a careful selection of the growth conditions allows for obtaining a high degree of Ni/Mn cation ordering, which is reflected in the values of the Curie temperature, TC, and saturation magnetization, MS, which are very close to those of bulk material.

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. We show an experimental study in the well-known Py/Pt system by using a coplanar waveguide (CPW). Results obtained demonstrate that the sign and size of the measured transverse voltage signal depends on the width of the sample along the CPW active line. A progressive reduction of this width evidences that SRE contribution to the measured transverse voltage signal becomes negligibly small for sample width below 200 µm. A numerical solution of the Maxwell equations in the CPW-sample setup, by using the Landau-Lifshitz equation with the Gilbert damping term (LLG) as the constitutive equation of the media, and with the proper set of boundary conditions, confirms the obtained experimental results.

Hydrotalcite-Embedded Magnetite Nanoparticles for Hyperthermia-Triggered Chemotherapy.

A magnetic nanocomposite, consisting of Fe3O4 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 (Fe2+, Fe3+) and Mg2+/Al3+ 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. Heat transfer was found to trigger a very rapid release of drug which reached 80% of the loaded mass within 10 min exposure to the applied field. The potential of the Fe3O4/LDH nanocomposites as cancer treatment agents with minimum side-effects, owing to the exclusive presence of inorganic phases, was validated by cell internalization and toxicity assays.

Formation of Nickel Oxide Nanocuboids in Ferromagnetic La2Ni1-xMn1+xO6.

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 La2Ni1-xMn1+xO6 double perovskite ferromagnetic thin films, epitaxially grown on SrTiO3 (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. The evolution of the structural and magnetic properties of the films is studied as a function of the annealing treatments at different temperatures. It is shown that the formation of NiOx nanocuboids leads to a nanostructured film surface with regions of locally different electrical transport characteristics.

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. 1-D macroscopic chains of several micrometer lengths are obtained with cube-shaped magnetic nanoparticles prepared by the gas-aggregation technique. Using an analytical model and molecular dynamics simulations, the energy landscape of interacting cube-shaped magnetic nanoparticles is analysed revealing unintuitive dependence of the force acting on particles with the displacement and explaining pathways leading to their assembly into long linear chains. The mechanical behaviour and magnetic structure of the chains are studied by a combination of atomic and magnetic force measurements, and computer simulation. The results demonstrate that [111] magnetic anisotropy of the cube-shaped nanoparticles strongly influences chain assembly features.

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). Among the tested sorbent materials, the synthetic nanostructured hydroromarchite, Sn6O4(OH)4, prepared by the hydrolysis of SnCl2 in a highly acidic environment (pH2), was deemed the best sorbent material and it was further investigated for its Cr(VI) uptake performance under reliable conditions (column experiments) for drinking water treatment. Specifically, Rapid Small-Scale (laboratory) Column Tests indicated that aggregates of the Sn6O4(OH)4 nanomaterial can achieve a maximum uptake capacity of around 19mg/g, keeping the levels of outflow Cr(VI) below 10µg/L during the treatment of natural-like water at pH7. The high efficiency is mainly attributed to the stabilization of Sn(II) content in nanoparticles, as well as the improved surface charge density, reaching 1.0mmol[OH-]/g, whereas the obtained thermodynamic data indicate a combined reduction-sorption process. The latter aspect was further verified by XPS, showing that even in the highly-loaded sorbent materials with adsorbed chromium, its trivalent form is the predominant one. These specific characteristics suggest that the product is a more favorable candidate for wider applications in water treatment units, regarding Cr(VI) removal, compared to other examined sorbent materials.

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. In addition, these particles showed strong stability after several months of exposure to ambient conditions, making them of potential interest in diverse technological applications. In particular, these hierarchical hollow particles turned out to be very efficient for both As(III) and As(V) absorption (326 and 190 mg/g, respectively), thus making them of strong interest for drinking water remediation.

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 2.5 nm. Upon film thickness increases, the dislocation density progressively increases, and the dislocation spacing distribution becomes narrower. At a film thickness of 7.0 nm, the misfit dislocation density is close to the saturation for full relaxation. The misfit dislocation arrangement produces a 2D lateral periodic structure modulation (Λ ≈ 16 nm) alternating two differentiated phases: one phase fully coherent with the substrate and a fully relaxed phase. This modulation is confined to the interface region between film and substrate. This phase separation is clearly identified by X-ray diffraction and further proven in the macroscopic resistivity measurements as a combination of two transition temperatures (with low and high Tc). Films thicker than 7.0 nm show progressive relaxation, and their macroscopic resistivity becomes similar than that of the bulk material. Therefore, this study identifies the growth conditions and thickness ranges that facilitate the formation of laterally modulated nanocomposites with functional properties notably different from those of fully coherent or fully relaxed material.

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. Starting from a metallic oxide the electroforming process is not required, thus avoiding one of the major drawbacks for the implementation of memory devices based on RS phenomena. The application of a bias voltage generates an electric field that promotes charge depletion, leading to a strong increase of the resistance, i.e. to the HRS. This effect is not only confined to the outermost surface layer, its spatial extension and final HRS condition can be modulated by the magnitude and duration of the potential applied, opening the door to the implementation of multilevel devices. In addition, the half-metallic character, i.e. total spin polarization, of LSMO might allow the implementation of memory elements and active spintronic devices in the very same material. The stability of the HRS and LRS as a function of temperature, magnetic field and compliance current is also analyzed, allowing the characterization of the nature of the switching process and the active material.

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(0.3)MnO(3) epitaxial thin films grown on SrTiO(3) substrates. Electronic softening of the Mn-O bonds near the substrate leads to the formation of an interfacial layer clamped to the substrate with strongly degraded magnetotransport properties, i.e., the so-called dead layer, while rigid octahedral tilts become relevant at advanced growth stages without significant effects on charge transport and magnetic ordering.