Persistent Structure and Frustrated Magnetism in High Entropy Rare-Earth Zirconates.

The configurational complexity and distinct local atomic environments of high entropy oxides remain largely unexplored, leaving structure-property relationships and the hypothesis that the family offers rich tunability for applications ambiguous. This work investigates the influence of cation size and materials synthesis in determining the resulting structure and magnetic properties of a family of high entropy rare-earth zirconates (HEREZs, nominal composition RE2 Zr2 O7 with RE = rare-earth element combinations including Eu, Gd, Tb, Dy, Ho, La, or Sc). The structural characterization of the series is examined through synchrotron X-ray diffraction and pair distribution function analysis, and electron microscopy, demonstrating average defect-fluorite structures with considerable local disorder, in all samples. The surface morphology and particle sizes are found to vary significantly with preparation method, with irregular micron-sized particles formed by high temperature sintering routes, spherical nanoparticles resulting from chemical co-precipitation methods, and porous nanoparticle agglomerates resulting from polymer steric entrapment synthesis. In agreement with the disordered cation distribution found across all samples, magnetic measurements indicate that all synthesized HEREZs show frustrated magnetic behavior, as seen in a number of single-component RE2 Zr2 O7 pyrochlore oxides. These findings advance the understanding of the local structure of high entropy oxides and demonstrate strategies for designing nanostructured morphologies in the class.

Nanostructured core-shell metal borides-oxides as highly efficient electrocatalysts for photoelectrochemical water oxidation.

Oxygen evolution reaction (OER) catalysts are critical components of photoanodes for photoelectrochemical (PEC) water oxidation. Herein, nanostructured metal boride MB (M = Co, Fe) electrocatalysts, which have been synthesized by a Sn/SnCl2 redox assisted solid-state method, were integrated with WO3 thin films to build heterojunction photoanodes. As-obtained MB modified WO3 photoanodes exhibit enhanced charge carrier transport, amended separation of photogenerated electrons and holes, prolonged hole lifetime and increased charge carrier density. Surface modification of CoB and FeB significantly enhances the photocurrent density of WO3 photoanodes from 0.53 to 0.83 and 0.85 mA cm-2, respectively, in transient chronoamperometry (CA) at 1.23 V vs. RHE (VRHE) under interrupted illumination in 0.1 M Na2SO4 electrolyte (pH 7), corresponding to an increase of 1.6 relative to pristine WO3. In contrast, the pristine MB thin film electrodes do not produce noticeable photocurrent during water oxidation. The metal boride catalysts transform in situ to a core-shell structure with a metal boride core and a metal oxide (MO, M = Co, Fe) surface layer. When coupled to WO3 thin films, the CoB@CoOx nanostructures exhibit a higher catalytic enhancement than corresponding pure cobalt borate (Co-Bi) and cobalt hydroxide (Co(OH)x) electrocatalysts. Our results emphasize the role of the semiconductor-electrocatalyst interface for photoelectrodes and their high dependency on materials combination.

Highly Efficient Spin-Orbit Torque and Switching of Layered Ferromagnet Fe3GeTe2.

Among van der Waals (vdW) layered ferromagnets, Fe3GeTe2 (FGT) is an excellent candidate material to form FGT/heavy metal heterostructures for studying the effect of spin-orbit torques (SOT). Its metallicity, strong perpendicular magnetic anisotropy built in the single atomic layers, relatively high Curie temperature (Tc ∼ 225 K), and electrostatic gate tunability offer a tantalizing possibility of achieving the ultimate high SOT limit in monolayer all-vdW nanodevices. In this study, we fabricate heterostructures of FGT/Pt with 5 nm of Pt sputtered onto the atomically flat surface of ∼15-23 nm exfoliated FGT flakes. The spin current generated in Pt exerts a damping-like SOT on FGT magnetization. At ∼2.5 × 1011 A/m2 current density, SOT causes the FGT magnetization to switch, which is detected by the anomalous Hall effect of FGT. To quantify the SOT effect, we measure the second harmonic Hall responses as the applied magnetic field rotates the FGT magnetization in the plane. Our analysis shows that the SOT efficiency is comparable with that of the best heterostructures containing three-dimensional (3D) ferromagnetic metals and much larger than that of heterostructures containing 3D ferrimagnetic insulators. Such large efficiency is attributed to the atomically flat FGT/Pt interface, which demonstrates the great potential of exploiting vdW heterostructures for highly efficient spintronic nanodevices.

A Simple, General Synthetic Route toward Nanoscale Transition Metal Borides.

Most nanomaterials, such as transition metal carbides, phosphides, nitrides, chalcogenides, etc., have been extensively studied for their various properties in recent years. The similarly attractive transition metal borides, on the contrary, have seen little interest from the materials science community, mainly because nanomaterials are notoriously difficult to synthesize. Herein, a simple, general synthetic method toward crystalline transition metal boride nanomaterials is proposed. This new method takes advantage of the redox chemistry of Sn/SnCl2 , the volatility and recrystallization of SnCl2 at the synthesis conditions, as well as the immiscibility of tin with boron, to produce crystalline phases of 3d, 4d, and 5d transition metal nanoborides with different morphologies (nanorods, nanosheets, nanoprisms, nanoplates, nanoparticles, etc.). Importantly, this method allows flexibility in the choice of the transition metal, as well as the ability to target several compositions within the same binary phase diagram (e.g., Mo2 B, α-MoB, MoB2 , Mo2 B4 ). The simplicity and wide applicability of the method should enable the fulfillment of the great potential of this understudied class of materials, which show a variety of excellent chemical, electrochemical, and physical properties at the microscale.

Graphene- and Phosphorene-like Boron Layers with Contrasting Activities in Highly Active Mo2B4 for Hydrogen Evolution.

Two different boron layers, flat (graphene-like) and puckered (phosphorene-like), found in the crystal structure of Mo2B4 show drastically different activities for hydrogen evolution, according to Gibbs free energy calculations of H-adsorption on Mo2B4. The graphene-like B layer is highly active, whereas the phosphorene-like B layer performs very poorly for hydrogen evolution. A new Sn-flux synthesis permits the rapid single-phase synthesis of Mo2B4, and electrochemical analyses show that it is one of the best hydrogen evolution reaction active bulk materials with good long-term cycle stability under acidic conditions. Mo2B4 compensates its smaller density of active sites if compared with highly active bulk MoB2 (which contains only the more active graphene-like boron layers) by a 5-times increase of its surface area.