Nanostructures of the conducting polymer poly(3,4-ethylenedioxythiophene) with large surface areas enhance the performance of energy storage devices such as electrochemical supercapacitors. However, until now, high aspect ratio nanofibers of this polymer could only be deposited from the vapor-phase, utilizing extrinsic hard templates such as electrospun nanofibers and anodized aluminum oxide. These routes result in low conductivity and require postsynthetic template removal, conditions that stifle the development of conducting polymer electronics. Here we introduce a simple process that overcomes these drawbacks and results in vertically directed high aspect ratio poly(3,4-ethylenedioxythiophene) nanofibers possessing a high conductivity of 130 S/cm. Nanofibers deposit as a freestanding mechanically robust film that is easily processable into a supercapacitor without using organic binders or conductive additives and is characterized by excellent cycling stability, retaining more than 92% of its initial capacitance after 10,000 charge/discharge cycles. Deposition of nanofibers on a hard carbon fiber paper current collector affords a highly efficient and stable electrode for a supercapacitor exhibiting gravimetric capacitance of 175 F/g and 94% capacitance retention after 1000 cycles.

A major challenge in the field of water electrolysis is the scarcity of oxygen-evolving catalysts that are inexpensive, highly corrosion-resistant, suitable for large-scale applications and able to oxidize water at high current densities and low overpotentials. Most unsupported, non-precious metals oxygen-evolution catalysts require at least ~350 mV overpotential to oxidize water with a current density of 10 mA/cm2 in 1 M alkaline solution. Here we report on a robust nanostructured porous NiFe-based oxygen evolution catalyst made by selective alloy corrosion. In 1 M KOH, our material exhibits a catalytic activity towards water oxidation of 500 mA/cm2 at 360 mV overpotential and is stable for over eleven days. This exceptional performance is attributed to three factors. First, the small size of the ligaments and pores in our mesoporous catalyst (~10 nm) results in a high BET surface area (43 m2/g) and therefore a high density of oxygen-evolution catalytic sites per unit mass. Second, the open porosity facilitates effective mass transfer at the catalyst/electrolyte interface. Third and finally, the high bulk electrical conductivity of the mesoporous catalyst allows for effective current flow through the electrocatalyst, making it possible to use thick films with a high density of active sites and ~3×104 cm2 of catalytic area per cm2 of electrode area. Our mesoporous catalyst is thus attractive for alkaline electrolyzers where water-based solutions are decomposed into hydrogen and oxygen as the only products, driven either conventionally or by photovoltaics.

To enhance the hardness of tungsten tetraboride (WB(4)), a notable lower cost member of the late transition-metal borides, we have synthesized and characterized solid solutions of this material with tantalum (Ta), manganese (Mn), and chromium (Cr). Various concentrations of these transition-metal elements, ranging from 0.0 to 50.0 at. %, on a metals basis, were made. Arc melting was used to synthesize these refractory compounds from the pure elements. Elemental and phase purity of the samples were examined using energy-dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD), and microindentation was utilized to measure the Vickers hardness under applied loads of 0.49-4.9 N. XRD results indicate that the solubility limit is below 10 at. % for Cr and below 20 at. % for Mn, while Ta is soluble in WB(4) above 20 at. %. Optimized Vickers hardness values of 52.8 ± 2.2, 53.7 ± 1.8, and 53.5 ± 1.9 GPa were achieved, under an applied load of 0.49 N, when ~2.0, 4.0, and 10.0 at. % Ta, Mn, and Cr were added to WB(4) on a metals basis, respectively. Motivated by these results, ternary solid solutions of WB(4) were produced, keeping the concentration of Ta in WB(4) fixed at 2.0 at. % and varying the concentration of Mn or Cr. This led to hardness values of 55.8 ± 2.3 and 57.3 ± 1.9 GPa (under a load of 0.49 N) for the combinations W(0.94)Ta(0.02)Mn(0.04)B(4) and W(0.93)Ta(0.02)Cr(0.05)B(4), respectively. In situ high-pressure XRD measurements collected up to ~65 GPa generated a bulk modulus of 335 ± 3 GPa for the hardest WB(4) solid solution, W(0.93)Ta(0.02)Cr(0.05)B(4), and showed suppression of a pressure-induced phase transition previously observed in pure WB(4).

Superhard metals are of interest as possible replacements with enhanced properties over the metal carbides commonly used in cutting, drilling, and wear-resistant tooling. Of the superhard metals, the highest boride of tungsten-often referred to as WB 4 and sometimes as W 1-x B 3 -is one of the most promising candidates. The structure of this boride, however, has never been fully resolved, despite the fact that it was discovered in 1961-a fact that severely limits our understanding of its structure-property relationships and has generated increasing controversy in the literature. Here, we present a new crystallographic model of this compound based on refinement against time-of-flight neutron diffraction data. Contrary to previous X-ray-only structural refinements, there is strong evidence for the presence of interstitial arrangements of boron atoms and polyhedral bonding. The formation of these polyhedra-slightly distorted boron cuboctahedra-appears to be dependent upon the defective nature of the tungsten-deficient metal sublattice. This previously unidentified structure type has an intermediary relationship between MB 2 and MB 12 type boride polymorphs. Manipulation of the fractionally occupied metal and boron sites may provide insight for the rational design of new superhard metals.A s demand increases for new superhard materials, the introduction of transition metal borides as candidate compounds has recently attracted a great deal of attention (1-4). This trend is at least partially driven by a need for greater efficiency in cutting tools compared with tungsten carbide (which is not superhard), as well as the shortcomings of the traditional superhard compounds-diamond (which is unusable for cutting ferrous materials) (5) and cubic boron nitride (which is very expensive to synthesize and difficult to shape) (6). Within the rapidly growing family of superhard borides, tungsten tetraboride (or WB 4 ) is of specific interest due to its excellent mechanical properties and its relatively lower cost compared with borides such as ReB 2 , OsB 2 , RuB 2 , and RhB 2 , which contain platinum group metals (3, 7-11). For instance, tungsten tetraboride demonstrates an extremely high indentation hardness of ∼43 GPa by the Vickers method (under an applied load of 0.49 N) (8) and ∼41.7 GPa by nanoindentation (maximum, at a penetration depth of 95.25 nm; Fig. 1), and can sustain a differential stress (a lower-bound estimate of compressive yield strength) of up to ∼19.7 GPa (12). More dramatically, it is like ReB 2 (2), capable of scratching natural diamond (11). We have, furthermore, previously shown that the hardness of this compound may be enhanced by the creation of solid solutions with other transition metals (9). However, to understand the underlying mechanisms for the hardness enhancements observed in WB 4 solid solutions, as well as to guide the design of new superhard borides with tailored mechanical properties, it is crucial to understand the crystal structure of this compound.Perhaps surprisingly for a simple binary ...

Solid solutions of mixed metal dodecaborides of ZrB12, YB12, and ScB12 were prepared by arc-melting and studied for their mechanical properties. Zr1–x Y x B12 formed an essentially perfect solid solution, closely following Vegard’s law. Zr1–x Sc x B12 and Y1–x Sc x B12 undergo a face centered-cubic to body-centered tetragonal transition at 90–95 at. % Sc as determined by powder X-ray diffraction and transmission electron microscopy. The compounds Zr0.5Y0.5B12, Zr0.5Sc0.5B12, and Y0.5Sc0.5B12 are superhard (Vickers hardness ≥ 40 GPa) and demonstrate an increase in hardness to 45.8 ± 1.3, 48.0 ± 2.1, and 45.2 ± 2.1 GPa under a load of 0.49 N, respectively, compared to 40.4 ± 1.8, 40.9 ± 1.6, and 41.7 ± 2.2 GPa for pure ZrB12, YB12, and ScB12, respectively. In addition, Zr0.5Y0.5B12, Zr0.5Sc0.5B12, and Y0.5Sc0.5B12 solid solutions show a substantial increase in oxidation resistance to approximately 630, 685, and 695 °C, respectively, when compared to other superhard metal borides (e.g., ∼400 °C for WB4) and their alloys and the traditional cutting tools material tungsten carbide (∼400 °C). Moreover, Zr0.5Y0.5B12, Zr0.5Sc0.5B12, and Y0.5Sc0.5B12 have relatively low densities of 3.52, 3.32, and 3.18 g/cm3, respectively, comparable to or even lower than that of diamond (3.52 g/cm3) and significantly lower than those of other superhard borides such as ReB2 (12.67 g/cm3) and WB4 (8.40 g/cm3) and traditional cutting tools materials, e.g., WC (15.77 g/cm3), making them of potential interest for lightweight protective coatings and/or as materials for cutting and machining.

Alloys of tungsten tetraboride (WB4) with the group 4 transition metals, titanium (Ti), zirconium (Zr), and hafnium (Hf), of different concentrations (0-50 at. % on a metals basis) were synthesized by arc-melting in order to study their mechanical properties. The phase composition and purity of the as-synthesized samples were confirmed using powder X-ray diffraction (PXRD) and energy dispersive X-ray spectroscopy (EDS). The solubility limit as determined by PXRD is 20 at. % for Ti, 10 at. % for Zr, and 8 at. % for Hf. Vickers indentation measurements of WB4 alloys with 8 at. % Ti, 8 at. % Zr, and 6 at. % Hf gave hardness values, Hv, of 50.9 ± 2.2, 55.9 ± 2.7 and 51.6 ± 2.8 GPa, respectively, compared to 43.3 GPa for pure WB4 under an applied load of 0.49 N. Each of the aforementioned compositions are considered superhard (Hv > 40 GPa), likely due to extrinsic hardening that plays a key role in these superhard metal borides. Furthermore, these materials exhibit a significantly reduced indentation size effect, which can be seen in the plateauing hardness values for the W1-xZrxB4 alloy. In addition, W0.92Zr0.08B4, a product of spinoidal decomposition, possesses nanostructured grains and enhanced grain hardening. The hardness of W0.92Zr0.08B4 is 34.7 ± 0.65 GPa under an applied load of 4.9 N, the highest value obtained for any superhard metal at this relatively high loading. In addition, the WB4 alloys with Ti, Zr, and Hf showed a substantially increased oxidation resistance up to ∼460 °C, ∼510 °C, and ∼490 °C, respectively, compared to ∼400 °C for pure WB4.

In tungsten monoboride (WB), the boron atoms are linked in parallel serpentine arrays, with tungsten atoms in between. This lattice is metallic, unlike conventional covalent superhard materials such as diamond or cubic boron nitride. By selectively substituting tungsten atoms with tantalum, the Vickers hardness can be increased to 42.8 GPa, creating a new superhard metal.

By creation of solid solutions of the recently explored low-cost superhard boride, tungsten tetraboride (WB4), the hardness can be increased. To illustrate this concept, various concentrations of molybdenum (Mo) in WB4, that is, W1–x Mo x B4 (x = 0.00–0.50), were systematically synthesized by arc melting from the pure elements. The as-synthesized samples were characterized using energy-dispersive X-ray spectroscopy (EDS) for elemental analysis, powder X-ray diffraction (XRD) for phase identification, Vickers microindentation for hardness testing, and thermal gravimetric analysis for determining the thermal stability limit. While the EDS analysis confirmed the elemental purity of the samples, the XRD results indicated that Mo is completely soluble in WB4 over the entire concentration range studied (0–50 at. %) without forming a second phase. When 3 at. % Mo is added to WB4, Vickers hardness values increased by about 15% from 28.1 ± 1.4 to 33.4 ± 0.9 GPa under an applied load of 4.90 N and from 43.3 ± 2.9 to 50.3 ± 3.2 GPa under an applied load of 0.49 N. Thermal gravimetric analysis revealed that the powders of this superhard solid solution, W0.97Mo0.03B4, are thermally stable in air up to ∼400 °C. These results indicate that the hardness of superhard transition-metal borides may be enhanced by making solid solutions with small amounts of other transition metals, without introducing a second phase to their structures.