Structure of superhard tungsten tetraboride: a missing link between MB2 and MB12 higher borides.

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 WB4 and sometimes as W(1-x)B3--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 polyhedral--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 MB2 and MB12 type boride polymorphs. Manipulation of the fractionally occupied metal and boron sites may provide insight for the rational design of new superhard metals.

Engineering three-dimensional hybrid supercapacitors and microsupercapacitors for high-performance integrated energy storage.

Supercapacitors now play an important role in the progress of hybrid and electric vehicles, consumer electronics, and military and space applications. There is a growing demand in developing hybrid supercapacitor systems to overcome the energy density limitations of the current generation of carbon-based supercapacitors. Here, we demonstrate 3D high-performance hybrid supercapacitors and microsupercapacitors based on graphene and MnO2 by rationally designing the electrode microstructure and combining active materials with electrolytes that operate at high voltages. This results in hybrid electrodes with ultrahigh volumetric capacitance of over 1,100 F/cm(3). This corresponds to a specific capacitance of the constituent MnO2 of 1,145 F/g, which is close to the theoretical value of 1,380 F/g. The energy density of the full device varies between 22 and 42 Wh/l depending on the device configuration, which is superior to those of commercially available double-layer supercapacitors, pseudocapacitors, lithium-ion capacitors, and hybrid supercapacitors tested under the same conditions and is comparable to that of lead acid batteries. These hybrid supercapacitors use aqueous electrolytes and are assembled in air without the need for expensive "dry rooms" required for building today's supercapacitors. Furthermore, we demonstrate a simple technique for the fabrication of supercapacitor arrays for high-voltage applications. These arrays can be integrated with solar cells for efficient energy harvesting and storage systems.

Superhard Rhenium/Tungsten Diboride Solid Solutions.

Rhenium diboride (ReB2), containing corrugated layers of covalently bonded boron, is a superhard metallic compound with a microhardness reaching as high as 40.5 GPa (under an applied load of 0.49 N). Tungsten diboride (WB2), which takes a structural hybrid between that of ReB2 and AlB2, where half of the boron layers are planar (as in AlB2) and half are corrugated (as in ReB2), has been shown not to be superhard. Here, we demonstrate that the ReB2-type structure can be maintained for solid solutions of tungsten in ReB2 with tungsten content up to a surprisingly large limit of nearly 50 atom %. The lattice parameters for the solid solutions linearly increase along both the a- and c-axes with increasing tungsten content, as evaluated by powder X-ray and neutron diffraction. From micro- and nanoindentation hardness testing, all of the compositions within the range of 0-48 atom % W are superhard, and the bulk modulus of the 48 atom % solid solution is nearly identical to that of pure ReB2. These results further indicate that ReB2-structured compounds are superhard, as has been predicted from first-principles calculations, and may warrant further studies into additional solid solutions or ternary compounds taking this structure type.

High Surface Area Tunnels in Hexagonal WO3.

High surface area in h-WO3 has been verified from the intracrystalline tunnels. This bottom-up approach differs from conventional templating-type methods. The 3.67 Å diameter tunnels are characterized by low-pressure CO2 adsorption isotherms with nonlocal density functional theory fitting, transmission electron microscopy, and thermal gravimetric analysis. These open and rigid tunnels absorb H(+) and Li(+), but not Na(+) in aqueous electrolytes without inducing a phase transformation, accessing both internal and external active sites. Moreover, these tunnel structures demonstrate high specific pseudocapacitance and good stability in an H2SO4 aqueous electrolyte. Thus, the high surface area created from 3.67 Å diameter tunnels in h-WO3 shows potential applications in electrochemical energy storage, selective ion transfer, and selective gas adsorption.

Tungsten tetraboride, an inexpensive superhard material.

Tungsten tetraboride (WB(4)) is an interesting candidate as a less expensive member of the growing group of superhard transition metal borides. WB(4) was successfully synthesized by arc melting from the elements. Characterization using powder X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDX) indicates that the as-synthesized material is phase pure. The zero-pressure bulk modulus, as measured by high-pressure X-ray diffraction for WB(4), is 339 GPa. Mechanical testing using microindentation gives a Vickers hardness of 43.3 ± 2.9 GPa under an applied load of 0.49 N. Various ratios of rhenium were added to WB(4) in an attempt to increase hardness. With the addition of 1 at.% Re, the Vickers hardness increased to approximately 50 GPa at 0.49 N. Powders of tungsten tetraboride with and without 1 at.% Re addition are thermally stable up to approximately 400 °C in air as measured by thermal gravimetric analysis.

Three-dimensional core-shell hybrid solar cells via controlled in situ materials engineering.

Three-dimensional core-shell organic-inorganic hybrid solar cells with tunable properties are demonstrated via electropolymerization. Air-stable poly(3,4-ethylenedioxythiophene) (PEDOT) shells with controlled thicknesses are rapidly coated onto periodic GaAs nanopillar arrays conformally, preserving the vertical 3D structure. The properties of the organic layer can be readily tuned in situ, allowing for (1) the lowering of the highest occupied molecular orbital level (|ΔE| ∼ 0.28 eV), leading to the increase of open-circuit voltage (V(OC)), and (2) an improvement in PEDOT conductivity that results in enhanced short-circuit current densities (J(SC)). The incorporation of various anionic dopants in the polymer during the coating process also enables the tailoring of the polymer/semiconductor interface transport properties. Systematic tuning of the device properties results in a J(SC) of 13.6 mA cm(-2), V(OC) of 0.63 V, peak external quantum efficiency of 58.5%, leading to a power conversion efficiencies of 4.11%.

Toward inexpensive superhard materials: tungsten tetraboride-based solid solutions.

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).

Vapor-phase polymerization of nanofibrillar poly(3,4-ethylenedioxythiophene) for supercapacitors.

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.

Patterning and electronic tuning of laser scribed graphene for flexible all-carbon devices.

Engineering a low-cost graphene-based electronic device has proven difficult to accomplish via a single-step fabrication process. Here we introduce a facile, inexpensive, solid-state method for generating, patterning, and electronic tuning of graphene-based materials. Laser scribed graphene (LSG) is shown to be successfully produced and selectively patterned from the direct laser irradiation of graphite oxide films under ambient conditions. Circuits and complex designs are directly patterned onto various flexible substrates without masks, templates, post-processing, transferring techniques, or metal catalysts. In addition, by varying the laser intensity and laser irradiation treatments, the electrical properties of LSG can be precisely tuned over 5 orders of magnitude of conductivity, a feature that has proven difficult with other methods. This inexpensive method for generating LSG on thin flexible substrates provides a mode for fabricating a low-cost graphene-based NO(2) gas sensor and enables its use as a heterogeneous scaffold for the selective growth of Pt nanoparticles. The LSG also shows exceptional electrochemical activity that surpasses other carbon-based electrodes in electron charge transfer rate as demonstrated using a ferro-/ferricyanide redox couple.

Synthesis of nanometre-thick MoO3 sheets.

The formation of MoO(3) sheets of nanoscale thickness is described. They are made from several fundamental sheets of orthorhombic alpha-MoO(3), which can be processed in large quantities via a low cost synthesis route that combines thermal evaporation and mechanical exfoliation. These fundamental sheets consist of double-layers of linked distorted MoO(6) octahedra. Atomic force microscopy (AFM) measurements show that the minimum resolvable thickness of these sheets is 1.4 nm which is equivalent to the thickness of two double-layers within one unit cell of the alpha-MoO(3) crystal.