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Graphene oxide (GO) membranes have great potential for separation applications due to their low-friction water permeation combined with unique molecular sieving ability. However, the practical use of deposited GO membranes is limited by the inferior mechanical robustness of the membrane composite structure derived from conventional deposition methods. Here, we report a nanostructured GO membrane that possesses great permeability and mechanical robustness. This composite membrane consists of an ultrathin selective GO nanofilm (as low as 32 nm thick) and a postsynthesized macroporous support layer that exhibits excellent stability in water and under practical permeability testing. By utilizing thin-film lift off (T-FLO) to fabricate membranes with precise optimizations in both selective and support layers, unprecedented water permeability (47 L·m-2·hr-1·bar-1) and high retention (>98% of solutes with hydrated radii larger than 4.9 A) were obtained.

The conversion of small bio-based molecules into electro-active functional carbon nanomaterials such as carbon nanodots or graphene is attracting increasing interest. In this communication we demonstrate the use of laser-reduced carbon nanodots (lrCND) as electrodes for electrochemical capacitors. A CO2-laser-assisted process is utilized to convert CNDs into highly conductive 3D-carbon monoliths. Exclusion of molecular oxygen from the reaction environment has a positive effect on device parameters and particularly on the frequency response. Using this simple and inexpensive method, an extremely fast RC time constant of 0.29 ms and a capacitance of 0.259 mF cm−2 at 120 Hz were obtained. This can be attributed to an effective conversion of CNDs into graphitic carbon in an oxygen-free environment and the presence of unconverted CNDs in the 3D-carbon network acting as doping agents.

Tungsten borides, such as tungsten tetraboride (WB4) exhibit a wide range of appealing physical properties, including superhardness, chemical inertness and electronic conductivity. Among the various tungsten borides, the most puzzling remains WB4, with its crystal structure to linger in question for over half a century (Lech et al. in Proc Natl Acad Sci USA 112:3223–3228, 2015). In the present investigation, polycrystalline WB4 samples have been synthesized with two different methods and characterized at the atomic level by combining X-ray diffraction, scanning electron microscopy and nuclear magnetic resonance spectroscopy. The 11B multiple quantum MAS experiment revealed a range of boron sites that were not resolved within the experiment. This result is in contrast to the 11B MAS spectrum of WB2 with four resolved, discernible boron resonances. However, despite the structural complexity and boron-site variety in WB4, the detection of a single exponential of 11B spin–lattice relaxation recovery suggested that all of the boron sites relaxed with a single time constant. The Knight shift (K) was found to be independent of temperature while the $$ T_{1}^{ - 1} $$ was governed by the Korringa law with a Korringa product T1T = 350 sK across the entire temperature range (168–437 K) of this study. The measured Korringa product was small, indicating substantial spin–lattice relaxation resulting from coupling with the conduction carriers. The abovementioned experimental results not only clearly rule out structures, such as the “MoB4-type phase” of WB4, with the resulting Fermi level in the pseudo-gap as has previously been predicted theoretically; but they also provide a comprehensible and valuable insight into the structural and electronic properties of WB4 at the atomic level.

Thin-film composite (TFC) membranes are favored for precise molecular sieving in liquid-phase separations; they possess high permeability due to the minimal thickness of the active layer and the high porosity of the support layer. However, current TFC membrane fabrication techniques are limited by the available materials for the selective layer and do not demonstrate the level of structural control needed to substantially advance organic solvent nanofiltration (OSN) membrane technology. In this work, we employ the newly developed thin-film lift-off (T-FLO) technique to fabricate polybenzimidazole (PBI) TFC membranes with porous support layers uniquely tailored to OSN. The drop-cast dense PBI selective layers endow the membranes with an almost complete rejection of common small dye molecules. The polymeric support layer is optimized by a combinatorial approach using four different monomers that alter the cross-linking density and polymer chain flexibility of the final composite. These two properties substantially affect the porogen holding capacity of the reticular polymer network, leading to the formation of different macropore structures. With a 150 nm thick PBI selective layer and fine-tuning of the support layer, the resulting membrane achieves stable and superior permeance of 14.0, 11.7, 16.4, 11.4, 17.1, and 19.7 L m-2 h-1 bar-1 for water, ethanol, methanol, isopropanol, tetrahydrofuran (THF), and acetonitrile, respectively.

In this work, we investigate the high-pressure behavior of the stabilized high-temperature (HT) orthorhombic phase of WB using radial X-ray diffraction in a diamond-anvil cell at room temperature. The experiments were performed under nonhydrostatic compression up to 52 GPa. For comparison, the low-temperature (LT) tetragonal phase of WB was also compressed nonhydrostatically to 36 GPa to explore structurally induced changes to its mechanical properties. Although our microindentation hardness tests indicate that the HT WB possesses slightly higher hardness, synchrotron-based high-pressure compression data yield significant distinct incompressibilities. The ambient pressure bulk modulus of the HT phase of WB is 341 ± 5 GPa obtained by using the second-order Birch–Murnaghan equation of state, while for the LT phase of WB the incompressibility increased to 381 ± 3 GPa. The elastically supported differential stress was measured in a lattice-specific manner and analyzed by using lattice strain theory. Greater s...

The structure of tungsten diboride, WB2, differs from those of metal diborides with AlB2- or ReB2-type structures that have been previously studied by 11B NMR spectroscopy. As opposed to the single 11B resonance reported for the metal diborides having those AlB2- or ReB2-type structures, four groups of 11B resonances are found for WB2. There is also 11B NMR spectral evidence to support the proposal by Kiesling in 1947 of an additional boron atom at the center of some of the six-membered boron rings. The 11B quadrupolar frequencies of all four groups of resonances in WB2 are all quite small (

Rhenium diboride is an established superhard compound that can scratch diamond and can be readily synthesized under ambient pressure. Here, we demonstrate two synergistic ways to further enhance the already high yield strength of ReB

Solid solutions of tungsten diboride (WB2) with increasing substitution of tungsten (W) by tantalum (Ta) and niobium (Nb)—ranging from 0 to 50 at. % on a metals basis—were synthesized through resis...

Solid solutions of mixed metal dodecaborides of ZrB12, YB12, and ScB12 were prepared by arc-melting and studied for their mechanical properties. Zr1–xYxB12 formed an essentially perfect solid solution, closely following Vegard’s law. Zr1–xScxB12 and Y1–xScxB12 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 all...

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.

Alloys of metal dodecaborides-YB12 with HfB12-were prepared via arc-melting in order to stabilize the metastable HfB12 high-pressure phase under ambient pressure. Previously, HfB12 had been synthesized only under high-pressure (6.5 GPa). Powder X-ray diffraction (PXRD) and energy-dispersive X-ray spectroscopy (EDS) were used to confirm the purity and phase composition of the prepared samples. The solubility limit for HfB12 in Y1-xHfxB12 (cubic UB12 structure type) was determined to be ∼35 at. % Hf by PXRD and EDS analysis. The value of the cubic unit cell parameter (a) changed from 7.505 Å (pure YB12) to 7.454 Å across the solid solution range. Vickers hardness increased from 40.9 ± 1.6 GPa for pure YB12 to 45.0 ± 1.9 GPa under an applied load of 0.49 N for the Y1-xHfxB12 solid solution composition with ∼28 at. % Hf, suggesting both solid solution hardening and extrinsic hardening due to the formation of secondary phases of hafnium.

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 (Hv40 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.

Analyses of the one-dimensional 11B NMR spectra from static and MAS experiments of a polycrystalline ReB2 sample have extracted parameters characterizing both the electric field gradient and the shielding at the boron site. In contrast to that previously assumed for AlB2, the principal axis systems for these two interactions are not coincident in ReB2. A brief discussion of the literature regarding spin–lattice relaxation for half-integer quadrupolar nuclei and the mathematical functions used for the extraction of relaxation time constants is presented. With radiofrequency conditions chosen to excite the central and satellite transitions, the saturation recovery spin–lattice relaxation rate of ReB2 is better described by a single exponential rather than the Andrew–Tunstall multiexponential model for I = 3/2. In addition, relaxation measurements for 11B in ReB2 have been extended to temperatures above ambient and show a deviation from the Korringa relationship.

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–xMoxB4 (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 5...

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 cm−2 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 cm−2 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−1) 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.

Understanding different bonding environments in various metal borides provides insight into their structures and physical properties. Polycrystalline aluminum diboride (AlB2) samples have been synthesized and compared both with a commercial sample and with the literature. One issue that arose is the relative ease with which boron-rich and aluminum deficient phases of aluminum borides can be presented in AlB2. Here, we report 27Al, 11B nuclear magnetic resonance (NMR) spectroscopy and first-principles calculations on AlB2 in order to shed light on these different bonding environments at the atomic level and compare the structural and electronic properties of the products of different preparations. Along with the aforementioned, the present study also takes an in-depth look at the nature of the 11B and 27Al nuclear spin–lattice relaxation recovery data for the AlB2 and other superhard materials. The nuclear spin–lattice relaxation has been measured for a static sample and with magic-angle spinning. The combination of NMR and band structure calculations highlights the synthetic challenges with superhard materials.

Tungsten tetraboride is an inexpensive, superhard material easily prepared at ambient pressure. Unfortunately, there are relatively few compounds in existence that crystallize in the same structure as tungsten tetraboride. Furthermore, the lack of data in the tetraboride phase space limits the discovery of any new superhard compounds that also possess high incompressibility and a three-dimensional boron network that withstands shear. Thus, the focus of the work here is to chemically probe the range of thermodynamically stable tetraboride compounds with respect to both the transition metal and the boron content. Tungsten tetraboride alloys with a variable concentration of boron were prepared by arc-melting and investigated for their mechanical properties and thermal stability. The purity and phase composition were confirmed by energy dispersive X-ray spectroscopy and powder X-ray diffraction. For variable boron WBx, it was found that samples prepared with a metal to boron ratio of 1:11.6 to 1:9 have simila...

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.

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 furth...

The differential strain behavior of TaxW1-xB solid solutions has been studied as a function of composition using high-pressure radial X-ray diffraction in a diamond-anvil cell under non-hydrostatic pressure (up to ∼65 GPa) to understand the hardening mechanisms in this family of materials. The hardness of tungsten monoboride (WB) can be increased by adding tantalum and reaches a maximum at a doping level of 50 at. % with a value of 42.8 ± 2.6 GPa under an applied load of 0.49 N. Plateaus were observed in the differential strain data for both the (020) and (002) directions, suggesting that this is the primary slip system in this material. These plateaus were modified by the addition of Ta, indicating that strengthening of the (002) and (020) planes by solid solution hardening was primarily responsible for the hardness enhancements in TaxW1-xB solid solutions. In contrast, the differential strain supported by the (200) plane linearly increases with pressure up to the highest pressures reached in this work (>60 GPa) and shows almost no change with metal composition. Because of the very different compression behavior in the (200) and (020) planes, change in the b/a ratio with pressure provides a unique way to visualize the onset of plastic behavior. This onset varies from ∼15 GPa for samples with 5% Ta to more than 30 GPa for the sample with 50% Ta. In addition, the ambient bulk modulus of each solid-solution sample was determined using the second-order Birch-Murnaghan equation-of-state and found to be ∼340 GPa for all phases.