Two-Dimensional Covalent Organic Framework Solid Solutions.

Covalent organic frameworks (COFs) generally leverage one or two monomers with specific sizes and shapes to access highly symmetric and periodic polymer networks. Almost all reported COFs employ the minimum sets of monomers needed for the polymerization (usually two, sometimes one) and crystallize in high-symmetry topologies. COFs synthesized from more than two monomers usually employ mixtures with different pendant functionalities to distribute these groups statistically throughout the structure, or monomers with different sizes in ratios targeting lower symmetry topologies. Here, we demonstrate that mixtures of monomers with different lengths generate single-phase, hexagonal two-dimensional covalent organic framework (2D COF) solid solutions at continuously variable feed ratios. X-ray diffraction measurements, Fourier-transform infrared spectroscopy, and Pawley refinement indicate that both monomers distribute randomly within the same lattice, and the lattice parameters continuously increase as more of the larger linker is incorporated. Furthermore, COF solid solutions are accessed directly by polymerizing a mixture of monomers but not via linker exchange from a preformed COF. As strain develops from the lattice accommodating monomers with different sizes, the nonlinear relationship between the monomer incorporation and the COF's lattice parameters suggests that bond-bending of the monomers plays a role in incorporating monomers of different lengths into the solid solutions. Solid solution formation represents a new strategy to design 2D COFs and increase their complexity. Specifically, varying the monomer composition of a given network enables many properties, such as the average pore size, to be continuously tuned between those of corresponding pure COFs.

Synthesis and Characterization of Single-Phase Metal Dodecaboride Solid Solutions: Zr1- xY xB12 and Zr1- xU xB12.

Single-phase metal dodecaboride solid solutions, Zr0.5Y0.5B12 and Zr0.5U0.5B12, were prepared by arc melting from pure elements. The phase purity and composition were established by powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and 10B and 11B solid-state nuclear magnetic resonance (NMR) spectroscopy. The effects of carbon addition to Zr1- xY xB12 were studied and it was found that carbon causes fast cooling and as a result rapid nucleation of grains, as well as "templating" and patterning effects of the surface morphology. The hardness of the Zr0.5Y0.5B12 phase is 47.6 ± 1.7 GPa at 0.49 N load, which is ∼17% higher than that of its parent compounds, ZrB12 and YB12, with hardness values of 41.6 ± 2.6 and 37.5 ± 4.3 GPa, respectively. The hardness of Zr0.5U0.5B12 is ∼54% higher than that of its UB12 parent. The dodecaborides were confirmed to be metallic by band structure calculations, diffuse reflectance UV-vis, and solid-state NMR spectroscopies. The nature of the dodecaboride colors-violet for ZrB12 and blue for YB12-can be attributed to charge-transfer. XPS indicates that the metals are in the following oxidation states: Y3+, Zr4+, and U5+/6+. The superconducting transition temperatures ( Tc) of the dodecaborides were determined to be 4.5 and 6.0 K for YB12 and ZrB12, respectively, as shown by resistivity and superconducting quantum interference device (SQUID) measurements. The Tc of the Zr0.5Y0.5B12 solid solution was suppressed to 2.5 K.

Effects of Variable Boron Concentration on the Properties of Superhard Tungsten Tetraboride.

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 similar hardness values (∼40 GPa at 0.49 N loading) as well as having a similar thermal oxidation temperature of ∼455 °C. A nearly single phase compound was successfully stabilized with tantalum and prepared with a nearly stoichiometric amount of boron (4.5) as W0.668Ta0.332B4.5. Therefore, the cost of production of WB4 can be decreased while maintaining its remarkable properties. Insights from this work will help design future compounds stable in the adaptable tungsten tetraboride structure.

Extrinsic Hardening of Superhard Tungsten Tetraboride Alloys with Group 4 Transition Metals.

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.

Stabilization of LnB12 (Ln = Gd, Sm, Nd, and Pr) in Zr1-xLnxB12 under Ambient Pressure.

We report ambient pressure stabilization of a previously synthesized high-pressure (6.5 GPa) phase, GdB12, in a Zr1-xGdxB12 solid solution (with ∼54 at. % Gd solubility, as determined by both powder X-ray diffraction and energy-dispersive spectroscopy). Limited solubilities of Sm (∼15 at. % Sm), Nd (∼7 at. % Nd), and Pr (∼4 at. % Pr), in ZrB12 were also achieved. Previous attempts at preparing these rare-earth borides were unsuccessful even under high pressure. On the basis of insights provided from the unit cell sizes observed via solid solutions, at least 6.5 GPa of pressure would be needed to synthesize these rare-earth borides since Sm, Nd, and Pr atomic radii are larger than that of Gd. The solid-solution formation for Zr1-xGdxB12 and Zr1-xSmxB12 can be seen in the change of the unit cell of each of the solid solutions relative to their pure parent compounds as well as in the change of color of the respective alloys. For Zr0.45Gd0.55B12 and Zr0.70Sm0.30B12, the cubic unit cell parameter (a) reached a value of 7.453 and 7.428 Å, respectively, compared to 7.412 Å for pure ZrB12.

Stabilization of HfB12 in Y1-xHfxB12 under Ambient Pressure.

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.

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.

Synthesis and High-Pressure Mechanical Properties of Superhard Rhenium/Tungsten Diboride Nanocrystals.

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 ReB2. The first approach builds on previous reports where tungsten is doped into ReB2 at concentrations up to 48 at. %, forming a rhenium/tungsten diboride solid solution (Re0.52W0.48B2). In the second approach, the composition of both materials is maintained, but the particle size is reduced to the nanoscale (40-150 nm). Bulk samples were synthesized by arc melting above 2500 °C, and salt flux growth at ∼850 °C was used to create nanoscale materials. In situ radial X-ray diffraction was then performed under high pressures up to ∼60 GPa in a diamond anvil cell to study mechanical properties including bulk modulus, lattice strain, and strength anisotropy. The differential stress for both Re0.52W0.48B2 and nano ReB2 (n-ReB2) was increased compared to bulk ReB2. In addition, the lattice-preferred orientation of n-ReB2 was experimentally measured. Under non-hydrostatic compression, n-ReB2 exhibits texture characterized by a maximum along the [001] direction, confirming that plastic deformation is primarily controlled by the basal slip system. At higher pressures, a range of other slip systems become active. Finally, both size and solid-solution effects were combined in nanoscale Re0.52W0.48B2. This material showed the highest differential stress and bulk modulus, combined with suppression of the new slip planes that opened at high pressure in n-ReB2.

Investigation of ternary metal dodecaborides (M1M2M3)B12 (M1, M2 and M3 = Zr, Y, Hf and Gd).

Samples of metal borides with a nominal composition of ((M1)(1-x-z)(M2)(x)(M3)(z)) : 20B (M1, M2 and M3 = Zr, Y, Hf and Gd) were prepared by arc-melting and studied for phase composition (using powder X-ray diffraction (PXRD) and energy dispersive X-ray spectroscopy (EDS)) and mechanical properties (Vickers hardness). Ternary metal dodecaboride phases were successfully synthesized for the majority of compositions, including stabilization of two high-pressure (6.5 GPa) phases (cubic-UB12 structure), HfB12 and GdB12, in (Zr1-x-zHfxGdz) : 20B and (Y1-x-zHfxGdz) : 20B nominal alloy compositions. Unit cell refinement for the samples showed solid solution formation in most cases. Vickers hardness measurements indicated that most samples possess enhanced hardness in comparison to their parent phases, with the alloy (Zr0.50Y0.25Gd0.25) : 20B having a hardness of 46.9 ± 2.4 GPa compared to 41.3 ± 1.1 and 41.6 ± 1.3 GPa for alloy compositions of 1.0 Zr : 20B and 1.0 Y : 20B, respectively, at 0.49 N of applied load. Using the data from this manuscript as well as previous work, pseudo-ternary phase diagrams (at a constant boron content) have been constructed.

Rediscovering the Crystal Chemistry of Borides.

For decades, borides have been primarily studied as crystallographic oddities. With such a wide variety of structures (a quick survey of the Inorganic Crystal Structure Database counts 1253 entries for binary boron compounds!), it is surprising that the applications of borides have been quite limited despite a great deal of fundamental research. If anything, the rich crystal chemistry found in borides could well provide the right tool for almost any application. The interplay between metals and the boron results in even more varied material's properties, many of which can be tuned via chemistry. Thus, the aim of this review is to reintroduce to the scientific community the developments in boride crystal chemistry over the past 60 years. We tie structures to material properties, and furthermore, elaborate on convenient synthetic routes toward preparing borides.

Lithium-Ion Insertion Properties of Solution-Exfoliated Germanane.

The high theoretical energy density of alloyed lithium and germanium (Li15Ge4), 1384 mAh/g, makes germanium a promising anode material for lithium-ion batteries. However, common alloy anode architectures suffer from long-term instability upon repetitive charge-discharge cycles that arise from stress-induced degradation upon lithiation (volume expansion >300%). Here, we explore the use of the two-dimensional nanosheet structure of germanane to mitigate stress from high volume expansion and present a facile method for producing stable single-to-multisheet dispersions of pure germanane. Purity and degree of exfoliation were assessed with scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. We measured representative germanane battery electrodes to have a reversible Li-ion capacity of 1108 mAh/g when cycled between 0.1 and 2 V vs Li/Li+. These results indicate germanane anodes are capable of near-theoretical-maximum energy storage, perform well at high cycling rates, and can maintain capacity over 100 cycles.

Superhard Monoborides: Hardness Enhancement through Alloying in W1- x Tax B.

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.

Characterization of Aniline Tetramer by MALDI TOF Mass Spectrometry upon Oxidative and Reductive Cycling.

By combining electrochemical experiments with mass spectrometric analysis, it is found that using short chain oligomers to improve the cycling stability of conducting polymers in supercapacitors is still problematic. Cycling tests via cyclic voltammetry over a potential window of 0 to 1.0 V or 0 to 1.2 V in a two-electrode device configuration resulted in solid-state electropolymerization and chain scission. Electropolymerization of the aniline tetramer to generate long chain oligomers is shown to be possible despite the suggested decrease in reactivity and increase in intermediate stability with longer oligomers. Because aniline oligomers are more stable towards reductive cycling when compared to oxidative cycling, future conducting polymer/oligomer-based pseudocapacitors should consider using an asymmetric electrode configuration.

Graphene-Assisted Solution Growth of Vertically Oriented Organic Semiconducting Single Crystals.

Vertically oriented structures of single crystalline conductors and semiconductors are of great technological importance due to their directional charge carrier transport, high device density, and interesting optical properties. However, creating such architectures for organic electronic materials remains challenging. Here, we report a facile, controllable route for producing oriented vertical arrays of single crystalline conjugated molecules using graphene as the guiding substrate. The arrays exhibit uniform morphological and crystallographic orientations. Using an oligoaniline as an example, we demonstrate this method to be highly versatile in controlling the nucleation densities, crystal sizes, and orientations. Charge carriers are shown to travel most efficiently along the vertical interfacial stacking direction with a conductivity of 12.3 S/cm in individual crystals, the highest reported to date for an aniline oligomer. These crystal arrays can be readily patterned and their current harnessed collectively over large areas, illustrating the promise for both micro- and macroscopic device applications.

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.