Boron doped defective graphene as a potential anode material for Li-ion batteries

Graphene with large surface area and robust structure has been proposed as a high storage capacity anode material for Li ion batteries. While the inertness of pristine graphene leads to better Li kinetics, poor adsorption leads to Li clustering, significantly affecting the performance of the battery. Here, we show the role of defects and doping in achieving enhanced adsorption without compromising on the high diffusivity of Li. Using first principles density functional theory (DFT) calculations, we carry out a comprehensive study of diffusion kinetics of Li over the plane of the defective structures and calculate the change in the number of Li atoms in the vicinity of defects, with respect to pristine graphene. Our results show that the Li-C interaction, storage capacity and the energy barriers depend sensitively on the type of defects. The un-doped and boron doped mono-vacancy, doped di-vacancy up to two boron, one nitrogen doped di-vacancy, and Stone-Wales defects show low energy barriers that are comparable to pristine graphene. Furthermore, boron doping at mono-vacancy enhances the adsorption of Li. In particular, the two boron doped mono-vacancy graphene shows both a low energy barrier of 0.31 eV and better adsorption, and hence can be considered as a potential candidate for anode material.

Defect induced plasticity and failure mechanism of boron nitride nanotubes under tension

The effects of Stone-Wales (SW) and vacancy defects on the failure behavior of boron nitride nanotubes (BNNTs) under tension are investigated using molecular dynamics simulations. The Tersoff-Brenner potential is used to model the atomic interaction and the temperature is maintained close to 300 K. The effect of a SW defect is studied by determining the failure strength and failure mechanism of nanotubes with different radii. In the case of a vacancy defect, the effect of an N-vacancy and a B-vacancy is studied separately. Nanotubes with different chiralities but similar diameter is considered first to evaluate the chirality dependence. The variation of failure strength with the radius is then studied by considering nanotubes of different diameters but same chirality. It is observed that the armchair BNNTs are extremely sensitive to defects, whereas the zigzag configurations are the least sensitive. In the case of pristine BNNTs, both armchair and zigzag nanotubes undergo brittle failure, whereas in the case of defective BNNTs, only the zigzag ones undergo brittle failure. An interesting defect induced plastic behavior is observed in defective armchair BNNTs. For this nanotube, the presence of a defect triggers mechanical relaxation by bond breaking along the closest zigzag helical path, with the defect as the nucleus. This mechanism results in a plastic failure. (C) 2014 AIP Publishing LLC.

Synthesis, properties and applications of graphene doped with boron, nitrogen and other elements

Chemical doping of graphene becomes necessary to create a band gap which is useful for various applications. Furthermore, chemical doping of elements like boron and nitrogen in graphene gives rise to useful properties. Since chemically doped graphene is both of academic and technical importance, we have prepared this article on the present status of various aspects of this important class of materials. In doing so, we have covered the recent literature on this subject citing all the major references. Some of the aspects that we have covered are the synthesis of chemically doped graphene followed by properties and applications. The applications discussed relate to gas adsorption, lithium batteries, supercapacitors, oxygen reduction reaction, field emission and photochemical water splitting. Characterization of chemically doped graphene also included. We believe that the article will be useful to all those interested in graphene and related materials and provides the present status of the subject. (C) 2014 Elsevier Ltd. All rights reserved.

Role of boron diffusion in CoFeB/MgO magnetic tunnel junctions

Several scientific issues concerning the latest generation read heads for magnetic storage devices, based on CoFeB/MgO/CoFeBmagnetic tunnel junctions (MTJs) are known to be controversial, including such fundamental questions as to the behavior and the role of B in optimizing the physical properties of these devices. Quantitatively establishing the internal structures of several such devices with different annealing conditions using hard x-ray photoelectron spectroscopy, we resolve these controversies and establish that the B diffusion is controlled by the capping Ta layer, though Ta is physically separated from the layer with B by several nanometers. While explaining this unusual phenomenon, we also provide insight into why the tunneling magnetoresistance (TMR) is optimized at an intermediate annealing temperature, relating it to B diffusion, coupled with our studies based on x-ray diffraction and magnetic studies.

Nonlinear Optical Properties and Temperature-Dependent UV-Vis Absorption and Photoluminescence Emission in 2D Hexagonal Boron Nitride Nanosheets

Recently, a lot of interest has been centred on the optical properties of hexagonal boron nitride (h-BN), which has a similar lattice structure to graphene. Interestingly, h-BN has a wide bandgap and is biocompatible, so it has potential applications in multiphoton bioimaging, if it can exhibit large nonlinear optical (NLO) properties. However, extensive investigation into the NLO properties of h-BN have not been done so far. Here, NLO properties of 2D h-BN nanosheets (BNNS) are reported for the first time, using 1064-nm NIR laser radiation with a pulse duration of 10 ns using the Z-scan technique. The reverse saturable absorption occurs in aqueous colloidal solutions of BNNS with a very large two-photon absorption cross section (sigma(2PA)) of approximate to 57 x 10(-46) cm(4) s(-1) photon(-1). Also, by using UV-Vis absorption spectroscopy, the temperature coefficient of the bandgap (dE(g)/dT) of BNNS is determined to be 5.9 meV K-1. Further defect-induced photoluminescence emission in the UV region is obtained in the 283-303 K temperature range, under excitations of different wavelengths. The present report of large sigma(2PA) combined with stability and biocompatibility could open up new possibilities for the application of BNNS as a potential optical material for multiphoton bioimaging and advanced photonic devices.

Boron and Nitrogen Co-doped Carbon Nanoparticles as Photoluminescent Probes for Selective and Sensitive Detection of Picric Acid

Here, we report the synthesis of boron and nitrogen Co-doped carbon nanoparticles (BN-CNPs) by a hydrothermal method using sucrose, boric acid, and urea as the precursors. The BN-CNPs show excellent photoluminescence with a quantum yield of similar to 14.2% in aqueous solution and can be used as photoluminescent probes for selective and sensitive detection of picric acid (PA). PA quenches the photoluminescence signal remarkably, while other explosives cause a little quenching confirming the high selectivity of BN-CNPs. The sensitivity toward PA sensing is high at pH 7 and increases with temperature. The detection limit as well as the sensitivity are shown to improve by adding NaCl to the PA. The low detection limit can be as low as 10 nM at room temperature and pH 7, which indicates the BN-CNPs are superior as compared to other luminescent probes reported in the literature.

Enhancement in Strain Hardening on Boron Addition in As-Cast Ti-6Al-4V Alloy

It has been previously reported that the addition of boron to Ti-6Al-4V results in significant refinement of the as-cast microstructure and enhancement in the strain hardening. However, the mechanism for the latter effect has not been adequately studied. The aim of this study was to understand the reasons for the enhancement in room temperature strain hardening on addition of boron to as cast Ti-6Al-4V alloy. A study was conducted on slip transmission using SEM, TEM, optical profilometry and four point probe resistivity measurements on un-deformed and deformed samples of Ti-6Al-4V-xB with five levels of boron. Optical profilometry was used to quantify the magnitude of offsets on slip traces which in turn provided information about the extent of planar or multiple slip. Studies on deformed samples reveal that while lath boundaries appear to easily permit dislocation slip transmission, colony boundaries are potent barriers to slip. From TEM studies it was also observed that while alloys containing lower boron underwent planar slip, deformation was more homogeneous in higher boron alloys due to multiple slip resulting from large number of colony boundaries. Multiple slip is also proposed to be the prime cause of the enhanced strain hardening.

Structure-mechanical property correlations in mechanochromic luminescent crystals of boron difluoride dibenzoylmethane derivatives

The structure and mechanical properties of crystalline materials of three boron difluoride dibenzoylmethane (BF(2)dbm) derivatives were investigated to examine the correlation, if any, among mechanochromic luminescence (ML) behaviour, solid-state structure, and the mechanical behaviour of single crystals. Qualitative mechanical deformation tests show that the crystals of BF(2)dbm(Bu-t)(2) can be bent permanently, whereas those of BF(2)dbm(OMe)(2) exhibit an inhomogeneous shearing mode of deformation, and finally BF(2)dbmOMe crystals are brittle. Quantitative mechanical analysis by nanoindentation on the major facets of the crystals shows that BF(2)dbm(Bu-t)(2) is soft and compliant with low values of elastic modulus, E, and hardness, H, confirming its superior suceptibility for plastic deformation, which is attributed to the presence of a multitude of slip systems in the crystal structure. In contrast, both BF(2)dbm(OMe)(2) and BF(2)dbmOMe are considerably stiffer and harder with comparable E and H, which are rationalized through analysis of the structural attributes such as the intermolecular interactions, slip systems and their relative orientation with respect to the indentation direction. As expected from the qualitative mechanical behaviour, prominent ML was observed in BF(2)dbm(Bu-t)(2), whereas BF(2)dbm(OMe)(2) exhibits only a moderate ML and BF(2)dbmOMe shows no detectable ML, all examined under identical conditions. These results confirm that the extent of ML in crystalline organic solid-state fluorophore materials can be correlated positively with the extent of plasticity (low recovery). In turn, they offer opportunities to design new and improved efficient ML materials using crystal engineering principles.

Boron-doped carbon nanoparticles: Size-independent color tunability from red to blue and bioimaging applications

Here, we report the hydrothermal synthesis of boron-doped CNPs (B-CNPs) with different size/atomic percentage of doping and size-independent color tunability from red to blue. The variation of size/atomic percentage of B is achieved by simply varying the reaction time, while the color tunability is obtained by diluting the solution. With dilution, the luminescence spectra are not only blue-shifted, the intensity increases as well. The huge blue-shift in the emission energy (similar to 1 eV) is believed to be due to the increase in the interparticle distance. The quantum yield with optimum dilution is found to increase with boron doping though it is very low as compared to CNPs and nitrogen-doped CNPs. Finally, we show that B-CNPs with a quantum yield of 0.5% can be used for bioimaging applications. (C) 2015 Elsevier Ltd. All rights reserved.

First principles DFT investigation Of Yttrium-decorated Boron-Nitride Nanotube: Electronic Structure and Hydrogen Storage

The electronic structure and hydrogen storage capability of Yttrium-doped BNNTs has been theoretically investigated using first principles density functional theory (DFT). Yttrium atom prefers the hollow site in the center of the hexagonal ring with a binding energy of 0.8048eV. Decorating by Y makes the system half-metallic and magnetic with a magnetic moment of 1.0 mu(B). Y decorated Boron-Nitride (8,0) nanotube can adsorb up to five hydrogen molecules whose average binding energy is computed as 0.5044eV. All the hydrogen molecules are adsorbed with an average desorption temperature of 644.708 K. Taking that the Y atoms can be placed only in alternate hexagons, the implied wt% comes out to be 5.31%, a relatively acceptable value for hydrogen storage materials. Thus, this system can serve as potential hydrogen storage medium.

Boron clusters in luminescent materials

In recent times, luminescent materials with tunable emission properties have found applications in almost all aspects of modern material sciences. Any discussion on the recent developments in luminescent materials would be incomplete if one does not account for the versatile photophysical features of boron containing compounds. Apart from triarylboranes and tetra-coordinate borate dyes, luminescent materials consisting of boron clusters have also found immense interest in recent times. Recent studies have unveiled the opportunities hidden within boranes, carboranes and metalloboranes, etc. as active constituents of luminescent materials. From simple illustrations of luminescence, to advanced applications in LASERs, OLEDs and bioimaging, etc., the unique features of such compounds and their promising versatility have already been established. In this review, recent revelations about the excellent photophysical properties of such materials are discussed.

Stimuli and shape responsive `boron-containing' luminescent organic materials

Recent advancements of material science and its applications have been immensely influenced by the modern development of organic luminescent materials. Among all organic luminogens, boron containing compounds have already established their stature as one of the indispensable classes of luminescent dyes. Boron, in its various forms e. g. triarylboranes, borate dyes and boron clusters, has attracted considerable attention owing to its several unique and excellent photophysical features. In very recent times, beyond the realms of solution-state studies, luminescent boron-containing compounds have emerged as a large and versatile class of stimuli responsive materials. Based on several fundamental concepts of chemistry, researchers have come up with an admirable variety of boron-containing materials with AIE (aggregation-induced emission), mechano-responsive luminescence, thermoresponsive-luminescence as well as a number of purely organic phosphorescent materials and other standalone examples. The unique chemical as well as physical properties of boron-containing compounds are largely responsible for the development of such materials. In this review these new findings are brought together.

A New, Convenient Reductive Procedure For The Deprotection Of 4-Methoxybenzyl (Mpm) Ethers To Alcohols

Selective introduction and removal of protecting groups is of great significance in organic synthesis.l The benzyl ether function is one of the most common protecting groups for alcohols. Selective oxidative removal of the 4-methoxybenzyl (MPM) ethers in the presence of benzyl ethers made the MPM moiety an alternative protecting group, and its utility in carbohydrate chemistry is well established. Several procedures have been developed for the cleavage of the 4-methoxybenzyl moiety, e.g. DDQ oxidation (eq 1),2e lectrochemical ~xidationh,~om ogeneous electron t r a n~f e rp,~ho toinduced single electron t r an~f e rb,o~ro n trichloride-dimethyl sulfide,6e tc. However, in all these methods isolation of the alcohol from the inevitable byproduct, 4-methoxybenzaldehyde [also dichlorodicyanohydroquinone (DDHQ) in the most commonly used method employing DDQI can be troublesome. Recently Wallace and Hedgetts7 discovered that acetic acid at 90 "C cleaves the aromatic MPM ethers into the corresponding phenols and 4-methoxybenzyl acetate (eq 21, whereas the aliphatic MPM ethers generated, instead of alcohols, the corresponding acetates (eq 3). Complimentary to this methodology, herein we report that sodium cyanoborohydride and boron trifluoride etherate reductively cleaves, cleanly and efficiently, the aliphatic MPM ethers to an easily separable mixture of the corresponding alcohols and 4-methylanisole

Phase Equilibria in the System $Al_{2}O_{3}-CaO-CoO$ and Gibbs Energy of Formation of $Ca_{3}CoAl_{4}O_{10}$

The floating-zone method with different growth ambiences has been used to selectively obtain hexagonal or orthorhombic DyMnO3 single crystals. The crystals were characterized by x-ray powder diffraction of ground specimens and a structure refinement as well as electron diffraction. We report magnetic susceptibility, magnetization and specific heat studies of this multiferroic compound in both the hexagonal and the orthorhombic structure. The hexagonal DyMnO3 shows magnetic ordering of Mn3+ (S = 2) spins on a triangular Mn lattice at T-N(Mn) = 57 K characterized by a cusp in the specific heat. This transition is not apparent in the magnetic susceptibility due to the frustration on the Mn triangular lattice and the dominating paramagnetic susceptibility of the Dy3+ (S = 9/2) spins. At T-N(Dy) = 3 K, a partial antiferromagnetic order of Dy moments has been observed. In comparison, the magnetic data for orthorhombic DyMnO3 display three transitions. The data broadly agree with results from earlier neutron diffraction experiments, which allows for the following assignment: a transition from an incommensurate antiferromagnetic ordering of Mn3+ spins at T-N(Mn) = 39 K, a lock-in transition at Tlock-in = 16 K and a second antiferromagnetic transition at T-N(Dy) = 5 K due to the ordering of Dy moments. Both the hexagonal and the orthorhombic crystals show magnetic anisotropy and complex magnetic properties due to 4f-4f and 4f-3d couplings.

Solid state stacked trimers of 1,10-phenanthroline in a supramolecular tubular motif of C-methyl calix[4]resorcinarene

The self-assembly of bidentate ligand, 1,10-phenanthroline with C-methyl calix[4]resorcinarene (CMCR) in presence of coumarin results in a unique trimer stacking arrangement of phenanthroline molecules in a nanotubular motif generated by the supramolecular assembly of the host.