Few-Layer Borocarbonitride Nanosheets: Platinum-Free Catalyst for the Oxygen Reduction Reaction

The present study demonstrates the use of few-layer borocarbonitride nanosheets synthesized by a simple method as non-platinum cathode catalysts for the oxygen reduction reaction (ORR) in alkaline medium. Composition-dependent ORR activity is observed and the best performance was found when the composition was carbon-rich. Mechanistic aspects reveal that ORR follows the 4e(-) pathway with kinetic parameters comparable to those of the commercial Pt/C catalyst. Excellent methanol tolerance is observed with the BCN nanosheets unlike with Pt/C.

Chirality dependent elastic properties of single-walled boron nitride nanotubes under uniaxial and torsional loading

The elastic behavior of single-walled boron nitride nanotubes is studied under axial and torsional loading. Molecular dynamics simulation is carried out with a tersoff potential for modeling the interatomic interactions. Different chiral configurations with similar diameter are considered to study the effect of chirality on the elastic and shear moduli. Furthermore, the effects of tube length on elastic modulus are also studied by considering different aspects ratios. It is observed that both elastic and shear moduli depend upon the chirality of a nanotube. For aspect ratios less than 15, the elastic modulus reduces monotonically with an increase in the chiral angle. For chiral nanotubes, the torsional response shows a dependence on the direction of loading. The difference between the shear moduli against and along the chiral twist directions is maximum for chiral angle of 15 degrees, and zero for zigzag (0 degrees) and armchair (30 degrees) configurations. (C) 2014 AIP Publishing LLC.

Remarkable influence of secondary catalyst site on enantioselective desymmetrization of cyclopentenedione

An efficient, robust and highly enantioselective catalytic desymmetrization of 2,2-disubstituted cyclopentene-1,3-diones is developed via direct vinylogous nucleophilic addition of deconjugated butenolides. A remarkable influence of the secondary catalyst site on the enantioselectivity points towards an intriguing mechanistic scenario, possibly by triggering a change in catalyst conformation.

An oxygen evolution Co-Ac catalyst - the synergistic effect of phosphate ions

Formation of an amorphous cobalt based oxygen evolution catalyst called Co-Pi has been recently reported from a neutral phosphate buffer solution containing Co2+. But the concentration of Co2+ is as low as 0.5 mM due to poor solubility of a cobalt salt in phosphate medium. In the present study, a cobalt acetate based oxygen evolution catalyst (Co-Ac) is prepared from a neutral acetate buffer solution, where the solubility of Co2+ is very high (>100 times in comparison with phosphate buffer solution). The Co-Ac possesses better catalytic activity than the Co-Pi with an additional advantage of easy bulk scale preparation. The comparative studies on the oxygen evolution reaction (OER) activity of Co-Ac and Co-Pi in phosphate and acetate buffer electrolytes reveal that the Co-Ac exhibits enhanced synergistic catalytic activity in phosphate solution, probably due to partial substitution of acetate in the catalyst layer by phosphate, resulting in the formation of a Co-Ac-Pi catalyst.

Tailor-Made Hollow Silver Nanoparticle Cages Assembled with Silver Nanoparticles: An Efficient Catalyst for Epoxidation

A novel approach toward the synthesis of hollow silver nanoparticle (NP) cages built with building blocks of silver NPs by layer-by-layer (LbL) assembly is demonstrated. The size of the NP cage depends on the size of template used for the LbL assembly. The microcages showed a uniform distribution of spherical silver nanoparticles with an average diameter of 20 +/- 5 nm, which increased to 40 +/- S nm when the AgNO3 concentration was increased from 25 to 50 mM. Heat treatment of the polyelectrolyte capsules at 80 degrees C near their pK(a) values yielded intact nano/micro cages. These cages produced a higher conversion for the epoxidation of olefins and maintained their catalytic activity even after four successive uses. The nanocages exhibited unique and attractive characteristics for metal catalytic systems, thus offering the scope for further development as heterogeneous catalysts.

Micromechanisms of fracture and strengthening in free-standing Pt-aluminide bond coats under tensile loading

Free-standing Pt-aluminide (PtAl) bond coats exhibit a linear stress strain response under tensile loading and undergo brittle cleavage fracture at temperatures below the brittle-to-ductile transition temperature (BDTT). Above the BDTT, these coatings show yielding and fail in a ductile manner. In this paper, the various micromechanisms affecting the tensile fracture stress (FS) below the BDTT and yield strength (YS) above the BDTT in a PtAl bond coat have been ascertained and quantified at various temperatures. The micromechanisms have been identified by carrying out microtensile testing of stand-alone PtAl coating specimens containing different levels of Pt at temperatures between room temperature and 1100 degrees C and correlation of the corresponding fracture mechanisms with the deformation substructure in the coating. An important aspect of the influence of Pt on the tensile behavior, slip characteristics, FS/YS and BDTT in the PtAl coating has also been examined. The addition of Pt enhances the FS of the coating by Pt solid solution strengthening and imparts a concomitant increase in fracture toughness and yet causes a significant increase in the BDTT of the coating. Published by Elsevier Ltd. on behalf of Acta Materialia Inc.

Reduced Graphene Oxide-Polypyrrole Composite as a Catalyst for Oxygen Electrode of High Rate Rechargeable Li-O-2 Cells

Polypyrrole (PPY) is grown on reduced graphene oxide (RGO) and the composite is studied as a catalyst for O-2 electrode in Li-O-2 cells. PPY is uniformly distributed on the two dimensional RGO layers. Li-O-2 cells assembled in a non-aqueous electrolyte using RGO-PPY catalyst exhibit an initial discharge capacity as high as 3358 mAh g(-1) (3.94 mAh cm(-2)) at a current density of 0.3 mA cm(-2). The voltage gap between the charge and discharge curves is less for Li-O-2(RGO-PPY) cell in comparison with Li-O-2(RGO) cell. The Li-O-2(RGO-PPY) cell delivers a discharge capacity of 550 mAh g(-1) (0.43 mAh cm(-2)) at a current density of 1.0 mA cm(-2). The results suggest that RGO-PPY is a promising catalyst of O-2 electrode for high rate rechargeable Li-O-2 cells. (C) 2014 The Electrochemical Society. All rights reserved.

Pristine and graphitized-MWCNTs as durable cathode-catalyst supports for PEFCs

Long-term deterioration in the performance of PEFCs is attributed largely to reduction in active area of the platinum catalyst at cathode, usually caused by carbon-support corrosion. Multi-walled carbon-nanotubes (MWCNTs) as cathode-catalyst support are found to enhance long-term stability of platinum catalyst (Pt) in relation to non-graphitic carbon. In addition, highly graphitic MWCNTs (G-MWCNTs) are found to be electrochemically more stable than pristine MWCNTs. This is because graphitic-carbon-supported-Pt (Pt/MWCNTs) cathodes exhibit higher resistance to carbon corrosion in-relation to non-graphitic-carbon-supported-Pt (Pt/C) cathodes in PEFCs during accelerated stress-test (AST) as evidenced by chronoamperometry and carbon dioxide studies. The corresponding change in electrochemical surface area (ESA), cell performance, and charge-transfer resistance are monitored through cyclic voltammetry, cell polarization, and impedance measurements, respectively. The extent of crystallinity, namely amorphous or graphitic nature of the three supports, is examined by Raman spectroscopy. X-ray diffraction and transmission electron microscopy studies both prior and after AST suggest lesser deformation in catalyst layer and catalyst particles for Pt/G-MWCNTs and Pt/MWCNTs cathodes in relation to Pt/C cathodes, reflecting that graphitic carbon-support resists carbon corrosion and helps mitigating aggregation of Pt particles. It is also found that with increasing degree of graphitization, the electrochemical stability for MWCNTs increases due to the lesser surface defects.

Characterizing Frictional Contact Loading via Isochromatics

Isochromatic patterns in the vicinity of frictional contacts furnish vital clues for characterizing friction. Though friction effects are evident in a diametrally loaded circular disk, three-point loading provides better results towards highlighting friction. In this paper, a new method of characterizing friction at loading contacts using photoelastic isochromatics patterns is presented. Location of isotropic points (IPs) formed in three-point and four-point loadings of circular disk is used as a main tool to quantify the friction component using theoretical analysis. Bifurcation of isochromatic fringe loops near the distributed loads is explained by the presence of anti-symmetric Hertzian shear traction in addition to Hertzian normal traction. The classical solution by Flamant for point load at the edge of half plane is used to derive stresses in circular disk for all required loading configurations. A semicircualr ring under three-point loading is examined using photoelasticity to understand the isochromatics pattern theoretically by considering normal and shear traction components at loaded regions.

Asymptotic expansions for wavenumbers in orthotropic fluid-filled circular cylindrical shells for intermediate fluid loading

Coupled wavenumbers in infinite fluid-filled isotropic and orthotropic cylindrical shells are considered. Using the Donnell-Mushtari (DM) theory for thin shells, compact and elegant asymptotic expansions for the wavenumbers are found at an intermediate fluid loading for both the coupled rigid-duct modes (''fluid-originated'') and the coupled structural wavenumbers (''structure-originated modes'') over the entire frequency range where DM theory is valid. The coupled rigid-duct expansions are found to be valid for O(1) orthotropy and for all circumferential orders, whereas the coupled structural wavenumber expansions are valid for small orthotropy and for low circumferential orders. These two above results are then used to derive the expansions for a set of multiple complex roots that display a locking behavior at this intermediate fluid-loading. The expansions are matched with the numerical solutions of the coupled dispersion relation and the match is found to be good over most of the frequency range. (C) 2014 Acoustical Society of America.

Effect of adsorbate loading on selectivity during adsorption of C/C and C/C n-alkane binary mixtures in silicalite

Adsorption experiments of mixtures of long chain alkanes into silicalite under liquid phase conditions show selectivity inversion and azeotrope formation. These effects are due to the subtle interplay between the size of the adsorbed molecules and pore topology of the adsorbent. In this study, the selective uptake of lighter component during liquid phase adsorption of C/C and C/C n-alkane binary mixtures in the zeolite silicalite is understood through configurational bias grand-canonical Monte Carlo molecular simulation technique and a coarse-grained siting analysis. The simulations are conducted under conditions of low and intermediate levels of loading. The siting pattern of the adsorbates inside the zeolite pores explain the selectivity as seen in experiments.

Orientation, Size, and Temperature Dependent Ductile Brittle Transition in NiAl Nanowire under Tensile Loading - A Molecular Dynamics Study

In the present paper, thermo-mechanical response of B2-NiAl nanowire along the < 100 >, < 110 >, and < 111 > orientations has been studied using molecular dynamics simulations. Nanowire with cross-sectional dimensions of similar to 20x20 angstrom(2), similar to 25x25 angstrom(2), and similar to 30x30 angstrom(2) and temperature range of 10 K-900 K has been considered. A Combined effect of size, orientation, and temperature on the stress-strain behavior under uniaxial tensile loading has been presented. It has been observed that < 111 > oriented NiAl nanowire that is energetically most stable gives highest yield stress which further reduces with < 110 > and < 100 > orientations. A remarkable ductile brittle transition (DBT) with an increase in temperature has also been reported for all the orientations considered in the present study. The DBT observed for the nanowire has also been compared with the reported DBT of bulk B2-NiAl obtained from experiments. Alternate technique has also been proposed to increase the toughness of a given material especially at lower temperature regions, i.e. below DBT.

Reduced graphene oxide-supported nickel oxide catalyst with improved CO tolerance for formic acid electrooxidation

The superior catalytic activity along with improved CO tolerance for formic acid electro-oxidation has been demonstrated on a NiO-decorated reduced graphene oxide (rGO) catalyst. The cyclic voltammetry response of rGO-NiO/Pt catalyst elucidates improved CO tolerance and follows direct oxidation pathway. It is probably due to the beneficial effect of residual oxygen groups on rGO support which is supported by FT-IR spectrum. A strong interaction of rGO support with NiO nanoparticles facilitates the removal of CO from the catalyst surface. The chronoamperometric response indicates a higher catalytic activity and stability of rGO-NiO/Pt catalyst than the NiO/Pt and unmodified Pt electrode catalyst for a prolonged time of continuous oxidation of formic acid. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Ag nanoparticles-anchored reduced graphene oxide catalyst for oxygen electrode reaction in aqueous electrolytes and also a non-aqueous electrolyte for Li-O-2 cells

Silver nanoparticles-anchored reduced graphene oxide (Ag-RGO) is prepared by simultaneous reduction of graphene oxide and Ag+ ions in an aqueous medium by ethylene glycol as the reducing agent. Ag particles of average size of 4.7 nm were uniformly distributed on the RGO sheets. Oxygen reduction reaction (ORR) is studied on Ag-RGO catalyst in both aqueous and non-aqueous electrolytes by using cyclic voltammetry and rotating disk electrode techniques. As the interest in non-aqueous electrolyte is to study the catalytic performance of Ag-RGO for rechargeable Li-O-2 cells, these cells are assembled and characterized. Li-O-2 cells with Ag-RGO as the oxygen electrode catalyst are subjected to charge-discharge cycling at several current densities. A discharge capacity of 11 950 mA h g(-1) (11.29 mA h cm(-2)) is obtained initially at low current density. Although there is a decrease in the capacity on repeated discharge-charge cycling initially, a stable capacity is observed for about 30 cycles. The results indicate that Ag-RGO is a suitable catalyst for rechargeable Li-O-2 cells.

Analysis of cracked and un-cracked semicircular rings under symmetric loading

Edge cracked specimens have been widely utilized for fracture testing. Edge cracked semicircular disk (ECSD) specimen has now been well characterized with regard to its form factor and weight function. This paper presents a modified semicircular ring version of this specimen to enhance the form factor in general while retaining other desirable features. The efficacy of the modified design is proved by combining theory of elasticity solutions with finite element results to arrive at the optimum design geometry. New insights emerging from this work are used to theoretically re-examine the arch-tension and the four-point bend specimens. (C) 2014 Elsevier Ltd. All rights reserved.