Facile hydrothermal synthesis of carbon nanoparticles and possible application as white light phosphors and catalysts for the reduction of nitrophenol

We report a simple hydrothermal synthesis of highly reproducible carbon nanoparticles in a size range between 2 and 7 nmfroma single precursor sucrose without either surface passivating agents or acids and bases. The carbon nanoparticles can be used as white light phosphors, especially for ultraviolet light emitting diodes and metal-free catalyst for the reduction of nitrophenol.

Analytical test functions for free vibration analysis of rotating non-homogeneous Timoshenko beams

In this paper, the governing equations for free vibration of a non-homogeneous rotating Timoshenko beam, having uniform cross-section, is studied using an inverse problem approach, for both cantilever and pinned-free boundary conditions. The bending displacement and the rotation due to bending are assumed to be simple polynomials which satisfy all four boundary conditions. It is found that for certain polynomial variations of the material mass density, elastic modulus and shear modulus, along the length of the beam, the assumed polynomials serve as simple closed form solutions to the coupled second order governing differential equations with variable coefficients. It is found that there are an infinite number of analytical polynomial functions possible for material mass density, shear modulus and elastic modulus distributions, which share the same frequency and mode shape for a particular mode. The derived results are intended to serve as benchmark solutions for testing approximate or numerical methods used for the vibration analysis of rotating non-homogeneous Timoshenko beams.

Microstructure Development, Nanomechanical, and Dynamic Compression Properties of Spark Plasma Sintered TiB2-Ti-Based Homogeneous and Bi-layered Composites

The growing threats due to increased use of small-caliber armor piercing projectiles demand the development of new light-weight body armor materials. In this context, TiB2 appears to be a promising ceramic material. However, poor sinterability and low fracture toughness remain two major issues for TiB2. In order to address these issues together, Ti as a sinter-aid is used to develop TiB2-(x wt pct Ti), (x = 10, 20) homogeneous composites and a bi-layered composite (BLC) with each layer having Ti content of 10 and 20 wt pct. The present study uniquely demonstrates the efficacy of two-stage spark plasma sintering route to develop dense TiB2-Ti composites with an excellent combination of nanoscale hardness (similar to 36 GPa) and indentation fracture toughness (similar to 12 MPa m(1/2)). In case of BLC, these properties are not compromised w.r.t. homogeneous composites, suggesting the retention of baseline material properties even in the bi-layer design due to optimal relief of residual stresses. The better indentation toughness of TiB2-(10 wt pct Ti) and TiB2-(20 wt pct Ti) composites can be attributed to the observed crack deflection/arrest, indicating better damage tolerance. Transmission electron microscope investigation reveals the presence of dense dislocation networks and deformation twins in alpha-Ti at the grain boundaries and triple pockets, surrounded by TiB2 grains. The dynamic strength of around 4 GPa has been measured using Split Hopkinson Pressure Bar tests in a reproducible manner at strain rates of the order of 600 s(-1). The damage progression under high strain rate has been investigated by acquiring real time images for the entire test duration using ultra-high speed imaging. An attempt has been made to establish microstructure-property correlation and a simple analysis based on Mohr-Coulomb theory is used to rationalize the measured strength properties.

Uninterrupted galvanic reaction for scalable and rapid synthesis of metallic and bimetallic sponges/dendrites as efficient catalysts for 4-nitrophenol reduction

Here, we demonstrate an uninterrupted galvanic replacement reaction (GRR) for the synthesis of metallic (Ag, Cu and Sn) and bimetallic (Cu M, M=Ag, Au, Pt and Pd) sponges/dendrites by sacrificing the low reduction potential metals (Mg in our case) in acidic medium. The acidic medium prevents the oxide formation on Mg surface and facilitates the uninterrupted reaction. The morphology of dendritic/spongy structures is controlled by the volume of acid used for this reaction. The growth mechanism of the spongy/dendritic microstructures is explained by diffusion-limited aggregate model (DLA), which is also largely affected by the volume of acid. The significance of this method is that the yield can be easily predicted, which is a major challenge for the commercialization of the products. Furthermore, the synthesis is complete in 1-2 minutes at room temperature. We show that the sponges/dendrites efficiently act as catalysts to reduce 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) using NaBH4-a widely studied conversion process.

Two-dimensional homogeneous isotropic fluid turbulence with polymer additives

We carry out an extensive and high-resolution direct numerical simulation of homogeneous, isotropic turbulence in two-dimensional fluid films with air-drag-induced friction and with polymer additives. Our study reveals that the polymers (a) reduce the total fluid energy, enstrophy, and palinstrophy; (b) modify the fluid energy spectrum in both inverse-and forward-cascade regimes; (c) reduce small-scale intermittency; (d) suppress regions of high vorticity and strain rate; and (e) stretch in strain-dominated regions. We compare our results with earlier experimental studies and propose new experiments.

Noble metal ion substituted CeO2 catalysts: Electronic interaction between noble metal ions and CeO2 lattice

In last 40 years, CeO2 has been found to play a major role in the area of auto exhaust catalysis due to its unique redox properties. Catalytic activity is enhanced when CeO2 is added to the noble metals supported Al2O3 catalysts. Reason for increase in catalytic activity is due to higher dispersion of noble metals in the form of ions in CeO2. This has led to the idea of substitution of noble metal ions in CeO2 lattice acting as adsorption sites instead of nanocrystalline noble metal particles on CeO2. In this article, a brief review of synthesis, structure and catalytic properties of noble metal ions dispersed on CeO2 resulting in noble metal ionic catalysts (NMIC) like Ce1-xMxO2-delta, Ce1-x-yTixMyO2-delta, Ce1-x-yZrxMyO2-delta, Ce1-x-ySnxMyO2-delta and Ce1-x-yFexMyO2-delta (M = Pt, Pd, Rh and Ru) are presented. Substitution of Ti, Zr, Sn and Fe in CeO2 increases oxygen storage capacities (OSC) due to structural distortion, whereas dispersion of noble metal ions in Ti, Zr, Sn and Fe substituted CeO2 supports increase both OSC and catalytic activities. Electronic interaction between noble metal ions and CeO2 in NMICs responsible for higher OSC and higher catalytic activities is discussed. (C) 2015 Published by Elsevier B.V.

Homogeneous isotropic superfluid turbulence in two dimensions: Inverse and forward cascades in the Hall-Vinen-Bekharevich-Khalatnikov model

We present the first direct-numerical-simulation study of the statistical properties of two-dimensional superfluid turbulence in the simplified, Hall-Vinen-Bekharevich-Khalatnikov two-fluid model. We show that both normalfluid and superfluid energy spectra can exhibit two power-law regimes, the first associated with an inverse cascade of energy and the second with the forward cascade of enstrophy. We quantify the mutual-friction-induced alignment of normal and superfluid velocities by obtaining probability distribution functions of the angle between them and the ratio of their moduli.

An Exponential Lower Bound for Homogeneous Depth Four Arithmetic Formulas

We show here a 2(Omega(root d.log N)) size lower bound for homogeneous depth four arithmetic formulas. That is, we give an explicit family of polynomials of degree d on N variables (with N = d(3) in our case) with 0, 1-coefficients such that for any representation of a polynomial f in this family of the form f = Sigma(i) Pi(j) Q(ij), where the Q(ij)'s are homogeneous polynomials (recall that a polynomial is said to be homogeneous if all its monomials have the same degree), it must hold that Sigma(i,j) (Number of monomials of Q(ij)) >= 2(Omega(root d.log N)). The above mentioned family, which we refer to as the Nisan-Wigderson design-based family of polynomials, is in the complexity class VNP. Our work builds on the recent lower bound results 1], 2], 3], 4], 5] and yields an improved quantitative bound as compared to the quasi-polynomial lower bound of 6] and the N-Omega(log log (N)) lower bound in the independent work of 7].

Hydrogen energy future with formic acid: a renewable chemical hydrogen storage system

Formic acid, the simplest carboxylic acid, is found in nature or can be easily synthesized in the laboratory (major by-product of some second generation biorefinery processes); it is also an important chemical due to its myriad applications in pharmaceuticals and industry. In recent years, formic acid has been used as an important fuel either without reformation (in direct formic acid fuel cells, DFAFCs) or with reformation (as a potential chemical hydrogen storage material). Owing to the better efficiency of DFAFCs compared to several other PEMFCs and reversible hydrogen storage systems, formic acid could serve as one of the better fuels for portable devices, vehicles and other energy-related applications in the future. This perspective is focused on recent developments in the use of formic acid as a reversible source for hydrogen storage. Recent developments in this direction will likely give access to a variety of low-cost and highly efficient rechargeable hydrogen fuel cells within the next few years by the use of suitable homogeneous metal complex/heterogeneous metal nanoparticle-based catalysts under ambient reaction conditions. The production of formic acid from atmospheric CO2 (a greenhouse gas) will decrease the CO2 content and may be helpful in reducing global warming.

Delineation of homogeneous temperature regions: a two-stage clustering approach

Homogeneous temperature regions are necessary for use in hydrometeorological studies. The regions are often delineated by analysing statistics derived from time series of maximum, minimum or mean temperature, rather than attributes influencing temperature. This practice cannot yield meaningful regions in data-sparse areas. Further, independent validation of the delineated regions for homogeneity in temperature is not possible, as temperature records form the basis to arrive at the regions. To address these issues, a two-stage clustering approach is proposed in this study to delineate homogeneous temperature regions. First stage of the approach involves (1) determining correlation structure between observed temperature over the study area and possible predictors (large-scale atmospheric variables) influencing the temperature and (2) using the correlation structure as the basis to delineate sites in the study area into clusters. Second stage of the approach involves analysis on each of the clusters to (1) identify potential predictors (large-scale atmospheric variables) influencing temperature at sites in the cluster and (2) partition the cluster into homogeneous fuzzy temperature regions using the identified potential predictors. Application of the proposed approach to India yielded 28 homogeneous regions that were demonstrated to be effective when compared to an alternate set of 6 regions that were previously delineated over the study area. Intersite cross-correlations of monthly maximum and minimum temperatures in the existing regions were found to be weak and negative for several months, which is undesirable. This problem was not found in the case of regions delineated using the proposed approach. Utility of the proposed regions in arriving at estimates of potential evapotranspiration for ungauged locations in the study area is demonstrated.

Delineation of homogeneous hydrometeorological regions using wavelet-based global fuzzy cluster analysis

Identification of homogeneous hydrometeorological regions (HMRs) is necessary for various applications. Such regions are delineated by various approaches considering rainfall and temperature as two key variables. In conventional approaches, formation of regions is based on principal components (PCs)/statistics/indices determined from time series of the key variables at monthly and seasonal scales. An issue with use of PCs for regionalization is that they have to be extracted from contemporaneous records of hydrometeorological variables. Therefore, delineated regions may not be effective when the available records are limited over contemporaneous time period. A drawback associated with the use of statistics/indices is that they do not provide effective representation of the key variables when the records exhibit non-stationarity. Consequently, the resulting regions may not be effective for the desired purpose. To address these issues, a new approach is proposed in this article. The approach considers information extracted from wavelet transformations of the observed multivariate hydrometeorological time series as the basis for regionalization by global fuzzy c-means clustering procedure. The approach can account for dynamic variability in the time series and its non-stationarity (if any). Effectiveness of the proposed approach in forming HMRs is demonstrated by application to India, as there are no prior attempts to form such regions over the country. Drought severity-area-frequency (SAF) curves are constructed corresponding to each of the newly formed regions for the use in regional drought analysis, by considering standardized precipitation evapotranspiration index (SPEI) as the drought indicator.

Prussian blue as a single precursor for synthesis of Fe/Fe3C encapsulated N-doped graphitic nanostructures as bi-functional catalysts

We report a unique, single source precursor Prussian blue (iron(III) ferrocyanide (Fe-4(III)Fe-II(CN)(6)](3))) for the synthesis of Fe/Fe3C nanoparticle encapsulated N-doped graphitic layers and bamboo-like graphitic nanotubes. Hollow N-doped graphite (N-HG) nanostructures are obtained when the encapsulated nanostructures are treated with an acid. Both the encapsulated nanostructures and N-HG are shown to be applicable as bi-functional electrocatalysts for oxygen reduction (ORR) and oxygen evolution reactions (OER). The ORR activity is shown to be improved for N-HG and is comparable to commercial Pt/C. On the other hand, encapsulated nanostructures exhibit OER activity with long-term stability comparable to commercial RuO2.

Molecular Cage Impregnated Palladium Nanoparticles: Efficient, Additive-Free Heterogeneous Catalysts for Cyanation of Aryl Halides

Two shape-persistent covalent cages (CC1(r) and CC2(r)) have been devised from triphenyl amine-based trialdehydes and cyclohexane diamine building blocks utilizing the dynamic imine chemistry followed by imine bond reduction. The cage compounds have been characterized by several spectroscopic techniques which suggest that CC1(r) and CC2(r) are 2+3] and 8+12] self-assembled architectures, respectively. These state-of-the-art molecules have a porous interior and stable aromatic backbone with multiple palladium binding sites to engineer the controlled synthesis and stabilization of ultrafine palladium nanoparticles (PdNPs). As-synthesized cage-embedded PdNPs have been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and powder X-ray diffraction (PXRD). Inductively coupled plasma optical emission spectrometry reveals that Pd@CC1(r) and Pd@CC2(r) have 40 and 25 wt% palladium loading, respectively. On the basis of TEM analysis, it has been estimated that as small as similar to 1.8 nm PdNPs could be stabilized inside the CC1(r), while larger CC2(r) could stabilize similar to 3.7 nm NPs. In contrast, reduction of palladium salts in the absence of the cages form structure less agglomerates. The well-dispersed cage-embedded NPs exhibit efficient catalytic performance in the cyanation of aryl halides under heterogeneous, additive-free condition. Moreover, these materials have excellent stability and recyclability without any agglomeration of PdNPs after several cycles.

Prussian blue as a single precursor for synthesis of Fe/Fe3C encapsulated N-doped graphitic nanostructures as bi-functional catalysts

We report a unique, single source precursor Prussian blue (iron(III) ferrocyanide (Fe-4(III)Fe-II(CN)(6)](3))) for the synthesis of Fe/Fe3C nanoparticle encapsulated N-doped graphitic layers and bamboo-like graphitic nanotubes. Hollow N-doped graphite (N-HG) nanostructures are obtained when the encapsulated nanostructures are treated with an acid. Both the encapsulated nanostructures and N-HG are shown to be applicable as bi-functional electrocatalysts for oxygen reduction (ORR) and oxygen evolution reactions (OER). The ORR activity is shown to be improved for N-HG and is comparable to commercial Pt/C. On the other hand, encapsulated nanostructures exhibit OER activity with long-term stability comparable to commercial RuO2.

Complex patterns arise through spontaneous symmetry breaking in dense homogeneous networks of neural oscillators

There has been much interest in understanding collective dynamics in networks of brain regions due to their role in behavior and cognitive function. Here we show that a simple, homogeneous system of densely connected oscillators, representing the aggregate activity of local brain regions, can exhibit a rich variety of dynamical patterns emerging via spontaneous breaking of permutation or translational symmetries. Upon removing just a few connections, we observe a striking departure from the mean-field limit in terms of the collective dynamics, which implies that the sparsity of these networks may have very important consequences. Our results suggest that the origins of some of the complicated activity patterns seen in the brain may be understood even with simple connection topologies.