Synthesis and characterization of porous flowerlike alpha-Fe2O3 nanostructures for supercapacitor application

Porous flower-like alpha-Fe2O3 nanostructures synthesized by an ethylene glycol mediated self-assembly process are crystalline and porous with BET surface area of 64.6 m(2) g(-1). The discharge capacitance is 127 F g(-1) when the electrodes are cycled in 0.5 M Na2SO3 at a current density of 1 A g(-1). Capacitance retention after 1000 cycles is about 80% of the initial capacitance. The high discharge capacitance and its retention are attributed to high surface area and porosity of the iron oxide. As the iron oxides are inexpensive, the nano alpha-Fe2O3 is expected to be of potential use for supercapacitor application.

Probing hemoglobin confinement inside submicron silica tubes using synchrotron SAXS and electrochemical response

The configuration of hemoglobin in solution and confined inside silica nanotubes has been studied using synchrotron small angle X-ray scattering and electrochemical activity. Confinement inside submicron tubes of silica aid in preventing protein aggregation, which is vividly observed for unconfined protein in solution. The radius of gyration (R-g) and size polydispersity (p) of confined hemoglobin was found to be lower than that in solution. This was also recently demonstrated in case of confined hemoglobin inside layered polymer capsules. The confined hemoglobin displayed a higher thermal stability with Rg and p showing negligible changes in the temperature range 25-75 degrees C. The differences in configuration between the confined and unconfined protein were reflected in their electrochemical activity. Reversible electrochemical response (from cyclic voltammograms) obtained in case of the confined hemoglobin, in contrary to the observance of only a cathodic response for the unconfined protein, gave direct indication of the differences between the residences of the electroactive heme center in a different orientation compared to that in solution state. The confined Hb showed loss of reversibility only at higher temperatures. The electron transfer coefficient (alpha) and electron transfer rate constant (k(s)) were also different, providing additional evidence regarding structural differences between the unconfined and confined states of hemoglobin. Thus, absence of any adverse effects due to confinement of proteins inside the inorganic matrices such as silica nanotubes opens up new prospects for utilizing inorganic matrices as protein ``encapsulators'', as well as sensors at varying temperatures.

Ethylenediamine assisted synthesis of wurtzite zinc sulphide nanosheets and porous zinc oxide nanostructures: near white light photoluminescence emission and photocatalytic activity under visible light irradiation

Porous fungus-like ZnO nanostructures have been synthesized by simple thermal annealing of the hydrothermally synthesized sheet-like ZnS(en)(0.5) complex precursor in air at 600 degrees C. Structural and morphological changes occurring during ZnS(en)(0.5) -> ZnS -> ZnO transformations have been observed closely by annealing the as-synthesized precursor at 100-600 degrees C. Wurtzite ZnS nanosheets and ZnS-ZnO composites are obtained at temperatures of 400 degrees C and 500 degrees C, respectively. Thermal decomposition and oxidation of the ZnS(en) 0.5 nanosheets have been confirmed by differential scanning calorimetry and thermo-gravimetric analysis. The visible light driven photocatalytic degradation of methylene blue dye has been demonstrated in the synthesized samples. ZnS-ZnO composite shows the highest dye degradation efficiency of 74% due to the formation of surface complex as well as higher visible light absorption as a result of band-gap narrowing effect. The porous ZnO nanostructures show efficient visible photoluminescence (PL) emission with a colour coordinate of (0.29, 0.35), which is close to that of white light (0.33, 0.33). The efficient visible PL emission as well as visible light driven photocatalytic activity of the materials synthesized in the present work might be very attractive for their applications in future optoelectronic devices, including in white light emitting devices.

An electron rich porous extended framework as a heterogeneous catalyst for Diels-Alder reactions

An electron rich porous metal-organic framework (MOF) has been synthesized, which acts as an effective heterogeneous catalyst for Diels-Alder reactions through encapsulation of the reactants in confined nano-channels of the framework.

Wafer scale fabrication of porous three-dimensional plasmonic metamaterials for the visible region: chiral and beyond

We report on a wafer scale fabrication method of a three-dimensional plasmonic metamaterial with strong chiroptical response in the visible region of the electromagnetic spectrum. The system was comprised of metallic nanoparticles arranged in a helical fashion, with high degree of flexibility over the choice of the underlying material, as well as their geometrical parameters. This resulted in exquisite control over the chiroptical properties, most importantly the spectral signature of the circular dichroism. In spite of the large variability in the arrangement, as well as the size and shape of the constituent nanoparticles, the average chiro-optical response of the material remained uniform across the wafer, thus confirming the suitability of this system as a large area chiral metamaterial. By simply heating the substrate for a few minutes, the geometrical properties of the nanoparticles could be altered, thus providing an additional handle towards tailoring the spectral response of this novel material.

Spatial Wavelet Approach to Local Matrix Crack Detection in Composite Beams with Ply Level Material Uncertainty

Wavelet coefficients based on spatial wavelets are used as damage indicators to identify the damage location as well as the size of the damage in a laminated composite beam with localized matrix cracks. A finite element model of the composite beam is used in conjunction with a matrix crack based damage model to simulate the damaged composite beam structure. The modes of vibration of the beam are analyzed using the wavelet transform in order to identify the location and the extent of the damage by sensing the local perturbations at the damage locations. The location of the damage is identified by a sudden change in spatial distribution of wavelet coefficients. Monte Carlo Simulations (MCS) are used to investigate the effect of ply level uncertainty in composite material properties such as ply longitudinal stiffness, transverse stiffness, shear modulus and Poisson's ratio on damage detection parameter, wavelet coefficient. In this study, numerical simulations are done for single and multiple damage cases. It is observed that spatial wavelets can be used as a reliable damage detection tool for composite beams with localized matrix cracks which can result from low velocity impact damage.

High Li storage capacity of poorly crystalline porous delta-MnO2 prepared by hydrothermal route

Poorly crystalline porous delta-MnO2 is synthesized by hydrothermal route from a neutral aqueous solution of KMnO4 at 180 degrees C and the reaction time of 24 h. The as-synthesized sample and also the sample heated at 300 degrees C have nanopetals morphology with large surface area. On heating at temperatures 400 degrees C, there is a decrease in BET surface area and also a change in morphology from nanopetals to clusters of nanorods. Furthermore, the poorly crystalline delta-MnO2 converts into well crystalline alpha-MnO2 phase. The electrochemical lithium intercalation and de-intercalation studies in a non-aqueous electrolyte provide a high discharge specific capacity (275 mAh g(-1)) at a specific current of 40 mA g(-1) for the poorly crystalline delta-MnO2 samples. The rate capability is also high. There is a decrease in capacity on repeated charge-discharge cycling. The specific capacity values of the crystalline alpha-MnO2 samples are considerably less than the values of poorly crystalline delta-MnO2 samples. Thus, the hydrothermal route facilitates preparation of poorly crystalline electrochemically active porous MnO2.

Role of silica nanoparticles in conductivity enhancement of nanocomposite solid polymer electrolytes: (PEG(x) NaBr): ySiO(2)

Nanocomposite solid polymer electrolytes (NCSPEs) with conducting species other than Li ions are being investigated for solid-state battery applications. Pristine solid polymer electrolytes (SPEs) do not show ionic conductivity suitable for batteries. Addition of inert fillers to SPEs is known to enhance the ionic conductivity. In this paper, we present the role of silica nanoparticles in enhancing the ionic conductivity in NCSPEs with sodium as conducting species. Sodium bromide is complexed with the host polyethylene glycol polymer by solution cast method and silica nanoparticles (SiO2, average particle size 7 nm) are incorporated into the complex in small amounts. The composites are characterized by powder XRD and IR spectroscopy. Conductivity measurements are undertaken as a function of concentration of salt and also as a function of temperature using impedance spectroscopy. Addition of silica nanoparticles shows an enhancement in conductivity by 1-2 orders of magnitude. The results are discussed in terms of interaction of nanoparticles with the nonconducting anions.

Tb3+ sensitization in a deoxycholate organogel matrix, and selective quenching of luminescence by an aromatic nitro derivative

In this article, we present the discovery of a metallo-organogel derived from a Tb3+ salt and sodium deoxycholate (NaDCh) in methanol. The gel was made luminescent through sensitization of Tb3+ by doping with 2,3-dihydroxynaphthalene (DHN) in micromolar concentrations. Rheological measurements of the mechanical properties of the organogel confirmed the characteristics of a true gel. Significant quenching of Tb3+ luminescence was observed in the deoxycholate gel matrix by 2,4,7-trinitrofluorenone (TNF), but not by several other polynitro aromatics. Microscopic studies (AFM, TEM and SEM) revealed a highly entangled fibrous network. The xerogels retained luminescent properties suggesting the possibility for application in coatings, etc.

Vertical electric field stimulated neural cell functionality on porous amorphous carbon electrodes

We demonstrate the efficacy of amorphous macroporous carbon substrates as electrodes to support neuronal cell proliferation and differentiation in electric field mediated culture conditions. The electric field was applied perpendicular to carbon substrate electrode, while growing mouse neuroblastoma (N2a) cells in vitro. The placement of the second electrode outside of the cell culture medium allows the investigation of cell response to electric field without the concurrent complexities of submerged electrodes such as potentially toxic electrode reactions, electro-kinetic flows and charge transfer (electrical current) in the cell medium. The macroporous carbon electrodes are uniquely characterized by a higher specific charge storage capacity (0.2 mC/cm(2)) and low impedance (3.3 k Omega at 1 kHz). The optimal window of electric field stimulation for better cell viability and neurite outgrowth is established. When a uniform or a gradient electric field was applied perpendicular to the amorphous carbon substrate, it was found that the N2a cell viability and neurite length were higher at low electric field strengths (<= 2.5 V/cm) compared to that measured without an applied field (0 V/cm). While the cell viability was assessed by two complementary biochemical assays (MTT and LDH), the differentiation was studied by indirect immunostaining. Overall, the results of the present study unambiguously establish the uniform/gradient vertical electric field based culture protocol to either enhance or to restrict neurite outgrowth respectively at lower or higher field strengths, when neuroblastoma cells are cultured on porous glassy carbon electrodes having a desired combination of electrochemical properties. (C) 2013 Elsevier Ltd. All rights reserved.

Polymer template-assisted microemulsion synthesis of large surface area, porous Li2MnO3 and its characterization as a positive electrode material of Li-ion cells

Lithium-rich manganese oxide (Li2MnO3) is prepared by reverse microemulsion method employing Pluronic acid (P123) as a soft template and studied as a positive electrode material. The as-prepared sample possesses good crystalline structure with a broadly distributed mesoporosity but low surface area. As expected, cyclic voltammetry and charge-discharge data indicate poor electrochemical activity. However, the sample gains surface area with narrowly distributed mesoporosity and also electrochemical activity after treating in 4 M H2SO4. A discharge capacity of about 160 mAh g(-1) is obtained. When the acid-treated sample is heated at 300 A degrees C, the resulting porous sample with a large surface area and dual porosity provides a discharge capacity of 240 mAh g(-1). The rate capability study suggests that the sample provides about 150 mAh g(-1) at a specific discharge current of 1.25 A g(-1). Although the cycling stability is poor, the high rate capability is attributed to porous nature of the material.

Synthesis, characterisation and application of an exfoliated graphite-diamond composite electrode in the electrochemical degradation of trichloroethylene

A composite electrode made up of exfoliated graphite (EG) and diamond was prepared for the electrochemical oxidation of trichloroethylene (TCE). The SEM images of the EG-diamond material showed that diamond powders were dispersed on the surface of EG materials. The N-2 adsorption-desorption isotherm of EG-diamond material resulted in a poor adsorption capability due to the insertion of diamond powders into the porous matrix of EG. Raman spectroscopy revealed the presence of characteristic sp(3) bands of diamond confirming good interaction of diamond with EG. Electrochemical characterisation of EG-diamond in 0.1 M Na2SO4 resulted in an enhanced working potential window. The EG-diamond electrode was employed for the electrochemical oxidation of trichloroethylene (0.2 mM) in a Na2SO4 supporting electrolyte. The EG-diamond, in comparison to the pristine EG electrode, exhibited a higher removal efficiency of 94% (EG was 57%) and faster degradation kinetics of 25.3 x 10(-3) min(-1) showing pseudo first order kinetic behaviour. Under the optimised conditions, 73% total organic content (TOC) removal was achieved after 4 h of electrolysis. The degradation of TCE was also monitored with gas chromatography-mass spectrometry. Dichloroacetic acid (DCAA) was identified as a major intermediate product during the electrochemical oxidation of TCE. The electrochemical degradation of TCE at the EG-diamond electrode represents a cost effective method due to the ease of preparation of EG-diamond composite material without the necessity of diamond activation which is normally achieved through doping.

Effect of analyte concentration on the laser-induced plasma temperature and electron density in liquid matrix

In the present work, we report spectroscopic studies of laser-induced plasmas produced by focusing the second harmonic (532nm) of a Nd:YAG laser onto the laminar flow of a liquid containing chromium. The plasma temperature is determined from the coupled Saha-Boltzmann plot and the electron density is evaluated from the Stark broadening of an ionic line of chromium Cr(II)] at 267.7nm. Our results reveal a decrease in plasma temperature with an increase in Cr concentration up to a certain concentration level; after that, it becomes approximately constant, while the electron density increases with an increase in analyte (Cr) concentration in liquid matrix.

Gas sensing response analysis of p-type porous chromium oxide thin films

The ethanol sensing properties of porous Cr2O3 thin films deposited by the ultrasonic nebulized spray pyrolysis of an aqueous combustion mixture is reported. The impact of the precursor selection and various deposition parameters on the film crystallinity, surface morphology and stoichiometry are studied using thermo-gravimetric analysis, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and atomic force microscopy techniques. The film morphology exhibits a highly porous nature, as a result of the exothermic combustion reaction during film deposition. The gas sensing properties of these films are investigated in the temperature range of 200-375 degrees C for ethanol. The films show two different regions of response for ethanol above and below 300 degrees C. A good relationship between the response and the ethanol concentration is observed, and is modeled using an empirical relation. The possible mechanism and the surface chemical reactions of ethanol over the chromium oxide surface are discussed.