Functionality preservation with enhanced mechanical integrity in the nanocomposites of the metal-organic framework, ZIF-8, with BN nanosheets

Metal-organic frameworks (MOFs) and boron nitride both possess novel properties, the former associated with microporosity and the latter with good mechanical properties. We have synthesized composites of the imidazolate based MOF, ZIF-8, and few-layer BN in order to see whether we can incorporate the properties of both these materials in the composites. The composites so prepared between BN nanosheets and ZIF-8 have compositions ZIF-1BN, ZIF-2BN, ZIF-3BN and similar to ZIF-4BN. The composites have been characterized by PXRD, TGA, XPS, electron microscopy, IR, Raman and solid state NMR spectroscopy. The composites possess good surface areas, the actual value decreasing only slightly with the increase in the BN content. The CO2 uptake remains nearly the same in the composites as in the parent ZIF-8. More importantly, the addition of BN markedly improves the mechanical properties of ZIF-8, a feature that is much desired in MOFs. Observation of microporous features along with improved mechanical properties in a MOF is indeed noteworthy. Such manipulation of properties can be profitably exploited in practical applications.

Metal-organic chemical vapor-deposited cobalt oxide films as negative electrodes for thin film Li-ion battery

In this study, thin films of cobalt oxide (Co3O4) have been grown by the metal-organic chemical vapor deposition (MOCVD) technique on stainless steel substrate at two preferred temperatures (450 degrees C and 500 degrees C), using cobalt acetylacetonate dihydrate as precursor. Spherical as well as columnar microstructures of Co3O4 have been observed under controlled growth conditions. Further investigations reveal these films are phase-pure, well crystallized and carbon-free. High-resolution TEM analysis confirms that each columnar structure is a continuous stack of minute crystals. Comparative study between these Co3O4 films grown at 450 degrees C and 500 degrees C has been carried out for their application as negative electrodes in Li-ion batteries. Our method of electrode fabrication leads to a coating of active material directly on current collector without any use of external additives. A high specific capacity of 1168 micro Ah cm(-2) mu m(-1) has been measured reproducibly for the film deposited at 500 degrees C with columnar morphology. Further, high rate capability is observed when cycled at different current densities. The Co3O4 electrode with columnar structure has a specific capacity 38% higher than the electrode with spherical microstructure (grown at 450 degrees C). Impedance measurements on the Co3O4 electrode grown at 500 degrees C also carried out to study the kinetics of the electrode process. (C) 2014 Published by Elsevier B.V.

Influence of dynamic operating conditions on the performance of metal hydride based solid sorption cooling systems

The performance of metal hydride based solid sorption cooling systems depends on the driving pressure differential, and the rate of hydrogen transfer between coupled metal hydride beds during cooling and regeneration processes. Conventionally, the mid-plateau pressure difference obtained from `static' equilibrium PCT data are used for the thermodynamic analysis. It is well known that the processes are `dynamic' because the pressure and temperature, and hence the concentration of the hydride beds, are continuously changing. Keeping this in mind, the pair of La0.9Ce0.1Ni5 - LaNi4.7Al0.3 metal hydrides suitable for solid sorption cooling systems were characterised using both static and dynamic methods. It was found that the PCT characteristics, and the resulting enthalpy (Delta H) and entropy (Delta S) values, were significantly different for static and dynamic modes of measurements. In the present study, the solid sorption metal hydride cooling system is analysed taking in to account the actual variation in the pressure difference (Delta P) and the dynamic enthalpy values. Compared to `static' property based analysis, significant decrease in the driving potentials and transferrable amounts of hydrogen, leading to decrease in cooling capacity by 57.8% and coefficient of performance by 31.9% are observed when dynamic PCT data at the flow rate of 80 ml/min are considered. Copyright 2014 (C) Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Semiconductor to metal transition in bilayer phosphorene under normal compressive strain

Phosphorene, a two-dimensional analog of black phosphorous, has been a subject of immense interest recently, due to its high carrier mobilities and a tunable bandgap. So far, tunability has been predicted to be obtained with very high compressive/tensile in-plane strains, and vertical electric field, which are difficult to achieve experimentally. Here, we show using density functional theory based calculations the possibility of tuning electronic properties by applying normal compressive strain in bilayer phosphorene. A complete and fully reversible semiconductor to metal transition has been observed at similar to 13.35% strain, which can be easily realized experimentally. Furthermore, a direct to indirect bandgap transition has also been observed at similar to 3% strain, which is a signature of unique band-gap modulation pattern in this material. The absence of negative frequencies in phonon spectra as a function of strain demonstrates the structural integrity of the sheets at relatively higher strain range. The carrier mobilities and effective masses also do not change significantly as a function of strain, keeping the transport properties nearly unchanged. This inherent ease of tunability of electronic properties without affecting the excellent transport properties of phosphorene sheets is expected to pave way for further fundamental research leading to phosphorene-based multi-physics devices.

Differential response of cholesterol based pyrimidine systems with oxyethylene type spacers to gelation and mesogen formation in the presence of alkali metal ions

A new series of lipophilic cholesteryl derivatives of 2,4,6-trichloro-pyrimidine-5-carbaldehyde has been synthesized. Oxyethylene spacers of variable lengths were inserted between the hydrogen bonding promoting pyrimidine core and the cholesteryl tail in order to understand their effect on the selfassembly of these compounds. Only compound 1a with the shortest spacer formed a gel in organic solvents such as n-butanol and n-dodecane. While other members (1b and c) having longer spacers led to sol formation and precipitation in n-butanol and n-dodecane respectively. The self-assembly phenomena associated with the gelation process were investigated using temperature-dependent UVVis and CD-spectroscopy. The morphological features of the freeze-dried gels obtained from different organic solvents were examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The solid phase behaviours of these molecules and their associated alkali metal ion complexes were explored using polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The molecular arrangements in the xerogel and in the solid state were further probed using a wide-angle Xray diffraction (WAXD) technique. Analysis of the wide-angle X-ray diffraction data reveals that this class of molecules adopts a hexagonal columnar organization in the gel and in the solid state. Each slice of these hexagonal columnar structures is composed of a dimeric molecular-assembly as a building block. Significant changes in the conformation of the oxyethylene chains could be triggered via the coordination of selected alkali metal ions. This led to the production of interesting metal ion promoted mesogenic behaviour.

A smart approach to achieve an exceptionally high loading of metal nanoparticles supported by functionalized extended frameworks for efficient catalysis

The problem associated with metal nanoparticle (NP) agglomeration when trying to achieve a high loading amount has been solved by a new method of functionalization of MOFs' pores with terminal alkyne moieties. The alkynophilicity of the Au3+ ions has been utilized successfully for an exceptionally high loading (similar to 50 wt%) of Au-NPs on supported functionalized MOFs.

Nanocomposite Made of an Oligo(p-phenylenevinylene)-Based Trihybrid Thixotropic Metallo(organo)gel Comprising Nanoscale Metal-Organic Particles, Carbon Nanohorns, and Silver Nanoparticles

A silver ion (Ag+)-triggered thixotropic metallo(organo)gel of p-pyridyl-appended oligo(p-phenylenevinylene) derivatives (OPVs) is reported for the first time. Solubilization of single-walled carbon nanohorns (SWCNHs) in solutions of the pure OPVs as well as in the metallogels mediated by pi-pi interactions has also been achieved. In situ fabrication of silver nanoparticles (AgNPs) in the SWCNH-doped dihybrid gel leads to the formation of a trihybrid metallogel. The mechanical strength of the metallogels could be increased step- wise in the order: freshly prepared gel metal organic particles (NMOPs), flowerlike aggregates of SWCNHs and AgNPs, and also their integration with each other. Detailed studies suggest lamellar organizations of the linear metal ligand complexes in the NMOPs, which upon association create a three-dimensional network that eventually immobilizes the solvent molecules.

Fish Inspired Biomimetic Ionic Polymer-Metal Composite Pectoral Fins Using Labriform Propulsion

In this article, we analyze and design ionic polymer metal composite (IPMC) underwater propulsors inspired from swimming of labriform fishes. The structural model of the IPMC fin accounts for the electromechanical dynamics of the bean in water. A quasi steady blade element model that accounts for unsteady phenomena, such as added mass effects, dynamic stall, and cumulativeWagner effect is used to estimate the hydrodynamic performance. Dynamic characteristics of IPMC actuated flapping fins having the same size as the actual fins of three different fish species, Gomphosus varius, Scarus frenatus, and Sthethojulis trilineata, are analyzed using numerical simulations.

Effect of mass loading on ionic polymer metal composite actuators and sensors

Ionic polymer metal composites (IPMC) actuator for flapping insect scale wing is advantageous due to its low mass, high deflection and simple actuation mechanism. Some of the factors that affect the actuation of IPMC are the amount of hydration in the polymer membrane and the environmental conditions such as temperature, humidity etc. In structural design, the attachment of wing on the IPMC actuators is an important concern as the attached wing increases the mass of actuators thereby affecting the parameters like displacement, stiffness and resonant frequencies. Such IPMC actuators have to produce sufficient actuation force and frequency to lift and flap the attached wing. Therefore, it is relevant to study the influence of attachment of wing on the actuator parameters (displacement, resonant frequency, block force and stiffness) and performance of the actuators. This paper is divided into two parts; the first part deals with the modeling of the IPMC actuators for its effect on the level of water uptake and temperature using energy based method. The modeling method adapted is validated with the experimental procedure used to actuate the IPMC. The second part deals with the experimental analysis of IPMC actuation at dry, wet and in water conditions. The effect of end mass loading on the performance of 20 Hz, high frequency actuator (HFA) and 8.7 Hz, low frequency IPMC actuators (LFA) and sensors is studied. The IPMC actuators are attached with IPMC flapping wing at its free end and performance analysis on the attached wing is also carried out.

Effect of the nature of a transition metal dopant in BaTiO3 perovskite on the catalytic reduction of nitrobenzene

In the present study, we have synthesized Fe, Co and Ni doped BaTiO3 catalyst by a wet chemical synthesis method using oxalic acid as a chelating agent. The concentration of the metal dopant varies from 0 to 5 mol% in the catalysts. The physical and chemical properties of doped BaTiO3 catalysts were studied using various analytical methods such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), BET surface area and Transmission electron microscopy (TEM). The acidic strength of the catalysts was measured using a n-butylamine potentiometric titration method. The bulk BaTiO3 catalyst exhibits a tetragonal phase with the P4mm space group. A structural transition from tetrahedral to cubic phase was observed for Fe, Co and Ni doped BaTiO3 catalysts with an increase in doped metal concentration from 1 to 5 mol%. The particle sizes of the catalysts were calculated from TEM images and are in the range of 30-80 nm. All the catalysts were tested for the catalytic reduction of nitrobenzene to azoxybenzene. The BaTiO3 catalyst was found to be highly active and less selective compared to the doped catalysts which are active and highly selective towards azoxybenzene. The increase in selectivity towards azoxybenzene is due to an increase in acidic strength and reduction ability of the doped metal. It was also observed that the nature of the metal dopant and their content at the B-site has an impact on the catalytic reduction of nitrobenzene. The Co doped BaTiO3 catalyst showed better activity with only 0.5 mol% doping than Fe and Ni doped BaTiO3 catalysts with maximum nitrobenzene conversion of 91% with 78% selectivity to azoxybenzene. An optimum Fe loading of 2.5 mol% in BaTiO3 is required to achieve 100% conversion with 93% selectivity whereas Ni with 5 mol% showed a conversion of 93% and a azoxybenzene selectivity of 84%.

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.

Lithium metal borate (LiMBO3) family of insertion materials for Li-ion batteries: a sneak peak

Rechargeable lithium-ion battery remains the leading electrochemical energy-storage device, albeit demanding steady effort of design and development of superior cathode materials. Polyanionic framework compounds are widely explored in search for such cathode contenders. Here, lithium metal borate (LiMBO3) forms a unique class of insertion materials having the lowest weight polyanion (i. e., BO33-), thus offering the highest possible theoretical capacity (ca. 220 mAh/g). Since the first report in 2001, LiMBO3 has rather slow progress in comparison to other polyanionic cathode systems based on PO4, SO4, and SiO4. The current review gives a sneak peak to the progress on LiMBO3 cathode systems in the last 15 years highlighting their salient features and impediments in cathode implementation. The synthesis and structural aspects of borate family are described along with the critical analysis of the electrochemical performance of borate family of insertion materials.

Metal-insulator transition characteristics of vanadium dioxide thin films synthesized by ultrasonic nebulized spray pyrolysis of an aqueous combustion mixture

We report the synthesis of high quality vanadium dioxide (VO2) thin films by a novel spray pyrolysis technique, namely ultrasonic nebulized spray pyrolysis of aqueous combustion mixture (UNSPACM). This simple and cost effective two step process involves synthesis of a V2O5 film on an LaAlO3 substrate followed by a controlled reduction to form single phase VO2. The formation of M1 phase (p21/c) is confirmed by Raman spectroscopic studies. A thermally activated metal-insulator transition (MIT) was observed at 61 degrees C, where the resistivity changes by four orders of magnitude. Activation energies for the low conduction phase and the high conduction phase were obtained from temperature variable resistance measurements. The infrared spectra also show a dramatic change in reflectance from 13% to over 90% in the wavelength range of 7-15 mu m. This indicates the suitability of the films for optical switching applications at infrared frequencies.

Tuning the metal-insulator transition in NdNiO3 heterostructures via Fermi surface instability and spin fluctuations

We employed in situ pulsed laser deposition (PLD) and angle-resolved photoemission spectroscopy (ARPES) to investigate the mechanism of the metal-insulator transition (MIT) in NdNiO3 (NNO) thin films, grown on NdGaO3(110) and LaAlO3(100) substrates. In the metallic phase, we observe three-dimensional hole and electron Fermi surface (FS) pockets formed from strongly renormalized bands with well-defined quasiparticles. Upon cooling across the MIT in NNO/NGO sample, the quasiparticles lose coherence via a spectral weight transfer from near the Fermi level to localized states forming at higher binding energies. In the case of NNO/LAO, the bands are apparently shifted upward with an additional holelike pocket forming at the corner of the Brillouin zone. We find that the renormalization effects are strongly anisotropic and are stronger in NNO/NGO than NNO/LAO. Our study reveals that substrate-induced strain tunes the crystal field splitting, which changes the FS properties, nesting conditions, and spin-fluctuation strength, and thereby controls the MIT via the formation of an electronic order parameter with QAF similar to (1/4,1/4,1/4 +/- delta).

Morphology control synthesis of Au-Cu2S metal-semiconductor hybrid nanostructures by modulating reaction constituents

A facile methodology for synthesizing Au-Cu2S hybrid nanoparticles is presented. Au-Cu2S nanoparticles have application in visible light driven photocatalytic degradation of dyes. Detailed microstructural and compositional characterization illustrated that the hybrid nanoparticles are composed of cube shaped Au-Cu solid solution and hemispherical shaped Cu2S phases. Investigation of nanoparticles extracted at different stages of the synthesis process revealed that the mechanism of formation of hybrid nanoparticles involved initial formation of isolated cube shaped pure Au nanoparticles and Cu-thiolate complex. In the subsequent stages, the Au nanoparticles get adsorbed onto the Cu-thiolate complex which is followed by the decomposition of the Cu-thiolate complex to form Au-Cu2S hybrid nanoparticles. This study also illustrates that an optimum concentration of dodecanethiol is required both for achieving size and morphological uniformity of the participating phases and for their attachment to form a hybrid nanoparticle.